Miškov, S. P., et al.: High Pressure Densities and Derived Properties of Biodiesel...

THERMAL SCIENCE: Year 2019, Vol. 23, Suppl. 5, pp. S1757-S1768 S1757

HIGH PRESSURE DENSITIES AND DERIVED PROPERTIES

OF BIODIESEL FUEL PRODUCED BY HETEROGENEOUS
TRANSESTERIFICATION FROM BIOWASTE
by
a b b
Sofija P. MIŠKOV , Gorica R. IVANIŠ , Ivona R. RADOVIĆ ,
b
and Mirjana Lj. KIJEVČANIN
a
Ministry of Education, Science and Technological Development of Republic of Serbia,
Belgrade, Serbia
b
Faculty of Technology and Metallurgy, University of Belgrade, Belgrade, Serbia

Original scientific paper

https://doi.org/10.2298/TSCI180723178M

High pressure density of biodiesel is a crucial parameter necessary for the Diesel engine
design and performance improvement as well as proper combustion optimization.
Biodiesel production utilizing biowaste as raw material reduces the capital costs and
environmental problems related to biowaste disposal. In this investigation, biodiesel was
synthesized in a heterogeneous transesterification reaction utilizing used cooking oil and
methanol as reactants and eggshell raw material as a calcium-oxide catalyst source.
Calcination was carried out at temperature 1073.15 K for 4 hours and transesterification
was conducted at 338.15 K. Densities of produced biodiesel were measured at pressures
up to 60 MPa and over the temperature range 288.15-413.15 K and fitted employing the
modified Tammann-Tait equation. Viscosities of biodiesel are also measured at
atmospheric pressure over the temperature range 288.15-338.15 K. From measured
density data, important mechanical properties, such as the isothermal compressibility
and the isobaric thermal expansivity, were calculated. High transesterification reaction
yield was obtained (almost 99 wt.%) while densities and viscosities of analyzed biodiesel
sample were in accordance with recommended standard values.
Key words: high pressure density, waste oil biodiesel, heterogeneous transesterification,
isothermal compressibility, isobaric thermal expansivity, viscosity

