You are on page 1of 7

Journal of Food Engineering 102 (2011) 348–354

Contents lists available at ScienceDirect

Journal of Food Engineering
journal homepage: www.elsevier.com/locate/jfoodeng

Fractionation of citronella (Cymbopogon winterianus) essential oil
and concentrated orange oil phase by batch vacuum distillation
Stephani C. Beneti a, Eline Rosset a, Marcos L. Corazza b, Caren D. Frizzo c, Marco Di Luccio a,
J. Vladimir Oliveira a,⇑
a
Department of Food Engineering, URI – Campus de Erechim, Av. Sete de Setembro, 1621, Erechim 99700-000, RS, Brazil
b
Department of Chemical Engineering, Paraná Federal University, Curitiba, PR, Brazil
c
Aripê Citrus Ltda, RS 124-Km 1.2, Bairro Estação, Montenegro 95780-000, RS, Brazil

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

Article history: The aim of this work was to assess the performance of a vacuum fractionating column for the fraction-
Received 24 May 2010 ation of citronella essential oil and concentrated orange oil phase during batch mode operation at differ-
Received in revised form 26 July 2010 ent pressures, from 20 to 1 mbar and reflux ratios from 1:1 to 10:1. Fractions from column top and
Accepted 20 September 2010
bottom were analyzed by gas chromatography (GC/FID) using authentic standards of major constituents
Available online 25 September 2010
of the oils. Good fractionation results for citronella essential oil were achieved, affording complete
removal of limonene, with a rich citronellal fraction and an output stream constituted mainly by citronel-
Keywords:
lol and geraniol. Likewise, the use of the vacuum fractionation column allowed almost complete removal
Citronella
Cymbopogon winterianus
of limonene (0.7 wt% at column bottom) from the orange oil phase at the lowest operating pressure,
Fractionation 1 mbar, while the higher valencene content (20.5 wt%) was obtained at 10 mbar and reflux ratio of 1:1.
Essential oil Ó 2010 Elsevier Ltd. All rights reserved.
Vacuum distillation
Orange oil phase
Orange essence

1. Introduction The orange oil phase or orange essence (Citrus sinensis) is an
important by-product obtained as the distillate, together with
Citronella is the common name of plants of the genus Cymbopo- orange aqueous phase, from the second stage of the evaporator
gon, popularly known by its characteristic insect repellent feature during the concentration of fresh orange juice (Moshonas and
(Rocha et al., 2000). The oil of citronella is composed mostly by Shaw, 1990). Monoterpenes, such as limonene, do not contribute
monoterpenes (±80%), although sesquiterpenes are also found. Cit- much to the flavor and are relatively unstable to heat and light
ronellal, citronellol and geraniol are the major terpenoids found in and insoluble in water; thus, it is often necessary to remove such
the citronella essential oil and are used as starting materials for the class of compounds, towards enrichment of the oxygenated com-
synthesis of fragrances (Bauer et al., 2001). Geraniol is a colorless, pounds, a fraction of much more industrial interest (Guenther
odor pleasant compound (aroma of roses); it is widely used in et al., 1975; Veriotti and Sacks, 2002; Corazza, 2002; Fang et al.,
perfumery and as a flavor component of blackcurrant, muskmelon, 2009). Valencene is a sesquiterpene present in orange species, con-
red apple, orange, lemon, pineapple, watermelon and blueberry. tributes to its flavor and aroma and it can be oxidized via chemical
Citronellol also presents an odor of roses, although its fragrance or microbial route to produce nootkatone and nootkatol, which
is not so sophisticated when compared to that of geraniol (Guen- contributes to the grapefruit aroma (Lücker et al., 2004). Many
ther et al., 1975). It is also relatively more stable than geraniol sesquiterpenes are biologically active as precursors of other meta-
and is used in fragrances and in insect repellents (Guenther bolic with biological function and exhibit flavor and medicinal
et al., 1975). Citronellal or rhodinal is the major component of properties (Shaffer et al., 1975; Furusawa et al., 2005; Sowden
the monoterpene fraction of citronella oil and gives the essential et al., 2005).
oil of citronella its characteristic lemon odor (Bauer et al., 2001), Batch vacuum distillation works at mild temperatures and of-
being also used in many chemical syntheses (Lenardão et al., 2007). fers flexibility to operate with different oils in the same industrial
plant. According to Oisiovici (2001) the main advantages of batch
processes are the flexibility and versatility and also the possibility
⇑ Corresponding author. Tel.: +55 54 35209000; fax: +55 54 35209090. of operating with small volumes, thus allowing performing raw
E-mail address: vladimir@uricer.edu.br (J.V. Oliveira). material tests before large-scale processing. It is known that the

