Renewable and Sustainable Energy Reviews 45 (2015) 574588

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

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

Recent trends of biodiesel production from animal fat wastes

and associated production techniques
Peter Adewale, Marie-Jose Dumont n, Michael Ngadi nn
Department of Bioresource Engineering, McGill University, 21111 Lakeshore Rd., Ste-Anne-de-Bellevue, QC, Canada H9X 3V9

art ic l e i nf o

a b s t r a c t

Article history:
Received 27 May 2014
Received in revised form
14 January 2015
Accepted 8 February 2015
Available online 25 February 2015

Non-edible feedstocks such as animal fat wastes (AFWs) have recently increased in popularity as
alternatives to vegetable oils in the production of biodiesel. They are low cost, mitigate environmental
damage and increase the quality of the resultant biodiesel fuel (low NOx emissions, high Cetane number
and oxidative stability). Therefore, AFWs are an excellent feedstock for biodiesel production. Here we
provide a comprehensive review trends and techniques in biodiesel production from AFWs. A critical
overview of homogeneous and heterogeneous (one- or two-step) catalytic transesterication of AFWs is
presented. Similarly, enzyme-catalyzed transesterication and the application of supercritical uids
conversion techniques in the production of biodiesel from AFWs are thoroughly assessed. Finally, cutting
edge advances in assisted transesterication processes for biodiesel production are critically reviewed.
& 2015 Elsevier Ltd. All rights reserved.

Keywords:
Animal fat wastes
Biodiesel
Transesterication
Production techniques
Assisted-transesterication

Contents
1.
2.

3.

4.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575
Non-edible feedstocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 576
2.1.
Non-edible vegetable oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 576
2.2.
Waste cooking oils. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 576
2.3.
Animal fats. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 576
2.3.1.
Chicken fat . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 578
2.3.2.
Lard . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
2.3.3.
Tallow. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
2.3.4.
Leather industry solid waste fat . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
2.3.5.
Fish oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
Biodiesel production techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
3.1.
Direct use and blending . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
3.2.
Microemulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
3.3.
Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581
3.4.
Transesterication reaction techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581
3.4.1.
Homogeneous catalytic conversion of AFWs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
3.4.2.
Heterogeneous catalytic conversion of AFWs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
3.4.3.
Enzyme catalytic conversion of AFWs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 583
3.4.4.
Supercritical non-catalytic conversion of AFWs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 583
Assisted transesterication techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 584
4.1.
Ultrasound-assisted technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 584
4.2.
Microwave-assisted technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 584

Corresponding author. Tel.: 1 514 398 7776; fax: 1 514 398 8387.
Corresponding author. Tel.: 1 514 398 7779; fax: 1 514 398 8387.
E-mail addresses: marie-josee.dumont@mcgill.ca (M.-J. Dumont),
michael.ngadi@mcgill.ca (M. Ngadi).
nn

http://dx.doi.org/10.1016/j.rser.2015.02.039
1364-0321/& 2015 Elsevier Ltd. All rights reserved.

P. Adewale et al. / Renewable and Sustainable Energy Reviews 45 (2015) 574588

575

5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 584
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 585
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 585

1. Introduction
Biodiesel production and use have enticed many countries to
invest in the technologies and equipment involved in its production. The European Biodiesel Board (2011) reported that the
European Union produced over 24.7  109 L yr  1 in 2011, while
the US produced 4.16  109 L yr  1of biodiesel in 2011 [1]. Due to
new production capacity, projected Canadian biodiesel production
for 2013 (0.471  109 L yr  1) was more than double estimates for
2012 (0.210  109 L yr  1). A forecasted rise to biodiesel production
of 0.65  109 L in 2014 was partly attributed to the expected
completion of a plant producing 2.65  108 L yr  1 [2]. The major
biodiesel feedstock in Europe, United States, and Canada is rapeseed (Brassica napus L.) oil, soybean (Glyine max (L.) Merr.), and
canola (low erucic acid varieties of B. napus L.) oil, respectively.
There has been a strong drive for the use of rendered animal fats,
rendered oils, as well as palm (Elaeis guineensis Jacq.) oil in order
to increase biodiesel production and meet biodiesel demand in
some countries such as United States, Europe, china, Malaysia and
Canada [2]. In the international market, rendered animal fats are
classied as feeds and industrial products which makes their price
low. Therefore, AFWs could drastically lower the cost of biodiesel
production and make biodiesel competitive with petro-diesel.
Biodiesel can be synthesized from different varieties of feedstocks such as edible vegetable oils (e.g. canola oil, sunower oil,
etc.), non-edible vegetable oils (e.g. Jatropha oil, Pongamia oil,
etc.), waste cooking oils, and animal fats. Price and availability are
important factors that determine different types of feedstocks
used for biodiesel production from one region of the world to
another [37]. Despite the current growth, sustainability of the
biodiesel industries may be limited due to the industrys inability
to secure cheap feedstock [2]. Most of the current and forecasted
biodiesel production in Canada comes from canola (Fig. 1). Similarly, other biodiesel producing countries (US and Europe) depend
on edible vegetable oils as feedstocks. This trend also implies the
need for large supply of vegetable oils, which if they are drawn
from neat edible oil sources, may lead to food security and ethical

Biodiesel feedstocks

250

Amount (1000 MT)

200

150

100

50

0
2006

2007

2008

2009

2010

2011

2012

2013

2014

Year
Canola

Animal Fat

Recycled Oils

Soybean

Fig. 1. The current and forecasted biodiesel production feedstocks in Canada (Data
source [2]).

issues. Such situation, regarding diversion of food crops to biofuel

production have engendered heated arguments worldwide [812].
Investigators have sought to eschew feedstocks which might
threaten food safety and produce higher quality biodiesel at a lower
cost [4,1316]. Some of these feedstocks include tallow, lard,
chicken fat, leather industry solid wastes, etc. AFWs are abundant
in some regions resulting in lower feedstock cost. Using waste
animal fats as feedstock for biodiesel production has the added
advantages of reducing environmental damage by creating a fuel
with lower or equal NOx emission as vegetable oil biodiesel [1719].
Biodiesel from AFW feedstocks also has high Cetane number, an
important quality parameter for diesel fuels [2022]. The AFWs
comprise of a high ratio of saturated fatty acids [23], which are the
reason behind high Cetane number (460) as compared to most
vegetable oils. A higher Cetane number is known to lower NOx by
lowering temperatures during the critical early part of the combustion process [4,20,24]. Similarly, the saturated fatty acids in AFWs
contribute to better oxidative stability for biodiesel [25,26]. But the
presence of a high content in free fatty acid (FFA) in AFWs has been
seen as a challenge, especially when synthesized by alkalinecatalyzed transesterication.
Biodiesel production techniques which lead to production
efciency are very important to be considered in the development
of a biodiesel plant. Two major production techniques namely
chemical and biological techniques are currently used to synthesize biodiesel from animal fats and vegetable oils. Chemical
synthesis involves the application of acidic or basic catalytic
conversion. Biological synthesis involves the application of enzymatic conversion, mainly lipases. Other production techniques
involving the use of non-catalytic methods and supercritical
temperature conversions are being investigated [2729]. Although
chemical-based production techniques are widely used in industrial scale production of biodiesel, but they have limitations
namely high pollution emission, a complex downstream purication process, and high equipment, energy, and alcohol requirements. Enzyme-based production techniques are suitable for
overcoming the limitations of chemical-based production techniques [7,2730] and have the advantages of overcoming the specic
limitations of base or acid transesterication technology (e.g. need
for feedstock extremely low in FFA content and moisture) through
an enzyme-catalyzed transesterication process. Compared to
chemical-based catalysis, biodiesel production by enzymatic catalysis limits the risk of soap formation and the need to use a high
molar ratio of alcohol to animal fat in the process [31]. High cost
and easy inactivation of lipases by methanol are the main shortcoming of enzyme-catalyzed technology however, enzyme immobilization techniques have generated more alcohol-tolerant
lipases, thus providing a cost-efcient and reusable enzyme [32].
This paper reviews current literature on the use of non-edible
feedstocks with special attention to AFWs for biodiesel production.
Conventional and emerging techniques for improved biodiesel
yields were also elucidated. Some of the new and emerging techniques involve the use of treatments to reduce reactor operation
time while achieving the highest yield possible. Ultrasoundassisted (UA) and microwave-assisted (MA) transesterication
are examples of the emerging techniques for the production of
biodiesel. UA technique is of interest to many researchers due to
its shorter reaction times, cheap reagents and the non-complexity
of the process reactors. Similarly, application of MA technique has