Introduction
Fuels produced from renewable resources and/or biowaste are seen as a potential
solution for oil crisis and environmental problems. Legal demands imposing the share of energy
from renewable sources at least 10% in the transport sector by 2020, overlapped with environ-
mental issues concerning biowaste disposal, have clearly defined sustainable biodiesel produc-
tion as scientific and industrial priority. On the other hand, the concerns related to the biodiesel
production from food crops imposed need for non-food biodiesel sources (second generation
biodiesel), e.g. used cooking oils or waste animal fats. In EU the total waste cooking oil (WCO)
capacity is estimated to significant amount of 700 000-1 000 000 t per year [1].
The biodiesel production plants mostly utilize traditional technology of fatty acids
alkyl esters (FAAE) production. The FAAE, main constituents of biodiesel, are usually produced
in transesterification reaction, which can be conducted using homogenous or heterogeneous
catalyst, lipases or alternative reaction treatment such as application of ultrasound or
*
Corresponding author, e-mail: [email protected]
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supercritical conditions, etc. Typical transesterification reaction can be carried out at moderate
temperature and atmospheric pressure with no significant capital costs and very high yield of
product [2-4].
The application of homogeneous catalyst gives high yield of biodiesel although with
many disadvantages. The main drawbacks are related to environmental issues and no possibility
of the catalyst reuse. The biodiesel production with homogenous catalyst is usually followed with
biodiesel washing, which generates large amounts of wastewater that must be treated before
disposal. On the other hand, heterogeneous catalyst is easily separable, recyclable and does not
create wastewater [2, 3, 5-12]. Solid base oxides, such as CaO, MgO, ZnO, BeO, lanthanum and
zeolite have been used as heterogeneous catalysts. They are applied separately or in a combined
mixture that is pre-treated before its application in transesterification reaction.
Among aforementioned, mostly used is CaO since it has shown a good catalytic
performance in transesterification reaction [5-12]. It is low soluble in methanol so it is easily
separable after reaction, cheap and environmentally friendly. Moreover, it can be produced from
industrial food waste as a raw material, which disposal makes problems all over the world. The
main biowaste sources of calcium-oxide are eggshells, bones or mollusk shells where it exists as
calcium-carbonate.
Transesterification reaction mechanism and advantages or weaknesses of chosen
reaction conditions have already been explained in [2, 5, 7, 9, 11, 13-17]. Ma and Hanna [2]
described transesterification conditions and that paper was used as initial source of reaction
conditions. According to Ma and Hanna [2] alkali-catalyzed transesterification is promoted by
low free fatty acids (FFA) content in triglycerides and anhydrous glycerides and alcohol. In the
case when water and FFA are present in triglycerides acid-catalyzed transesterification can be
used. Further, Ma and Hanna [2] examined effect of temperature on yield of transesterification
reaction and concluded that optimal temperature depends on the oil used but it is mostly in the
range 303.15-333.15 K. Kawashima et al. [5] studied influence of CaO pretreatment with
methanol on transesterification reaction. They found that maximum yield of FAME was obtained
when CaO was activated at 298.15 K for 1.5 hours and the transesterification reaction was
conducted at 333.15 K for 3 hours [5]. Taufiq-Yap et al. [7] investigated methanolysis of Jatropha
curcas oil and in their case optimal temperature for thansesterification was 338.15 K and the
conversion of fatty acids to biodiesel were increasing gradually during the first 2 hours of reaction
time and after that period remained nearly constant. Granados et al. [11] described production of
biodiesel from sunflower oil by using activated calcium oxide and their transesterification
reaction was performed for 2 hours at 333.15 K. They also considered the reutilization of the CaO
for several runs and noticed that the yield of FAME was more than 90% when fresh catalyzator
was used and then decrease to 80% in the second run but stays at that level even after eight cycles
of reutilization [11]. It is obvious that changing of specific reaction conditions may lead to smaller
percentage of FAME in biodiesel sample, with same or similar quality.
There are defined standards [18, 19] to be fulfilled by produced mixture of alkyl esters
of fatty acids in order to be considered biodiesel [20].
One of the most important properties for high performance of Diesel engine and proper
combustion is fuel's density, especially at high pressure and temperature conditions. From the
accurate density data very important derived mechanical coefficients can be calculated, e.g.
isothermal compressibility, isobaric thermal expansion coefficient, molar isobaric heat capacity,
etc. Biodiesel can be used in conventional or modified diesel engines, usually blended with diesel
fuel.
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In this work biodiesel was synthesized from WCO as a feedstock while the catalyst was
prepared from eggshell waste as a raw material. Raw eggshell was characterized using thermo-
gravimetric analysis/differential scanning calorimetry (TGA/DSC). Transesterification was
conducted at 338.15 K, with 15:1 methanol/oil molar ratio and 5 wt.% of catalyst loading. In our
recent papers [21, 22] as well as in the works of other groups, high pressure density data for
biodiesels produced from various vegetable oils, e.g. rapeseed, sunflower, soybean, palm, corn,
cotton, pumpkin have been reported [3, 6, 9-11, 23]. However, no data related to WCO high
pressure densities and derived properties are available. Here, densities and viscosities of
biodiesel produced from WCO are reported at temperatures 288.15-338.15 K and at atmospheric
pressure. Additionally, densities were measured at high pressure (up to 60 MPa) and over the
temperature range from 288.15-413.15 K. From measured data the following mechanical
properties were calculated: isothermal compressibility, isobaric thermal expansion coefficient,
internal pressure and difference between specific heat capacity at constant pressure and at
constant volume. All mentioned properties are very important for technical application of
biodiesel, especially in modelling of heat and mass transfer in moving fluids [24].

