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ABSTRACT
Biodiesel is composed by mono-alkyl esters, derived from
renewable sources such as vegetable oils or animal fats,
obtained by the transesterification process in which performs
the conversion from triglycerides to smaller molecules of fatty
acid , that are, esters of fatty acids.
A critical point in the production and storage of biodiesel is
the susceptibility to degradation when its exposed at
atmospheric ambient. One disadvantage of this fuel is its high
capacity to absorb moisture from the ambient, causing a
degradation process and alterations in the specifications
required for use. Studies show that biodiesel has thirty times the
hygroscopicity of the common diesel because biodiesel has
different ranges of acidity, which are very susceptible to
oxidation.
The degradation process of biodiesel includes intrinsically
corrosive molecules, process of hydrolysis and oxidation that is
why the applicability of techniques to get improved control and
monitoring of biodiesels degradation stages is investigated.
The temperature and relative humidity during storage determine
the stability and preservation of the product in different periods.
Degradation characteristics are attributed to the presence of
carbon chains with multiple unsaturations and unstable
particularly structures, causing deficiencies in the engine
performance.
The biodiesel was produced using waste oil from cooking of
fried potatoes, with a transesterification methodology with
ethanol in a basic medium and under the following rules,
Peruvian Technical Norm for Biodiesel (NTP 321.125-2008),
Resolution ANP N 7, de 19.3.2008 DOU 20.3.2008, and
European Standards. We obtain a 70% yield for a 2:1 ratio with
a method for suppressing the presence of starch, acceptable
results on stability, and 5.71 h, 4.818 mm2/s, and 0.256 KOH/g
as values for oxidation periods (OEI).
Physicochemical
characteristics
quantitatively
and
qualitatively are analyzed periodically in extreme conditions for
pure biodiesel, B50 and B20 blends, to realize a comparative
with commercial diesel S500 as reference. We obtain the
following results out of specifications for pure biodiesel, 1850
mg/kg for water presence, 5.52 mm2/s and a significant
elevation of acidity to 0.71 mgKOH/g; for B50 resulted an
acidity value out of specification with 0.58mgKOH/g, 1.92h
from degradation stability analysis and 1100mg/kg for water
presence; and for B20 we have 730.70 mg/kg, that also is out of
specification for water presence.
We concluded that exposure to temperature conditions and
moisture presence affects directly the degradation and
variability in the physicochemical properties of B100 and its
blends with common diesel; by observing stability for B20 and
its behavior, we suggest suitable thermal and moisture control
systems for long storage periods.
INTRODUCTION
The terms of traditional energy in current decades are very
controversial due to many limitations and mainly by high
contents of contamination; Traditional energy sources have
become very controversial in current decades due to several
limitations and its high rates of contamination. which drives it
leads us to seek alternative energy sources. Therefore, biodiesel
obtained from waste oil introduces a possibility makes possible
to reuse and obtain potential energy sources with low costs and
especially friendly to the environment [1].?
In Europe, projects for the production of biodiesel of
biodiesel obtention from waste oils stand out, particularly those
used by various food companies. In South America, there are
countries that several countries lead the production of biodiesel
like Brazil and Argentina. The obtained biodiesel is mixed up
added with diesel to be used in public transport vehicles.
Research Institute of Engineering (COPPE), Federal University
proportions B20, B50 and B100 and B5, this last one not
requires any adaptation for motors.
Biodiesel has high hygroscopicity. Studies reveal that is
thirty times greater than the water absorbing capacity of the
common diesel. So in mixture with the natural tendency alters
diesel oxidation catalyst because sulphur. The presence of free
water brings degradative processes such as the presence of
corrosion of engine components and storage tanks. The
formation of deposited microorganisms can cause problems
with engine parts, wear injection systems and clogging of filters
and tubes [5].
Free water is also responsible for the establishment of a
third set of processes associated with the metabolic activity of
microorganisms (bacteria and fungus). It promotes biocorrosion
and sediment formation of biological origin or biodeposits [6].
Going deeper in biodiesel studies, we observe that despite it
was not an inherently corrosive molecules, his hygroscopicity
turns the mixture with biodiesel in a corrosive liquid for some
engine materials. This characteristic is analyzed by simulating
storage for different periods of aging. It lets find information
about the material behavior and its tendency to degrade over
time. This paper studies this biodiesel production obtained from
waste cooking oil and consequently it exposes an evaluation of
performance under extreme conditions during storage.
EXPERIMENTAL PART
Materials used in the production:
Process inputs: Ethanol, sodium hydroxide, waste oil from
cooking, and diesel.
Laboratory materials: Pear of Decantation for 500ml, beaker of
500ml, digital scale, Becquer of 500ml, thermo-magnetic
stirrer, heating stove, analog multimeter, thermometer and
temperature sensors.
Production equipment: Stainless steel tank AISI 306L of fifty
liters for the ethoxide obtainment, stainless steel reactor AISI
306L of one hundred liters for the esters obtainment and a
variable mechanical stirrer controlled by a speed reducer motor
for homogenization. For parameters measurement like
temperature and conductivity, we used thermocouples type K
(Chromel-Alumel), HP Agilent 34970 data acquisition
equipment and a computer to collect the data.
Biodiesel characterization equipment: Anton Paar density
analyzer, Ostwald viscometer, Karl Fischer coulometric titrator
ASTM D6304, analyzer of Oxidative Stability Index by
Rancimat method EN 14112, potentiometric titrator of acid
number ASTM 664.
