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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, Palhoça, SC, Brazil
b
Environmental Engineering, University of Southern Santa Catarina (Unisul), CEP 80137270, Palhoça, SC, Brazil
c
Post Graduation in Environmental Engineering, Federal University of Santa Catarina (UFSC), CEP 88040900, Florianópolis, SC, Brazil
d
Production Engineering, University of Southern Santa Catarina (Unisul), CEP 80137270, Palhoça, SC, Brazil
e
Departament of Science and Technology of Food, Federal University of Santa Catarina (UFSC), CEP 88034001, Florianópolis, SC, Brazil
a r t i c l e i n f o a b s t r a c t
Article history: This article aims to describe an alternative and innovative methodology to transform waste, frying oil in a
Received 9 March 2015 potential energy source, the biodiesel. The biodiesel was produced from fatty acids, using a waste product
Revised 26 May 2015 of the food industry as the raw material. The methodology to be described is the corona discharge
Accepted 26 May 2015
plasma technology, which offers advantages such as acceleration of the esterification reaction, easy
Available online xxxx
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
Keywords:
30 mL of sample. The acid value indicates the content of free fatty acids in the biodiesel and the value
Fatty acids
Waste frying oil
obtained in this study was 0.43 mg KOH/g. Peaks corresponding to octadecadienoic acid methyl ester,
Methyl esters octadecanoic acid methyl ester and octadecenoic acid methyl ester, from the biodiesel composition, were
Corona discharge plasma identified using GC–MS. A major advantage of this process is that the methyl ester can be obtained in the
Biodiesel absence of chemical catalysts and without the formation of the co-product (glycerin).
Ó 2015 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.wasman.2015.05.040
0956-053X/Ó 2015 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Cubas, A.L.V., et al. Biodiesel production using fatty acids from food industry waste using corona discharge plasma tech-
nology. Waste Management (2015), http://dx.doi.org/10.1016/j.wasman.2015.05.040
2 A.L.V. Cubas et al. / Waste Management xxx (2015) xxx–xxx
scope, it is observed that the production of biodiesel was conceived promising than the conventional catalytic processes due to a
as a means of social inclusion of family farming in the production shorter reaction time, no formation of glycerin and ease of
chain and the economy as a whole, benefiting from the creation of biodiesel separation.
jobs and income. The corona plasma process is also known as corona plasma, as
The use of waste frying oil as a feedstock for biodiesel produc- well as dielectric barrier (Ragazzi et al., 2014), plasma jet, electron
tion can therefore reduce the cost of the final product, besides beam, etc. (Fridman, 2008; Fridman et al., 2007; Kim, 2004; Preis
being environmentally friendly. Due to the rapid decline in crude et al., 2013; Pankaj et al., 2014). The corona discharge plasma
oil reserves, the use of vegetable oils for the production of diesel comprised of a partially ionized gas, in which the average energy
fuels is being promoted in many countries. Depending on the of the electrons is considerably higher than the energy of the ions
climatic and soil conditions, different nations are looking into and the gas molecules. Plasma discharges are widely used for
different vegetable oils for diesel fuel production. For example, processing and are indispensable in many technological applica-
soybean oil in the USA, rapeseed and sunflower oils in Europe, tions (Milosavljević et al., 2007).
palm oil in Southeast Asia (mainly Malaysia and Indonesia), and The plasma discharge is formed by applying an intense electric
coconut oil in Philippines are being considered as substitutes for field, which causes the formation of an electronic self-propagating
mineral diesel (ElSolh, 2011). arc within the gas volume. Once the ionized gas is generated, the
The world production of waste oils and fats in 2008 was around electrons collide with molecules, creating chemically-active
154 million tons. A variety of raw materials can be used to produce species known as radicals. Radicals, once produced, can replace
biodiesel (MPCO, 2008). These include virgin oil feedstock the conventional chemical form of the catalyst during transesteri-
(U.S Energy Information, 2013), waste vegetable oil (WVO), animal fication reactions, facilitating the separation of the biodiesel
fats (Leonard, 2007), algae (Kiong, 2006), oil from halophytes such formed (Istadi, 2006; Istadi et al., 2009; Kogelschatz, 2003).
as Salicornia bigelovii (Glenn et al., 1998) and sewage sludge The corona discharge plasma reactor technology offers
(Casey, 2010). Many researchers have suggested that WVO is the advantages related to the production of biodiesel compared to
best raw material to produce biodiesel, but since the available conventional methods due to faster reaction times and the easy
supply is considerably less than the amount of petroleum separation of the final product (Istadi et al., 2009).
based-fuel that is burned for transportation and home heating
globally, this local solution does not scale well.
