175

A publication of

CHEMICAL ENGINEERING TRANSACTIONS

VOL. 38, 2014
Guest Editors: Enrico Bardone, Marco Bravi, Taj Keshavarz
Copyright 2014, AIDIC Servizi S.r.l.,
ISBN 978-88-95608-29-7; ISSN 2283-9216

The Italian Association

of Chemical Engineering
www.aidic.it/cet
DOI: 10.3303/CET1438030

Properties and Sustainability of Biodiesel from Animal Fats

and Fish Oil
Teresa M. Mata*a, Adlio M. Mendesa, Ndia S. Caetanob, Antnio A.Martinsc
a
LEPABE Laboratory for Process Engineering, Environment, Biotechnology and Energy, Faculty of Engineering,
University of Porto (FEUP), R. Dr. Roberto Frias S/N, 4200-465 Porto, Portugal
b
Department of Chemical Engineering, School of Engineering (ISEP), Polytechnic Institute of Porto (IPP), R. Dr. Antnio
Bernardino de Almeida S/N, 4200-072 Porto, Portugal
c
Department of Environmental Engineering, Faculty of Natural Sciences, Engineering and Technology (FCNET), Oporto
Lusophone University, R. Dr. Augusto Rosa, 24, 4000-098 Porto, PortugalPortugal
*[email protected]

This work presents and analyses the fat and fuel properties and the methyl ester profile of biodiesel from
animal fats and fish oil (beef tallow, pork lard, chicken fat and sardine oil). Also, their sustainability is
evaluated in comparison with rapeseed biodiesel and fossil diesel, currently the dominant liquid fuels for
transportation in Europe. Results show that from a technological point of view it is possible to use animal
fats and fish oil as feedstock for biodiesel production. From the sustainability perspective, beef tallow
biodiesel seems to be the most sustainable one, as its contribution to global warming has the same value
of fossil diesel and in terms of energy efficiency it has the best value of the biodiesels under consideration.
Although biodiesel is not so energy efficient as fossil diesel there is room to improve it, for example, by
replacing the fossil energy used in the process with renewable energy generated using co-products (e.g.
straw, biomass cake, glycerine).

1. Introduction
Currently dominant feedstocks for biodiesel production, in particular vegetable oils, are problematic as they
are normally expensive and may have limited availability due to seasonal, social and economic
constraints. Thus, there is strong interest in using lower cost feedstocks (Caetano et al., 2012) that do not
interfere with important aspects of human societies and contribute to increase its role in sustainability. One
interesting possibility is to use fatty residues from food processing or waste collecting systems, such as:
spent coffee grounds (Caetano et al., 2013b), animal fats (Mata et al., 2011), fish wastes (Vilela et al.,
2010), brewers spent grains (Caetano el al., 2013a) among others, representing this an opportunity for
waste valorisation. This study focuses on the usage of animal fats and fish oil for biodiesel production,
analysing their properties and evaluating their contribution to sustainability in comparison with rapeseed
biodiesel and fossil diesel, in order to determine which feedstocks are more adequate, and which issues
need to be addressed to effectively use these abundant residues as fuel sources.

2. Materials and Methods

2.1 Animal fats and fish oil extraction
The animal residues were collected in slaughterhouses and food processing companies. They were
melted, at around 110 C, to remove moisture (about 70 %) and separate the liquid fat (beef tallow, pork
lard and chicken fat) from solids (gums, protein residues, and suspended particles) by percolation and
filtering.
The fishs viscera and heads were collected at the local fish market. They were first cooked thoroughly in
boiling water and the supernatant oil was placed in a separating funnel, where it was washed (with distilled
water at 60 C) and separated from water and solid particles. Then, the fish soapstock was squeezed to

Please cite this article as: Mata T., Mendes A., Caetano N., Martins A., 2014, Properties and sustainability of biodiesel from animal fats
and fish oil, Chemical Engineering Transactions, 38, 175-180 DOI: 10.3303/CET1438030

