Renewable Energy 118 (2018) 752e760

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

The influence of animal fat type and purification conditions on

biodiesel quality
Aleksandra Sander a, *, Mihael Antonije Ko
s
cak a, Dominik Kosir a, Nikola Milosavljevi
c a,
c b, Lana Magi
Jelena Parlov Vukovi cb
a
Faculty of Chemical Engineering and Technology, University of Zagreb, Marulicev trg 19, 10000 Zagreb, Croatia
b
INAeIndustrija nafte d.d., Lovin
ciceva bb, 10000 Zagreb, Croatia

a r t i c l e i n f o a b s t r a c t

Article history: Production of biodiesel from waste animal fats has a great potential since this feedstock does not
Received 19 June 2017 compete with the food industry and leads to the global reduction of wastes. The type of feedstock as well
Received in revised form as the presence of impurities highly influences the quality of biodiesel. Too high concentrations of
6 October 2017
glycerol and glycerides in biodiesel negatively influence the fuel quality and can generally reduce the
Accepted 23 November 2017
Available online 23 November 2017
engine durability, so crude biodiesel needs to be purified. One alternative method of purifying biodiesel
is extraction with deep eutectic solvents.
Biodiesels were synthesised from five types of waste animal fats: veal and beef tallow, lard, chicken
Keywords:
Animal fats
and goose fat, by means of chemical transesterification catalysed by alkali catalyst. Due to the fact that
Biodiesel the presence of impurities negatively influences the quality of biodiesel, crude biodiesels were purified.
Deep eutectic solvents Liquid-liquid extraction with previously prepared deep eutectic solvent choline-chloride/ethylene-glycol
Extraction (molar ratio 1:2.5) was selected as the purification method. Experiments were performed at different
mass ratio solvent/biodiesel in a laboratory scale batch extractor equipped with mechanical stirrer and
optimal mass ratio was defined. Biodiesels were characterised and their properties were compared with
the standard specification. Free glycerol from animal fats biodiesels was efficiently removed by the
selected solvent.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction encourage economic development because of the raw materials

During the past decade a great attention has been paid to the
development of alternative fuels that could partially or fully replace
the existing fossil fuels [1,2]. An alternative fuel has to be techno-
logically acceptable, economically competitive, environmentally
friendly and easily accessible. The greatest potential is observed in
biodiesel because previous studies showed that the combustion of
biodiesel greatly reduced emissions, so biodiesel is now the most
commonly used renewable energy source [3]. In addition to
reduced emissions, biodiesel production will greatly relieve the
transport sector, i.e. its dependence on fossil fuels and it will
* Corresponding author. University of Zagreb, Faculty of Chemical Engineering
and Technology, Department of Mechanical and Thermal process Engineering,
Marulicev trg 20, 10000 Zagreb, Croatia.
E-mail addresses: asander@fkit.hr (A. Sander), mihaelantonije@yahoo.com
(M. Antonije Ko
s cak), dominikkosir21@gmail.com (D. Kosir), nmilosavl@fkit.hr
(N. Milosavljevic), Jelena.Parlov-Vukovic@ina.hr (J. Parlov Vukovi
c), Lana.Magic@
ina.hr (L. Magi
c).
that are available, renewable and environmentally friendly [4].
Biodiesel is by definition a mixture of mono-alkyl esters of long
chain fatty acids derived from different types of oils or animal fats.
Commercially, it is produced by chemical transesterification of oil
with alcohol in the presence of a catalyst. Despite the fact that bio-
diesel is mostly produced from fresh and vegetable oils, various
feedstocks can be used, many of them investigated during the past
decade. Based on the type of feedstock biodiesel can be categorised as
first-, second-, third- and fourth-generation biodiesel [5]. First gen-
eration biodiesel refers to a fuel produced from edible oils and fats.
Second generation biodiesel is produced from nonedible crops and
wastes, while third generation biodiesel is produced from microalgae.
The quality of biodiesel produced by transesterification is influ-
enced by the type and quality of feedstock used, reaction conditions
(alcohol to oil molar ratio, temperature, catalyst) and present im-
purities like moisture or free fatty acids [6]. In the production of
biodiesel from lower quality feedstock, it is necessary to pretreat the
raw material or, if this does not guarantee satisfactorily low