0260-8774/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2010.09.011
S.C. Beneti et al. / Journal of Food Engineering 102 (2011) 348–354 349

quality of distillate can be controlled through manipulation of re- item 1) equipped with a sampling pipette and a PT-100 probe
flux ratio, because higher reflux ratios cause the distillate to be en- (0.1 °C accuracy) (11) for temperature monitoring, surrounded by
riched in the lightest products (Adari and Jana, 2008; Reid et al., a heating mantle connected to a PID controller. The column bottom
1987). In fact, the reflux ratio is often used to keep the quality of was connected to a jacketed column (2), insulated by vacuum
a product, which is determined by market demand or required in (spaced 15 mm between internal and external walls), with an inner
the downstream processing (Adari and Jana, 2008). diameter of 15 mm and 1.5 m length. The column is packed with
Although the use of vacuum fractionating column for fraction- Raschig rings (2 mm diameter and 2 mm height). A double coil
ation of essential oils is widely known method information regard- condenser is positioned at the column top (4), in which a cold mix-
ing the fractionation of citronella oil (Cymbopogon winterianus) and ture of glycerin–water flows (5 °C) (12) to condense vapors from
concentrated orange oil phase was not found in the open literature the distillation column. The reflux was controlled by a solenoid
and thus may be of commercial relevance. Some works involving valve activated by an electromagnetic switch (3). A schematic dia-
Eucalyptus cinerea and Tagetes minuta L. (wild marigold) were re- gram of the experimental apparatus is depicted in Fig. 1.
cently reported (Babu and Singh, 2009; Babu and Kaul, 2007). To After leaving the reflux section, vapor phase passes through a
our knowledge, the essential oil industry only concentrates the cit- second condenser (5) and then follows to a sample collector (7).
ronella oil, without exploring the valuable fractions. Also, the con- The sampling system consisted of a 100 mL round-bottom flask
centrated oil phase can be enriched in valencene, which is a and manual control valves that allows the isolation of column
valuable product of interest to the industry. Given the importance without disturbing its vacuum pressure. This guarantees sampling
of such raw materials, the aim of this work was to investigate the without changing column operation. System pressure was main-
performance of a vacuum distillation column operated in batch tained by a high performance vacuum pump (Edwards, Model
mode for the fractionation of both essential oils, evaluating the ef- RV8, USA) and was monitored by an absolute pressure transducer
fects of vacuum pressure and reflux ratio on the chemical profile of (Smar, LD 301), with a precision of ±0.5 mm Hg connected to a por-
the distilled fraction during operation. table programmer (Smar, HT 201) for the pressure data acquisition.

2. Experimental 2.2. Evaluation of distillation column

2.1. Distillation column At first, some preliminary tests were carried out to assess the
operation procedure and check the reliability of the experimental
The vacuum fractionation column was built in borosilicate glass apparatus. Such tests were accomplished with a prepared ethanol
by FGG Ltda (São Paulo, SP, Brazil). The column consists of a (Merck, 99.9%) and bi-distilled water solution (40 wt% ethanol).
500 mL-reboiler – a three-necked rounded glass flask (Fig. 1, Concentration of ethanol in aqueous solutions was quantified by
means of density measurements (Anton Paar, DMA 4500, Digital
Density Meter), previously calibrated with standard ethanol–water
solutions at 25 °C. For the preliminary tests, the reboiler was
loaded with 300 g of ethanol–water solution and every 15 min
samples were collected from the top and bottom of the column,
4 and the ethanol content was determined. The operation conditions
of the tests carried out with ethanol–water mixtures are presented
3
in Table 1.
T

2.3. Fractionation of citronella essential oil

Citronella oil, obtained by hydrodistillation of the raw leaves,
5 was purchased at the local market. Batch distillation experiments
10 were carried out randomly covering the pressures of 5, 10 and
15 mbar and reflux ratios of 1:1, 5:1 and 10:1. The experimental
12
conditions were chosen based on differences in vapor pressure val-
6 ues of the major compounds of the oil, which were determined
through the Lee–Kesler correlation and Joback group contribution
2 7
method (Reid et al., 1987). Fractionation of citronella oil was per-
8

