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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 Kos
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., Lovinciceva 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


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

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 753

biodiesel can be divided in three groups: wet washing, dry washing


Nomenclature and novel methods. Simple and effective wet washing methods use
water, water and organic solvent or mineral acid and water. Those
AMe integration values of the methyl ester peak methods very successfully remove glycerol, methanol, soap and
ACH2 integration values of the glyceridic peaks in various hydrophobic compounds and the resulting biodiesel is of
triacylglycerides high purity. However, there are several major drawbacks. First of all,
CN cetane number large amount of deionized water is used, and consequently large
db number of double bonds amount of waste water that needs to be purified is produced. Several
DES deep eutectic solvents steps of washing is followed by separation of biodiesel and water
FAME fatty acid methyl esters and finally it needs to be dried, so it can be stated that wet washing
FFA free fatty acid methods are space, time and energy consuming methods. Moreover,
FP flash point in the presence of water hydrolysis can occur, while in the presence
FTIR Fourier transform infrared spectroscopy of soaps stable emulsion can be formed.
HHV higher heating value Dry washing methods are based on adsorption and ion-
1
HNMR proton nuclear magnetic resonance exchange. Dry washing methods purify biodiesel in a shorter
IL ionic liquids time, less space is required and there is no risk of residual water in
w, wi weight fraction, % biodiesel. However, biodiesel might not comply with the standard
wF weight fraction of glycerol in biodiesel before specification due to the difficult separation of adsorbents from
extraction, % biodiesel, and low efficiency of ion exchange resins in removal of
wR weight fraction of glycerol in biodiesel after glycerol and methanol. Besides, when ion exchange resins are used,
extraction, % solid waste that cannot be regenerated is produced.
X carbon number In order to overcome disadvantages of both washing methods,
ε extraction efficiency, % scientists have started to investigate new environmentally friendly
y kinematic viscosity, m2 s1 methods for biodiesel purification, liquid e liquid extraction with
h dynamic viscosity, Pa s ionic liquids and deep eutectic solvents as well as membrane based
r density, kg m3 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
concentrations of free fatty acids, to carefully select a catalyst that used at atmospheric pressure and room temperature [16]. If an
will provide conversion of free fatty acids into high-quality oil. The environmentally friendly solvent that can be easily regenerated is
most commonly used methods of pretreatment of raw materials used, this method is both environmentally and economically
with a high content of free fatty acids are the neutralization of acids accepted. Ionic liquids are defined as salts composed of organic
or their esterification with acid catalysts, although vacuum steam cation and organic or inorganic anion with the melting point below
distillation is sometimes used as well. Some alternative methods of the room temperature [17]. Deep eutectic solvent, the greener al-
pre-treatment of raw materials have been investigated, such as ternatives to the ionic liquids, are a mixture of hydrogen-bond donor
transesterification by glycerol, biological pretreatment by microor- and hydrogen-bond acceptor with the melting point below the
ganisms or enzymes, adsorption, liquid-liquid extraction or extrac- melting point of the individual components [18]. Both types of sol-
tion by supercritical fluids [7]. Each method has its advantages and vents have numerous advantages over commercially used organic
disadvantages, but in most cases the economic aspect dictates the solvents, but DESs can be easily prepared, and the majority of them
final decision regarding the selection of pretreatment method. are non-toxic and biodegradable. The properties of ILs and DESs can
Commercially, biodiesel is produced by a well established technol- be altered by different combinations of cations and anions, or
ogy of chemical transesterification of refined oil in the presence of hydrogen-bond donors and hydrogen-bond acceptors. Because of
methanol and sodium hydroxide as catalyst [8e10]. This method their properties, these solvents found their place in various pro-
requires high quality feedstock since in the presence of water or free cesses [19]. Considering only production of biodiesel, ILs and DESs
fatty acids hydrolysis or saponification will occur. Lower quality were used for purification of feedstocks and biodiesel, as well as
feedstocks need to be pretreated or different types of catalyst should catalyst, solvent or cosolvent in esterification and transesterification
be used [11]. Marchetti [8] compared different technologies for steps [19e23]. Some studies on vegetable oils have shown that the
biodiesel production. As mentioned, base catalysed homogeneous use of DESs reduces the content of all impurities present in crude
transesterification is sensitive to the presence of FFA and water, but biodiesel [19,21,22,24,25]. The major drawback of utilization of these
the reaction is fast and technology is the cheapest. Purification of solvents in the purification step is the absence of the regeneration