https://doi.org/10.1016/j.renene.2017.11.068
0960-1481/© 2017 Elsevier Ltd. All rights reserved.
 A. Sander et al. / Renewable Energy 118 (2018) 752e760
Nomenclature
AMe integration values of the methyl ester peak
ACH2 integration values of the glyceridic peaks in
triacylglycerides
CN cetane number
db number of double bonds
DES deep eutectic solvents
FAME fatty acid methyl esters
FFA free fatty acid
FP flash point
FTIR Fourier transform infrared spectroscopy
HHV higher heating value
1
HNMR proton nuclear magnetic resonance
IL ionic liquids
w, wi weight fraction, %
wF weight fraction of glycerol in biodiesel before
extraction, %
wR weight fraction of glycerol in biodiesel after
extraction, %
X carbon number
ε extraction efficiency, %
y kinematic viscosity, m2 s
1
h dynamic viscosity, Pa s
r density, kg m
3
concentrations of free fatty acids, to carefully select a catalyst that
will provide conversion of free fatty acids into high-quality oil. The
most commonly used methods of pretreatment of raw materials
with a high content of free fatty acids are the neutralization of acids
or their esterification with acid catalysts, although vacuum steam
distillation is sometimes used as well. Some alternative methods of
pre-treatment of raw materials have been investigated, such as
transesterification by glycerol, biological pretreatment by microor-
ganisms or enzymes, adsorption, liquid-liquid extraction or extrac-
tion by supercritical fluids [7]. Each method has its advantages and
disadvantages, but in most cases the economic aspect dictates the
final decision regarding the selection of pretreatment method.
Commercially, biodiesel is produced by a well established technol-
ogy of chemical transesterification of refined oil in the presence of
methanol and sodium hydroxide as catalyst [8e10]. This method
requires high quality feedstock since in the presence of water or free
fatty acids hydrolysis or saponification will occur. Lower quality
feedstocks need to be pretreated or different types of catalyst should
be used [11]. Marchetti [8] compared different technologies for
biodiesel production. As mentioned, base catalysed homogeneous
transesterification is sensitive to the presence of FFA and water, but
the reaction is fast and technology is the cheapest. Purification of
glycerol and biodiesel is difficult. All other technologies (enzyme,
supercritical, monolithic, resin or acid) can produce biodiesel of
good to high quality from the low quality feedstocks. The reaction
time is longer, up to 70 h for acid and enzyme catalysed reactions,
except for supercritical reaction (4e10 min). When enzymes, su-
percritical alcohol or heterogeneous catalyst is used, both biodiesel
and glycerol can easily be purified. The major drawback of using
enzymes or supercritical alcohol is high technology cost.
When biodiesel is synthesised it needs to be purified. The pres-
ence of various impurities, such as excess alcohol, residual catalyst,
unconverted fats, soap, metals or glycerol [12] will negatively in-
fluence the quality of biodiesel as well as the engine performance.
There are several methods that can be used for the purification of
biodiesel [13e15]. In general, methods for purification of crude
753
biodiesel can be divided in three groups: wet washing, dry washing
and novel methods. Simple and effective wet washing methods use
water, water and organic solvent or mineral acid and water. Those
methods very successfully remove glycerol, methanol, soap and
various hydrophobic compounds and the resulting biodiesel is of
high purity. However, there are several major drawbacks. First of all,
large amount of deionized water is used, and consequently large
amount of waste water that needs to be purified is produced. Several
steps of washing is followed by separation of biodiesel and water
and finally it needs to be dried, so it can be stated that wet washing
methods are space, time and energy consuming methods. Moreover,
in the presence of water hydrolysis can occur, while in the presence
of soaps stable emulsion can be formed.
Dry washing methods are based on adsorption and ion-
exchange. Dry washing methods purify biodiesel in a shorter
time, less space is required and there is no risk of residual water in
biodiesel. However, biodiesel might not comply with the standard
specification due to the difficult separation of adsorbents from
biodiesel, and low efficiency of ion exchange resins in removal of
glycerol and methanol. Besides, when ion exchange resins are used,
solid waste that cannot be regenerated is produced.