Experimental section
Materials
Biodiesel investigated in this work was synthesized by transesterification reaction from
WCO collected from restaurants in Serbia. Chemical composition of WCO was determined using
gas chromatography with flame ionic detector (GC-FID 6890, Agilent) Column: CP-Sil 88 (100
m × 0.25 mm, film thickness 0.2 µm).
Methanol used in transesterification reaction was produced by Ficher Chemical with high
purity (99.99 % mas). Eggshells that served as CaO catalyst source in biodiesel production were
provided by Melange Company from Serbia.
Table 1. Chemical composition Table 1 shows weight percentage of fatty acids that are
of WCO and produced biodiesel mainly present in WCO and water and FFA content, as well as
WCO componentsa wt.% the produced biodiesel composition.
Palmitic 8.38
Stearic 3.42 Catalyst preparation and characterization
Oleic 33.40 Chicken eggshells were collected from the local factory.
Linoleic 50.52 After careful washing, it was dried in laboratory drier for 24
0.82
hours at 343.15 K, since those conditions were confirmed as
FFA content
optimal for preparation of sample for further use. Dry eggshells
Water content 0.06
were kept in closed jars ready for grinding in a mill. Thermal
Biodiesel composition wt.% behavior of raw eggshells was determined using a SDT Q600
FAMEb 98.88 instrument, (TA Instruments). The DSC and TGA were perf-
MGc 0.33 ormed under a nitrogen flow of 100 cm3 per minute with linear
DGd 0.25 temperature programming at 10 K per minute in the temperature
TGe 0.54 range of 298.15-1273.15 K. Calcination of eggshells was
Iodine value [18] 116.2 carried out at temperature 1073.15 K [12].
Cetane number [25] 51
Reaction yield 99 wt.% Transesterification procedure
a
fatty acids present in traces are not shown
A series of tests were performed, where reaction time,
b
determined by applying European standard calcinations temperature, molar ratio oil/methanol, catalyst
EN ISO 4259:2006 [25]
c
d
MG - monoglyceride amount, reaction temperature and reaction feedstock (vegeta-
DG - diglyceride
e
TG - triglyceride ble, animal, fresh, and recycled oil) were investigated as
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reaction variables, in order to find the optimal conditions for biodiesel production from WCO.
Based on the gathered results and thorough review of literature the following procedure and
reaction conditions, which gave the highest reaction yield, were chosen.
The transesterification reaction was conducted using the heterogeneous CaO based
catalyst produced from chicken eggshells. The molar ratio of methanol to oil was 15:1, while the
catalyst was added with a weight content of 5% (catalyst/oil weight ratio). Transesterification
reaction was conducted in a batch reactor at 338.15 K. Catalyst and methanol were mixed in
reactor until stationary conditions were achieved under methanol reflux and preheated oil was
added into the reactor. Comparing reaction time and yield, it was concluded that there was no
increase in yield after 2 hours of reaction, so this time was chosen as optimal reaction time. After
cooling, biodiesel and methanol were separated from glycerol and catalyst using centrifuge and
stratified in separating funnel. Methanol was evaporated in a rotary evaporator. Biodiesel was
filtered through double filter paper.
Biodiesel characterization
The content of WCO was analysed using gas chromatography (6890, Agilent) with
flame ionization detector Agilent, column CP-Sil 88 (length = 100 m, inner diameter = 0.25 mm,
film thickness = 0.2 µm), in licensed laboratory, SP laboratory Novi Bečej. For evaluation of fatty
acid methyl-ester content, normalization method was used (all the components of the sample are
presented at chromatogram, so that total area below the peaks represents 100% of all the com-
pounds).
The content of fatty acid methyl esters (FAME) in biodiesel was analyzed using gas
chromatography with flame ionization detector model Varian 3400 by applying european
standard EN ISO 4259:2006 [25], while iodine value and cetane number of obtained biodiesel
were calculated according to eqautions presented in European standard [18, 26], respectively,
tab. 1.
Based on data reported in papers [2, 16, 27] it can be assumed that cooking oil used here
is a mixture of sunflower and palm oil. Amount of FFA and water is in accordance with previously
suggested limits [9]. The yield was calculated in relation to product mass/WCO feedstock mass.
Density measurements at atmospheric pressure were performed using an Anton Paar
DMA 5000 digital vibrating U-tube densimeter which have a stated accuracy of ± 5·10-3 kg/m3.
Temperature was regulated with a built in solid-state thermostat to ± 0.001 K. Calibration of the
apparatus was performed using ambient air and Millipore quality water. The combined expanded
uncertainty in density was within 2·10-2 kg/m3. Biodiesel viscosities were measured with a digital
Stabinger viscometer (model SVM 3000/G2). The temperature in the cell was regulated to ± 0.01
K with a built in solid-state thermostat. The reproducibility of the dynamic viscosity is 0.35%,
while the relative standard uncertainty in dynamic viscosity measurements was estimated to be
within ± 1% [28, 29].
Density measurements at high pressures were experimentally studied employing an
Anton Paar DMA HP density measuring cell connected to an Anton Paar HP DMA 5000 vibrating
tube densimeter. Details of experimental procedure are already described in our previous work
[30]. The apparatus was used in temperature range 288.15-413.15 K and pressures up to 60 MPa.
Each selected temperature was controlled with an integrated Peltier thermostat having stability
within ± 0.05 K. Pressure in the system was measured using a pressure transducer WIKA S-10.
The transducer was calibrated up to 60 MPa and the maximum value of the sums of deviation and
expanded measurement uncertainty was ± 0.1815% in relation to the full range [30]. The proce-
dure of Comunas et al. [31] has been employed to calibrate the Anton Paar DMA HP densimeter.
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The influence of sample' s viscosity on density was estimated by using the information retrieved
from a personal correspondence with the supplier Anton Paar and it was less than 0.07 kg/m3. The
expanded uncertainty in the reported densities with confidence level of 95% (k = 2), estimated
considering the uncertainties of pressure, temperature, oscillation period measurements and the
damping effects on the vibrating tube, is 0.8 kg/m3 in the temperature range 288.15-363.15 K and
2.0 kg/m3 at temperatures 373.15-413.15 K.