glycerol and biodiesel is difficult. All other technologies (enzyme, method. However, due to their high solvation capacity ILs and DESs
supercritical, monolithic, resin or acid) can produce biodiesel of can be reused multiple times without regeneration.
good to high quality from the low quality feedstocks. The reaction The aim of this research is to synthesise biodiesel from different
time is longer, up to 70 h for acid and enzyme catalysed reactions, types of animal fats by alkali-catalysed transesterification and pu-
except for supercritical reaction (4e10 min). When enzymes, su- rification of biodiesel by liquid e liquid extraction with deep
percritical alcohol or heterogeneous catalyst is used, both biodiesel eutectic solvent, choline chloride:ethylene glycol (molar ratio
and glycerol can easily be purified. The major drawback of using 1:2.5). Purified biodiesels were characterised and compared with
enzymes or supercritical alcohol is high technology cost. biodiesel standard.
When biodiesel is synthesised it needs to be purified. The pres-
ence of various impurities, such as excess alcohol, residual catalyst, 2. Material and methods
unconverted fats, soap, metals or glycerol [12] will negatively in-
fluence the quality of biodiesel as well as the engine performance. 2.1. Material
There are several methods that can be used for the purification of
biodiesel [13e15]. In general, methods for purification of crude 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 densities and viscosities of melted fats.
chloride (purity: > 99%), ethylene glycol (purity: > 99%) and sodium Crude animal fats biodiesels were purified with the prepared
hydroxide (purity: 98%) were purchased from Acros Organics and deep eutectic solvent. Density, viscosity, HHV and initial glycerol
vacuum dried at 60  C for 8 h before use. Methanol free of water concentration of purified biodiesels were measured, and the ob-
(Ultra Gradient HPLC Grade) was purchased from J.T. Baker. tained results are given in Table 2.
All synthesised biodiesels were clear liquids except the one
2.2. Rendering of animal fats based on beef tallow, due to the highest concentration of saturated
fatty acids methyl esters, as it will be seen later. As expected, both
Crude animal fats were cut into small pieces and placed in the density and viscosity are lower for biodiesel than for the melted fat.
open jacketed vessel equipped with the mechanical stirrer. Fat was Density of all synthesised biodiesels meets the EN 14214 specifi-
melted for 12 h at 70  C. Unmelted fats and small meaty bits were cation standard (860e900 kg m3). Viscosity is higher for all bio-
filtrated. Clear filtrate (melted fat) was used for synthesis of diesel except for biodiesel synthesised from chicken fat. Density
biodiesel. and viscosity of beef tallow biodiesel is higher than previously re-
ported [26e29]. Density and viscosity of lard biodiesel are in the
2.3. Preparation of deep eutectic solvent range of previously reported values [28,30,31] as well as for chicken
fat [32e35]. Differences in the viscosity and density of animal fats
Dried choline chloride and ethylene glycol (molar ratio 1:2.5) biodiesels resulted from the different compositions in fatty acids
were directly weighed in a flask and the mixture was placed on a methyl esters [36]. Generally speaking, the increase in length of
rotary vacuum evaporator (250 mbar and 60  C) until clear ho- fatty acid chain results in decreasing density and increasing vis-
mogeneous liquid was obtained. cosity. On the other hand, saturated fatty acid methyl esters have
lower density and higher viscosity than unsaturated ones. Initial
2.4. Biodiesel synthesis concentration of glycerol ranges from 0.349 for goose fat biodiesel
to 3.026% for beef tallow biodiesel.
Biodiesel was synthesised by alkali-catalysed (NaOH) trans- At 25  C, density of prepared DES is 1.122 g cm3 and its vis-
esterification of waste animal fats with methanol. 0.6 g of NaOH cosity is 0.0355 Pa s. Relatively high viscosity of DES will increase
was dissolved in 20 mL of methanol. Sodium methoxide was added the mass transfer resistance during extraction step performed at
to the 100 g of filtrated animal fat heated at 60  C and intensively room conditions. In order to determine the influence of tempera-
mixed in a jacketed vessel. Heterogeneous mixture was left for 24 h ture on the DES viscosity, viscosity was measured in the range of
to ensure complete phase separation. Residual methanol was temperatures between 15 and 55  C. It is visible from Fig. 1 that
removed by vacuum evaporation. viscosity is significantly lowered with increasing temperature. As a
consequence at higher temperatures, resistances to mass transfer
2.5. Extraction of free glycerol will be lowered, DES will be easily dispersed in biodiesel and larger
interphase area will be available for mass transfer.
After phase separation, crude biodiesel was purified by means of
liquid e liquid extraction. Liquid-liquid extraction experiments 3.2. Purification of biodiesel
were carried out in a laboratory batch extractor equipped with a
mechanical stirrer at different mass ratios of DES and biodiesel, The applicability of the selected DES for the extraction of glyc-
mixing rate of 500 rpm for 3 h. Extraction was carried out at 25 and erol from biodiesel is evaluated in terms of extraction efficiency,
50  C. For each process condition extraction was performed three calculated from the mass fraction of glycerol before and after
times, except for biodiesel synthesised from veal. extraction:

