Renewable Energy 143 (2019) 295e300

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Evaluation of the oxidative and thermal stability of soybean methyl

biodiesel with additions of dichloromethane extract ginger (Zingiber
officinale Roscoe)
Rafael Cardoso Rial a, *, Osmar Nunes de Freitas b, Gemima dos Santos b,
Carlos Eduardo Domingues Naza
rio b, Luíz Henrique Viana b
a
Federal Institute of Mato Grosso do Sul, Nova Andradina, MS, 79750-000, Brazil
b
Institute of Chemistry, Federal University of Mato Grosso do Sul, Campo Grande, MS, 79070-900, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The objective of the present work was to evaluate the effect of the addition of dichloromethane extract
Received 24 August 2018 obtained from Ginger rhizomes (Zingiber officinale Roscoe) in biodiesel, as well as to compare the results
Received in revised form obtained with the synthetic antioxidants BHT and TBHQ. The soybean methyl biodiesel (BMS) used was
8 April 2019
produced in our laboratory. The thermal behavior of the extract, synthetic antioxidants and biodiesel
Accepted 30 April 2019
Available online 9 May 2019
produced were evaluated using TG/DTG techniques. The additions of EDG and BHT and TBHQ were
performed in increasing proportions relative to the mass of the extract: mass of the methyl biodiesel and
the samples were stored under the same conditions and studied for storage time of up to ninety days
Keywords:
Soybean biodiesel
using TG/DTG and method to evaluate the action of the addition of these antioxidants in inhibiting and/
Natural antioxidants or retarding the oxidative stability of the biodiesel samples. After 90 days of storage, the BAN-4 sample
Ginger had the highest initial decomposition temperature. Regarding the oxidative stability, the samples with
Oxidative stability EDG additions also presented values higher than the minimum regulated by the ANP, confirming the
Thermal stability action of the antioxidants present in the EDG in the control of the oxidation reactions of BMS.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction storage process. Some chemical species with considerable antiox-

The biodiesel has been shown as an important alternative to
diesel oil. This biofuel has several advantages, among them a lower
emission of particles, less toxic, free of sulfur and aromatic sub-
stances, besides having a higher flash point and being biodegrad-
able [1,2]. From the economic point of view, biodiesel stimulates
agricultural production and rural development. In relation to its
performance, biodiesel adapts easily without the need for me-
chanical adjustments in diesel engines [3e5]. Several oilseeds are
used in the production of biodiesel and their use as raw material
can vary according to the production and availability of the vege-
table source in a given region and/or country. Soybean has a well-
known agricultural technology and is now the main raw material
in biodiesel production in Brazil. (see Figs. 1 and 2)
Due to its content of unsaturations, presence of oxygen, metals
and temperature, oxidative processes occur during the biodiesel
* Corresponding author.
E-mail address: rafael.rial@ifms.edu.br (R.C. Rial).
idant activity have been extensively researched in order to contain
or retard oxidative processes in biodiesel in order to provide a
quality product to the consumer market.
Ginger rhizomes present important antioxidant activity due to
the presence of gingerols and shogaols in their extracts [6]. It has
been demonstrated that gingerol is endowed with an antioxidant
action both in vivo and in vitro [7]. According to Shukla and Singh
[8], the main bioactive constituents of ginger are 6 - gingerol, 8 -
gingerol, 10 -gingerol and 6 - shogaol, possessing diverse phar-
macological properties includes an important antioxidant activity,
being 10 -gingerol and 6 - shogaol were the substances that had a
higher antioxidant activity [9]. Andreo and Jorge [10] evaluated the
oxidative stability, using the Rancimat® equipment, of samples
with extract of the rhizomes of ginger in soybean oil. The Induction
Period (PI) of the samples evaluated increased as the concentration
of extract in the oil increased. Devi [11] added ginger extract in the
concentration of 250e2000 ppm in the Pongamia pinnata biodiesel
and tested the inhibition of the oxidation of the biofuel, the
250 ppm extract sample being the most advantageous because it

https://doi.org/10.1016/j.renene.2019.04.164
0960-1481/© 2019 Elsevier Ltd. All rights reserved.