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P. Adewale et al. / Renewable and Sustainable Energy Reviews 45 (2015) 574588

gained positive attention due to its rapid reaction rates, the high
purity of products, the improved yields, and the greater energy
efciency.

[4648]. The highly fertilized cultivation of non-edible oil crops

on arable areas for use as biofuel feedstocks may decrease their
price advantage and contribute to conicting land usage.

2. Non-edible feedstocks

2.2. Waste cooking oils

With an increasing world population the rising demand for

edible oils and animal fats has led to price increase on the world
markets and has limited their use as fuel, particularly in developing countries [33]. Several studies have shown greases and AFWs
are viable, reliable and environmental friendly feedstocks for
biodiesel production [16,3436]. These materials are available on
the order of teragrams in most developed countries. Similarly,
non-edible oil plants are naturally accessible worldwide [37,38].
Although there has not been any direct food vs. fuel competition
reported, indirect competition for land between food vs. nonedible oil crops might become a strong controversial debate.

The use of waste oils as biodiesel feedstock offers no direct

conict with food availability and land usage. Waste cooking or
frying oils (WFO) can be categorized into yellow grease and brown
grease. Used cooking oil contains vegetable oil or animal fat that
has been heated and used for cooking a wide variety of food such
as meat, sh, or vegetable products and may therefore include
grease rendered from hamburger, bacon or cooked meat entrees.
With FFA contents of less than 15%, yellow grease, generated from
used cooking oil, fats, and oils collected from restaurant or
industrial cooking operations, offers a considerable potential as a
low-cost raw material for biodiesel production [15].
Brown grease (i.e. trap grease) is collected from grease traps
installed in restaurant, industrial, or municipal sewage facilities to
separate grease and oil from waste water. Grease traps are sealed
containers installed in sewer lines in such a manner as to allow the
lighter grease and oil that is ushed down a drain to oat to the
top of the trap. These traps allow the water to ow under the
grease and through to the main sewer or water treatment area.
Brown grease is high in FFA (415%) and water content [15], which
negatively affects its potential conversion to biodiesel [49,50].
Alkaline catalyzed transesterication [5153], acid catalyzed
transesterication [5457], two-step transesterication [58,59],
enzymatic catalysis [27,60,61] and supercritical temperature processing [51,62] are all techniques for converting waste cooking oils
to biodiesel. Prolonged heating of initially virgin oil leads to waste
cooking oil accumulating FFA, which interferes with the alkaline
transesterication process since the alkaline catalyst acts on the FFA
to produce soap (saponication reaction). The saponication reaction reduces biodiesel yield and requires a more complex downstream separation of biodiesel, glycerol, and washing water [15,63].

2.1. Non-edible vegetable oils

In recent years, several investigations have been conducted on
the suitability of non-edible oilseed plants such as Oleaginous,
Leguminosae, Brassicaceae and Euphorbiaceae to produce biodiesel [6,30,37,3943]. The mature seeds of these oilseed plants bear
high oil content, but these oils are unsuitable for human consumption or animal feed given their high FFA content and the
presence of toxic substances. As in the case of edible oils, the use
of non-edible oils can actually polarize direct competition in terms
of food availability and safety. Some of the non-edible crops used
in biodiesel production, include: physic nut (Jatropha curcas L.),
karanja (Pongamia pinnata (L.) Pierre), rubber seed (Hevea brasiliensis (Willd. ex A. Juss.) Mll.Arg.), castor bean (Ricinus communis
L.), yellow oleander (Thevettia peruviana (Pers.) K. Schum), tobacco
(Nicotiana tabacum L), chinese tallow (Sapium sebiferum (L.) Dum.
Cours.), Rice (Oryza sativa L.) bran, sea mango (Cerbera odollam
Gaertn), cotton (Gossypium hirsutum L.), mahua (Madhuca indica
(J. Koenig ex L.) J.F.Macbr.) and ethiopian mustard (Brassica carinata
A. Braun) [5,8,44,45]. The research performed on non-edible plant
oils and their cultivations differs from region to region around the
world. For example, in the USA, Canada, and the EU, research on
lipid-based feedstocks focuses on oleaginous microorganisms

2.3. Animal fats

Animal fats are primarily derived as by-products from meat
animal processing facilities and by the rendering process. The

Table 1
Fatty acid compositions (%) of AFWs.
Fatty acids

Carbon number

Reference
Lauric
Myristic
Palmitic
Palmitioleic
Stearic
Oleic
Linoleic
Linolenic
Arachidic
Eicosenoic
Eicosadienoic
Eicosapentaenoic
Docosapentaenoic
Docosahexanoic
a

Yellow grease.
Brown grease.
c
Choice white grease.
d
Chicken fat.
e
Fish oil.
b

C12:0
C14:0
C16:0
C16:1
C18:0
C18:1
C18:2
C18:3
C20:0
C20:1
C20:2
C20:5
C22:5
C22:6

Animal fat wastes

YGa
[23]

BGb
[54,63]

CWGc
[23]

Lard
[23]

Tallow
[23]

CFd
[54]

FOe
[160]

1.02
14.83
1.50
8.41
47.88
19.11
4.68
2.56

1.7
23.8
3.1
12.5
42.4
12.1
0.8

1.60
22.39
3.40
9.15
44.14
11.90

7.43

1.41
25.69
2.82
14.50
40.88
12.93

0.50
1.34

2.76
25.95
2.84
17.54
41.67
6.91

0.44
1.88

22.20
8.40
5.10
42.50
19.30
1.00

0.14
5.77
16.94
5.42
4.31
19.20
16.05
2.82

15.55
2.45
11.36

P. Adewale et al. / Renewable and Sustainable Energy Reviews 45 (2015) 574588

577

Poultry wastes
(chicken feather, Blood, Offal and Trims)

Heating
eating

Wet
Wet heating
heating
Crushing

Dry Method

Wet Method

Drying

Solid

Liquid
Press

Defatting

Evaporating

High Protein Meal

Chicken Fat
Fig. 2. Poultry wastes rendering process.

