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Waste Management
journal homepage: www.elsevier.com/locate/wasman
Biodiesel production using fatty acids from food industry waste using
corona discharge plasma technology
A.L.V. Cubas a,, M.M. Machado b,c, C.R.S.C. Pinto c, E.H.S. Moecke b,e, A.R.A. Dutra d
a
UNA PCA, Articulation Academic Unit of Production, Construction and Agribusiness, Environmental Engineering, University of Southern Santa Catarina UNISUL, Avenue
Pedra Branca, 25, CEP: 88279900, Palhoa, SC, Brazil
b
Environmental Engineering, University of Southern Santa Catarina (Unisul), CEP 80137270, Palhoa, SC, Brazil
c
Post Graduation in Environmental Engineering, Federal University of Santa Catarina (UFSC), CEP 88040900, Florianpolis, SC, Brazil
d
Production Engineering, University of Southern Santa Catarina (Unisul), CEP 80137270, Palhoa, SC, Brazil
e
Departament of Science and Technology of Food, Federal University of Santa Catarina (UFSC), CEP 88034001, Florianpolis, SC, Brazil
a r t i c l e
i n f o
Article history:
Received 9 March 2015
Revised 26 May 2015
Accepted 26 May 2015
Available online 7 July 2015
Keywords:
Fatty acids
Waste frying oil
Methyl esters
Corona discharge plasma
Biodiesel
a b s t r a c t
This article aims to describe an alternative and innovative methodology to transform waste, frying oil in a
potential energy source, the biodiesel. The biodiesel was produced from fatty acids, using a waste product
of the food industry as the raw material. The methodology to be described is the corona discharge
plasma technology, which offers advantages such as acceleration of the esterication reaction, easy
separation of the biodiesel and the elimination of waste generation. The best conditions were found to
be an oil/methanol molar ratio of 6:1, ambient temperature (25 C) and reaction time of 110 min and
30 mL of sample. The acid value indicates the content of free fatty acids in the biodiesel and the value
obtained in this study was 0.43 mg KOH/g. Peaks corresponding to octadecadienoic acid methyl ester,
octadecanoic acid methyl ester and octadecenoic acid methyl ester, from the biodiesel composition, were
identied using GCMS. A major advantage of this process is that the methyl ester can be obtained in the
absence of chemical catalysts and without the formation of the co-product (glycerin).
2015 Elsevier Ltd. All rights reserved.
1. Introduction
Waste oils and fats should not be discarded in the public
sewage system, because they can cause signicant environmental
impact (Giraol et al., 2011). Oils in rainwater and sanitary sewage
systems emulsify with organic matter, causing blockages in grease
traps and pipes. Due to their immiscibility with water and lower
density, there is a tendency toward the formation of oily lms on
the water surface, inhibiting the exchange of gases with the
atmosphere. This leads to the depletion of oxygen and anaerobic
conditions in water bodies, resulting in the death of sh and other
aerobic organisms (Reis et al., 2007).
In the public sewage system, blockages can cause pressure to
build up, leading to the inltration of sewage into the soil, groundwater pollution and/or surface reux% (Reis et al., 2007).
Furthermore, in areas where sewage treatment is installed, when
waste oil enters the system it interferes with the treatment
processes and increases the cost by up to 45% (Reis et al., 2007).
Corresponding author.
E-mail address: anelisecubas@gmail.com (A.L.V. Cubas).
http://dx.doi.org/10.1016/j.wasman.2015.05.040
0956-053X/ 2015 Elsevier Ltd. All rights reserved.
150
2. Methodology
2.1. Raw material acquisition and preparation
The raw material, waste frying oil originating from the food
frying process, was purchased from local restaurants. The oils
and fats initially underwent a pretreatment step with heating to
50 C and ltering for the removal of impurities.
Before starting the experiments to obtain biodiesel, the raw
material was characterized by determining the acidity number
by titration (AOAC n. 940.28, 2005) and the water content by using
the Karl-Fischer method (ISO 12937, 2000). Saponication and
peroxide values were determined by the AOAC ofcial method
920.160 and 965.33, respectively. The AOAC ofcial method
993.20 (Wijs method) was used to determine the Iodine values.
2.2. Corona discharge reactor
The body of the reactor was comprised of a cylindrical quartz
tube (300 110 mm), wrapped with a spiral of stainless steel
250 mm in length, which served as an electrode. A stainless steel
screw (400 5 mm) in the center of the quartz tube was used to
seal the exits and keep the second electrode (screw) in the center
of the tube (Fig. 1).
The used frying oil with methanol and water was introduced
into the reactor through an access positioned at the right side of
the reactor cap, throughout the process was injected 1 L/min of
argon into the reactor. The nal product, methyl ester (biodiesel),
is pulled across the reactor and a source of alternating current
voltage of 17 kV is used to generate the plasma.
A photo of the system transporting the waste frying oil can be
seen in Fig. 2 (note the violet uorescence emitted by the plasma).
2.3. Pilot optimization
To establish the appropriate conditions for the pilot and obtain
better oil to biodiesel conversion rates using the corona discharge
plasma technology, tests were carried out varying the residence
time of the sample in the reactor (15120 min), and the sample
151
quantity in the reactor (20 and 30 ml), keeping the molar fraction
of methanol:oil equal to 1:6.