Density correlation and

calculation of derived properties
Experimental values of densities were fitted to the modified Tammann-Tait equation.
This correlation involves fitting parameters ai, bi, and ci and relates density, ρ, with temperature, T,
and pressure, p, according to the eqs. (1)-(4):
ρ ref (T )
ρ (T,p) =
B (T ) + p ù (1)
1 - C (T )ln é
êë B(T) + p ref úû
2
ρref ( T ) = å aiT i (2)
i= 0
2
B (T ) = å biT i (3)
i =0
2
C (T ) = å ciT i (4)
i= 0

where ρref is density at reference pressure, pref. In our case the parameter C is treated as temperature
independent.
From density data valuable derived properties can be calculated.
Isothermal compressibility, κT, describes the effect of a pressure on density at constant
temperature as follows [32, 33]
1 æ ¶ρ ö
κ = ç (5)
ρ è ¶p ÷øT
T

Isobaric thermal expansion coefficient, αp, expresses the temperature influence on a

fluid density at constant pressure and can be calculated by using the following equation [31, 32]:
-1
1 æ ¶p ö æ ¶p ö 1 æ ¶ρ ö
αp = ç =- ç (6)
ρ è ¶T ÷ø ρ çè ¶ρ ÷ø T ρ è ¶T ÷ø p

Also, using experimental density at high temperatures and pressures, the difference
between specific heat capacity at constant pressure, cp, and specific heat capacity at constant
volume , cv, could be calculated [32, 33]:
2
æ ¶p ö
ç ÷ αT 2
¶T ø ρ
c = c +T è
p
p v = (7)
2 æ ¶p ö ρκ T
ρ ç ÷
è ¶ρ øT
Additionally, the thermal pressure coefficient, γ, presenting the ratio between isobaric
thermal expansibility and isothermal compressibility is determined [32, 33]:
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αp
γ = (8)
κT
From the isobaric thermal expansion coefficient and the isothermal compressibility
coefficient the internal pressure, pint, can be determined as follows [32, 33]:
æ ¶U ö æ ¶p ö Tα p
p int = ç ÷T = T ç ÷ ρ - p = Tγ - p = κ - p (9)
è ¶V ø è ¶T ø T

Internal pressure describes the intermolecular interactions and represents the change of
internal energy during isothermal expansion or contraction.