176

release crude fish oil and separate it from the cake of fish dregs. Since this crude fish oil still contained
some solid impurities, it was centrifuged and placed in a separating funnel to be washed as described
above. Finally, the fish oil was vacuum filtered to remove any remaining impurities.
2.2 Biodiesel production and purification
Biodiesel was produced in stirred flasks operating in batch mode by alkali-catalysed transesterification,
using KOH as catalyst and methanol. In a typical experiment 300 g of fat were weighed in a screw cap
Pyrex bottle, with 500 mL of capacity, and placed in a thermostatic bath to heat the fat up to the reaction
temperature (60 C). Excess methanol was used in an approximated molar alcohol/oil ratio of 6/1. Around
3 g of KOH catalyst (p.a., Pronalab) were measured and dissolved in a closed cup in the required volume
of absolute methanol (Pronalab), slightly warming and stirring the mixture. This operation took place in a
hood for about 5 minutes (approximate methanol dissolution time). Then, the alcohol/catalyst mixture was
added to the previously pre-heated oil and shaked vigorously in order to promote contact between the
reactants. This bottle was placed in the thermostatic bath where the reaction took place for 2 hours at 60
C and at 60 rpm of stirring speed. After completing the reaction time the flask was removed from the bath,
and the mixture was allowed to settle for about half an hour in a separating funnel to remove the heavier
glycerol phase, that was transferred to a previously weighed beaker to determine its mass.
The lighter phase (biodiesel) was subjected to distillation at 80 C to recover the excess alcohol, and then
placed in the separating funnel, where it was neutralized with hot water slightly acidified with concentrated
phosphoric acid. The washing procedure was repeated several times using hot water until a clear phase
was obtained with neutral pH. The purified biodiesel was placed in a beaker and about 2 g of
diatomaceous earth was added to remove any water remaining in biodiesel. The mixture was stirred for
about 15 min, after which biodiesel was left to stand, and then vacuum filtered through cellulose
membranes (4-7 m pore) to remove the diatomaceous earth. Finally biodiesel was stored in dark glass
flasks for subsequent characterization.
2.3 Characterisation of animal fats, fish oil and biodiesel
Animal fats, fish oil and the corresponding biodiesels were characterized using the standard methods
described in Table 1. In particular, for the animal fats and fish oil, the acid value, iodine value, kinematic
viscosity at 40 C, density at 15 C, and higher heating value were determined. The resulting biodiesels
were characterized following the EN 14214:2009 standard that defines the FAME quality requirements, in
particular for the following parameters: acid value, iodine value, kinematic viscosity at 40_C, density at 20
C, water content, flash point, copper corrosion, CFPP, FAME content, and higher heating value (not an
EN 14214 standard requirement).
Table 1: Standard methods applied for the animal fats, fish oil and biodiesel characterization
Parameter
Acid value
Iodine value
Kinematic viscosity
Density
Water content
Flash point
Copper corrosion
CFPP
FAME content
Higher heating value

Method
Titrimetric method, ISO 14104:2011 standard
Titrimetric method with Wijs reagent, EN 14111:2009 standard
Glass capillary viscometers Cannon-Fenske Series 200, ISO 3104:1994
Hydrometer method, EN ISO 3675:1998 standard
Karl Fischer coulometric titration, NP EN ISO 12937:2003 standard
Rapid equilibrium closed cup method, ISO 3679:2004 standard
Copper strip test, ISO 2160:1998 standard
Standardized filtration equipment, EN 116:2002 standard
Gas chromatography (GC), EN 14103:2010 standard
Oxygen bomb calorimeter, ASTM method D240-87

2.4 Sustainability evaluation

For the sustainability evaluation the methodology described by Mata et al (2013) was considered, in which
the full fuel value chain is taken into account. Two sustainability indicators were selected for this study the
life cycle energy efficiency (LCEE) and the contribution to global warming (GW) calculated as Eq (1) and
(2), respectively. LCEE is the ratio of the total energy output, consisting of the energy content of the
biofuel, plus that of byproducts only if they are used to supply energy to the biofuel production system, to
the amount of energy expended to obtain the biofuel (dimensionless). The GW measures the potential
contribution of different GHG emissions to global warming, expressed as equivalent CO2 emission per unit
energy of fuel product (kg CO2-eq/MJ fuel).

177

Life Cycle Energy Efficiency (LCEE) =

Total energy Output

Total energy Input

Contribution to Global Warming (GW) =

GWP E
i

(1)

(2)

where Ei is the mass of compound i emitted to the air and GWPi is the global warming potential of the
compound i, calculated as the net GHG emissions through the fuel life cycle.
For these indicators calculation, life cycle inventory data was obtained from literature for biodiesel from
beef tallow (R-Power, 2013), fish oil (Ronde et al., 2010), rapeseed (Reinhardt and Jungk, 2001) and fossil
diesel (Mata et al., 2013). It is assumed that there are no significant differences among the sustainability of
animal fats (beef tallow, chicken fat and pork lard).