296 R.C. Rial et al. / Renewable Energy 143 (2019) 295e300
Nomenclatures
PI The Induction Period
ppm parts per million
ASTM American Society for Testing and Materials
EN European Standard
kg kilogram - (unit of mass)
C degrees Celsius
Campo Grande MS - Brazil - (MS - State of Mato Grosso do Sul)
ml milliliter - (unit of volume)
CH2Cl2 dichloromethane
h clock time
g grams (unit of mass)
EDG dichloromethane ginger extract
BMS soybean methyl biodiesel
MeOH KOH - methyl alcohol: potassium hydroxide
complied with both standard specifications American (ASTM D-
6751) and European (EN 14214).
The susceptibility of biodiesel to oxidation reactions affects its
quality, especially during storage, since the presence of air, light,
heat or even the existence of metals favors its oxidation. To prevent
oxidation, this biofuel additive is required with some antioxidant.
On the other hand, it is possible to retard and/or block the forma-
tion of free radicals by the addition of antioxidant substances,
which are responsible for interfering with the oxidation processes.
Antioxidants are chemical species that are capable of retarding or
inhibiting oxidation reactions. They act at the initial stage of
autoxidation, removing free radicals from the medium, and
photooxidation, preventing the formation of hydroperoxides. Nor-
mally, antioxidants are phenolic derivatives in which it is possible
to stabilize the free radical through the resonance effect, an elec-
tronic delocalization occurring by the aromatic ring, thus avoiding
the propagation of the oxidative reactions of the me
dium [12].
The most widely used synthetic antioxidants are polyphenols,
such as 3,5-di-t-butyl-4-hydroxytoluene (BHT) and tert-
butylhydroquinone (TBHQ). BHT is also added in foods, medi-
cines, fuels, among them biodiesel, reacting in the stabilization of
free radicals due to the presence of the aromatic ring activating
groups in the ortho and para positions, which contributes to the
delocalization of electrons, retarding oxidation [13]. TBHQ is an
efficient antioxidant in food preservation and is used as a preser-
vative for unsaturated vegetable oils and edible animal fats [14]. It is
also used as a stabilizer to inhibit self-polymerization, oxidation,
and to prevent the corrosion of biodiesel [15].
Borsato [16] evaluated the oxidative stability of soybean
Fig. 1. BMS samples with addition of EDG.
MgSO4 magnesium sulfate
ANP Age^ncia Nacional do Petro

leo - Brazil
TG-DTG thermogravimetry (TG), differential
thermogravimetry (DTG)
BHT Butylated hydroxytoluene - IUPAC 2,6-Di-tert-butyl-
4-methylphenol
TBHQ tertiary butylhydroquinone - IUPAC-(1,1-
Dimethylethyl) 1,4-benzenediol
mg milligram (unit of mass)
min minute
I2 iodine
T initial initial temperature
T final final temperature
T peak peak temperature
D Mass (%) Percentage of mass variation
UV spectroscopy Ultra violet spectroscopy
biodiesel oil, B100, with the addition of TBHQ at different tem-
peratures. The results suggested that the biodiesel B100 with TBHQ
had a storage time, at 25  C, three times more than the estimated
time for pure B100. Ferrari and Souza [17] carried out a study on the
activities of BHT and TBHQ, in the concentration of 5%, in sunflower
biodiesel, using techniques of peroxide index analysis, UV spec-
troscopy and Rancimat ® test. The results showed the TBHQ with
activity superior to BHT. Domingos and his collaborators [18]
studied the BHT and TBHQ evaluating the time of induction of
ethylic biodiesel from the Rancimat® method. BHT showed greater
efficacy in the concentration range between 200 and 7000 ppm.
TBHQ presented a higher stabilization potential when used at
higher concentrations (8000 ppm). It was also carried out, a com-
bined study of these antioxidants that did not show any positive
synergistic effect that justified its use in mixture.