Prior procedure of feedstock:
This part is divided into the pre-treatment for solids
separation and the main stage of biodiesel production.
Pre-treatment: Stage to prepare the waste frying oil and also to
separate solids by sieve filters. Consequently were filtered
present solids of 200, 150 and 50 microns of size. Then they
were treated with chemical solutions to precipitate the mineral
salts, proteins, phosphates and other components by the method
of hydration. So water is added (0.15 v/v) to avoid increasing
acidity. Was performed finally a drying to remove water present
in the solute at 110 C of temperature for 40 minutes preventing
the raw material degrade.
Biodiesel production:
EVALUATION RESULTS
Biodiesel making process:
The obtained results determine the quality conditions. The
physical chemistry characterization of waste frying oils is
substantial as much as mass balance for biodiesel production in
laboratory and pilot-scale plant and its respective
characterization. These initial conditions of raw material
determine the conversion efficiency to biodiesel and also are
highly relevant for related costs and benefits.
Table 2 Physicochemical properties of waste frying oil.
Waste frying
oil
Density at 20 C, kg/m3
980,1 1,0%
Kinematic viscosity at 40 C, mm2/s
40,8 1,0%
Humidity index (Karl Fischer), mg/kg
310 0,1%
Acid number, mg KOH/g
0,98 1,5%
Table 2 shows the initial parameters of residual oil within
the limits set by the NTP (Peruvian Technical Norm). Hence it
is shown that a lower specific mass does greater viscosity and a
substantial reduction in acidity. It can determine that with a
higher density and viscosity, the conversion of triglycerides will
be lower, on the other hand, the greater presence of water also
means a greater possibility of saponifying.
Table 3 Mass balance of biodiesel production in laboratory and
pilot-scale from waste frying oil.
Residual frying oil
Residual frying oil
Component
(Laboratory)
(Pilot plant)
Input (g)
Output (g)
Input (g)
Output (g)
Oil
Ethanol
KOH
Glycerol
Ester
196,0
79
3
24502,5
9875
375
87,6
138,8
11972,0
16319,1
Ethanol
Excess
Lost by
manipulation
Performance
68,5%
64,4%
Total
278,1
34752,5
48,7
6086,4
3,0
375,0
Humidity
index (ppm)
IP (h)
B100
B5
30
60
90
120
150
IP (h)
>30
16,74
15,13
11,13
11,00
9.41
Humidity
index (ppm)
72.3
87.2
90.21
92.11
98.52
100.12
13,81
6.01
5.11
3.78
3.65
3.04
14.82
5.97
5.19
3.21
3.7
3.11
13.86
6.1
5.2
4.03
3.8
3.13
150
380.2
525.7
674
731
810.5
9.14
6.72
2.95
1.99
1.92
1.29
IP (h)
B20
B50
Time (days)
Humidity
index (ppm)
IP (h)
Humidity
index (ppm)
6.45
2.91
1.91
1.18
10.59
6.62
2.88
1.93
0.53
300,0
467.9
949.3
987
1100
1350
5.61
0.54
0.17
0.01
0.51
6.02
3.05
0.64
0.17
0.07
0.3
5.51
3.09
0.64
0.13
0.35
740,0
755.32
1050
1430
1850
2543
30
25
Period of oxidation, h
8.74
20
Monitoring of storagem
Period Storagem
0- dias
30 - dias
60 - dias
90 - dias
120 - dias
150 - dias
15
10
Accepted
5
0
B5
B20
B50
B100
2.25
2750
2500
2250
2000
1750
Monitoring of storagem
1500
1250
Tempo Storagem
0- dias
30 - dias
60 - dias
90 - dias
120 - dias
150 - dias
2.00
1.75
Acidity, mg KOH/g
Period Storagem
0- dias
30 - dias
60 - dias
90 - dias
120 - dias
150 - dias
3000
1.50
1.25
1.00
monitoring of storagem
0.75
accepted
0.50
1000
750
0.25
500
Accepted
250
B5
B20
B50
0.00
B5
B20
B50
B100
B100
150
0.37
0.67
0.84
1.91
150
3.76
5.21
4.92
5.57
Period Storagem
0- dias
30 - dias
60 - dias
90 - dias
120 - dias
150 - dias
10
Viscosity, m2/s
THANKS
0
B5
B20
B50
B100
CONCLUSION
Obtaining biodiesel from waste cooking oil is generally
satisfactory. Acceptable yields were achieved with the terms of
the raw material up to 64.5%. However, it needs to improve the
biodiesel production by removing the presence of water, and
reducing oxidative stability indexes by summing stability
additives.
The implementation of new methods of production would
bring great social and economic impacts. In this way we could
reuse contaminant residues and we also could optimize the
characteristics regarding their use and storage. The
physicochemical properties shown in this monitoring of
biodiesel and its mixtures B5, B20 and B50 show significant
variations throughout the storage time. Is showed the behaviors
based on the experiences and obtained results in relation to
specifications of international organizations such as ANP. The
gradual performance for the degradative stability in each
biofuel mixture is also shown.
In some cases, it was noted that oxidized fatty acid chains
may be broken to form shorter chain acids and aldehydes,
which could form gum and sediments to viscosity increase. The
existence of peroxides and hydroperoxides present in the
oxidation reaction with other radicals is caused by high molar
mass molecules as gums, acids and aldehydes.
REFERENCES
[1] Wilhelm, H.M. Penteado, R.A.N. Silva, E.L. Kruger,