Fig. 3. Flow diagram of wet rendering.

main animal fats include tallow from processing cattle, lard and
choice white grease from swine processing, and poultry fat from
the processing of chicken, turkey, or other birds. The fats/oils
generated by sh processing plant and leather industry eshing
wastes have also been found to be viable biodiesel feedstocks
[14,64,65]. Some animal fat based feedstocks are already in used at
the industrial scale (e.g. chicken, tallow, lard fats) for biodiesel
production [6668]. The use of animal fat wastes as biodiesel

feedstocks offers economic, environmental, and food security advantages over the more commonly used edible vegetable oils. AFWs
contain high levels of saturated fatty acids and FFA (Table 1),
requiring more complex production techniques, and this result in
biodiesel with a lower physical and chemical quality; however low
unsaturation of AFWs fatty acids has several advantages ( e.g. high
caloric value, high Cetane number and high oxidation stability)
[14,21,22].

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P. Adewale et al. / Renewable and Sustainable Energy Reviews 45 (2015) 574588

Fig. 4. Flow diagram of dry rendering.

Live Cattle or Sheep

Condemned
carcass

Slaughter

Animal co-product
Fat, inedible
offals

Ear, lungs tripe

Edible
Rendering

Meat &
Offals

Drying

Fat & waste

trims
Human
Concumptiom

High Content
protein

Tallow

Pet food

Fig. 5. Rendering process for the production of tallow.

2.3.1. Chicken fat

Chicken fat is generated during rendering of chicken feathers
and poultry by-products to produce feather meal (Fig. 2). Poultry
by-products consists of ground dry- or wet-rendered portion of the
clean carcass (e.g. heads, feet, undeveloped eggs, and intestines,
exclusive of feathers) [69]. The amount of fat extracted from the
feather meal varies from 2% to 12%, depending on feather type
[70,71]. Gr et al. [72] produced biodiesel from chicken fat through
a two-step catalytic process, using methanol (CH3OH), sulphuric
acid (H2SO4) and sodium hydroxide (NaOH) catalysts. The authors
studied the effects of a synthetic Mg additive to chicken fat
biodiesel in a single-cylinder, direct injection diesel engine and its

effects on engine performance and exhaust emissions. It was also

reported that increase in the magnesium concentration from 0 to
16 mmol L  1 led to decrease in viscosity and ash point from 5.184
to 4.812 and 129 1C to 122 1C, respectively. More so, a dosage of
16 mmol L  1 Mg into the chicken fat methyl ester caused a 7 1C
pour point decrease. Optimum pre-treatment and methyl ester
production conditions for chicken fat investigation were reported to
be 20% sulfuric acid and 40:1 methanol molar ratio based on the
amount of FFA (13.45%) in the chicken fat for 80 min at 60 1C, and
the methyl ester yield was 87.4% [73,74]. Supercritical CH3OH
transesterication method for converting chicken fat to biodiesel
was investigated at various temperatures (e.g. 350, 375, and 400 1C),

P. Adewale et al. / Renewable and Sustainable Energy Reviews 45 (2015) 574588

pressures (e.g. 100, 200, and 300 bar), molar ratios (3:1 to 12:1),
and reaction times (310 min), in which the best triglycerides
conversion and decomposition of glycerol were obtained at temperature, pressure, molar ratio, and reaction time: 400 1C, 300 bar,
9:1, and 6 min, respectively [75,76].
2.3.2. Lard
Lard is basically pig fat in its rendered form. Pig fat can be
rendered by a wet or dry process. In wet rendering (Fig. 3), pig fat
is boiled in water or steamed at a high temperature and the lard,
which is insoluble in water, is skimmed off the surface of the
mixture, or separated in an industrial centrifuge [77]. In dry
rendering (Fig. 4), the fat is exposed to high heat in a pan or oven
without the presence of water [77]. The two processes yield
different products. Wet-rendered lard has a more neutral avor,
a lighter color, and a high smoke point. Dry-rendered lard is
browner in color and has lower smoke point. Edible lard is
commonly used in many cuisines such as cooking fat or shortening, or as a spread similar to butter.
Dias et al. [78], studying the acid transesterication generation
of biodiesel from acid waste lard pretreated with up to 14.57 mg
KOH per g of FFA reported that the pre-treatment adopted
effectively enable acid waste lard to serve as a single raw material
for biodiesel production with acceptable quality, but a low yield
(65 % by weight). Mixtures of waste frying oil and pork lard were
investigated for the production of biodiesel which was reported to
have biodiesel yields varied from 81.7 to 88.0 (wt%) with the
lowest yields obtained by waste frying oil and lard alone as raw
materials [79]. The application of biocatalyst transesterication of
lard using Candida sp. 99125 was studied by investigating the
effect of temperature, water content, enzyme amount, solvent, and
three-step methanolysis on the yield of biodiesel from lard and the
optimal reaction conditions for processing 1 g of lard were: 0.2 g
immobilized lipase, 8 mL n-hexane as solvent, 20% water based on
the fat weight, temperature 40 1C, and three-step addition of
methanol which yielded 87.4% fatty acid methyl esters [80].
Similarly, process optimization of biodiesel production from lard
was reported on the effect of agitation speed (most suitable
600 rpm) and catalyst concentration (most suitable 0.9 wt%) by
developing a regression model to predict the methyl ester concentration which adequately described the experimental parameters range [81]. Shin et al. [82] reported the production of
biodiesel from waste lard by a supercritical temperature method in
the absence of catalyst and found that biodiesel produced from
waste lard under the optimal reaction conditions without pretreatment was comparable to that produced from rened lard,
even though waste lard samples contained various free fatty acid
contents and water.
2.3.3. Tallow
The rendering process converts slaughter house animal byproducts to a fat and protein meal (Fig. 5). In most tallows, 50% of
the total fatty acids are saturated [23,67]. Tallow has higher stearic
and palmitic acid contents which leads to high melting point and
viscosity [67,83,84], causing it to be solid at room temperature
[85]. One of the most commonly used animal fats employed as
substrate for biodiesel production is derived from beef or mutton
in the form of edible or non-edible tallow. The edible form is
relatively expensive and has a low FFA content, making it a viable
substrate for an alkaline transesterication reaction. Resource
availability, energetic efciency, and economic feasibility of converting edible and inedible beef tallow into biodiesel has previously been investigated [86]. The authors concluded that beef
tallow generated from the slaughter of cattle could provide a
historically cheap feedstock, which if converted to biodiesel,