Table 1
Results of the distillation of ethanol–water mixtures in terms of ethanol exhaustion
and ethanol content in the last point before exhaustion.
13 9

Packing Reflux Pressure Exhaustion time of Mass fraction of
fill ratio (mbar)b ethanol (min) ethanol (wt%)
11
No No Ambient 75 77.4
1 No 1:1 Ambient 120 82.4
No 5:1 Ambient 225 82.7
Yesa No Ambient 60 83.7
Yes 1:1 Ambient 75 91.3
Yes 5:1 Ambient 135 95.1
Fig. 1. Schematic diagram of the batch-mode distillation column: (1) reboiler; (2) Yes 1:1 100 60 92.7
fractionation column; (3) reflux controller; (4) condenser; (5) secondary condenser Yes 5:1 100 75 94.6
for sample collecting; (6) vacuum control valve; (7) sample collecting flask; (8)
a
pressure transducer; (9) vacuum pump; (10) control panel; (11) PT-100 thermo Raschig rings.
b
resistance; (12) thermostatic water bath; and (13) foam-breaker. Ambient pressure 715 mm Hg.
350 S.C. Beneti et al. / Journal of Food Engineering 102 (2011) 348–354

formed without packing because preliminary assays led to great oil (Merck, 99% purity) with internal standard. The quantification of
retention in the packing fills, resulting in column flooding, an the compounds by GC/FID was carried out by injection of external
undesirable operating feature. standards and comparison of their retention times with their
Typically, about 300 g of the essential oil was loaded into the respective compounds. Calibration curves with authentic stan-
column bottom, and pressure was adjusted to the desired value. dards of limonene (Sigma–Aldrich, >99%) and valencene (90%, sup-
Then, the operation was started after 1 h of total reflux so as to al- plied by Aripê Citrus Ltda – Montenegro, RS, Brazil) were used for
low the stabilization of the whole equipment. Afterwards, a pre- quantification. All samples were stored at 5 °C prior to analysis.
established reflux ratio was set and samples of around 2 mL were Samples were prepared by dilution of 50 lL of sample up to 1 mL
collected from the top (distillate), every 30 min and in a non- with n-hexane (GC-Quality, Merck, SP, Brazil).
cumulative way, and operation proceeded until around 7-fold oil
(based on the mass of the original raw oil) was obtained.