Results and discussion

TGA/DSC
Figure 1 shows weight loss -1 and endothermic peak -2 for eggshell that occurs at
temperatures around 1073.15 K, which corresponds to the results reported previously [10, 15]. This
loss is attributed to decomposition of CaCO3 and out gassing of CO2. Organic compounds and water
are lost at temperatures below 673.15 K.
Catalyst calcined at 1073.15 K gave very high yield of FAME, almost 99 wt.%. Viriya-
Empikul et al. [10] also reported that optimum calcination temperature is 1073.15 K, while
higher calcination temperatures cause severe sintering of catalyst particles, resulting in sup-
pressed smaller active sites and consequently smaller biodiesel yields. Wang et al. [34] suggest
that the basest sites are in the interior
of catalyst, since surface of the
c a t a l y s t s h o w s l o w p o r o s i t y.
Khemthong et al. [8] reported that
derived eggshell is dense material due
to its very low surface area and pore
volume with very high basic site
density which makes it active for
transesterification reaction. Besides,
it is important to point out that
activation of catalysts just before the
reaction plays important role in
biodiesel yield, since remove of
gaseous water molecules creates high
porosity [15]. Figure 1. TGA (1) and DSC (2) curves of raw eggshell

Densities and viscosities of biodiesel

at atmospheric pressure
Table 2 shows densities and viscosities of biodiesel sample over the temperature range
288.15 to 338.15 K and at atmospheric pressure. It is obvious that both, density and viscosity,
decrease with temperature increase. Biodiesel sample meets the density demand from standards
EN 14214 [18] and ASTM D6751 [19], which recommends the density range of 860-900 kg/m3 at
288.15 K. According to EN 14214 [18] standard biodiesel kinematic viscosity at 313.15 K should
be in range 3.5-5.0 mm2/s, while by ASTM D6751 [19] acceptable range is 1.9-6.0 mm2/s.
Produced biodiesel has the kinematic viscosity near upper limit of EN 14214 [18] standard,
4.9567 mm2/s, but fulfil the ASTM D6751 standard [19]. According to this and to the values
presented in tab. 1, the produced mixture of WCO methyl esters meets the most of relevant
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conditions, i.e. referent values for the properties studied in

this work, to be called biodiesel.
The knowledge of biodiesel viscosity at atmospheric
pressure allows prediction of viscosity values at high
pressures using the method proposed by Freitas et al. [35]:
p -p 0
lnη = lnη + a
0 (10)
Tb
where η0 [mPa·s] stand for the dynamic viscosity at refer-
ence pressure p0 (0.1 Mpa), T [K] and p [MPa] denote
absolute temperature and absolute pressure, respectively.
Fitting parameters a and b have the values 1.2 K0.84Pa-1 and
0.84, respectively [35].

Densities and derived

properties at pressures up to 60 Mpa
Densities of the biodiesel were measured at pressures
0.1-60 Mpa and at temperatures 288.15-413.15 K and are
given in tab. 3.
Experimental density data were fitted to the modified
Tammann-Tait equation. For the optimization of ai, bi, and ci
parameters reference pressure was set to 1 MPa, while
Marquardt's algorithm was applied in order to minimize the
objective function, i.e. standard deviation σ:
N