579

would offer a wide range of energy, environmental, and economic

advantages. Ma and Hanna [85,87] studied the effects of catalysts,
FFA content, water content and mixing intensities on the yield of
biodiesel from edible tallow and reported that no reaction
occurred without mixing, but when a mixture of NaOH and CH3OH
was added to the melted beef tallow in the reactor only very
limited stirring was required for the process to occur. They further
found that adding NaOH and CH3OH solution to melted beef
tallow before stirring would require higher stirring speeds and
longer stirring times to mix the two phases.
Non-edible tallow is high in FFAs content; therefore, a more
expensive processing method will be needed for its conversion to
biodiesel. Feasibility studies of biodiesel production from low
grade or inedible tallow have been reported. Bhatti et al. [84]
studied the effect of process parameters on biodiesel production
from waste tallow by acid catalyzed transesterication. They
reported that under optimal processing conditions (60 1C, oil/
CH3OH molar ratio of 1:30, and 2.5 g of H2SO4) 5 g of mutton
tallow yielded a 93.21 % of biodiesel after 24 h. ner and Altun
[88] studied injection of biodiesel synthesized from inedible
animal tallow and its blends directly into diesel engines. The
authors observed decrease in the effective efciency of the engine
and increase in the specic fuel consumption [89] but signicant
reduction in emissions of carbon monoxide (CO), NOx, sulphur
dioxide (SO2), and smoke opacity were reported to be around 15%,
38.5%, 72.7% and 56.8%, respectively, for tallow methyl esters
(B100) as compared to petro-diesel. Teixeira et al. [90] compared
conventional and ultrasonic-assisted production of biodiesel from
beef tallow and found that the reaction rate and biodiesel quality
were similar in both cases but the use of ultrasonic irradiation
decreased the reaction time. However, the authors did not account
for the effects of ultrasonication parameters and optimization of
these parameters. The effectiveness of enzymatic transesterication of beef tallow using experimental enzyme ns88001 with
methanol and n-hexane as a solvent was reported by Kumar
et al. [91]. The authors showed that using n-hexane in the reaction
stabilized the enzyme and minimized toxicity of alcohol and the
activity of experimental enzyme catalyst (NS88001) in the presence n-hexane was found to slightly reduce after 10 cycles of
reusability. Hsu et al. [92] investigated the effects of the presence
of alcohol and the amount of enzyme used for production of alkyl
esters from tallow and grease using lipase immobilized in a
phyllosilicate solgel. The authors reported that transesterication
of tallow with primary alcohols (e.g. methanol) was effective using
immobilized PS-30 lipase with good conversions from 82 to 94%,
while free lipase under the same reaction conditions gave lower
conversions from 47 to 89% and the poorest yields were found in
methyl esters.

2.3.4. Leather industry solid waste fat

In the leather industry, solid waste fat is obtained from the
waste generated during the pre-eshing, lime eshing, shaving,
bufng and trimming processes [93]. The fat is in solid state at
room temperature and bears a high water content. It is subjected
to a heating at 110 1C for 1 h to remove water and then ltered to
remove the insoluble materials [14]. The Turkish research group of
Colak et al. [94,95] were the rst to investigate the use of leather
industry pre-eshing in biodiesel production. They proved that the
fat generated from tanneries eshing wastes could be utilized in
the production of an environmentally friendly fuel that could work
with petrodiesel engine without a need for a major adjustment. In
the study of the effects of biodiesel production parameters (e.g.
catalyst weight percentage, temperature and oil/alcohol molar
ratio) on base-catalyzed transesterication of raw eshing oil, ler
et al. [96] reported optimum reaction conditions for efcient

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P. Adewale et al. / Renewable and Sustainable Energy Reviews 45 (2015) 574588

biodiesel yield to consist of molar ratio of a 1:6 oil/alcohol; a

reaction temperature of 50 1C; a catalyst weight percentage of
0.75% and reaction period of 15 min.
Alptekin et al. [14] evaluated leather industry wastes as a
feedstock for biodiesel production by alkaline catalyzed transesterication. The authors studied the effects of catalyst type,
catalyst quantity and the alcohol molar ratio on the fuel properties
of methyl esters generated. The fuel properties was reported to t
the biodiesel standards except for cold lter plugging point (CFPP),
ester and sulfur content and improvement of CFPP was recommended by adding cold ow enhancers or mixed with petroleum
diesel fuel which has better cold ow properties. Ong et al. [64]
applied a supercritical methanol approach to the transesterication of leather tanning waste to produce biodiesel. The authors
modeled the kinetic reactions of fatty acid methyl esters (FAMEs)
formation from leather tanning waste, encompassing reversible
esterication, non-reversible and rst-order esterication singlestep, pseudo-rst order, and irreversible transesterication.
2.3.5. Fish oil
The sh processing industry generates signicant amount of
oil-rich wastes appropriate for biodiesel production [97]. Before
disposal, the efuents from the sh processing industry contain
heads, viscera, bones, trimmings, tails, ns and skin mixed with
wastewater. A substantial portion (611 wt%) of the efuent is oil
and a good yield is achieved with physical separation technique
[97]. The sh oil is recovered from the efuent by grinding/
homogenizing the waste, heating it to 95100 1C for 1520 min,
screw pressing to remove the liquid from the solids, centrifuging
the liquid to remove the water from the oil, and polishing the oil
by water washing [98]. A two-step transesterication method for
biodiesel production using oil from sh canning industry wastes
was investigated by Costa et al. [99]. The authors found that the
catalyst concentration during esterication to have the greatest
inuence on product yield and quality. The best conditions were
1 wt% catalyst and 60 vol% of methanolic solution. Recently,
Tanwar et al. [100] and Jayasinghe and Hawboldt [97] investigated
biodiesel production from sh processing plant efuents, which
included waste characterization and quality assessments. The
feedstock quality and type are the major factors in determining
the transesterication technique to adopt for biodiesel production
technique. Similar studies were carried out on the engine performance, emission and combustion of biodiesel synthesized from
sh processing industry efuent [101103].

3. Biodiesel production techniques

Four main techniques exist to reduce the potentially high
viscosity of biofuels made from animal fats and vegetable oils
and eliminate any operational problems from its use in a common
diesel engine: direct use and blending, microemulsions (cosolvent
blending), thermal cracking (pyrolysis) and transesterication
(alcoholysis) [104,105]. Leading to the products commonly known
as biodiesel (alkyl esters of oils and fats), transesterication is the
most commonly used method to reduce viscosity associated with
animal fats and vegetable oils. Methodologies such as microemulsions and pyrolysis of animal fats and vegetable oils can produce
compounds that are smaller than their triglyceride (TG) source,
resulting in lesser viscosity and making them suitable for use as a
fuel. However, they cannot be used for biodiesel production [85].
3.1. Direct use and blending
The main issues of direct use of animal fats as fuel in diesel
engines are their high viscosity and poor volatility. Some