Due to the concern with the non-renewable character of the
synthetic antioxidants, the search for antioxidants that had good
performance and could be obtained from natural and renewable
sources was motivated. Numerous researches have been found in
the literature reporting the presence of antioxidants in plant ex-
tracts, as well as studies on the isolation, purification and chemical
elucidation of species that play a significant role in antioxidant
activity, such as vitamins, nitrogen compounds (alkaloids, amino
acids, peptides) and phenolic compounds. Phenolic substances,
derived from the secondary metabolism of plants, are the most
important and abundant group, occurring in plants contributing to
the antioxidant and sensory properties of fruits, honey and vege-
tables [19]. In general, phenolic antioxidants demonstrate as
mechanism of action a preferential affinity with the peroxyl radical,
 R.C. Rial et al. / Renewable Energy 143 (2019) 295e300
Fig. 2. TG/DTG curve of the BMS sample without and with EDG added after: A - 24 h B - 15 days C - 30 days D - 45 days E - 60 days and F - 90 days storage.
because it has lower energy than the other radicals and is more
resistant to the oxidation step, favoring the abstraction of its
hydrogen [20].
Tocopherol, an antioxidant naturally present in most vegetable
oils and some fish, is widely applied as an inhibitor of the oxidation
of oils and fats. Tocopherol has four types of structure, depending
on the location of the methyl groups in the ring: a, b, g and d. The
antioxidant activity of tocopherols can be attributed to their ability
to donate their phenolic hydrogen to free radicals, inhibiting the
propagation of oxidation. Liang [21] carried out a study in which
the objective of investigating the effect of a-tocopherol, when
added to the palm oil biodiesel using the Rancimat ® technique, was
compared with the synthetic antioxidants BHT and TBHQ. Although
the results showed beneficial action of a-tocopherol in biodiesel,
the synthetic antioxidants presented the best results even at low
concentrations. In a study carried out by Rodrigues Filho [22], the
action of hydrogenated natural antioxidants, cardanol and eugenol,
extracted from cashew nuts and cloves of India, were studied when
added to cotton biodiesel against oxidative stability tests,
comparing the results with the synthetic antioxidant BHT. The
study showed an order of inhibitory activity in the following order
hydrogenated eugenol > hydrogenated cardanol > BHT, showing
satisfactory results regarding the inhibitory activity of the natural
antioxidant oxidative processes.
Although numerous studies reporting the potential of natural
antioxidants found in many plant species extracts, few studies have
been carried out by adding these statements in biodiesel in order to
extend the life of the biofuel. Of the plant species, some studies are
found in the literature reporting the antioxidant activity of extracts
of ginger rhizomes in which gingerols and shogaols are the main
constituents. The shogaols are formed from the corresponding
gingerols during the heat treatment [23]. In a study by Kikuzaki and
Nakatami [24], the non-volatile fraction of the dichloromethane
extract of ginger rhizomes was the one that exhibited a higher
antioxidant activity. Dugasani [9] conducted a study on the
297
antioxidant activity of 6 -gingerol, 8-gingerol, 10-gingerol and 6-
shogaol, and obtained results in which 6-shogaol exhibited activ-
ity antioxidant. The chemical compound 10-gingerol was the one
with the highest antioxidant activity among the gingerols, while 6-
gingerol presented the lowest activity. From these results, the au-
thors verified that the influence of the presence of the a, b unsat-
urated side chain carbonyl group is of extreme importance for the
antioxidant property.
The objective of this work was to evaluate the oxidative and
thermal stability of soybean methyl bromide samples, added with
dichloromethane ginger extract, in four different concentrations
during a storage period of up to 90 days.
2. Materials and methods
2.1. Preparation of the extract
The ginger rhizomes (1.5 kg) were purchased in a supermarket
in Campo Grande - MS eBrazil and washed individually, cut and
placed to dry in an oven at 55  C for five days. They were then
ground in a blender and transferred to erlenmeyer (72 g) for
preparation of the extract according to methodology described by
Kikuzaki and Nakatami [24] with modifications. In his work, the
dichloromethane extract was prepared and then subjected to
distillation. The fraction that obtained the highest antioxidant ac-
tivity was non-volatile. In this way, the substances responsible for
the marked antioxidant activity do not volatilize and remain in the
extract. Therefore, in this work, it was decided not to carry out the
distillation. In the preparation of the extract, about 720 ml of
dichloromethane (CH2Cl2) were added to the flask and kept under
constant stirring at room temperature for 12 h, which was repeated
three times. After the period, the solutions obtained in the three
extractions were pooled and concentrated using a rotary evapo-
rator, yielding 6.8 g of dichloromethane ginger extract (EDG).