3. Results and Discussion

3.1 Fat and fuel properties and quality requirements
Tables 2 and 3 present the characteristics of the animal fats and fish oil and biodiesel produced from them,
respectively, and Table 4 presents the FAME profiles for the several biodiesels obtained by gas
chromatography.
Table 2: Animal fats and fish oil properties
Fat or oil property

Unit

Density at 20 C
Kinematic viscosity at 40 C
Acid value
Iodine value
Higher heating value
Average molecular mass

kg/m3
mm2/s
mg KOH/g fat
g iodine/100 g fat
MJ/kg fat
g/mol

Chicken
fat(a)
932
41.06
0.56
76.7
39.6
856.1

Beef
tallow(a)
929
46.37
1.07
45.3
38.9
846.6

Pork
Lard(a)
948
39.53
0.63
77.9
39.5
860.0

Sardine
oil(b)
923
41.06
0.56
76.7
39.6
873.7

(a) Mata et al., 2011; (b) Vilela et al., 2010

Table 3: Properties of biodiesels from animal fats and fish oil

Biodiesel property (a)
Reaction yield (wt%)
Higher heating value (MJ/kg biodiesel)
Density at 15 C (kg/m3)
Kinematic viscosity at 40 C (mm2/s)
Water content (mg/kg)
Iodine value (g iodine/100 g biodiesel)
Acid value (mg KOH/g biodiesel)
Group I metals (Na+ + K+) (mg/kg)
Copper strip corrosion (3 h at 50 C)
Flash point (C)
CFPP (C)

Chicken
fat (b)
76.8
39.4
883
5.85
1237
76
0.32
53.5
1B
171
+3

Beef
tallow (b)
90.8
40.0
870
5.40
585
45
0.21
3.9
1B
172
+10

Pork
Lard (b)
91.4
39.9
872
4.96
149
76
0.20
39.7
1B
147
+5

Sardine EN 14214
oil (c)
limits
89.5

39.7

886
860-900
4.33 3.50-5.00
200
500
163
120
0.20
0.50
13.0
5.0
1A
class 1
160
101
-1
+5 (d)

(a) Reaction conditions were: 6:1 Alcohol/oil or fat molar ratio; 2h Reaction time; 60 C reaction temperature, 1 %
catalyst (KOH)/fat weight percentage; (b) Mata et al. 2011; (c) Vilela et al. 2010; (d) Limit for temperate climates.

With the exception of chicken fat, conversions to biodiesel of at least 90 % were obtained, showing that the
transesterification reaction conditions were adequate. In this case an esterification pre-treatment was not
needed, since as shown in Table 2, the acid value of all fats was below 1 mg KOH/g fat (corresponding to
less than 3 % acidity) (Mata et al., 2011). Biodiesel density generally decreases with increased reaction
time and temperature, and is lower as the biodiesel molecular mass is lower and its degree of unsaturation
is higher (Mata et al., 2010). Table 3 shows no significant difference among biodiesel densities.
Biodiesel viscosity is another important parameter as it influences atomization and thus, the quality of fuel
combustion in the vehicle engine. High viscosity values may promote the formation of deposits in the
engine, reducing their efficiency and resulting in costly repairs. This is the main reason why fats and oils

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are transesterified to biodiesel, to reduce viscosity by one order of magnitude. The kinematic viscosity of
fats and oil is within 39 and 46 mm2/s and that of the corresponding biodiesel within 4 and 7 mm2/s (Tables
2 and 3). Generally, viscosity increases with the number of CH2 moieties in the fatty ester chain
(corresponding to larger molecules), and generally decreases with the increasing number of double bonds
between carbon atoms in their molecules (Knothe, 2008), which is confirmed by the data presented in
Table 4.
Table 4: FAME profile of some biodiesels from animal fats (in terms of relative weight percentage)
FAME relative
percentage, wt%
Chicken fat (a)
Beef tallow (a)
Pork lard (a)
Sardine oil (b)