å (ρ
i =1
exp
i - ρ cali )2
(11)
σ=
N -m

where ρexp and ρcal stand for experimentally determined density and density calculated by eq. (1),
respectively, N is the number of experimental data and m represents the number of parameters
included in the modified Tammann-Tait equation. The adjusted fitting parameters are given in
tab. 4 along with the corresponding standard deviation.
Figures 2(a) and 2(b) depict dependencies of the isothermal compressibility, κT, and the
isobaric thermal expansion coefficient, αp, on pressure along isotherms for examined biodiesel,
respectively. As it was expected, both κT and αp decrease with the increase in pressure at isother-
mal conditions whereas at lower temperatures the pressure influence is less pronounced.
Curves of isothermal compressibility at higher temperatures have more parabolic shapes
compared to almost linear form at lower temperatures. The κT values lay between 0.47 and 1.36
GPa-1. The former values correspond to pressure 60 MPa and temperatures 293.15 K, while the
latter correspond to 0.1 MPa and 413.15 K.
Values of the isobaric thermal expansion coefficient are ranging (0.66-0.92)·10-3 K-1 at
investigated temperature and pressure ranges. Lower αp values are favored since larger isobaric
expansion coefficient means a larger engine power loss because of fuel heating [36]. Addition-
ally, αp isotherms show an intersection point around 45 MPa, at this point αp is temperature
independent. At pressures lower than at the intersection point, αp increases with temperatures rise,
while the temperature influence is opposite at higher pressures. For the biodiesel analyzed in the
work of Schedemann et al. [37] the same behavior occurs having the intersection point at pressure
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around 65 MPa, while in the work of Dzida and Prusakiewicz [38] the intersection point is in
accordance with ours, approximately at 40 ± 5 Mpa.
Table 3. Experimental values of density for produced biodiesel sample at
pressures up to 60 MPa within the temperature range from 293.15-413.15 K
ρ [kg·m-3]
T [K]
p [MPa] 293.15 298.15 303.15 308.15 313.15 318.15 323.15
0.1 880.2 876.6 872.9 869.2 865.6 862.0 858.3
1 880.7 877.1 873.5 869.8 866.2 862.6 858.9
5 883.0 879.5 875.9 872.3 868.8 865.2 861.6
10 885.9 882.4 878.9 875.3 871.9 868.3 864.8
15 888.6 885.2 881.7 878.2 874.9 871.4 868.0
20 891.3 887.9 884.5 881.1 877.8 874.4 871.1
25 893.9 890.6 887.3 883.9 880.6 877.3 874.0
30 896.5 893.2 889.9 886.6 883.4 880.1 876.9
35 899.0 895.7 892.5 889.2 886.1 882.8 879.7
40 901.4 898.2 895.0 891.8 888.7 885.4 882.4
45 903.7 900.6 897.4 894.3 891.2 888.0 885.0
50 906.0 902.9 899.8 896.7 893.6 890.5 887.5
55 908.2 905.1 902.0 899.0 895.9 892.8 889.9
60 910.3 907.3 904.2 901.2 898.2 895.1 892.2
p [MPa] 333.15 343.15 353.15 363.15 373.15 393.15 413.15
0.1 851.1 843.8 836.5 829.2 821.6
1 851.7 844.5 837.2 830.0 822.7 808.1 793.4
5 854.5 847.4 840.3 833.2 826.1 811.8 797.5
10 857.9 850.9 844.0 837.1 830.1 816.3 802.4
15 861.2 854.4 847.6 840.8 834.1 820.6 807.1
20 864.4 857.7 851.1 844.4 837.9 824.7 811.6
25 867.4 860.9 854.4 847.9 841.5 828.7 815.9
30 870.4 864.0 857.7 851.3 845.0 832.5 820.1
35 873.3 867.0 860.8 854.6 848.4 836.2 824.0
40 876.1 869.9 863.8 857.7 851.7 839.7 827.8
45 878.8 872.7 866.7 860.7 854.8 843.0 831.3
50 881.4 875.4 869.5 863.6 857.7 846.1 834.7
55 883.9 878.0 872.1 866.3 860.6 849.2 837.9
60 886.3 880.5 874.7 868.9 863.2 852.0 840.9

Temperature and pressure influence on the internal pressure, was also examined. It is
evident from eq. (9) that internal pressure represents the change of internal energy during
isothermal expansion or contraction. As temperature increases internal pressure decreases.
However, the influence of pressure is rather different. Up to 343.15 K internal pressure decreases
with pressure rise, while at higher temperatures 393.15 and 413.15 K as pressure increases values
of internal pressure also increase fig. 3. Prieto et al. [38] performed thorough analysis of
temperature and pressure influence on internal pressure for 19 fuels of different compositions. It
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was presented that for temperatures between 283.15 K and