3. Results and discussion
2.4. Fractionation of concentrated orange oil phase

3.1. Column validation with ethanol–water mixtures
The concentrated orange oil phase, obtained from the industrial
folding process of orange oil phase, kindly provided by Aripê Citrus
The performance of the fractionation column was evaluated
Ltda, was fractioned in the distillation column filled with Raschig
using ethanol aqueous solutions. Although it was not possible to
rings in an attempt to improve mass and heat transfer between va-
obtain anhydrous alcohol as product due to the azeotropic mixture
por and liquid phases (Ibarz and Barbosa-Cánovas, 2003). The
condition, results showed that the column could allow proper dis-
packing amount used was approximately 150 g, which means a
tillation of the aforementioned mixture, and thus served as guid-
column almost complete filled out, leaving only 5 cm height with-
ance regarding column operation to the subsequent step with the
out packing and totalizing a surface contact area of 1322 cm2. Frac-
oils. In general, at the beginning of the batch distillation, a rapid in-
tionation experiments were accomplished at varying operating
crease in the concentration of ethanol in the distillate was ob-
pressures, up to 1 mbar, and with the same reflux ratios used for
served, possibly due to the stabilization of the temperature
citronella oil. About 300 g of the concentrated orange oil phase
gradient in the column. Then, for a certain period of time, the con-
was charged into the column bottom.
centrations of ethanol and water at the column top do not change
with time, while the concentration of ethanol in the bottom flask
2.5. Chromatographic analysis of citronella essential oil
gradually decreases, with consequent increase of water content
in the reboiler with time.
The analysis of samples from the fractionation column was per-
The experimental conditions and results of ethanol–water batch
formed by gas chromatography (GC, Shimadzu 2010, with auto-
distillation are summarized in Table 1. One can see from this table
sampler, and flame ionization detector). A capillary polar column
that the best ethanol fractionation was obtained when the column
was used (RTx-wax, Restek 833, 551, 30 m  0.25 mm  0.25 lm).
was packed with Raschig rings and operated at the highest reflux
The temperature program of the column oven was 40 °C for 8 min,
ratio. This is an expected result since mass transfer was likely to
3 °C/min until 180 °C and 30 °C/min until 250 °C, holding at this
be improved in such condition. Compared to operation under vac-
temperature for 3 min. The temperature of the detector and injec-
uum pressure at the same reflux ratio, however, such operation
tor was 250 °C. Hydrogen was used as carrier gas, at a flow rate
condition means a much larger increased time for complete etha-
40 mL/min. The split ratio was 1:50 and the injected volume 1 lL.
nol stripping from the feed.
For qualitative identification of the compounds present in the
Thus, the use of low pressure (100 mbar) caused the operation
citronella oil, gas chromatography coupled to mass spectrometry
time to decrease, without causing appreciable losses of separation
was used (GC/MS, Shimadzu, model QP5050 A, Wiley library
performance. At a reflux ratio of 5:1, it was possible to obtain a
229). The same column and conditions used in the GC/FID were ap-
product with 94.6 wt% of ethanol in 75 min. However, the use of
plied to the GC/MS. Biphenyl (Merck, 99% purity) was used as
vacuum brought some complications to operation. The reduced
internal standard. The quantification of the compounds by the
pressure favored turbulent boiling, hence requiring a more effec-
GC/FID system was carried out by injection of external standards
tive temperature control in the reboiler to prevent mixture over-
and comparison of the retention times of the respective com-
heating in the column bottom.
pounds. Calibration curves with authentic standards of limonene,
citronellal, citronellol and geraniol (Sigma–Aldrich) were used for
quantification. All samples were stored at 5 °C prior to analysis.
Samples were prepared by dilution of 50 lL of sample up to 1 mL 3.2. Chemical composition of citronella essential oil
with n-hexane (GC-Quality, Merck, SP, Brazil).
The chromatogram of the raw essential oil of citronella obtained
2.6. Chromatographic analysis of concentrated orange oil phase by GC/MS analysis yielded the peaks identified by the mass spectra
library, which are presented in Table 2. Baranauskiene et al. (2006)
The GC/FID analysis of concentrated orange oil phase samples reported that citronella essential oil is major constituted by limo-
from the batch vacuum fractionation column was performed in nene 5.2%, citronellal 33.9%, citronellol 8.7% and geraniol 16.4%.
the same device mentioned above, but with a non-polar capillary In the present work, the content of citronellal, geraniol and citro-
column (DB-5, J&W Scientific, US7162944H, 30 m  0.25 nellol was found to be higher than that reported in literature,
mm  0.1 lm). The temperature program was 50 °C for 3 min whereas the amount of limonene was lower than the one reported
and 4 °C/min until 300 °C. The complete run time was 65.5 min. by Baranauskiene et al. (2006). As mentioned by Marco et al.
The temperature of the detector and injector was 280 °C. Hydrogen (2007) and Valle et al. (2004), wide compositional differences for
was used as carrier gas, at a flow rate 40 mL/min. The split ratio given essential oil species are not uncommon and divergences in
was 1:10 and the injected volume 1 lL. chemical content of the constituents may be explained in terms
GC/MS analysis to qualitative identification of the compounds of genetic variability, geographic localization, harvest time, climate
present in the oil was performed with the same device, column conditions, cultivation handling, age of vegetable material, period
and conditions employed in the GC/FID and also with biphenyl and storing conditions, among others (Farias, 1999).
S.C. Beneti et al. / Journal of Food Engineering 102 (2011) 348–354 351