2.6. Characterization of deep eutectic solvent, oil and biodiesel wF  wR


ε¼ $100 % (1)
wF
Analytical methods used for biodiesel characterization are: FTIR The influence of mass ratio DES/biodiesel on the extraction ef-
(Bruker Vertex 70), GC (Shimadzu GC-2014) and 1H NMR (Bruker ficiency at 25  C was determined experimentally for all prepared
Avance 300). Viscosity was measured using Brookfield DV-III Ultra animal fat biodiesels except for veal tallow (not enough amount of
Programmable Rheometer. Density was measured with Mettler feedstock) (Fig. 2). In general, the highest efficiency was obtained at
Toledo densitometer Densito 30PX. Biodiesel heating value (HHV) equal masses of biodiesel and DES. Further increase of mass ratio
was measured with calorimeter IKA C 2000. Viscosity, density and resulted in decrease of the extraction efficiency. The reason for that
HHV measurements were performed three times, and average was too large volume of viscous solvent that needed to be
values are reported here. Standard uncertainties,u, are: u(h) dispersed. Due to the high hydrodynamic resistances at the same
 0.0002 Pa s, u(r)  0.0005 g cm3 and u(HHV)  0.0465 MJ kg1. mixing intensity (500 rpm) the power draw was too low to assure
Biodiesel samples were further analysed in an accredited Central complete dispersion and large interfacial area.
Testing Laboratory of INA e Industrija nafte d.d., Zagreb, Croatia. Since extraction efficiency was low, another set of extraction
experiments at elevated temperature (50  C) was performed and
3. Results and discussion biodiesels were completely characterised.

3.1. Properties of biodiesels and DES Table 1


Density, viscosity and acid value of animal fats.

In order to determine if animal fats biodiesel can be synthesised Animal fat Density, g cm3 Viscosity, Pa s Acid value, mgKOH/gfat
by means of the alkali catalysed transesterification, acid values veal 0.9188 0.0350 1.075
were determined for all prepared melted fats. Acid values of all beef 0.9190 0.0355 1.076
prepared fats were lower than 2 mg(KOH) per g(fat), Table 1, so lard 0.9156 0.0338 0.592
there was no need for pretreatment of feedstocks prior to alkali chicken 0.9171 0.0311 1.120
goose 0.9187 0.0340 1.185
catalysed reaction. Table 1 also presents measured value of
A. Sander et al. / Renewable Energy 118 (2018) 752e760 755

Table 2
Properties of animal fats biodiesels.