373.15 K and pressures up to 40 MPa values of internal
pressure were in the range 281 MPa and 386 MPa with the
average minimum and maximum values at 304 and 367 MPa
for 19 analyzed fuels. In fig. 3 the influence of temperature on
the internal pressure for the produced biodiesel at 0.1 MPa is
presented, since at this pressure changes are most pro-
nounced. The internal pressure at atmospheric pressure
deviates from about 360-311 MPa in temperature range
293.15-373.15 K, which is in good agreement with the results
presented in the work of Prieto et al. [39]. Analyzing the
values of internal pressures and cohesion pressure Prieto et al.
[39] concluded that biodiesel behaves as non-associated
liquid with no strong molecular interactions.

Figure 2. (a) Isothermal compressibility and (b) isobaric thermal expansion coefficient of
produced biodiesel sample vs. pressure at; (■) 293.15 K, (▲) 313.15 K, (♦) 333.15 K, (⋆) 353.15 K,
(●) 373.15 K, (꘎) 393.15 K and (▼) 413.15 K, Lines are guides for eyes

Figure 3. Internal pressure of produced biodiesel sample vs.

pressure at; (■) 293.15 K, (▲) 313.15 K, (♦) 333.15 K,
(⋆) 353.15 K, (●) 373.15 K, (꘎) 393.15 K and (▼) 413.15 K,
Lines are guides for eyes
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Conclusions
Biodiesel was synthesized in heterogeneous transesterification reaction from waste
cooking oil and methanol. CaO based catalyst was produced by calcination of the eggshells at
1073.15 K and analyzed using TGA/DSC. Viscosities and densities of the produced biodiesel
sample were determined at atmospheric pressure over the temperature range 288.15-338.15 K.
Additionally, densities of biodiesel were measured at pressures up to 60 MPa over the tempera-
ture range 288.15-413.15 K and fitted using the modified Tammann-Tait equation. From
measured density data the isothermal compressibility, the isobaric thermal expansion coefficient,
the internal pressure and the difference between specific heat capacity at constant pressure and at
constant volume are calculated. Calculated isobaric thermal expansion coefficient ranges (0.66-
0.92)·10-3 K-1 showing an intersection point around 45 MPa. Internal pressure deviates from about
360-282 MPa at temperatures 293.15-413.15 K and at atmospheric pressure.
High reaction yield (almost 99 wt.%), as well as high percentage of FAME in the
biodiesel product and its thermodynamic and mechanical properties confirm that biodiesel can be
efficiently produced from biowaste in heterogeneous transesterification reaction.

Supplementary material*
Supplementary data associated with this article can be found, in the online version.
– Figure S1 - densities and viscosities of biodiesel sample over the temperature range
288.15 to 338.15 K and at atmospheric pressure
– Figure S2 - experimental densities of analyzed biodiesel sample at pressures from
atmospheric up to 60 MPa over the temperature range 288.15 to 413.15 K
– Figure S3 - the influence of temperature on the internal pressure for the produced
biodiesel at 0.1 MPa
– Table S1 - High pressure viscosities calculated using eq. (10) for produced biodiesel
– Table S2 - derived thermodynamic properties: the isothermal compressibility (κT), the
isobaric thermal expansion coefficient (αp), the difference between specific heat
capacities (cp-cv) and the internal pressure (pint).
Acknowledgment
The authors gratefully acknowledge the financial support received from the Research
Fund of Ministry of Education, Science and Technological Development (project No 172063 and
IP-1-38), Serbia and the Faculty of Technology and Metallurgy, University of Belgrade. Addi-
tionally, the authors are grateful for help received from ArumDec and Melange companies from
Serbia in providing raw material, waste cooking oil and eggshells necessary for the experimental
work.
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For a Supplementory material file look at Online version of this paper
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Paper submitted: July 23, 2018 © 2019 Society of Thermal Engineers of Serbia.
Paper revised: March 15, 2019 Published by the Vinča Institute of Nuclear Sciences, Belgrade, Serbia.
Paper accepted: April 21, 2019 This is an open access article distributed under the CC BY-NC-ND 4.0 terms and conditions.
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