In order to overcome disadvantages of both washing methods,
scientists have started to investigate new environmentally friendly
methods for biodiesel purification, liquid e liquid extraction with
ionic liquids and deep eutectic solvents as well as membrane based
separation. Ceramic membranes can remove catalyst, soap and
glycerol from crude biodiesel. However, this method is expensive
and membranes need to be cleaned up after usage.
Liquid e liquid extraction is a separation method that can be
used at atmospheric pressure and room temperature [16]. If an
environmentally friendly solvent that can be easily regenerated is
used, this method is both environmentally and economically
accepted. Ionic liquids are defined as salts composed of organic
cation and organic or inorganic anion with the melting point below
the room temperature [17]. Deep eutectic solvent, the greener al-
ternatives to the ionic liquids, are a mixture of hydrogen-bond donor
and hydrogen-bond acceptor with the melting point below the
melting point of the individual components [18]. Both types of sol-
vents have numerous advantages over commercially used organic
solvents, but DESs can be easily prepared, and the majority of them
are non-toxic and biodegradable. The properties of ILs and DESs can
be altered by different combinations of cations and anions, or
hydrogen-bond donors and hydrogen-bond acceptors. Because of
their properties, these solvents found their place in various pro-
cesses [19]. Considering only production of biodiesel, ILs and DESs
were used for purification of feedstocks and biodiesel, as well as
catalyst, solvent or cosolvent in esterification and transesterification
steps [19e23]. Some studies on vegetable oils have shown that the
use of DESs reduces the content of all impurities present in crude
biodiesel [19,21,22,24,25]. The major drawback of utilization of these
solvents in the purification step is the absence of the regeneration
method. However, due to their high solvation capacity ILs and DESs
can be reused multiple times without regeneration.
The aim of this research is to synthesise biodiesel from different
types of animal fats by alkali-catalysed transesterification and pu-
rification of biodiesel by liquid e liquid extraction with deep
eutectic solvent, choline chloride:ethylene glycol (molar ratio
1:2.5). Purified biodiesels were characterised and compared with
biodiesel standard.
2. Material and methods
2.1. Material
Waste animal fats (veal, beef, pork, goose, chicken) were
754 A. Sander et al. / Renewable Energy 118 (2018) 752e760
collected at several butcher's shops in Zagreb, Croatia. Choline
chloride (purity: > 99%), ethylene glycol (purity: > 99%) and sodium
hydroxide (purity: 98%) were purchased from Acros Organics and
vacuum dried at 60  C for 8 h before use. Methanol free of water
(Ultra Gradient HPLC Grade) was purchased from J.T. Baker.
2.2. Rendering of animal fats
Crude animal fats were cut into small pieces and placed in the
open jacketed vessel equipped with the mechanical stirrer. Fat was
melted for 12 h at 70  C. Unmelted fats and small meaty bits were
filtrated. Clear filtrate (melted fat) was used for synthesis of
biodiesel.
2.3. Preparation of deep eutectic solvent
Dried choline chloride and ethylene glycol (molar ratio 1:2.5)
were directly weighed in a flask and the mixture was placed on a
rotary vacuum evaporator (250 mbar and 60  C) until clear ho-
mogeneous liquid was obtained.
2.4. Biodiesel synthesis
Biodiesel was synthesised by alkali-catalysed (NaOH) trans-
esterification of waste animal fats with methanol. 0.6 g of NaOH
was dissolved in 20 mL of methanol. Sodium methoxide was added
to the 100 g of filtrated animal fat heated at 60  C and intensively
mixed in a jacketed vessel. Heterogeneous mixture was left for 24 h
to ensure complete phase separation. Residual methanol was
removed by vacuum evaporation.
2.5. Extraction of free glycerol
After phase separation, crude biodiesel was purified by means of
liquid e liquid extraction. Liquid-liquid extraction experiments
were carried out in a laboratory batch extractor equipped with a
mechanical stirrer at different mass ratios of DES and biodiesel,
mixing rate of 500 rpm for 3 h. Extraction was carried out at 25 and
50  C. For each process condition extraction was performed three
times, except for biodiesel synthesised from veal.
2.6. Characterization of deep eutectic solvent, oil and biodiesel
Analytical methods used for biodiesel characterization are: FTIR
