Beruflich Dokumente
Kultur Dokumente
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
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.
2.1. 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
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
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.
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%.
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
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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.
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