Table 2 pounds of the oil (limonene, geraniol, citronellal, citronellol) in
Chemical composition of unprocessed citronella essential oil analyzed by GC/MS. the distillate stream is presented in Fig. 2 for experiments 1 (reflux
RTa (min) Area (%)b Identified compound ratio 1:1 and 5 mbar) and 2 (reflux ratio 1:1 and 15 mbar). This fig-
9.61 3.41 Limonene ure shows that limonene was the first compound to be removed
24.20 40.23 Citronellal from the system, with quick stripping from the batch feed, in such
27.06 0.97 l-Linalol way that for the condition of 5 mbar and reflux ratio of 1:1 it did
28.21 2.71 Elemene not even appear in the distillate after 30 min of operation and
31.52 4.58 Citronellyl acetate
32.64 1.75 Germacene
was practically absent in the column top for the same operation
33.78 1.13 Geranial/citral time in experiment 2.
34.57 2.87 d-Cadinene It should also be noted that citronellal was the next compound
35.02 4.67 Geranyl acetate collected in the distillate. Such time-separation results seem to be
35.84 13.39 Citronellol
coherent with vapor pressure values of the pure compounds (a
38.76 17.70 Geraniol
44.96 1.82 1,6-Germacradien-ol measure of relative volatility) previously estimated. The separation
46.18 4.77 Elemol of citronellol from geraniol was, on the other hand, not effective, as
a
also expected from the slight differences of vapor pressure of such
Retention time.
b
Standard deviations <5%.
compounds. This behavior may be attributed to the great similarity
of these two molecules. Nevertheless, geraniol was slightly more
concentrated due to its higher volatility compared to citronellol.
3.3. Fractionation of citronella essential oil Results of experiments 3 (reflux ratio 10:1 and 5 mbar) and 4
(reflux ratio 10:1 and 15 mbar) are shown in Fig. 3. The same com-
Although the experimental results conducted with ethanol– ments made for experiments 1 and 2 in Fig. 2 are applicable, with
water solutions showed that the use of a packed column led to a the exception that distillation time was longer than that performed
very satisfactory separation performance, experiments with citro- with reflux ratio of 1:1, thus impacting on the concentration profile
nella oil could not be performed with the packed column. This oc- of the compounds; e.g., limonene removal was not as fast as previ-
curred due to the characteristics of the essential oil, with intense ously registered. In experiment 4, carried out with the highest level
foaming during solution boiling. Indeed, the foam formation was of reflux ratio (10:1) and pressure (15 mbar), the total time for
so intense that the foam-breaker device at the column bottom fractionation of the compounds was 330 min, while in experiment
(reboiler) was not able to avoid column flooding. 3 it was 240 min. Lower operation time may be beneficial, because
As citronella essential oil was concentrated up to about 7-fold, in addition to higher productivity, the compounds of the essential
the operation time depended on the system pressure and on the re- oil are exposed to high temperatures for shorter times, hence
flux ratio. It is worth mentioning that in all experimental runs, the decreasing possible thermal degradation. Concentrations of gera-
four major compounds of citronella oil were almost completely re- niol and citronellol were higher in experiment 3 when compared
moved from the feed and collected in the distillate. to those found in experiment 4, but in both cases a satisfactory
Based on the mass balance accounting for the oil collected in separation of the two compounds could not be achieved. Though
the top (samples and cumulative) and retained in the column bot- operation with the highest reflux ratio (10:1) required more time
tom, the amount of essential oil retained on the distillation column for compounds to exit the distillation column, the concentration
walls was estimated between 5 and 8 wt% of the whole mass of the of each fraction in the distillate was slightly higher in comparison
starting oil. The changes in the composition of the major com- with the experiments carried out at lowest reflux ratio (1:1).

100
Compound - Run
Limonene - 1
Citronellol - 1
Geraniol - 1
80
Citronellal - 1
Limonene - 2
Citronellol - 2
Geraniol - 2
60 Citronellal - 2
Content (wt%)

40

20

0
0 30 60 90 120 150 180
Time (min)

Fig. 2. Time-course of chemical composition of citronella essential oil distillate for experiment 1 (reflux ratio 1:1 and 5 mbar) and experiment 2 (reflux ratio 1:1 and
15 mbar). The content at 0 min is the composition of distillate after 1 h stabilization.
352 S.C. Beneti et al. / Journal of Food Engineering 102 (2011) 348–354

100
Compound - Run
Limonene - 3
Citronellol - 3
80 Geraniol - 3
Citronellal - 3
Limonene - 4
Citronellol - 4
Geraniol - 4
60 Citronellal - 4
Content (wt%)

40

20

0
0 30 60 90 120 150 180 210 240 270 300 330
Time (min)

Fig. 3. Time-course of chemical composition of citronella essential oil distillate for experiment 3 (reflux ratio 10:1 and 5 mbar) and experiment 4 (reflux ratio 10:1 and
15 mbar).