Animal fat Density, g cm3 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


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
Fig. 1. The influence of temperature on the viscosity of DES. point and lower low temperature operability. Based on the results
presented in Table 3, beef tallow biodiesel has the lowest low
3.3. Distribution of FAME in animal fats biodiesels temperature stability. The quality of biodiesel will change in stor-
age. According to reports, the iodine value is decreased, especially
Composition of animal fats biodiesels is presented in Table 3. for biodiesels with higher initial iodine value, while the acid and
Beef tallow based biodiesel has the highest concentration of pal- peroxide number increases over time [37]. Biodiesels with higher
mitic and stearic acid methyl esters, goose fat biodiesel has the concentration of unsaturated FAME will have lower oxidative sta-
highest concentration of oleic ester methyl ester, while chicken fat bility. The increase in concentration of high molecular weight long
biodiesel has the highest concentration of linoleic acid methyl ester. chain saturated FAME was also observed. This means that chicken
Degree of saturation of biodiesel decreases in the following line: and goose fat biodiesels will be prone to oxidation. The concen-
beef tallow, veal tallow, lard, chicken and goose. The initial con- tration of polyunsaturated FAME, with number of double bonds
centration of glycerol in animal fats biodiesels follows the same higher than 3, in all purified biodiesels is below the upper limit
trend, so probably there is a connection between the degree of (<1). Molecular weight of animal fats biodiesels was calculated
saturation and the residual glycerol. Composition of fatty acid from FAME distribution and the corresponding molecular weight of
methyl esters slightly differ from the previously reported due to the individual FAME.
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- 3.4. Evaluation of Cetane number
ported that the chicken fat biodiesel has the highest concentration
of polyunsaturated FAME, beef tallow biodiesel of saturated and pig Distribution data of FAME in biodiesel can be used for prediction
lard biodiesel of monounsaturated FAME, which is in concordance of Cetane number for biodiesel. Cetane numbers were evaluated by
with results presented in Table 3. using the following equations:
Concentration of different FAME in biodiesel defines biodiesel 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]: calculate CN for FAME with the highest concentration in majority
X of biodiesels. However, one should have in mind that the compo-
CN ¼ 1:068$ ðCNi $wi Þ  6:747 (4) sition of biodiesel strongly depends on feedstock quality so it is
very likely that different CN, as well as other properties influenced
For prediction of cetane number of saturated FAME: by the composition of biodiesel, are reported for the same type of
biodiesel.
CN ¼ 107:71 þ 31:126$X  2:042$X 2 þ 0:0499$X 3 (5) Cetane number as well as the energy content is higher for bio-
For prediction of cetane number for monounsaturated FAME: diesel with higher concentration of longer chain saturated FAME.
Higher concentration of unsaturated, especially polyunsaturated
CN ¼ 109  9:292$X þ 0:354$X 2 (6) FAME will negatively influence those values. Beef and veal tallow
based biodiesel have the highest cetane number and energy con-
For prediction of cetane number for polyunsaturated FAME: tent. Evaluated CN for all biodiesels is above the standard specifi-
  cation (CN > 51).
CN ¼ 52:974 þ 13:767  1:202$db þ 0:152$db2 $X

 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 Higher heating value of biodiesels was calculated from viscosity
concluded that equation proposed by Tong [40] gives the best re- and density data using three different models as proposed by the
sults due to the closest agreement between evaluated and previ- literature. Flash point data was taken from the literature [43].
ously reported data [38,41,42]. Tong equation takes into account CN Evaluated values were compared with the measured ones and the
of all FAME present in biodiesel, while equations (2) and (3) 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. commercial biodiesel (Biodiesel Vukovar, Croatia) was also pre-
Sivaramakrishnan and Ravikumar equation [44]: sented. In the region from 1800 to 1700 cm1, the peak that can be
attributed to the stretching of C]O, typical of esters, and thus
HHV ¼ 0:4527$y  0:008$r  0:0003$FP þ 40:3667 (8) common in FAME spectra, is clearly visible. Broad band between
Sivaramakrishnan and Ravikumar equations [45]: 3200 and 3600 cm1 that corresponds to alcohols (in this case
glycerol) cannot be observed. No significant difference can be
HHV ¼ 0:4652$y þ 39:450 (9) observed between animal fats biodiesels and commercial one.