investigators have attempted to directly inject animal fats into

an unmodied diesel engine. Senthil Kumar et al. [106] preheated
animal fat at different temperatures before injection into a singlecylinder direct injection diesel engine with a rated power of
2.8 kW at 1500 rpm. The preheated animal fat showed a reduced
ignition delay, reduced combustion duration, a rise in peak
pressure and lower smoke emissions than diesel. In a comparative
study of different methods of using animal fat as a fuel in a
compression ignition engine, Kumar et al. [107] used a singlecylinder air-cooled, direct injection diesel engine to test fuels at
100% and 60% of the engines maximum power output. The
authors reported a drop in cylinder peak pressure, a longer
ignition delay, and a lower premixed combustion rate with neat
animal fat as compared to neat diesel at normal temperature.
Numerically investigating a compression ignition engines operation using animal fats and vegetable oils as fuels, Bousbaa et al.
[108] reported slightly different combustion characteristics when
comparing neat diesel to biofuels. Fuel derived from AFWs
decreased the total unburned fuel as well as the nitrogen oxides
(NOx) emissions as compared to neat diesel. They concluded that
numerical results concurred with those obtained experimentally.
Blends of animal fats with petrodiesel has been used to reduce
the latters viscosity. Diesel engines have been reported to use the
resulting animal fats blends efciently. The major advantages of
the blending are the absence of technical modications and the
ease of implementation. Blending of animal fats with alcohols
results in a signicant improvement in their physical properties
[107109]. Storage stability of poultry fat and diesel fuel mixtures
in terms of: specic gravity and viscosity were studied and slight
changes in viscosity and specic gravity of the biofuels blends over
the course of one year storage period was found [110]. In a
comprehensive review of the direct use of vegetable oil and animal
fat as an alternative fuel in internal combustion engines, Mondal
et al. [111] reported that the effects of the high viscosity of animal
fats and their blends as a major cause of poor atomization and
difculty in handling by conventional fuel injection system of
compression ignition engines. Micro-emulsications permit a
greater atomization of fuel, improved brake thermal efciency,
and decrease smoke, particulate and nitric oxide emissions due to
micro-explosion [112].
3.2. Microemulsions
Microemulsication is a process used to formulate hybrid
diesel fuels by solubilisation of vegetable oil/alcohol mixtures
through the addition of amphiphiles. Alcohols such as CH3OH or
ethanol (CH3CH2OH) have limited solubility in nonpolar animal
fats and vegetable oils; therefore, amphiphilic compounds such as
phospholipids, sorbitan sesquiolate (Span83), n-butanol, 2-octanol, carboxylate surfactants and the like, are added to increase
solubility, dilute the oil, and reduce viscosity. An equilibrium
dispersion of optically isotropic uid microstructures with an
average diameter less than one quarter the wavelength of visible
light that spontaneously form upon the addition of amphiphiles to
a mixture of otherwise nearly immiscible liquids is known as a
microemulsion [112]. Microemulsions do not require agitation to
remain in a single-phase, translucent solution at constant temperature and pressure because they are thermodynamically stable
[113].
Investigating the use of animal fats as compression-ignition (CI)
engine fuel by making stable emulsion with water and CH3OH,
Kerihuel et al. [114] used Span 83 (sorbitan sesquiolate) and span
80 (sorbitan monooleate) as surfactants to prepare and stabilize
animal fat-water emulsions. They concluded that animal fats can
be transformed into a stable biofuel emulsions with improved
physical and chemical properties and can be used as a viable fuel

P. Adewale et al. / Renewable and Sustainable Energy Reviews 45 (2015) 574588

581

Table 2
Animal fats transesterication process parameters and techniques for biodiesel production.
Feedback

Production technique

Catalyst (wt/wt of fat)

Chicken fat

Homogeneous acid
Base
Homogeneous acid
Base
Heterogeneous acid
Homogeneous two
steps
Enzymatic
Homogeneous
Base
Homogeneous
Base
Homogeneous
Base
Homogeneous two
steps
Homogeneous
Base
Heterogeneous
Base
Heterogeneous
Base
Homogeneous two
steps

1:30
H2SO4 25%
KOH 1%

H2SO4 25%
1:30
KOH 1%

Surfonated polystyrene 20 mol%

Step 1: H2SO4 0.08%

Step 2: NaOH 0.001%

Immobilized-lipase (candida sp. 99125) 20 % 1:1
KOH 2%

KOH 1%

Lard

Enzymatic

Animal fats and sh oil

Chicken fat
Waste lard

Enzymatic
Supercritical methanol
Supercritical methanol

Mutton fat
Beef tallow
Waste animal fat
Lard
Beef tallow
Feather meal fat
(Beef tallow:sunower oil)
blends
(Lard:soybean oil) blend
Beef tallow
Poultry fat
Mutton tallow
Acid waste lard

Molar
ratio

T
(1C)

Time (h)

Conversion
(%)

Reference

50
30
60
30
64
62

24
1
24
1
18
2

99.01
88.10
93.21
79.70
75.00
89.00

[84]

40
60

30
1.5

87.40
95.00

[80]
[89]

1:9

70

1/4

[69]

NaOH 1%

1:6

60

711 (dry
basis)

NaOH 0.8%

1:6

65

81.788.6

[131]

KOH 1.5%

1:6

65

[67]

MgAl hydrocalcite 10%

1:30

120

93.00

[134]

MgOKOH

1:22

65

1/3

98.00

[136]

Step 1: H2SO4 2%
Step 2: NaOH 1%

1:6

65

66.20

[78]

(Novozym435 and Lipozyme TLIM) combine

4%
Lipozyme-IM

1:2

50

Step 1:5
Step
2:1
20

97.20

[159]

96
1/10
1/4

50.00
88.00
89.91

[160]
[75]
[82]

in diesel engines. Kerihuel et al. [115] studied the effects of

formulation and other inuential parameters on the CH3CH2OH
animal fat emulsions as a diesel engine fuel based on stability,
structure, viscosity, fat content and economic aspects. They determined optimum emulsions conditions to be 36.4% CH3CH2OH, 3.6%
of SPAN 83, 10% of water and 50% animal fat by volume. Kumar
et al. [116], performed diesel engine test on CH3CH2OH-animal fat
emulsions based fuels, and reported an improvement in the heat
release pattern during the premixed combustion phase with
animal fat emulsion vs. neat animal fat. At high power outputs
they found the fuel emulsion to show a drastic reduction in smoke,
nitric oxide, hydrocarbon and carbon monoxide emissions compared to neat fat and neat diesel.
3.3. Pyrolysis
Pyrolysis or cracking involves the thermal decomposition of
organic material to smaller molecules through the application of
heat without the addition of supplemental air or oxygen. Thermal
cracking of triglyceride materials (animal fats and vegetable oils)
represents an alternative method of producing renewable biobased products suitable for use in fuel and chemical applications.
Considerable investigations have been done on the pyrolysis of
different varieties of vegetable oils to produce chemicals and
diesel-like fuel [117121]. Animal fat pyrolysis has received much
less interest as compared to vegetable oils. Adebanjo et al. [122],
pioneers in the study of lard pyrolysis, investigated the production
of diesel-like fuel and other value-added chemicals from the pyrolysis of lard and reported the potential for producing a diesel-like
liquid and a high caloric-value (68165 MJ m  3) gaseous fuel
through lard pyrolysis. The authors reported diesel-like liquid
product maximum yield from lard as 37 g/100 g at reaction conditions: temperature, residence time, and packing particle size to
be 600 1C, 1.2 s, and 1.72.4 mm, respectively.