Results presented in Figs. 2 and 3 show that a decrease in sys- file of the four major compounds in the cumulated sample of
tem pressure, keeping the reflux ratio constant, decreased the experiment 6 over time is presented in Fig. 5, where one can see
operation time. Of course, lower operation pressure increases vol- that removal of the four major compounds from the crude citro-
atilization of the liquid mixture (by reducing the solution boiling nella oil seems to be possible and also that proper manipulation/
point temperature), thus accelerating the distillation process. operation of distillation column might afford three reasonably sep-
The good reproducibility achieved for the triplicate runs carried arated fractions of the oil.
out at 10 mbar and 5:1 reflux ratio is shown in Fig. 4, thus assuring
the reliability of the experiments conducted in the batch distilla- 3.4. Chemical composition of concentrated orange oil phase
tion column. The separation sequence followed the same order of
the other tests, i.e., limonene was the first collected, followed by The peaks of major compounds in the chromatogram of concen-
citronellal, citronellol and geraniol. It should be noted that for all trated orange oil phase obtained by GC/MS analysis, identified
experimental conditions limonene was easily removed from the through comparison with the mass spectra library are presented
essential oil of citronella. For completeness, the concentration pro- in Table 3. The concentration of limonene in the orange oil phase

100
Compound - Run
Limonene - 5
Citronellol - 5
Geraniol - 5
80 Citronellal - 5
Limenone - 6
Citronellol - 6
Geraniol - 6
Citronellal - 6
60
Content (wt%)

Limonene - 7
Citronellol - 7
Geraniol - 7
Citronellal - 7
40

20

0
0 30 60 90 120 150 180 210 240 270 300
Time (min)

Fig. 4. Time-course of chemical composition of the distillate of citronella essential oil for the triplicate runs 5, 6 and 7 (reflux ratio 5:1 and 10 mbar).
S.C. Beneti et al. / Journal of Food Engineering 102 (2011) 348–354 353

90

Limonene
80 Citronellol
Geraniol
Citronellal
70

60
Content (wt%)
50

40

30

20

10

0
0 30 60 90 120 150 180 210 240
Time (min)

Fig. 5. Time-course of chemical composition of cumulative distillate of citronella essential oil for experiment 6 (reflux ratio 5:1 and 10 mbar).

Table 3 Table 4
Chemical composition of unprocessed concentrated orange oil phase analyzed by Results obtained for the batch vacuum fractionation of concentrated orange oil phase
GC/MS. in terms of limonene and valencene concentrations in the column top and bottoma.
RTa (min) Area (%)b Identified compound Experimental Content – column top Content – column Oil losses
8.72 14.68 Limonene condition (wt%) bottom (wt%) (wt%)
11.60 5.30 Linalool Limonene Valencene Limonene Valencene
14.93 2.97 a-Terpineol
15.23 6.81 n-Decanal R = 1:1
16.06 3.43 Trans-carveol 10 mbar 14.2 2.3 0.9 20.5 12.1
16.72 6.29 Carvone 5 mbar 17.2 2.6 0.9 18.2 10.8
18.02 2.84 Neral R = 5:1
20.79 2.15 a-Copaene 1 mbar 23.7 3.9 0.7 18.3 11.9
24.75 20.48 Valencene 5 mbar 19.1 3.5 1.1 17.3 13.9
25.59 1.57 d-Cadinene 20 mbar 22.9 1.7 3.0 16.0 8.7
27.46 1.03 Caryophyllene oxide
R = 10:1
34.37 0.63 Nootkatone
20 mbar 16.3 1.2 1.9 17.2 7.7
a
Retention time. 5 mbar 17.8 1.8 0.8 17.9 6.7
b
Standard deviations <5%. a
Content in the raw concentrated orange oil phase loaded into the reboiler:
valencene (13.9 wt%) and limonene (8.3 wt%). Standard deviation <1%.

