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ABSTRACT
Vegetable oils become susceptible to oxidation during their processing.
The appropriate extraction and refining conditions of oil from two experimental cultivars (Madero-91 and Cianoc-2) of sunflower seeds and a commercial
one (Victoria) as a control, were studied. Isopropyl alcohol was used in the
extraction and refining, and compared with hexane. The refining was performed by the miscella method at 40, 50, 60 and 70%. Free fatty acids (FFA)
and malonaldehyde analysis of crude oils afforded no significant differences
among solvents and sunflower varieties. In refined oils, differences found with
the miscella concentration, the malonaldehyde content and FFA content were
not significant. Cianoc-2 was the best source for oil production because of its
lower values in FFA and malonaldehyde content.
PRACTICAL APPLICATIONS
The use of hexano in refining vegetable oil in Mexico is common, lack of
knowledge about the use of new solvents and their impact on the processing
conditions with sunflower seed cultivars is lack. The present work describes at
lab scale, the work conditions, advantages and posibilities and limitations of
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the use on isopropyl alcohol in comparison with hexane and the use of three
Mexican cultivar with this approach, with emphasize in oxidation conditions
of refined vegetable oil.
INTRODUCTION
Sunflower oil is an important source of long-chain unsaturated fatty acids,
especially those that are essential such as linoleic acid and linolenic acid
(Willis et al. 1998). Their presence has been related with beneficial effects in
human cell metabolism.
Among edible oils, those that contain highly unsaturated fatty acids are
particularly prone to oxidation and this affects their quality as well as that of
products prepared from them (Godley 1997).
Lipid oxidation can be divided in three stages: initiation, propagation and
termination. Free radicals react with unsaturated lipids (LH), which leads to
the formation of lipid radicals (L* and LOO*). The lipid oxidation chain
reaction propagates as these lipid radicals react with other lipids in their
immediate vicinity. Some of the lipid radicals formed may be terminated when
they react with other radicals (Velasco et al. 2006).
Formation of alkoxy radicals also leads to b-scission reactions that in turn
result in the generation of a wide variety of different molecules, including
aldehydes, ketones, alcohols and hydrocarbons, which are responsible for the
physicochemical and sensorial properties of oxidized oils (McClements and
Decker 2000).
Free radicals are known to bind covalently to vital macromolecules such
as proteins and DNA. The covalent binding to proteins usually results in their
denaturation or impairment of the normal physiological function, while interaction with DNA is associated with damage or induction of mutation (Kasai
et al. 2005).
For oil extraction, light petroleum fractions are commonly used, generally hexane. After extraction, the crude oil is refined. In certain stages of the
refining process (degumming, neutralization and bleaching), the carotenoids
are removed from the oil, and they are exposed to high temperatures and
metallic catalysts (Diosady 2005). The refining is critical as polyunsaturated
fatty acids are particularly sensitive to oxidation at high temperatures (Sahu
and Gray 1997).
In the edible oil industry, the solvent currently used for extracting oil is
commercial grade hexane. However, this solvent is a hazardous air pollutant
and its use is being questioned and limited because of its toxicity and flammability (Lusas et al. 1991). For this reason, there is considerable interest in
415
finding a suitable replacement for hexane. Short-chain alcohols, such as isopropyl alcohol, were found to be potential extraction solvents (Lusas et al.
1991).
Most oil industries in Mexico use chemical and physical refining. The
chemical method includes a water degumming step, which is intended to
remove impurities known generically as gums (Karabulut et al. 2005). This is
followed by a caustic treatment for removal of additional impurities and most
of the free fatty acids (FFA), then a bleaching step to improve color and a final
deodorization or steam distillation to remove any traces of fatty acids and
impurities remaining (Tasan and Demirci 2005).
Since the 1960s, miscella refining has been a common method for edible
oils. This method uses an adsorbent bed such as diatomaceous earth, activated
charcoal or silica, which can trap some pigments, FFA and polar components.
Oil quality and reduced refining losses make miscella refining process
attractive and economical compared with the conventional caustic refining
process. The advantages of miscella refining are lower neutral oil loss,
minimal color problems due to temperature and time, less caustic required,
lower neutral oil entrapment in soapstock and less soapstock in oil (Chau et al.
1996). The objective of this work was to evaluate three new varieties of
sunflower in function of quality oil obtained with two solvents.
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The hexane extraction was carried out with 189 mL of solvent at 69.5C
during six cycles. The extraction with isopropyl alcohol was performed with
159 mL of solvent at 82C in six cycles.
Four different concentrations of miscella were used: 40, 50, 60 and 70%
for each variety of oil (three varieties) (concentrations were made volume to
volume). The miscella was prepared with the same solvent used for the
extraction, using 3% of silica under 60 rpm at 60C in all cases. FFA determination and the TBA test were performed according to Kirk et al. (1996).
Statistical Analysis
The experimental design used was a factorial 3 4 with two replicates for
each experimental run. One-way analysis of variance for data analysis was
applied and the means were tested with the Tukeys statistical test (P < 0.05).
RESULTS AND DISCUSSION
Yield Values in Crude Oil
Crude oil yields from hexane and isopropyl alcohol extractions are shown
in Table 1. The type of solvent and seed variety did not influence the yield.
Yield values can be positively compared with Russian reports on yields around
48.5% (Gordon and Vick 1997).