298 R.C. Rial et al. / Renewable Energy 143 (2019) 295e300

2.2. Obtaining and Physical-chemical characterization of biodiesel 15 mg of sample, at a heating rate of 20  C. min 1 in the range of
(BMS) 25e500  C in synthetic air atmospheres for all samples.

To obtain methyl biodiesel, 900 mL of commercial soybean oil 3. Results and discussion
purchased at a Campo Grande e MS - Brazil supermarket was used.
Subsequently, a prepared solution of methyl alcohol: potassium 3.1. Physical chemical properties of biodiesel used
hydroxide (MeOH: KOH) was added to the commercial oil, keeping
the reaction medium under heating (60  C) and constant stirring The physical-chemical properties analyzed for the BMS in this
for 60 min. After the period, it was transferred to a separatory work, all presented values within the limits stipulated by the ANP.
funnel and allowed to stand for 12 h. Then, biodiesel: glycerin was In the table below are the results obtained with the established
separated by washing the supernatant with deionized water. To the limits.
obtained product was added anhydrous magnesium sulfate
(MgSO4) to eliminate traces of water and then filtered and dried in 3.2. Preliminary thermogravimetric studies
an evaporator route to eliminate methanol, thus obtaining soybean
methyl biodiesel (BMS). The confirmation of the transesterification In order to verify the thermal decomposition in an oxidizing
reaction of the oil in methyl biodiesel was performed by 1H NMR. atmosphere (synthetic air), the BMS, the dichloromethane ginger
For the physical-chemical characterization of the BMS produced, extract (EDG), the synthetic antioxidants TBHQ and BHT, were
the following tests were performed: Acidity Index; Water content; submitted to TG/DTG thermogravimetric assays. Since the oxidative
Iodine content; Specific mass at 20  C; Cold Filter Clogging Point; stability analysis is performed at 110  C, checking the temperature
Oxidation Stability, all indicated by the inspection body through at which the antioxidants are decomposed is of extreme impor-
ANP Resolution no. 14 of 2012. tance in verifying whether at this temperature the substances can
volatilize and/or decompose, as well as cause modifications in their
2.3. Thermal analysis molecules resulting in the decrease or nullification of their activity
(see Table 1).
TG-DTG curves were obtained in a TA Instruments model Q50 Of the antioxidants isolated from EDG, only 10-gingerol and 6-
thermal analyzer and the objective was to verify the thermal profile shogaol have a decomposition temperature higher than the tem-
of soybean methyl biodiesel obtained without antioxidant addi- perature of 110.00  C. The EDG TG/DTG curve showed five thermal
tions, the dichloromethane extract of the ginger rhizomes and the decomposition steps starting at 129.31  C. The mixture of sub-
synthetic antioxidants BHT and TBHQ, using between 3 and 15 mg stances present in EDG prevents the decomposition of 6-gingerol
of sample, at a heating rate of 20  C. min 1 in the range of and 8-gingerol at lower temperatures, thus maintaining the anti-
25e500  C in atmospheres of synthetic air for all samples. oxidant activity of the extract as a whole, inhibiting and/or
retarding the oxidation of BMS during the stability test oxidative.
2.4. Additions of EDG in biodiesel and additions of BHT and TBHT The TG/DTG curve of the BMS exhibited only one thermal event,
synthetic antioxidants in biodiesel initiating its mass loss at 113.55  C due to the degradation and/or
volatilization of the methyl esters or by-products formed. The table
The additions of the dichloromethane ginger extract (EDG) in below shows the events, the initial, final, peak, and% loss mass
the biodiesel were carried out in mass: mass proportions. A sample temperatures per event.
was maintained throughout the storage time without any addition
of BAN-0 extract. To the BAN -1 sample, 250 ppm of EDG was added
3.3. Study of the oxidative stability of the samples with addition of
to the biodiesel, and in the other samples, the ratio of extract to
EDG, BHT and TBHQ in BMS
ginger mass increased to 500, 1000 and 2000 ppm in the samples
BAN-2, BAN-3 AND BAN -4, respectively.