is ranges from 92 to 95 wt% (Moshonas and Shaw, 1990). It is
important to mention that orange oil phase is a distillate recovered
ange oil phase even with the use of low operating pressures, col-
from the volatile fraction of the second stage of the orange juice
umn bottom temperatures reached up to 200 °C, an undesirable
evaporation. Thus, it contains substances of flavor of the freshly
feature due to possible thermal degradation of the processing
squeezed juice and residual contents of cold-pressed orange oil
material. Moshonas and Shaw (1979) pointed out that the fractions
where the limonene is present as the major component, typically
present in the orange oil that contribute to aroma flavor possess
around 95 wt% (Oliveira et al., 2001; Lopes et al., 2003). To our
high boiling point.
knowledge, no previous work regarding the chemical composition
The temperature difference between column top and bottom
of the concentrated orange oil phase was found in the open litera-
(reboiler) was noticed to reach in some cases up to 50 °C, with a
ture. The concentration of valencene in non-concentrated Brazilian
clear distinction in color, becoming progressively intensified gold
orange oil phase is 0.25% (area percent) (Moshonas and Shaw,
yellow as distillation evolves, with a stronger characteristic odor
1990) but increases to 20.5% (area percent) after industrial concen-
of sesquiterpenes in the remaining oil. The orange oil phase could
tration. One should notice that valencene and nootkatone, com-
be concentrated only up to 1.5-fold because greater heat charges
pounds of great commercial interest, are originally present in
might lead to thermal degradations.
such oil.
Table 4 shows that the content of limonene was verified to in-
crease from 8.3 wt% (8.6% area) in the original oil to 23 wt%
3.5. Orange oil phase (33.9% area) in the column top with only 1 wt% remained at the
column bottom, while the concentration of valencene was raised
Although the experimental results obtained for ethanol–water from 14 wt% (27.6% area) in the original oil to 21 wt% (44.9% area)
solutions showed that the use of the column packing provided at the column bottom with a maximum concentration of 3 wt%
superior separation performance, in the case of concentrated or- (7.0% area) at the column top.
354 S.C. Beneti et al. / Journal of Food Engineering 102 (2011) 348–354