C14:0

C16:0

C16:1

C17:0

C18:0

C18:1

C18:2

C18:3

9.2

7.4

34.8
30.1
29.8
18.7

7.7

20.3

4.9
17.1
11.4
2.5

44.4
38.3
37.5
11.5

14.2
4.2
18.5
0.0

1.7
0.6
2.8
3.1

C20:0 Others

0.4

14.3

14.5

(a) Mata et al. 2011; (b) Vilela et al. 2010

The cold-filter plugging point (CFPP) is used to characterize biodiesel and determine its adequacy for
usage at low temperatures. Biodiesel derived from animal fats generally has significant amounts of
saturated esters, which leads to higher CFPP values when compared with biodiesel from vegetable oils,
because those compounds have higher melting points, making it difficult or even impossible to use it in
pure form during cold weather periods.
In Table 3, beef tallow methyl esters displayed very high CFPP value of 10 C, above the standard limit of
5 C, an indication that those fats contain large amounts of saturated fatty compounds, as shown in the
FAME profiles of Table 4.
On the other hand, biodiesel of animal origin has positive properties, such as large values of heating value
(HHV) and cetane number (CN) (Lebedevas et al., 2006). The heating value, or heat of combustion, is a
measure of the energy available from the fuel. Generally, it increases with increasing chain length and
decreases with increasing unsaturation. Although the heating value is not specified in the biodiesel
standard EN 14214, the EN 14213 specifies a minimum heating value of 35 MJ/kg for using biodiesel as
heating oil. The heating value of the various biodiesels is around 39-40 MJ/kg biodiesel, slightly lower than
that of fossil diesel (45 MJ/kg diesel), but all above the minimum value given in the standard EN 14213.
The acid value of biodiesel indicates the presence of free fatty acid (FFA), which can have a significant
effect on the fuel storage stability and thermal properties, as a high amount of FFA corresponds to a more
reactive fuel, with more potential to oxidize and corrode the engine metal components (Mata et al., 2010).
However, the acid values in Table 3 are all below the standard limit of 0.50 mg KOH/g biodiesel.
The copper strip corrosion test is used for detecting the potential corrosiveness of biodiesel, as corrosion
affects the metallic materials in contact with the fuel, particularly the engine components and the storage
and maintenance equipment (Mata et al., 2012). Table 3 shows the lowest level of corrosiveness for all
cases, meaning that corrosion is not a problem.
The alkaline metals (potassium and sodium) concentration should be below the standard limit of 5.0
mg/kg, as their presence is related to the possibility of formation of metallic soaps or abrasive solids that
can clog filters and injectors in the vehicles engine. Table 3 shows a higher concentration of these metals
in several biodiesels, which can be reduced by improving the purification step (Mata et al., 2012).
Concerning the water content, during water washing and storage biodiesel can absorb a certain amount of
water leading to the presence of moisture, which should be limited as much as possible. The presence of
water in biodiesel can cause problems in cold climates and increases the risk of microbial proliferation in
the engine that will clog engine filters. Table 3 shows for some biodiesels (chicken fat and beef tallow) a
water content higher than the standard limit (500 mg/kg) that may be due to an incomplete drying step.
The flash point is one of the most important advantages of biodiesel relatively to fossil diesel, as biodiesel
has higher flash point, resulting in safer storage, handling and transportation. Yet, it also depends on how
much of the excess methanol used in transesterification is removed during the final biodiesel purification.
All biodiesels flash points are much above the minimum standard limit (101 C), meaning that the
distillation step was effective and independent of the specific chemical composition of the residual fats.
The iodine value is a measure of the unsaturation degree, and gives an indication of the biodiesel
oxidative stability. Unsaturated compounds contain molecules with double bonds, which are very reactive
toward iodine, and give a measure of the reactivity with oxygen. The higher the iodine value the more
reactive, less stable, softer, and more susceptible to oxidation and rancidification is the fat or biodiesel.
Although unsaturated esters (especially polyunsaturated) have reduced oxidative stability, undesirable for
a diesel fuel, they have lower melting points, desirable to improve biodiesel low-temperature properties