In Table 3 are the induction periods measured during the storage
In order to compare the results obtained with the added sam-
time of the BMS samples with EDG additions and in Table 4, of the
ples of dichloromethane ginger extract, the following additions of
samples with TBHQ and BHT (see Table 5).
synthetic antioxidants TBHQ and BHT were carried out in biodiesel
Samples supplemented with synthetic antioxidants had the
(BAS) samples in mass: mass proportions similar to EDG samples.
highest induction periods during the entire ninety day storage
The sample, BAS-1, BAS-2 and BAS-3 was added 250 ppm, 1000 and
period. However, some samples with EDG addition also had a
2000 ppm of TBHQ respectively, and in the samples BAS-4, BAS-5
minimum value regulated by ANP. As the mass of EDG added in the
and BAS-6, the same quantity of BHT.
BMS increased, there was an increase in the oxidative stability of
the stored samples. The BAN-3 and BAN-4 samples presented in-
2.5. Storage and evaluation of the action of antioxidants during the
duction periods higher than those stipulated by ANP (8 h) over the
period of storage
storage period. The BAN-2 sample had a minimum oxidative sta-
bility of up to 45 days and after that period no longer meets the
The additive samples were stored in amber flasks and protected
standard specification. The BAN-1 sample did not present the
from light and at room temperature. The synthetic antioxidants
TBHQ and BHT were chosen for this work due to their wide in-
dustrial use. After additives, oxidative stability and thermal stability Table 1
were evaluated at the intervals of 24 h, 15 days, 30 days, 45 days, 60 Physical - chemical properties analyzed for BMS.
days and 90 days with the purpose of evaluating the action of these Parameter UNIT LIMIT METHOD BMS
antioxidants in delaying the oxidation of biodiesel. For the oxida-
Acidity index mg KOH/g 0.5 ASTM D 664 0.2
tive stability test, the samples were analyzed according to the Water content mg/Kg 500 ASTM D 6304 250
Rancimat® method according to the European Standard (EN 14112), Iodine Index g I2/100 g e EN 14111 120
using the METROHM brand equipment (Model Rancimat 873). For Specific Mass at 20  C Kg/m3 850e900 ASTM D 4052 877

the study of thermal stability, TG-DTG curves were obtained on a TA Cold filter clogging point C 19 ASTM D 664 1.0
Oxidative stability at 110  C hours 8.00 EN 14112 6.05
Instruments model Q50 thermal analyzer using between 3 and
 R.C. Rial et al. / Renewable Energy 143 (2019) 295e300 299

Table 2 Table 5
Temperatures of thermal decomposition obtained by TG/DTG. Thermogravimetric data of the BMS without and with additions of EDG during the
period of storage.
Step T initial ( C) T final ( C) T peak ( C) D Mass (%)a
Time (days) Tinitial ( C) Tfinal ( C) Tpeak ( C)
(BMS)
Single step 113.55 250.30 225.80 93.05 BAN-0 Single step 110.42 245.43 218.48
(EDG) BAN-1 Single step 112.56 249.71 219.82
1 129.31 312.22 261.37 54.18 1 BAN-2 Single step 114.83 251.35 221.45
2 312.22 341.17 327.75 8.92 BAN-3 Single step 118.77 254.53 223.63
3 341.17 387.08 369.42 10.39 BAN-4 Single step 120.98 285.37 231.56
4 387.08 474.64 431.57 10.84 BAN-0 Single step 108.22 212.56 202.18
5 474.64 641.31 558.68 15.67 BAN-1 Single step 110.54 214.88 206.37
TBHQ 15 BAN-2 Single step 112.69 216.59 208.83
Single step 120.80 210.40 198.30 100.00 BAN-3 Single step 117.10 225.66 210.59
BHT BAN-4 Single step 119.72 257.48 224.40
Single step 119.80 242.30 226.70 100.00 BAN-0 Single step 106.55 210.34 200.22
a BAN-1 Single step 108.41 213.90 204.53
D Mass (%) - Percentage of mass variation.