(Bruker Vertex 70), GC (Shimadzu GC-2014) and 1H NMR (Bruker
Avance 300). Viscosity was measured using Brookfield DV-III Ultra
Programmable Rheometer. Density was measured with Mettler
Toledo densitometer Densito 30PX. Biodiesel heating value (HHV)
was measured with calorimeter IKA C 2000. Viscosity, density and
HHV measurements were performed three times, and average
values are reported here. Standard uncertainties,u, are: u(h)
 0.0002 Pa s, u(r)  0.0005 g cm
3 and u(HHV)  0.0465 MJ kg
1.
Biodiesel samples were further analysed in an accredited Central
Testing Laboratory of INA e Industrija nafte d.d., Zagreb, Croatia.
3. Results and discussion
3.1. Properties of biodiesels and DES
In order to determine if animal fats biodiesel can be synthesised
by means of the alkali catalysed transesterification, acid values
were determined for all prepared melted fats. Acid values of all
prepared fats were lower than 2 mg(KOH) per g(fat), Table 1, so
there was no need for pretreatment of feedstocks prior to alkali
catalysed reaction. Table 1 also presents measured value of
densities and viscosities of melted fats.
Crude animal fats biodiesels were purified with the prepared
deep eutectic solvent. Density, viscosity, HHV and initial glycerol
concentration of purified biodiesels were measured, and the ob-
tained results are given in Table 2.
All synthesised biodiesels were clear liquids except the one
based on beef tallow, due to the highest concentration of saturated
fatty acids methyl esters, as it will be seen later. As expected, both
density and viscosity are lower for biodiesel than for the melted fat.
Density of all synthesised biodiesels meets the EN 14214 specifi-
cation standard (860e900 kg m
3). Viscosity is higher for all bio-
diesel except for biodiesel synthesised from chicken fat. Density
and viscosity of beef tallow biodiesel is higher than previously re-
ported [26e29]. Density and viscosity of lard biodiesel are in the
range of previously reported values [28,30,31] as well as for chicken
fat [32e35]. Differences in the viscosity and density of animal fats
biodiesels resulted from the different compositions in fatty acids
methyl esters [36]. Generally speaking, the increase in length of
fatty acid chain results in decreasing density and increasing vis-
cosity. On the other hand, saturated fatty acid methyl esters have
lower density and higher viscosity than unsaturated ones. Initial
concentration of glycerol ranges from 0.349 for goose fat biodiesel
to 3.026% for beef tallow biodiesel.
At 25  C, density of prepared DES is 1.122 g cm
3 and its vis-
cosity is 0.0355 Pa s. Relatively high viscosity of DES will increase
the mass transfer resistance during extraction step performed at
room conditions. In order to determine the influence of tempera-
ture on the DES viscosity, viscosity was measured in the range of
temperatures between 15 and 55  C. It is visible from Fig. 1 that
viscosity is significantly lowered with increasing temperature. As a
consequence at higher temperatures, resistances to mass transfer
will be lowered, DES will be easily dispersed in biodiesel and larger
interphase area will be available for mass transfer.
3.2. Purification of biodiesel
The applicability of the selected DES for the extraction of glyc-
erol from biodiesel is evaluated in terms of extraction efficiency,
calculated from the mass fraction of glycerol before and after
extraction:
wF
wR
ε¼ $100 % (1)
wF
The influence of mass ratio DES/biodiesel on the extraction ef-
ficiency at 25  C was determined experimentally for all prepared
animal fat biodiesels except for veal tallow (not enough amount of
feedstock) (Fig. 2). In general, the highest efficiency was obtained at
equal masses of biodiesel and DES. Further increase of mass ratio
resulted in decrease of the extraction efficiency. The reason for that
was too large volume of viscous solvent that needed to be
dispersed. Due to the high hydrodynamic resistances at the same
mixing intensity (500 rpm) the power draw was too low to assure
complete dispersion and large interfacial area.
Since extraction efficiency was low, another set of extraction
experiments at elevated temperature (50  C) was performed and
biodiesels were completely characterised.
Table 1
Density, viscosity and acid value of animal fats.
Animal fat Density, g cm
3 Viscosity, Pa s Acid value, mgKOH/gfat
veal 0.9188 0.0350 1.075
beef 0.9190 0.0355 1.076
lard 0.9156 0.0338 0.592
chicken 0.9171 0.0311 1.120
goose 0.9187 0.0340 1.185
 A. Sander et al. / Renewable Energy 118 (2018) 752e760 755