One should also notice from Table 4 that the reflux ratio did not Babu, G.D.K., Singh, B., 2009. Simulation of Eucalyptus cinerea oil distillation: a study
on optimization of 1,8-cineole production. Biochemical Engineering Journal 44,
have a relevant effect on the valencene concentration. This behav-
226–231.
ior is possibly due to the higher viscosity observed and higher boil- Corazza, S., 2002. Aromacologia: Uma Ciência de Muitos Cheiros. Editora SENAC, São
ing point of concentrated orange oil phase when compared to the Paulo.
citronella oil, which caused the orange oil to flow direct to the sam- Fang, T., Goto, M., Sasaki, M., Hirose, T., 2009. Combination of supercritical CO2 and
vacuum distillation for the fractionation of bergamot oil. Journal of Agricultural
pling system before reaching the condenser at the column top. and Food Chemistry 52, 5162–5167.
The highest valencene concentration was obtained at the condi- Farias, M.R., 1999. Farmacognosia da planta ao medicamento: Avaliação da
tion of 10 mbar and 1:1 reflux ratio, 20.5 wt%, representing a 50% Qualidade de matéria primas vegetais, UFSC e UFRGS, Ed. Porto Alegre, Brazil.
Furusawa, M., Hashimoto, T., Noma, Y., Asakawa, Y., 2005. Biotransformation of
valencene enrichment compared to the unprocessed orange oil. citrus aromatics nootkatone and valencene by microorganisms. Chemical and
However, some valencene losses (3.9 wt%) were verified to occur Pharmaceutical Bulletin 53, 1423–1429.
at the column top, especially at 1 mbar and 5:1 reflux ratio. Also, Guenther, E., Althausen, D., Sterrett, F.S., 1975. The Essential Oils. Krieger Publishing
Company, I, II, Florida, USA.
some important oil amounts were verified to remain in the frac- Ibarz, A., Barbosa-Cánovas, G.V., 2003. Unit Operations in Food Engineering. Food
tionation column, mostly adhered to the packing fills. No previous Preservation Technol Series. CRC, Washinton, DC.
works were found in the literature concerning the concentration of Lenardão, E.J., Botteselle, G.V., Azambuja, F., Perin, G., Jacob, R.G., 2007. Citronellal as
key compound in organic synthesis. Tetrahedron 63, 6671–6712.
orange oil towards enrichment of valencene. Lopes, D., Raga, A.C., Stuart, G.R., Oliveira, J.V., 2003. Influence of vacuum distillation
parameters on the chemical composition of a 5-fold sweet orange oil (Citrus
4. Conclusions sinensis Osbeck). Journal of Essential Oil Research 15, 408–411.
Lücker, J., Bowen, P., Bohlmann, J., 2004. Vitis vinifera terpenoid cyclases: functional
identification of two sesquiterpene synthase cDNAs encoding (+)-valencene
In this work we investigated the performance of a vacuum dis- synthase and ( )-germacrene D synthase and expression of mono- and
tillation column operated in batch mode for the fractionation of sesquiterpene synthases in grapevine flowers and berries. Phytochemistry 65,
2649–2659.
citronella and concentrated orange oil phase essential oils. The Marco, C.A., Innecco, R., Mattos, S.H., Borges, N.S.S., Nagao, E.O., 2007. Essential oil
process was very effective in the fractionation of citronella oil, characteristics from citronella grass depending on planting space, cutting
and the optimum conditions for fractionation was reflux ratio height and harvesting time. Horticultura Brasileira 25, 429–432.
Moshonas, M.G., Shaw, P.E., 1979. Composition of essence oil from overripe orange.
10:1 and 5 mbar, yielding two fractions, one rich in citronellal Journal of Agricultural and Food Chemistry 27, 1337–1339.
and the other rich in geraniol and citronellol. For concentrated or- Moshonas, M.G., Shaw, P.E., 1990. Flavor and compositional comparison of orange
ange oil fractionation, it was possible to obtain an optimum frac- essences and essence oils produced in the United States and in Brazil. Journal of
Agricultural and Food Chemistry 38 (3), 799–801.
tion rich in valencene (20.5 wt%) at 10 mbar and 1:1 reflux ratio.
Oisiovici, R.M., 2001. On-line Control of Batch Distillation Columns, Ph.D. thesis (in
Portuguese). Universidade Estadual de Campinas, Campinas, São Paulo, Brazil.
Acknowledgments Oliveira, J.V., Stuart, G.R., Lopes, D., 2001. Deterpenation of Brazilian orange peel oil
by vacuum distillation. Journal of American Oil Chemists Society 78, 1041–
1044.
The authors thank Dr. Lourdes Cabral from CTAA/EMBRAPA for Reid, R.C., Prausnitz, J.M., Poling, B.E., 1987. The Properties of Gases and Liquids,
the chromatographic standards and Secretaria de Ciência e Tecno- fourth ed. McGraw-Hill, New York, USA.
logia/RS and CNPq for the financial support and scholarships. Rocha, S.F.R., Ming, L.C., Marques, M.O.M., 2000. The influence of drying
temperature on the yield composition of citronella (Cymbopogon winterianus
Jowitt) essential oil. Revista Brasileira Plantas Medicinais 3, 73–78.
References Shaffer, G.W., Eschinasi, E.H., Purzycki, K.L., Doerr, A.B., 1975. Oxidations of
valencene. Journal of Organic Chemistry 40, 2181–2185.
Adari, P.V., Jana, A.K., 2008. Comparative control study of a high-purity ternary Sowden, R.J., Yasmin, S., Rees, N.H., Bell, S.G., Wong, L.L., 2005. Biotransformation of
batch distillation. Chemical Product and Process Modeling 3, 1–20. the sesquiterpene (+)-valencene by cytochrome P450cam and P450BM-3.
Baranauskiene, R., Venskutonis, P.R., Dewettinck, K., Verhé, R., 2006. Properties of Organic and Biomolecular Chemistry Oxford 3, 57–64.
oregano (Origanum vulgare L.), citronella (Cymbopogon nardus G.) and marjoram Valle, J.M., Godoy, C., Asencio, M., Aguilera, J.M., 2004. Recovery of natural
(Majorana hortensis L.) flavors encapsulated into milk protein-based matrices. antioxidants from boldo (Peumus boldus M.) using conventional solvents and
Food Research International 39, 413–425. supercritical CO2 extraction. Food Research International 37, 695–702.
Bauer, K., Garbe, D., Surburg, H., 2001. Common Fragrance and Flavor Materials. Veriotti, T., Sacks, R., 2002. High-speed characterization and analysis of orange oils
Preparation, Properties and Uses, fourth ed. Wiley-VCH, Germany. with tandem-column stop-flow GC and time-of-flight MS. Analytical Chemistry
Babu, K.G.D., Kaul, V.K., 2007. Variations in quantitative and qualitative Michigan 74, 5635–5640.
characteristics of wild marigold (Tagetes minuta L.) oils distilled under
vacuum and at NTP. Industrial Crops and Products 26, 241–251.