2.4. Biodiesel production process
In the production of biodiesel using plasma technology, the
transesterication reaction occurred inside the corona discharge
plasma reactor after mixing the raw material with a short-chain
alcohol (in this case 99.8% methanol, obtained from Audaz
Brasil), gas argon (1 L/min). The corona discharge plasma reactor
promoted the transesterication reaction, where the highly energetic plasma atmosphere promotes the formation of methyl esters
(biodiesel) in the absence of a chemical catalyst, thereby replacing
chemical catalysis.
The transesterication reaction that may occur in the plasma
process can be seen in Fig. 3.
The sample of waste frying oil used in the production of biodiesel through the cold plasma technology contained high concentrations of free fatty acids and high levels of peroxides, as shown in
Table 1.
The peroxide value (19.60 mEq/kg) and the content of free fatty
acids (2.16%) indicate that changes in the waste frying oil occurred
during its use. These changes are expected for this type of oil,
which is generally discarded since it is unt for food preparation.
Frying oil should not be used when the content of free fatty acids
exceeds 0.9% (Brazil, 2004). Yuan et al. (2008) recommends that
the content of free fatty acids for the production of ethyl and
methyl esters (biodiesel) with alkaline chemical catalysis should
be less than 2% and the oil must be pretreated in order to decrease
the amount of acidity.
The saponication number is an indication of the relative
amount of fatty acids of high and low molecular weight present
in the oil composition. The iodine value is a measure of the
amount of fats present and is expressed in terms of the number
of centigrams of iodine absorbed per gram of sample (% of
absorbed iodine). This value indicates the amount of unsaturated
fatty acids, such as linolenic acid (C18H30O2 C18:3), linoleic acid
(C18H32O2 C18:2) and oleic (C18H34O2 C18:1), present in the
oil (Singh and Singh, 2010).
152
Table 1
Properties of the waste frying oil used in the production of biodiesel through an
innovative process of non-thermal plasma corona discharge. Source: Author.
Properties
Value
2.16
19.60
0.58
174.89
106.03
0.9276
The free fatty acids in the oils were transesteried using the
non-thermal plasma technology. Fig. 4 shows the GCFID
(Fig. 4A) and CGMS chromatograms obtained for the waste frying
oil methyl esters. The GCMS analysis showed the three fatty acid
components of the esters: octadecadienoic acid methyl ester
(C18:2 D9,12) (Fig. 4 E), octadecanoic acid methyl ester (C18:1
D9) (Fig. 4F) and octadecenoic acid methyl ester (C18:0) (Fig. 4G).
The nonexistence of specic papers in the literature on the
application of plasma corona discharge to produce biodiesel hampers the description of the exact mechanism of plasma biodiesel
forming reaction, but studies of possible reactions of the
non-thermal plasma (Debacher et al., 2015) suggest that the
high-energy atmosphere of plasma facilitates the breakage of the
double bonds and hydroxyl groups, which leads to the conclusion
that, besides the formation of the methylated esters, there is the
formation of H2O present in a small percentage of methanol which
does not react with triglyceride and appears with biodiesel formed
in the end of the process (Fig. 3).
The addition of water molecules in biodiesel production processes with discharge leads to generation of H+ and OH via dissociation, ionization and vibrational/rotational excitation of water
molecules. In the reaction with organic compounds is generated
three basic mechanisms of reaction, are hydrogen abstraction,
the unsaturated electrophilic addition reaction and electron transfer (Jiang et al., 2014). In the case of compounds having aliphatic
hydrocarbons such as waste cooking oil, the hydrogen abstraction
is the primary mechanism for producing methylated esters and
water. (Jiang et al., 2014).
Table 2
Waste frying oil methyl ester biodiesel properties. Source: Author.
Properties
Value
0.48
9.60
0.82
Clear and free of impurities
4. Conclusions
Based on the results of this study, it is possible to produce biodiesel from waste frying oil (saturated) using corona discharge
plasma technology. Gas chromatography (GCFID) was used to
verify the formation of methyl esters of fatty acids. Peaks corresponding to octadecadienoic acid methyl ester, octadecanoic acid
methyl ester and octadecenoic acid methyl ester, from the biodiesel composition, were identied using GCMS. A major advantage
of this process is that the methyl ester can be obtained in the
absence of chemical catalysts and without the formation of the
co-product (glycerin).
This study showed that corona discharge plasma is a promising
technology, since it does not require a catalyst and the formation of
a co-product does not occur. Thus, with the use of waste frying oil
as a raw material and the application of the innovative technology
of cold plasma an environmentally-friendly product.
153
4.00
uV(x100,000)
Chrom atogram
3.75
(A)
3.50
325.0
300.0
3.25
275.0
III
3.00
2.75
250.0
2.50
225.0
2.25
200.0
II
2.00
175.0
1.75
1.50
150.0
1.25
125.0
1.00
100.0
0.75
0.50
75.0
0.25
50.0
0.00
25.0
-0.25
5.0
(B)
10.0
15.0
20.0
25.0
30.0
35.0
40.0
45.0
50.0
min
0.0
(E)
(C)
(D)
(F)
(G)
Fig. 4. Comparison of results for the same sample of waste frying oil methyl esters analyzed by GCFID and GCMS; (A) GCFID spectrum; (BD) NIST library ndings for the
unidentied peak of interest using GCMS; (E) GCMS showing unidentied peak of interest now identied as octadecadienoic acid methyl ester; (F) GCMS showing
unidentied peak of interest now identied as octadecanoic acid methyl ester; (G) GCMS showing unidentied peak of interest now identied as octadecenoic acid methyl
ester.
154
Acknowledgements
The authors acknowledge UNISUL, UFSC and nancial support
from Foundation for Research and Innovation of Santa Catarina
State FAPESC (Brazil).
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