Table 2
Properties of animal fats biodiesels.

Animal fat Density, g cm
3 Viscosity, Pa s wF (glycerol), %

veal 0.8825 0.0063 1.695

beef 0.8900 0.0065 3.026
Lard 0.8795 0.0051 1.654
chicken 0.8816 0.0044 0.558
goose 0.8820 0.0048 0.349

Fig. 2. The influence of mass ratio DES/biodiesel on the extraction efficiency

(T ¼ 25  C).

properties like low temperature operability, oxidative and storage

Fig. 1. The influence of temperature on the viscosity of DES.
3.3. Distribution of FAME in animal fats biodiesels
Composition of animal fats biodiesels is presented in Table 3.
Beef tallow based biodiesel has the highest concentration of pal-
mitic and stearic acid methyl esters, goose fat biodiesel has the
highest concentration of oleic ester methyl ester, while chicken fat
biodiesel has the highest concentration of linoleic acid methyl ester.
Degree of saturation of biodiesel decreases in the following line:
beef tallow, veal tallow, lard, chicken and goose. The initial con-
centration of glycerol in animal fats biodiesels follows the same
trend, so probably there is a connection between the degree of
saturation and the residual glycerol. Composition of fatty acid
methyl esters slightly differ from the previously reported due to the
different origin of feedstocks [6], even though the total concen-
tration of saturated, monounsaturated and polyunsaturated FAME
are in the similar proportions. S. Saraf and B. Thomas [6] have re-
ported that the chicken fat biodiesel has the highest concentration
of polyunsaturated FAME, beef tallow biodiesel of saturated and pig
lard biodiesel of monounsaturated FAME, which is in concordance
with results presented in Table 3.
Concentration of different FAME in biodiesel defines biodiesel
stability, viscosity, exhaust emissions, cetane number and energy
content. Increase in the chain length of saturated FAME results in
the increase of the melting point, while increasing levels of unsa-
turation lowers the melting point. Biodiesel with higher concen-
tration of long-chain saturated FAME will have higher melting
point and lower low temperature operability. Based on the results
presented in Table 3, beef tallow biodiesel has the lowest low
temperature stability. The quality of biodiesel will change in stor-
age. According to reports, the iodine value is decreased, especially
for biodiesels with higher initial iodine value, while the acid and
peroxide number increases over time [37]. Biodiesels with higher
concentration of unsaturated FAME will have lower oxidative sta-
bility. The increase in concentration of high molecular weight long
chain saturated FAME was also observed. This means that chicken
and goose fat biodiesels will be prone to oxidation. The concen-
tration of polyunsaturated FAME, with number of double bonds
higher than 3, in all purified biodiesels is below the upper limit
(<1). Molecular weight of animal fats biodiesels was calculated
from FAME distribution and the corresponding molecular weight of
individual FAME.
3.4. Evaluation of Cetane number
Distribution data of FAME in biodiesel can be used for prediction
of Cetane number for biodiesel. Cetane numbers were evaluated by
using the following equations:
Bamgboye and Hansen equation [38]:

CN ¼ 61:1 þ 0:0881$wðC12 : 0Þ þ 0:133$wðC14 : 0Þ þ 0:152$wðC16 : 0Þ

(2)

0:101$wðC18 : 0Þ
0:039$wðC16 : 1Þ
0:243$wðC18 : 1Þ
0:395$wðC18 : 2Þ

Gopinath et al. equation [39]:

CN ¼ 62:2 þ 0:017$wðC12 : 0Þ þ 0:074$wðC14 : 0Þ þ 0:115$wðC16 : 0Þ

(3)
þ0:177$wðC18 : 0Þ
0:103$wðC18 : 1Þ
0:279$wðC12 : 2Þ
0:366$wðC18 : 3Þ
756 A. Sander et al. / Renewable Energy 118 (2018) 752e760

Table 3
Fatty acid methyl ester concentration in animal fats biodiesels after extraction at 50  C and molecular weight of biodiesels.