FFA in Crude Oil
Marked differences were found in the acidity of crude oils extracted from
the three varieties with isopropyl alcohol. Madero-91 seeds afforded an oil
with the highest values of FFA (0.48% expressed as oleic acid), while Victoria
seeds oil was the lowest (0.29% expressed as oleic acid); Cianoc-2 showed a
medium value (0.32% expressed as oleic acid). The oils extracted with hexane
from Victoria and Madero-91 seeds showed a similar value of FFA (0.21%
expressed as oleic acid), while Cianoc-2 oil exhibited a lower value (0.18%
expressed as oleic acid).
The acidity differences may be explained by the different polar components content in the crude oils. This is accentuated by the type of solvent, i.e.,
isopropyl alcohol-extracted oils were more acidic than the hexane-extracted
oils. Hexane polarity is zero, while isopropyl alcohol is about 0.2. Hexane
then, is more likely to interact with neutral compounds as triacylglycerides,
while isopropyl alcohol interacts easier with phospholipids and some fatty
acids. According with the official Mexican norm, FFA values should not be
superior to 0.55%; then, only the variety Madero-91 extracted with isopropyl
alcohol is not acceptable.
40.21 3.9
44.43 6.8
38.40 2.6
Sample
Victoria
Madero-91
Cianoc-2
0.017 0.001
0.009 0.0012
0.011 0.009
Malonic aldehyde
(hexane) (mg/L)
0.016 0.009
0.025 0.007
0.020 0.007
Malonic aldehyde
(isopropyl alcohol) (mg/L)
TABLE 1.
CRUDE OIL YIELD AND MALONIC ALDEHYDE OBTAINED IN EXPERIMENTAL SAMPLES (MEAN SD)
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Sample
Victoria
Madero-91
Cianoc-2
Miscella concentration
76.44 8.0
69.72 2.7
73.40 4.5
79.50 2.0
74.97 3.5
85.05 4.2
83.80 1.1
83.42 8.4
77.63 1.9
76.30 6.0
88.44 2.7
85.76 4.3
70
54.97 4.5
45.49 0.1
58.83 5.4
69.64 1.0
52.66 5.3
55.02 6.5
50
69.64 4.5
55.00 6.7
64.69 6.3
60
40
60
40
50
TABLE 2.
REFINED OIL YIELD RESULTS FOR ALL REFINING CONDITIONS USED (MEAN SD)
71.02 7.9
63.02 1.9
67.15 1.2
70
SAMPLE
Victoria
Madero-91
Cianoc-2
Miscella concentration
0.36 0.00
0.36 0.01
0.36 0.00
0.36 0.00
0.36 0.00
0.36 0.00
0.36 0.00
0.41 0.02
0.36 0.00
0.33 0.03
0.36 0.00
0.40 0.03
70
0.36 0.00
0.36 0.00
0.36 0.01
0.36 0.00
0.36 0.00
0.36 0.00
50
40
60
40
50
TABLE 3.
FREE FATTY ACIDS IN REFINED OIL (MEAN SD)
0.76 0.00
0.36 0.00
0.36 0.00
60
0.55 0.00
0.36 0.00
0.55 0.00
70
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J.-A. GALLEGOS-INFANTE ET AL.
Sample
Victoria
Madero-91
Cianoc-2
Miscella
concentration
0.023 0.000
0.042 0.000
0.010 0.000
0.012 0.001
0.005 0.000
0.008 0.000
0.0125 0.000
0.012 0.000
0.007 0.001
0.03 0.000
0.038 0.000
0.006 0.000
70
0.01 0.000
0.01 0.000
0.015 0.000
0.025 0.000
0.005 0.000
0.014 0.000
50
40
60
40
50
TABLE 4.
MALONIC ALDEHYDE FOUND IN REFINED OIL (MEAN SD)
0.003 0.000
0.006 0.000
0.010 0.000
60
0.032 0.000
0.02 0.000
0.004 0.000
70
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more acidic than the one extracted with hexane, 0.180 versus 0.040 (as % of
oleic acid) respectively, and the acidity levels were higher in crude oils than in
refined ones (Chau et al. 1996).
Miscella concentration was a factor for the acidity index in both solvents.
The observed tendency was a higher acidity in refined oils with more diluted
miscellas (60, 70%). The low viscosity of these suspensions eases the interaction among the adsorbent (silica) and the adsorbates (polar compounds). In
higher concentrated miscellas (40, 50%), the viscosity plays a role in avoiding
such interaction (Mndez Montealvo 1994). The refined oils with different
miscellas are acceptable except for variety Victoria oil extracted with isopropyl alcohol and refined with miscella at 60%, with an acidity of 0.76% of oleic
acid.
Malonaldehyde Contained in Refined Oil
The malonaldehyde content for the sunflower seeds is shown in Table 4.
Variety, miscella concentration and solvent type have influence in malonaldehyde content. The higher content was present in Madero-91 oil refined with
hexane and miscellas of 40 and 70%. One of the explanations for this is the
recommendation on using middle concentrated miscellas. If they are concentrated, suspension viscosity impedes the interaction between the adsorbent and
malonaldehyde. If miscellas are diluted, malonaldehyde is far away from the
adsorbent particles (Mndez Montealvo 1994). Thus, more concentrated miscellas, i.e., 70%, make molecular diffusion easy and favor oil solubility and
FFA extraction.
ACKNOWLEDGMENTS
This project was funded by CONACyT-SIVILLA, Grant No.
20000401012. We acknowledge the donation of sunflower seeds from Daniel
Gomez Sanchez.
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