179

(Knothe, 2008). Normally biodiesels from animal fats have lower iodine value and lower degree of
unsaturation than biodiesels from vegetable oils (Mata et al., 2010). Table 3 shows that iodine values of
biodiesel from animal fats, with the exception of sardine biodiesel, are below the maximum standard limit
(120 g iodine/100 g biodiesel). It was expected that the iodine value of sardine biodiesel was also below
this limit, because the sardine oil has a much lower Iodine value and its FAME profile has the largest
relative amounts of saturated fats. Yet, the FAME profile has also the largest relative amount of other
components, and that may have contributed to this result. However, as those compounds were not
identified, more experiments are needed to identify the real culprit. For the remaining residual fats the rule
holds true, as beef tallow has the lowest iodine value and the largest percentage of saturated esters. Most
biodiesels from animal fat are mainly comprised of C16:0 and C18s FAME, but sardine oil biodiesel
presents a lower percentage of C16:0, a very low percentage of C18:0 and C18:2 and a significant amount
of C17:0, C20:0 and others.
Among unsaturated esters, special attention should be given to linolenate (C18:3) with a maximum
standard limit of 12 % (w/w). This is verified by the biodiesels FAME profile in Table 4. Verification of the
linolenate standard limit is relevant because this ester is more susceptible to oxidation, and has a lower
cetane number than other esters (i.e. lower tendency to ignite and more difficulty to combust).
3.2 Biodiesel sustainability evaluation
Table 5 presents and compares the sustainability evaluation of biodiesel from beef tallow and fish oil with
rapeseed biodiesel and fossil diesel.
Table 5: Sustainability evaluation of biodiesel from beef tallow, fish oil and rapeseed and fossil diesel
Outputs/ Inputs/ Indicators
Energy (MJ/MJ biofuel):
- Farming/ Cultivation
- Rendering/ Pressing/ Extraction
- Transesterification/ Refining
- Fuel energy output
GHG emissions (kg CO2 eq/MJ biofuel):
- Farming/ Cultivation
- Rendering/ Pressing/ Extraction
- Transesterification/ Refining
- Tailpipe emissions(d)
- CO2 sequestration
Sustainability indicators(e):
- LCEE (dimensionless)
- GW (kg CO2-eq/MJ biofuel)

Beef tallow
biodiesel(a)

Fish oil
Rapeseed
biodiesel(b,e) biodiesel(c)

Fossil
diesel(d,e)

0.35
0.12
1.00

0.43
0.06
0.99

0.62
0.14
0.19
1.00

0.06
0.10
1.13

0.02
0.01
0.07
-

0.04
0.01
0.07
-

0.06
0.01
0.01
0.07
0.07

0.01
0.01
0.09
-

2.11
0.10

2.04
0.12

1.05
0.08

7.03
0.10

(a) R-Power, 2013; (b) Ronde et al., 2010; (c) Reinhardt and Jungk, 2001; (d) Mata et al., 2013; (e) This study

Results show a LCEE above the unit for all biodiesels, meaning that their production is energy viable,
although they are still far from fossil diesel that presented the best value. This is because the petroleum
refining process is already highly optimized and energy integrated. The biodiesel process can also follow
the same principle, according to the biorefinery concept, using for example the co-products (straw,
biomass cake and glycerine) as energy sources in the process. Also, the heat capacity of fossil diesel is
higher than that of biodiesel, which gives it a higher fuel energy output.
The LCEE of rapeseed biodiesel is lower than that of animal and fish wastes. Rapeseed needs to be
cultivated and harvested, each of these steps involving energy. For residual fats farming is not considered
as an energy consumption step since its purpose is meat production for human food and not for biofuel.
Thus, there is only energy consumption for rendering the animal wastes and for the transesterification
steps. However, in terms of GW, rapeseed biodiesel is advantageous over animal and fish biodiesels
because there is CO2 sequestration by plants during their growth which compensates for the tailpipe
emissions during the fuel combustion.

4. Conclusions
This study analyses the fat and fuel properties of biodiesel from animal and fish wastes, and evaluates
their sustainability in comparison to rapeseed biodiesel and fossil diesel. Results show that biodiesel
properties such as density, flash point, heat of combustion, acid value and copper strip corrosion depend
on the type of waste fat, in particular on its esters profile. Important fuel properties that can be estimated

180

by the esters profile of a biodiesel are the oxidative stability, low-temperature properties, and kinematic
viscosity. Relatively small amounts of minor components (e.g., linolenate and some contaminants) can
have a significant effect on the fuel properties (especially on the oxidative stability and low-temperature
properties). Beef tallow and sardine oil biodiesels seem to be the best waste fat options to be used alone,
even though there may be some problems such as iodine value or CFPP. Nevertheless, a possible blend
of these fats may result in a biodiesel that fully complies with the EN 14214 standard, as there might be
compensation effect. An efficient conversion of animal and fish wastes to biodiesel must take into account
the differences between them, and more studies are necessary to identify the optimal operation conditions,
in particular for the transesterification reaction and potential pre and post treatment steps. Regarding
sustainability considerations, from the biodiesels under consideration, Beef tallow biodiesel seems to be
the most sustainable one, as its GW value is the same as the one of fossil diesel and the LCEE is the
highest of the biodiesels under consideration.
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