FAME structure w/%

veal beef lard chicken goose

Caproic acid methyl ester C6:0 0.017 0.020 0.015 e 0.014

Caprylic acid methyl ester C8:0 0.006 0.014 0.011 0.008 0.012
Capric acid methyl ester C10:0 0.052 0.076 0.056 0.076 0.008
Undecylic acid methyl ester C11:0 0.014 0.017 0.005 0.003 0.005
Lauric acid methyl ester C12:0 0.717 0.085 0.068 0.034 0.019
Tridecylic acid methyl ester C13:0 0.015 0.013 0.003 0.003 e
Myristic acid methyl ester C14:0 5.751 3.116 1.137 0.500 0.328
Tetradeceonic acid methyl ester C14:1 0.647 0.586 0.037 0.029 0.050
Pentadecylic acid methyl ester C15:0 0.294 0.405 0.076 0.073 0.049
Palmitic acid methyl ester C16:0 23.170 31.376 19.794 22.055 20.503
Palmitoleic acid methyl ester C16:1 3.158 1.815 2.047 6.181 2.592
Margaric acid methyl ester C17:0 0.702 1.206 0.405 0.135 0.083
Stearic acid methyl ester C18:0 13.003 25.236 11.814 5.050 5.587
Oleic acid methyl ester C18:1 37.778 31.091 44.660 40.341 46.399
Linoleic acid methyl ester C18:2 6.314 1.434 10.867 16.515 13.622
Linolenic acid methyl ester C18:3 0.589 0.233 0.990 0.625 0.691
Arachidic acid methyl ester C20:0 0.146 0.277 0.234 0.106 0.089
Paulinic acid methyl ester C20:1 0.322 0.214 1.132 0.320 0.290
Eicosapentaenoic acid methyl ester C20:5 0.006 0.021 0.007 0.009 e
Behenic acid methyl ester C22:0 0.027 0.063 0.034 0.032 0.046
Erucic acid methyl ester C22:1 0.002 0.006 0.005 0.009 e
Docosahexaenoic acid methyl ester C22:6 0.020 0.027 0.057 0.043 e
Tricosylic acid methyl ester C23:0 0.002 0.006 0.004 0.011 0.003
Lignoceric acid methyl ester C24:0 0.017 0.117 0.083 0.023 0.146
Nervonic acid methyl ester C24:1 e 0.008 e e 0.066

Saturated 43.93 62.03 33.74 28.11 26.89

Monounsaturated 41.91 33.72 47.88 46.88 49.40
Polyunsaturated 6.93 1.71 11.92 17.19 14.31

Molecular weight 251.07 264.88 258.15 252.42 249.70

Tong et al. equations [40]:
X of biodiesels. However, one should have in mind that the compo-
CN ¼ 1:068$ ðCNi $wi Þ
6:747
For prediction of cetane number of saturated FAME:
CN ¼
107:71 þ 31:126$X
2:042$X 2 þ 0:0499$X 3
For prediction of cetane number for monounsaturated FAME:
CN ¼
109
9:292$X þ 0:354$X 2
For prediction of cetane number for polyunsaturated FAME:
 
CN ¼
52:974 þ 13:767
1:202$db þ 0:152$db2 $X
calculate CN for FAME with the highest concentration in majority
(4) sition of biodiesel strongly depends on feedstock quality so it is
very likely that different CN, as well as other properties influenced
by the composition of biodiesel, are reported for the same type of
biodiesel.
(5) Cetane number as well as the energy content is higher for bio-
diesel with higher concentration of longer chain saturated FAME.
Higher concentration of unsaturated, especially polyunsaturated
(6) FAME will negatively influence those values. Beef and veal tallow
based biodiesel have the highest cetane number and energy con-
tent. Evaluated CN for all biodiesels is above the standard specifi-
cation (CN > 51).

0:351$X 2 (7) 3.5. Higher heating value of animal fats biodiesels

Based on the obtained results shown in Table 4, it can be
concluded that equation proposed by Tong [40] gives the best re-
sults due to the closest agreement between evaluated and previ-
ously reported data [38,41,42]. Tong equation takes into account CN
of all FAME present in biodiesel, while equations (2) and (3)
Higher heating value of biodiesels was calculated from viscosity
and density data using three different models as proposed by the
literature. Flash point data was taken from the literature [43].
Evaluated values were compared with the measured ones and the
obtained results are shown in Table 5. In the following equations

Table 4
Evaluated cetane number of animal fats biodiesels.

Animal fat Cetane number Ref.

Predicted by eq. (2) Predicted by eq. (3) Predicted by eq. (4) Reported value

veal 52.34 59.42 56.52 e e

beef 55.55 63.68 64.64 64.8 [38]
lard 47.85 56.68 55.45 57.8 [41]
chicken 47.44 54.47 52.22 57.0 [42]
goose 46.94 54.69 51.72 e e
 A. Sander et al. / Renewable Energy 118 (2018) 752e760 757

Table 5
Higher heating value of animal fats biodiesels.