However, oils and fats undergo several physical and chemical 2. Methodology
changes when used repeatedly in the frying process. The physical
changes observed in vegetable oil after frying include: (i) increased 2.1. Raw material acquisition and preparation
viscosity, (ii) increased specific heat, (iii) a change in the
surface tension, and (iv) a change in the color (Cvengros and The raw material, waste frying oil originating from the food
Cvengrosova, 2004). frying process, was purchased from local restaurants. The oils
During the frying process, different types of reactions occur in and fats initially underwent a pretreatment step with heating to
the oils, for instance, thermolytic, hydrolytic and oxidative 50 °C and filtering for the removal of impurities.
(Kulkarni and Dalai, 2006; Bensmira et al., 2007; Cvengro and Before starting the experiments to obtain biodiesel, the raw
Cvengroová, 2004). These reactions can lead to the formation of material was characterized by determining the acidity number
undesirable compounds which are harmful to human health, such by titration (AOAC n. 940.28, 2005) and the water content by using
as free fatty acids (FFA). These polar compounds – FFA significantly the Karl-Fischer method (ISO 12937, 2000). Saponification and
affects the conversion to alkyl esters (biodiesel) in the conventional peroxide values were determined by the AOAC official method
transesterification process with basic catalysts. In the transesterifi- 920.160 and 965.33, respectively. The AOAC official method
cation of vegetable oils, a triglyceride reacts with an alcohol in the 993.20 (Wijs method) was used to determine the Iodine values.
presence of a strong acid or base, producing a mixture of fatty
acids, alkyl esters and glycerol (Schuchardt et al., 1998).
2.2. Corona discharge reactor
Among the most commonly used alkaline catalysts in the bio-
diesel industry are potassium hydroxide and sodium hydroxide
The body of the reactor was comprised of a cylindrical quartz
flakes which are inexpensive, easy to handle in transportation
tube (300 110 mm), wrapped with a spiral of stainless steel
and storage, and are preferred by small producers (Singh et al.,
250 mm in length, which served as an electrode. A stainless steel
2006). However, these catalysts are now considered to be out-
screw (400 5 mm) in the center of the quartz tube was used to
dated, since even when using refined vegetable oils with a low con-
seal the exits and keep the second electrode (screw) in the center
tent of free fatty acids and low water content, small amounts of
of the tube (Fig. 1).
soap are formed, promoting the entrainment of esters with varying
The used frying oil with methanol and water was introduced
amounts with glycerin phase, thereby reducing the ester yield in
into the reactor through an access positioned at the right side of
the light phase containing glycerin and generating more contami-
the reactor cap, throughout the process was injected 1 L/min of
nants. In biodiesel production carried out through traditional
argon into the reactor. The final product, methyl ester (biodiesel),
processes the amount of glycerol generated is equivalent to 10%
is pulled across the reactor and a source of alternating current
of the biodiesel produced, and this negatively influences the
voltage of 17 kV is used to generate the plasma.
national and international market for glycerin (Dasari et al., 2005).
A photo of the system transporting the waste frying oil can be
In this article, different biodiesel production processes which
seen in Fig. 2 (note the violet fluorescence emitted by the plasma).
involve the use of a corona plasma reactor are described. For this
purpose, a pilot corona discharge plasma system was built for
the production of biodiesel, appropriate pilot conditions being set 2.3. Pilot optimization
to obtain the best rates for the conversion of waste into biodiesel.
The batch production of biodiesel occurred without the use of acid To establish the appropriate conditions for the pilot and obtain
or alkaline catalysts, while the biofuel samples were subjected to better oil to biodiesel conversion rates using the corona discharge
chromatography analysis (GC–MS) to confirm the presence of plasma technology, tests were carried out varying the residence
esters (biodiesel). This technology is considered to be more time of the sample in the reactor (15–120 min), and the sample
Please cite this article in press as: Cubas, A.L.V., et al. Biodiesel production using fatty acids from food industry waste using corona discharge plasma tech-
nology. Waste Management (2015), http://dx.doi.org/10.1016/j.wasman.2015.05.040
A.L.V. Cubas et al. / Waste Management xxx (2015) xxx–xxx 3
Please cite this article in press as: Cubas, A.L.V., et al. Biodiesel production using fatty acids from food industry waste using corona discharge plasma tech-
nology. Waste Management (2015), http://dx.doi.org/10.1016/j.wasman.2015.05.040
4 A.L.V. Cubas et al. / Waste Management xxx (2015) xxx–xxx
Table 1 The free fatty acids in the oils were transesterified using the
Properties of the waste frying oil used in the production of biodiesel through an non-thermal plasma technology. Fig. 4 shows the GC–FID
innovative process of non-thermal plasma – corona discharge. Source: Author.