30 BAN-2 Single step 110.24 215.73 206.21
BAN-3 Single step 114.56 223.85 209.75
BAN-4 Single step 117.33 250.34 223.47
Table 3 BAN-0 Single step 105.87 209.58 199.86
Oxidative Stability of BMS without and with additions of EDG during storage period. BAN-1 Single step 107.76 211.66 203.38
45 BAN-2 Single step 109.48 214.57 205.73
Storage time (days) BAN-0 BAN-1 BAN-2 BAN-3 BAN-4
BAN-3 Single step 113.62 222.93 208.54
Induction period (hours) BAN-4 Single step 116.89 242.75 222.96
BAN-0 Single step 104.62 206.47 197.69
1 5.24 5.73 6.36 7.36 8.26
BAN-1 Single step 106.85 208.59 202.86
15 4.87 5.65 6.30 7.26 8.04
60 BAN-2 Single step 108.41 213.62 204.73
30 4.84 5.60 6.13 7.12 7.57
BAN-3 Single step 112.93 217.84 206.59
45 4.32 5.36 6.10 7.00 7.34
BAN-4 Single step 115.55 228.47 218.31
60 4.15 5.09 5.60 6.85 7.26
BAN-0 Single step 98.49 200.80 190.08
90 3.80 4.70 5.20 6.10 6.20
BAN-1 Single step 101.50 202.53 192.35
90 BAN-2 Single step 102.86 204.55 195.50
BAN-3 Single step 103.77 206.47 200.15
Table 4 BAN-4 Single step 106.43 215.45 201.74
Oxidative Stability of BMS without and with additions of BHT and TBHQ during the
storage period.

Storage time (days) BAS-0 BAS-1 BAS-2 BAS-3 BAS-4 BAS-5 BAN-6 the extract-additive samples had higher temperatures than the
Induction period (hours)
sample with no addition and after 90 days of storage, temperatures
dropped to 98.49; 101.50; 102.86; 103.77; 106.43  C for the 4 BAN
1 5.25 28.18 45.28 68.15 19.52 27.31 35.08
samples cited above.
15 4.82 27.13 44.35 67.45 18.26 26.20 34.18
30 4.57 26.55 42.40 66.60 17.31 25.08 33.16
45 4.38 25.31 40.34 65.48 16.54 23.43 32.02 4. Conclusion
60 4.18 24.49 39.12 64.28 15.38 22.10 30.14
90 4.06 22.18 37.24 60.32 14.30 20.51 29.37
In the ninety days of storage, the increase in the oxidative sta-
bility of samples with natural antioxidant additions (EDG) and
synthetic antioxidants (BHT and TBHQ) was verified in relation to
minimum limit in any of the analyzes performed during storage the sample with no addition. Samples with BHT and TBHQ had the
time, however, its induction period was higher than the sample highest induction periods and values greater than 8.00 h recom-
without addition, BAN-0, which shows the action of the antioxi- mended by the ANP during the entire storage period. Samples with
dants present in EDG delays the oxidation of BMS. EDG additions, only BAN-3 and BAN-4 maintained the induction
periods longer time during the ninety days of storage. The BAN-2
3.4. Study of the thermal stability of the samples with addition of sample no longer meets the ANP specification during the period
EDG, BHT and TBHQ in BMS between 45 and 60 days. The BAN-1 sample did not present the
minimum induction period in any of the analyzes performed during
The oxidative stability by the Rancimat method evaluates the storage. However, its induction period was higher than that of the
time that the biofuel takes to totally oxidize, losing its usefulness, sample without additions, BAN-0, demonstrating once again the
while the thermal stability by the TG/DTG method evaluates in action of the antioxidants present in EDG, this time in the control of
what initial temperature the degradation of the material begins and BMS oxidation.
shows at what final temperature the material is totally degraded.
As for the thermal stability, in the TG-DTG curves it was also Appendix A. Supplementary data
possible to detect the action of the antioxidants, this time in rela-
tion to the temperature of the samples. For the EDG-added samples, Supplementary data to this article can be found online at
as the extract mass increased, it was possible to notice that the https://doi.org/10.1016/j.renene.2019.04.164.
initial decomposition temperature of the samples increased,
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