Animal fat HHV, MJ/kg Absolute error eq. (10)

Measured value Predicted by eq. (8) Predicted by eq. (9) Predicted by eq. (10)

veal 39.930 36.022 42.752 40.919 0.989

beef 39.932 36.037 42.828 40.725 0.793
lard 39.931 35.515 42.132 40.997 1.066
chicken 39.911 35.060 41.758 40.943 1.032
goose 39.834 35.261 41.967 40.932 1.098

viscosity is given in cst.
Sivaramakrishnan and Ravikumar equation [44]:
HHV ¼ 0:4527$y
0:008$r
0:0003$FP þ 40:3667
Sivaramakrishnan and Ravikumar equations [45]:
HHV ¼ 0:4652$y þ 39:450
commercial biodiesel (Biodiesel Vukovar, Croatia) was also pre-
sented. In the region from 1800 to 1700 cm
1, the peak that can be
attributed to the stretching of C]O, typical of esters, and thus
(8) common in FAME spectra, is clearly visible. Broad band between
3200 and 3600 cm
1 that corresponds to alcohols (in this case
glycerol) cannot be observed. No significant difference can be
(9) observed between animal fats biodiesels and commercial one.

HHV ¼
0:0259$r þ 63:776 (10) 3.7. 1

Higher heating value, (HHV) is similar for all synthesised bio-
diesels, and lower than the heating value of fossil diesel
(45.4 kJ g
1) as stated in the literature [46]. The closes agreement
between the measured and calculated data was obtained using
equation based on density of biodiesel. Absolute error, when using
equation (10) for prediction of HHV, ranges between 0.793 and
1.098. Equations were developed for vegetable oil biodiesels, and
this can be the reason for deviation from the measured values.
3.6. FTIR analysis of animal fats biodiesels
The FTIR spectra for purified biodiesels are presented in Fig. 3. In
order to compare FTIR spectra of animal fats biodiesels spectrum of
HNMR analysis of animal fats biodiesels
In order to compare 1H NMR spectra of feedstock and biodiesel,
an example for goose fat and goose fat biodiesel is presented on
Fig. 4.
In the region between 0 and 3 ppm the two NMR spectra are the
same, both showing signals that correspond to olefinic protons. The
biodiesel sample spectrum contains a peek at 3.67 ppm corre-
sponding to eCOOCH3 group, while goose fat spectrum contains
peeks at 4.10e4.35 ppm and 5.25 ppm corresponding to eCHOCOR
groups.
1
H NMR spectra of all synthesised biodiesels are shown in Fig. 5.
1
H NMR was used to quantify the conversion of animal fats in
biodiesel by transesterification reaction [47]. Integration values of
the methyl ester peak at 3.624 ppm (AMe) and of the glyceridic

Fig. 3. FTIR spectra of animal fats biodiesels.

758 A. Sander et al. / Renewable Energy 118 (2018) 752e760
Fig. 4. 1H NMR spectra of goose fat and goose fat biodiesel.
peaks in triacylglycerides at 2.279 ppm (ACH2) were used for
calculation. The equation used to quantify the yield of trans-
esterification was:
2$AMe
%FAME ¼ 100$
3$ACH2
The obtained results are presented in Table 6.
3.8. Purified animal fats biodiesels specification
Experimentally determined properties of animal fats bio-
diesels are presented in Table 6. Ester content of all biodiesels
except for beef tallow was below the EN 14214 limit. Lower
content of FAME in biodiesel indicates that biodiesels are
contaminated with unreacted mono-, di- and triglycerides, but
also with other impurities like unreacted catalyst or some other
compounds.
The higher sulfur content of animal fat biodiesel indicates that
some protein and phosphoglycerides (essential constituents of the
animal cell membranes that concentrates in the lipids) still remain
in the feedstock [48]. However, these values are still below the
upper limit of the standard specification.
Sulfated ash content as a measure of the amount of metals and
some other inorganic compounds, like unremoved catalyst pre-
sent in biodiesel, is below the specified limit for animal fats
biodiesels.
Iodide number as a measure of unsaturation of biodiesels
corresponds to the composition of biodiesels. Beef tallow based
biodiesel, which is highly saturated, has the lowest value, while
chicken and goose fat based biodiesels (the lowest concentration
of saturated FAME) has the highest iodide number. Iodide values
(11)
of all purified biodiesels complied with the standard
specification.
Limitation of unsaturated fatty acids methyl esters is expressed
by the concentration of linolenic acid methyl ester. Concentration
of linolenic acid methyl ester is below the limiting value for all
animal fats biodiesels. This is important because on heating, poly-
unsaturated fatty acids, methyl esters can form deposits as a result
of polymerization of glycerides [49].
Methanol was successfully removed by evaporation prior to the
purification step since it concentration is below the standard
limitation.
All animal fats biodiesel fulfilled the standard specifications for
biodiesel fuel in terms of free glycerine content. However, con-
centration of total glycerine was higher than allowed due to the
unreacted mono-, di- and triglycerides.
3.9. The influence of temperature on the extraction efficiency
The influence of temperature on the extraction efficiency is
shown in Fig. 6. Increase in temperature resulted in significant in-
crease in extraction efficiency. Density and viscosity of both phases
(biodiesel and DES) was lowered at 50  C and consequently
 A. Sander et al. / Renewable Energy 118 (2018) 752e760 759