1:4
1:6
1:45

25
400
335

[84]
[141]
[34]

[130]

In recent years, pyrolysis of animal fats has been reported by a

number of investigators. Wiggers et al. [123] and Wisniewski Jr
et al. [124] investigated the pyrolysis of waste sh oil at a pilot
plant scale and studied the chemical compositions of the pyrolysates. The authors reported the compositional yields to be: liquid
(72.83%), bio-gas (15.85%), and coke (11.32%) at the operation
conditions: average reaction temperature, residence time, and
water content to be 525 1C, 17 s, and 5%, respectively. Ben
Hassen-Trabelsi et al. [125] reported the production of bio-oil
and bio-char by pyrolysis of lamb, poultry and swine AFWs in a
xed-bed reactor. They concluded that pyrolysis was a viable
method of converting AFWs to high yield liquid products (hydrocarbons). However, bio-oils generated still required an enhancement in composition and fuel properties before their use as engine
fuels. Asomaning et al. [126] used a two-stage thermal conversion
approach to produce renewable chemicals and fuels from inedible
lipid feedstocks e.g. beef tallow, yellow grease, brown grease and
cold pressed camelina (Camelina sativa (L.) Crantz) oil were rst
hydrolyzed and the fatty acids produced were recovered and
pyrolyzed in batch reactors. The authors reported similar product
yield for all the feedstocks used with the organic liquid fraction
(OLF) accounting for 7680% of the product. They concluded that
the research demonstrated the viability of a novel two-stage
thermal hydrolysispyrolysis conversion method for producing
OLF from inedible feedstocks and low-value lipids.
3.4. Transesterication reaction techniques
Transesterication is the most commonly used method to
reduce viscosity of animal fats and vegetable oils. It generates
products commonly known as biodiesel (alkyl esters of fats or oils)
[105,127]. This biodiesel production technique has been reported
to have particular advantages over other processes: (1) reaction
conditions are mild, (2) the process is environmentally friendly

582

P. Adewale et al. / Renewable and Sustainable Energy Reviews 45 (2015) 574588

and (3) a wide variety of feedstocks can be processed through this

technique. Transesterication of TAGs can be classied into two
types: catalyzed or non-catalyzed. Catalyzed transesterication
can be further grouped according to the type of catalyst employed
(e.g. homogeneous, heterogeneous and enzymatically-catalyzed).
Supercritical process (a non-catalyzed transesterication reaction)
has been employed to mitigate critical issues in the production
process and lower cost of production [64,128]. Conventionally,
homogeneous base or acid catalysts are the most commonly used
transesterication processes. In recent years, enzymes immobilized or in their free-forms have been reported as very promising
reaction agents for biodiesel production [29,91]. While the process
commercialization is still limited by enzyme production costs,
enzyme reusability and the lack of complex downstream products
and associated separation problems have overshadowed the
enzyme shortcomings. AFWs transesterication for biodiesel production had been investigated by researchers using all four
transesterication methods (Table 2).

3.4.1. Homogeneous catalytic conversion of AFWs

Homogeneous catalytic transesterication is the most commonly used commercial transesterication process for the production of biodiesel. It can be divided into two types: homogeneous
base catalytic transesterication and homogeneous acid catalytic
transesterication. In most cases, AFWs require pre-heating and
preprocessing steps prior to transesterication through homogeneous catalytic conversion by one- or two-step catalytic processes.
Biodiesel production from AFWs under homogeneous catalysis
and process parameters (e.g. molar (alcohol:fat) ratio, catalyst
concentration, reaction temperature, and time) effects on the yield
and the purity of biodiesel have been the subject of numerous
critical investigation.
Homogeneous base catalytic transesterication is mostly a onestep catalytic process in which sodium or potassium hydroxide
serve as catalyst for the transesterication of AFWs [3]. Bhatti et al.
[84] investigated biodiesel production from waste mutton tallow
and chicken fat by a homogeneous base and acid (H2SO4 and KOH)
catalyzed transesterication. They reported high biodiesel yield in
a one-step acid transesterication reaction as compared to the
one-step KOH method which was attributed to soap formation
under the KOH process. Encinar et al. [129], studied the effects of
homogeneous base and acid catalysts at different concentrations
on the biodiesel yield from beef tallow and concluded that NaOH
was a more efcient base catalyst than sodium methoxide for the

transesterication of beef tallow. They obtained optimum yield of

biodiesel at a 9% catalyst concentration. Several other studies have
employed this method for the production of biodiesel either as a
one-step or two-step homogeneous catalytic transesterication
process. Some of the different feedstocks were animal fats and
their blends, especially chickenswine fat blends, sunower oilbeef tallow blends, duck oil, lard etc. The process was monitored
under different reaction conditions reecting catalyst load, molar
ratio, temperature and time [67,69,78,88,99,130,131].

3.4.2. Heterogeneous catalytic conversion of AFWs

In the quest to solve the issue of high FFA biodiesel feedstocks,
many recent studies have reported the application of heterogeneous catalysis for biodiesel production from animal fats. The
shortcomings of homogeneous catalytic transesterication are
reported to be considerably minimized through the application
of heterogeneous catalysts such as solid and enzymatic catalysts
[132]. Most researchers prefer using heterogeneous over homogeneous catalysts to produce biodiesel because of their inherent
advantages: catalyst regeneration and reusability, simple downstream separation and purication, and production of less hazardous wastewater [27,132,133]. Heterogeneous catalysis can be
classied according to the types of catalysts used: heterogeneous
base catalytic transesterication and heterogeneous acid catalytic
transesterication. Heterogeneous catalysis using various solid
catalysts can be further grouped according to the number of
reaction steps (e.g. one- and two-step processes).
Liu et al. [134] investigated the use of heterogeneous base
catalysts derived from MgAl hydrotalcite in a one-step processing
approach for the conversion of poultry fat to biodiesel. They
reported that a 94% biodiesel yield was achieved at 120 1C when
a xed catalyst added at a rate of 0.04 g mL  1 and a 60:1 molar
ratio. They also found the mixed MgAl oxide to be thermally and
mechanically stable after operation with no signicant difference
in particle size or morphology occurring. The use of nanocrystalline calcium oxide as a heterogeneous base catalyst for the
transesterication of poultry fat (fat to methanol ratio 3:10) at
room temperature was investigated by Venkat Reddy et al. [135],
who reported that the maximum conversion of the poultry fat to
biodiesel under the reaction conditions would require 6 hr.
Mutreja et al. [136] investigated the production of biodiesel from
mutton fat using KOH impregnated MgO as a heterogeneous base
catalyst, where the KOH impregnation level was 520 wt%, the
catalyst/fat ratio 1.54 wt%, the reaction temperature ranged from

Fig. 6. Enzyme catalyzed transesterication of triglycerides. TAG triacylglyceride; DAG diacylglyceride; MAG monoacylglyceride.

P. Adewale et al. / Renewable and Sustainable Energy Reviews 45 (2015) 574588

45 to 65 1C, the fat:methanol molar ratio ranged from 1:111:22.