HHV ¼ 0:0259$r þ 63:776 (10) 3.7. 1


HNMR analysis of animal fats biodiesels
Higher heating value, (HHV) is similar for all synthesised bio-
In order to compare 1H NMR spectra of feedstock and biodiesel,
diesels, and lower than the heating value of fossil diesel
an example for goose fat and goose fat biodiesel is presented on
(45.4 kJ g1) as stated in the literature [46]. The closes agreement
Fig. 4.
between the measured and calculated data was obtained using
In the region between 0 and 3 ppm the two NMR spectra are the
equation based on density of biodiesel. Absolute error, when using
same, both showing signals that correspond to olefinic protons. The
equation (10) for prediction of HHV, ranges between 0.793 and
biodiesel sample spectrum contains a peek at 3.67 ppm corre-
1.098. Equations were developed for vegetable oil biodiesels, and
sponding to eCOOCH3 group, while goose fat spectrum contains
this can be the reason for deviation from the measured values.
peeks at 4.10e4.35 ppm and 5.25 ppm corresponding to eCHOCOR
groups.
1
3.6. FTIR analysis of animal fats biodiesels 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
The FTIR spectra for purified biodiesels are presented in Fig. 3. In biodiesel by transesterification reaction [47]. Integration values of
order to compare FTIR spectra of animal fats biodiesels spectrum 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 Iodide number as a measure of unsaturation of biodiesels
calculation. The equation used to quantify the yield of trans- corresponds to the composition of biodiesels. Beef tallow based
esterification was: biodiesel, which is highly saturated, has the lowest value, while
chicken and goose fat based biodiesels (the lowest concentration
2$AMe of saturated FAME) has the highest iodide number. Iodide values
%FAME ¼ 100$ (11)
3$ACH2 of all purified biodiesels complied with the standard
The obtained results are presented in Table 6. specification.
Limitation of unsaturated fatty acids methyl esters is expressed
by the concentration of linolenic acid methyl ester. Concentration
3.8. Purified animal fats biodiesels specification of linolenic acid methyl ester is below the limiting value for all
animal fats biodiesels. This is important because on heating, poly-
Experimentally determined properties of animal fats bio- unsaturated fatty acids, methyl esters can form deposits as a result
diesels are presented in Table 6. Ester content of all biodiesels of polymerization of glycerides [49].
except for beef tallow was below the EN 14214 limit. Lower Methanol was successfully removed by evaporation prior to the
content of FAME in biodiesel indicates that biodiesels are purification step since it concentration is below the standard
contaminated with unreacted mono-, di- and triglycerides, but limitation.
also with other impurities like unreacted catalyst or some other All animal fats biodiesel fulfilled the standard specifications for
compounds. biodiesel fuel in terms of free glycerine content. However, con-
The higher sulfur content of animal fat biodiesel indicates that centration of total glycerine was higher than allowed due to the
some protein and phosphoglycerides (essential constituents of the unreacted mono-, di- and triglycerides.
animal cell membranes that concentrates in the lipids) still remain
in the feedstock [48]. However, these values are still below the 3.9. The influence of temperature on the extraction efficiency
upper limit of the standard specification.
Sulfated ash content as a measure of the amount of metals and The influence of temperature on the extraction efficiency is
some other inorganic compounds, like unremoved catalyst pre- shown in Fig. 6. Increase in temperature resulted in significant in-
sent in biodiesel, is below the specified limit for animal fats crease in extraction efficiency. Density and viscosity of both phases
biodiesels. (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 Animal fats biodiesels were successfully synthesised by means
transfer. In general, for biodiesels of similar ratio of saturated, of chemical transesterification using methanol and sodium hy-
monounsaturated and polyunsaturated FAME (in this case lard, droxide. Optimum mass ratio solvent/biodiesel was defined based
chicken and goose fat biodiesels) extraction efficiency at 25  C in- on the extraction efficiency obtained at different mass ratios. Deep
creases with decreasing initial glycerol content. Glycerol is highly eutectic solvent, choline-chloride/ethylene-glycol (molar ratio
viscous liquid. The rate of mass transfer to another viscous liquid, in 1:2.5) is very efficient for extraction of free glycerol, especially at
this case DES, is very slow due to high resistances to momentum elevated temperature. The ester content in all biodiesels, except
and mass transfer. Since the duration of all experiments was the beef tallow biodiesel, was a little lower than specified by the EN
same and equilibrium wasn't reached, it is obvious that extraction 14214 standard due to the residual glycerides in biodiesels. Con-
efficiency should be higher for lower concentration of glycerol. centration of glycerides in biodiesel can be reduced by modification
760 A. Sander et al. / Renewable Energy 118 (2018) 752e760

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