Fig. 5. 1H NMR spectra of animal fats biodiesels.

Table 6
Specification of biodiesel after extraction at 50  C.

property unity veal beef pork chicken goose standard method

Ester content % (m/m) 92.77 97.46 93.54 92.18 90.60 >96.5 HRN EN ISO 23015:1997
Sulfated ash content % (m/m) <0.005 <0.005 0.019 0.015 0.019 <0.02 HRN EN ISO 3987:2011
Sulfur content mg/kg 4.5 6.3 <3.0 <3.0 <3.0 <10 HRN EN ISO 20846:2011
Methanol content % (m/m) <0.01 <0.01 <0.01 0.01 <0.01 <0.2 HRN DIN EN 14110:2003
Iodide number g I2/100 g 50.1 31.2 63.5 74.3 72.6 <120 HRN EN 16300:2012
Linolenic acid methyl ester % (m/m) 0.60 0.20 0.90 0.60 0.70 <12 HRN EN 14103:2011
Monoglyceride content % (m/m) 0.55 0.64 0.77 0.78 0.80 <0.7 HRN EN 14105:2011
Diglyceride content % (m/m) 0.47 1.07 1.24 1.25 0.76 <0.2 HRN EN 14105:2011
Triglyceride content % (m/m) 2.10 2.42 3.10 4.21 6.05 <0.2 HRN EN 14105:2011
Free glycerine % (m/m) <0.005 <0.005 <0.005 0.005 <0.005 <0.02 HRN EN 14105:2011
Total glycerine % (m/m) 0.425 0.569 0.697 0.815 0.938 <0.25 HRN EN 14105:2011

resistances to mass transfer was reduced, resulting in better solu- 4. Conclusions

bility of glycerol in DES. Besides that, at 50  C DES is easily
dispersed in biodiesel, so high interphase area is available for mass
transfer. In general, for biodiesels of similar ratio of saturated,
monounsaturated and polyunsaturated FAME (in this case lard,
chicken and goose fat biodiesels) extraction efficiency at 25  C in-
creases with decreasing initial glycerol content. Glycerol is highly
viscous liquid. The rate of mass transfer to another viscous liquid, in
this case DES, is very slow due to high resistances to momentum
and mass transfer. Since the duration of all experiments was the
same and equilibrium wasn't reached, it is obvious that extraction
efficiency should be higher for lower concentration of glycerol.
Animal fats biodiesels were successfully synthesised by means
of chemical transesterification using methanol and sodium hy-
droxide. Optimum mass ratio solvent/biodiesel was defined based
on the extraction efficiency obtained at different mass ratios. Deep
eutectic solvent, choline-chloride/ethylene-glycol (molar ratio
1:2.5) is very efficient for extraction of free glycerol, especially at
elevated temperature. The ester content in all biodiesels, except
beef tallow biodiesel, was a little lower than specified by the EN
14214 standard due to the residual glycerides in biodiesels. Con-
centration of glycerides in biodiesel can be reduced by modification
760 A. Sander et al. / Renewable Energy 118 (2018) 752e760
Fig. 6. Efficiency of removal of glycerol from biodiesels by extraction at different
temperatures (mass ratio DES/biodiesel ¼ 1).
of operating conditions and/or use of solvent efficient in removal of
both free glycerol and glycerides. Tong et al. equation was used for
predicting cetane number. Higher heating value is evaluated from
the measured density of biodiesels.
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