They also investigated the effect of adding up to 1 wt% of water/
oleic acid/palmitic acid to the reaction mix. The authors concluded
that impregnation with 20 wt% KOH increased the of MgO and
biodiesel yield ( 498%) in the transesterication of mutton fat
under operating conditions of: 20 min reaction time at 65 1C, fat:
methanol molar ratio of 1:22 and use of MgOKOH catalyst. Many
other solid catalysts have been investigated by researchers for the
production of biodiesel from AFWs under different reactions
conditions. These have generally shown reasonable results, highlighting the greater feasibility of heterogeneous over homogeneous catalysis [137140].
Heterogeneous acid catalytic transesterication of AFWs has
been reported to have a slower reaction rate than heterogeneous
base catalytic transesterication [140143]. Bianchi et al. [140]
studied direct esterication of FFA in animal fat using solid acid
resins as heterogeneous catalysts. The FFA ( 490%) in the lard
samples were converted such that the FFA concentration in the
lard were lowered below 0.5%, a practical value suitable for direct
biodiesel production. Investigating the Zr-SBA-15 acid catalyst:
optimization and reaction conditions for biodiesel production
from low-grade oils and fats, Melero et al. [139] found this catalyst
to be highly active in the simultaneous esterication of FFAs and
transesterication of TAGs from low-grade AFWs in the presence
of methanol, completely independently of their acid value or
unsaponiable matter content. While few reports of two-step
transesterication of AFWs using heterogeneous catalysts have
appeared in the literature, heterogeneous catalysts have been used
to pre-treat high FFA AFWs, thus reducing their FFA levels below
certain threshold thereby allowing direct transesterication [139].
Kim M [144] developed a heterogeneous ZrO2 supported metal
oxide catalysts for brown grease esterication and sulfur removal.
These catalysts were claimed to achieve high yields through
esterication of FFA and simultaneously desulfurization and demetallization. The authors further noted that methanolysis with
the zirconia supported catalysts, was more effective for desulfurization than an acid washing process. Ngo [145], Ngo [146] and
Ngo et al. [147] presented different heterogeneous catalysts capable of reducing greases FFA content to below 1% under mild
reaction conditions and thereafter achieve a high conversion.
However, the major drawbacks of using heterogeneous catalysts
include: (1) complexity in preparation, (2) a requirement of high
selectivity for the desired product formation, (3) difculty in reuse
in some cases, (4) high molar ratio of alcohol:fat as compared to
homogeneous catalysts, (5) long reaction time.
3.4.3. Enzyme catalytic conversion of AFWs
Biodiesel production using an enzymatic transesterication
process could solve problems associated with AFWs physicochemical properties as well as be more environmental friendly than
conventional catalytic processes [80,92,148,149]. The advantages
of using enzyme-catalyzed transesterication include: ease of
enzyme recovery, reusability and thermal stability of enzyme
Table 3
Commonly used SCFs.
Fluid

Tc (1C)

Pc (MPa)

Density (g L  1)

Methanol (CH4O)
Ethanol (C2H6O)
Acetone (C3H6O)
Water (H2O)
Carbon dioxide (CO2)
Methane (CH4)
Fluoroform (CHF3)
Ethane (C2H6)

239.6
240.9
235.1
374.3
31.3
 82.6
26.2
32.3

8.09
6.14
4.70
22.12
7.29
4.60
4.85
4.88

272
276
278
348
469
162
516
203

583

under mild reaction conditions (pH, temperature, and pressure),

and the easy downstream recovery of products etc. Lipases from
different organisms Mucor miehei, Candida rugosa, Penicillium
camembertii, Penicillium roqueforti, Pseudomonas uorescens,
Pseudomonas cepacia, Candida lypolytica, Candida Antarctica, and
Bacillus subtilis have been effectively employed in transesterication of high FFA feedstocks as free-form or immobilized enzymes
[150152]. While the higher cost of enzymes compared to chemical catalysts and the risk of product contamination by enzyme
residues are cited as drawbacks [153]. Enzyme immobilization
techniques which have enabled reuse and easy recovery of enzyme has been found to remediate these problems [29]. Likewise,
tailored derivatives with minimum undesirable side reactions are
also positive elements of enzyme-catalyzed process [153]. Fig. 6
shows a typical enzymatic transesterication process.
Several studies have been carried out on enzyme-catalyzed
transesterication (free-form and immobilized form) of vegetable
oils in solvent free and solvent media [7,152,154,155]. However, in
depth studies of enzymatic transesterication of AFWs have been
sparsely reported in the literature. So far, the most commonly used
lipases for AFWs transesterication are: Burkholderia cepacia [156
158], Candida antarctica [80,159] and Rhizomucor miehei [160,161].
Aryee et al. [160] investigated ethanolysis of enzymatic transesterication of three feedstocks: salmon skin oil, Rothsay composite
(blend of yellow grease and rendered animal fats), and olive oil
with Lipozyme-IM as catalyst. The authors assessed the effects of
operational parameters (e.g. temperature, oil:alcohol molar ratio,
and reaction time) on the yield of biodiesel and reported a
generally moderate oil to fatty acid ethyl ester conversion rate of
50% at the optimal operation parameters. Assessing the reusability
of immobilized lipases during methanolysis of lard, Lu et al. [80]
reused the enzymes over seven consecutive cycles with no
signicant decrease in lipase activity, while maintaining a biodiesel yield exceeding 80%. Huang et al. [159] optimized lipasecatalyzed transesterication of lard for biodiesel production using
a response surface methodology. In their study, two enzymes
(Novozym 435 and Lipozyme TLIM) were combined to catalyze
biodiesel production from lard and process optimization. The
response surface methodology identied the optimal reaction
conditions for biodiesel yield (97.2% methyl ester yield) as a
lipase:fat ratio of 0.04:1, a Novozym435/total lipases (w/w) ratio
of 0.49:1, a tert-butanol/fat (v/v) ratio of 0.55:1, a 5.12:1 methanol/
fat (mol/mol) ratio, for 20 h reaction time. The optimum temperature for enzymatic AFWs transesterication lies in the range
between 30 1C and 50 1C [80,149,159], outside of which enzyme
denaturation and solvent volatilization may occur [159,160].

3.4.4. Supercritical non-catalytic conversion of AFWs

A supercritical uid (SCF) is any substance (compound, mixture
or element) above its critical pressure (Pc) and critical temperature
(Tc), where distinct liquid and gas phases do not exist. SCFs can
diffuse through solids like a gas, and dissolve materials like a
liquid. The properties of SCFs can be classied as an intermediate
between a gas and a liquid. Table 3 shows the properties of
commonly used SCFs. Decaffeination of coffee with supercritical
carbon dioxide (CO2) was one of the rst applications of SCFs
[162]. In the literature, different SCFs techniques have been
employed for the production of biodiesel from vegetable oils
feedstocks. The SCF transesterication of rapeseed oil was
reported by Kusdiana and Saka [163], Saka et al. [164], and Wang
et al. [165]. SCF transesterication of soybean oil was reported by
Wang and Yang [166], Yin et al. [167], and Anitescu and Bruno
[168,169]. Similarly, SCF transesterication of sunower
(Helianthus annuus L.) oil was reported by Madras et al. [170],

584

P. Adewale et al. / Renewable and Sustainable Energy Reviews 45 (2015) 574588

and Tateno and Sasaki [171]. Few studies have been reported in the
literature about the SCF transesterication of AFWs.
Marulanda et al. [75] investigated the effect of reaction parameters under supercritical conditions: temperature (350, 375, and
400 1C), pressure (10, 20, and 30 MPa), alcohol:fat molar ratio (3:1
to 12:1) and residence time (310 min) on the yield and quality of
biodiesel derived from chicken fat, low-cost lipid feedstocks. The
optimum reaction conditions for the conversion of triglycerides
and the decomposition of glycerol to fuel components were:
400 1C, 30 MPa, 9:1 alcohol:fat ratio, and residence time 6 min.
Taher et al. [172] and Al-Zuhair et al. [173], studied the production
of biodiesel from fat extracted from lamb meat in supercritical CO2
media. They assessed the effects of reaction parameters (e.g.
enzyme concentration, reaction temperature and methanol:fat
molar ratio) on the biodiesel yield. In a continuous extraction of
fat from lamb meat and biodiesel synthesis using supercritical CO2,
the authors observed a decrease in enzymatic activity in the third
cycle of meat replacement. They concluded that biodiesel yield
increased with both the quantity of enzyme and the length of the
reaction time. Shin et al. [128] investigated the production of
biodiesel from waste lard using supercritical methanol. They
reported that biodiesel obtained from waste lard without pretreatment was of equal quality to biodiesel from rened lard, even
though waste lard samples contained high FFA and a high water
contents. This conrmed that water content and high FFA have no
effect on the SCF transesterication of animal fats for the production of biodiesel.