(Fig. 4A) and CG–MS chromatograms obtained for the waste frying
Properties Value oil methyl esters. The GC–MS analysis showed the three fatty acid
Acid value (mg KOH/g) 2.16 components of the esters: octadecadienoic acid methyl ester
Peroxide value (mEq/kg) 19.60 (C18:2 – D9,12) (Fig. 4 E), octadecanoic acid methyl ester (C18:1
Moisture (%) 0.58 – D9) (Fig. 4F) and octadecenoic acid methyl ester (C18:0) (Fig. 4G).
Saponification value (mg KOH/g) 174.89 The nonexistence of specific papers in the literature on the
Iodine value (g iodine/100 g sample) 106.03
Density at 20 °C (g/cm3) 0.9276
application of plasma corona discharge to produce biodiesel ham-
pers 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
thin-layer chromatography (TLC) and the retention factor (Rf) value
high-energy atmosphere of plasma facilitates the breakage of the
of 0.8 verified the formation of methyl esters.
double bonds and hydroxyl groups, which leads to the conclusion
The best conditions were found to be an oil/methanol molar
that, besides the formation of the methylated esters, there is the
ratio of 6:1, ambient temperature (25 °C) and reaction time of
formation of H2O present in a small percentage of methanol which
110 min and 30 mL of sample and 1 ml of H2O.
does not react with triglyceride and appears with biodiesel formed
Table 2 shows the properties of the biodiesel obtained from the
in the end of the process (Fig. 3).
waste frying oil. The acid value indicates the content of free fatty
The addition of water molecules in biodiesel production pro-
acids in the biodiesel and the value obtained in this study was
cesses with discharge leads to generation of H+ and OH via dissoci-
0.43 mg KOH/g. The presence of free fatty acids can lead to corro-
ation, ionization and vibrational/rotational excitation of water
sion and may be a symptom of water in the fuel (Gerpen, 2005).
molecules. In the reaction with organic compounds is generated
The acid value of 0.48 mg KOH/g complies with the ANP
three basic mechanisms of reaction, are hydrogen abstraction,
Resolution n.45 of 25/8/2014 which deals with the biodiesel spec-
the unsaturated electrophilic addition reaction and electron trans-
ifications, with regard to marketing, certification and tax docu-
fer (Jiang et al., 2014). In the case of compounds having aliphatic
ments (Brazil, 2014).
hydrocarbons such as waste cooking oil, the hydrogen abstraction
is the primary mechanism for producing methylated esters and
water. (Jiang et al., 2014).
3.3. Identification of esters by chromatography (CG–FID and CG–MS)
Please cite this article in press as: Cubas, A.L.V., et al. Biodiesel production using fatty acids from food industry waste using corona discharge plasma tech-
nology. Waste Management (2015), http://dx.doi.org/10.1016/j.wasman.2015.05.040
A.L.V. Cubas et al. / Waste Management xxx (2015) xxx–xxx 5
uV(x100,000)
Chrom atogram C
4.00
I-Octadecanoic acid methyl ester
3.75
(A) 325.0
3.50 II-Octadecenoic, acid methyl ester
300.0
3.25
3.00 III 275.0
2.75 250.0
2.50
225.0
2.25
II 200.0
2.00
1.75 175.0
1.50 150.0
1.25 I
125.0
1.00
100.0
0.75
0.50 75.0
0.25 50.0
0.00
25.0
-0.25
0.0
5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0 min
(C) (F)
(D) (G)
Fig. 4. Comparison of results for the same sample of waste frying oil methyl esters analyzed by GC–FID and GC–MS; (A) GC–FID spectrum; (B–D) NIST library findings for the
unidentified peak of interest using GC–MS; (E) GC–MS showing unidentified peak of interest now identified as octadecadienoic acid methyl ester; (F) GC–MS showing
unidentified peak of interest now identified as octadecanoic acid methyl ester; (G) GC–MS showing unidentified peak of interest now identified as octadecenoic acid methyl
ester.
Please cite this article in press as: Cubas, A.L.V., et al. Biodiesel production using fatty acids from food industry waste using corona discharge plasma tech-
nology. Waste Management (2015), http://dx.doi.org/10.1016/j.wasman.2015.05.040
6 A.L.V. Cubas et al. / Waste Management xxx (2015) xxx–xxx
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Please cite this article in press as: Cubas, A.L.V., et al. Biodiesel production using fatty acids from food industry waste using corona discharge plasma tech-
nology. Waste Management (2015), http://dx.doi.org/10.1016/j.wasman.2015.05.040