4. Assisted transesterication techniques

The aim of ATT is to reduce reactor operation time while
achieving the highest yield possible. Apart from benets in terms
of reaction time, ATT employs low reaction reagent levels (i.e. low
catalyst concentrations and lower alcohol to fat ratio), thus
reducing the overall cost of production. Two types of ATTs are
commonly used in biodiesel production from vegetable oils and
animal fats. These include UA and MA.
4.1. Ultrasound-assisted technique
Ultrasound is the process of propagating an oscillating sound
pressure wave with a frequency greater than the upper limit of the
human hearing range. Ultrasound frequencies range between
20 kHz and l0 MHz, with associated acoustic wavelengths in
liquids of roughly 1000.15 mm. Application of ultrasound in the
chemical processing enhances both mass transfer and chemical
reactions, leading to shorter reaction times, and cheaper reagents.
Acoustic cavitation which is the most important element of ultrasonication is the formation, growth, and implosive collapse of
bubbles in a liquid irradiated with sound or ultrasound. The
propagation of sound through the liquid causes expansion waves
and compression waves, which forms an aerosol of solvent, solute
vapor and previously dissolved gases. This phenomena causes
bubbles to grow and recompress due to the high mass transfer
rates arising from the formation of a microemulsion through
ultrasonic cavitation [174].
The application of UA to the transesterication of different
vegetable oils has been widely investigated and reported [41,174
176]. This technique has been proven to enhance reaction rates. Its
implementation has been shown to overcome the inherent issues
of slow batch reaction rates and time-consuming phase separation
of conventional transesterication process [177179]. Compared to
vegetable oils, few reports of UA transesterication of AFWs
appear in the literature. Comparing conventional and UA transesterication of beef tallow to produce biodiesel, Teixeira et al. [90]

showed that the ultra-sonication process led to similar yields of

alkyl esters as the conventional procedure, while signicantly
decreasing the reaction time. They concluded that methanolysis
of triglycerides using ultrasonic irradiation was an efcient, time
saving and economical method of producing biodiesel fuel, but the
effects of reaction parameters and ultrasound conditions were not
reported.
Armenta et al. [180], evaluated the ethanolysis production of
biodiesel from sh oil using ultrasound energy. They examined the
effects of different parameters such as: ultrasonic device (bath vs.
probe), catalyst type (KOH vs. C2H5ONa), catalyst concentration
(0.5 vs. 1%), temperature (20 vs. 60 1C), and duration of exposure
(1090 min) on the production process. The authors reported that
sodium ethoxide was a more efcient catalyst than KOH. The best
reaction conditions for the ethanolysis of sh oil were reported as
a reaction time of 30 min, a temperature of 60 1C, a catalyst
concentration of 0.8% C2H5ONa. Through this conditions, a yield
of over 98% can be expected.
4.2. Microwave-assisted technique
The microwave radiation region is located between infrared
radiation and radio-waves in the electromagnetic spectrum.
Microwaves have wavelengths of 1 mm1 m, corresponding to
frequencies between 0.3 and 300 GHz [181,182]. The band frequencies in this region are occupied by telecommunication and
microwave radar equipment. In order to avoid interference with
these systems, the household and industrial microwave ovens
operate at a xed frequency of 2.45 GHz [183,184]. Microwave
irradiation has been employed in different applications including
organic synthesis [185,186], where chemical reactions are accelerated because of selective absorption of microwave energy by
polar molecules, nonpolar molecules being inert to the microwave
dielectric loss [181,182]. Other benets of microwave-assisted
chemical syntheses are rapid reactions, the high purity of products, improved yields and greater energy efciency. The application of the MA transesterication process to the production of
biodiesel from vegetable oils has been well investigated [121,187
189]. These studies have reported the feasibilities of using MA for
the production of biodiesel from different varieties of vegetable
oils, but have only paid limited attention to the use of AFWs as
feedstocks. However, Da Rs et al. [157] have reported optimal
conditions for the MA enzymatic synthesis of biodiesel from beef
tallow. They noted an almost total conversion of the fatty acid
original beef tallows fatty acids optimum conditions of: beef
tallow:ethanol molar ratio of 1:6, a temperature of 50 1C and a
reaction time of 8 h. This represented a six-fold increase in the rate
of the process carried out under conventional heating. They
concluded that MA process promises to be energy efcient, limit
destructive effects to enzymes and delivered higher biodiesel
production compared to conventional heating.

5. Conclusion
In terms of availability and low cost, compared to virgin
vegetable oils, AFWs have been proven to be very good potential
feedstocks for high quality biodiesel production. The use of AFWs
as biodiesel feedstock represents one of the possible ways biodiesel productions impact on food security can be limited, while
reducing production costs and environmental damage. The combustion of animal fat based biodiesel has been shown to produce
lesser NOx emission than vegetable oil based biodiesel. The former
have high Cetane number, which is an important quality parameter for diesel fuels. Seen as a challenge to good biodiesel yield
by homogeneous base catalyzed reaction due to formation of soap,

P. Adewale et al. / Renewable and Sustainable Energy Reviews 45 (2015) 574588

the signicant quantity of FFAs in AFWs and their elevated water

contents have proved problematic. The application of non-catalytic
(SCFs) as well as two-step homogeneous (acid/base), heterogeneous, enzymatically catalyzed transesterication processes have
shown a tremendous success compared to one-step homogeneous
base catalyzed transesterication of AFWs for the production of
biodiesel. Although, the enzymatic transesterication process is
usually time consuming as compared to the conventional methods, this technique offers advantages in processing high FFA
feedstocks without chemical pre-treatment. Assisted transesterication techniques such as ultrasonic irradiation and microwave
heating have been applied as novel processes to enhance biodiesel
production from AFWs. The overall energy-consumption and
production cost to biodiesel synthesis can be drastically reduced
through the application of these techniques given their capability
to reduce reaction time, temperature and pressure required during
biodiesel production. In conclusion, further intensive research on
assisted transesterication techniques (ultrasound irradiation and
microwaves heating) for the production of biodiesel should be
carried out on AFWs. Similarly, SFCs processes for AFWs should be
well researched.

Acknowledgements
The authors are acknowledging the McGill University Start-Up
grant and the National Science and Engineering Research Council
of Canada (Grant number: STPGP 350707 07) (NSERC).
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