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Journal of Food Engineering xxx (2016) 1e5

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Fractionating of green mandarin (Citrus deliciosa Tenore) essential oil

by vacuum fractional distillation
W.P. Silvestre a, c, *, F. Agostini b, L.A.R. Muniz a, G.F. Pauletti c
Course of Chemical Engineering, Center of Exact Sciences and Technology, University of Caxias do Sul (UCS), Brazil
Institute of Biotechnology, University of Caxias do Sul, Brazil
Course of Agronomy, Center of Biological and Health Sciences, University of Caxias do Sul, Brazil

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

Article history: This work aims to evaluate the technical viability of vacuum fractional distillation to separate the
Received 14 August 2015 components of green mandarin (Citrus deliciosa Tenore) essential oil. Thermal degradation was also
Received in revised form analyzed. The obtained results demonstrate that vacuum fractional distillation is capable to separate the
29 December 2015
hydrocarbon terpenes, which were removed from the top/stages of the column, from the terpenes with
Accepted 14 January 2016
Available online xxx
other chemical functions, which remained in the bottom. Some trace compounds, such as methyl-N-
methyl anthranilate (mass fraction of 0,006 in the raw oil) and alpha sinensal (mass fraction of 0,004
in the raw oil), had their concentrations increased more than ten times after the separation, to mass
Fractioning column
fraction of 0,153 and 0,109, respectively. The mass fraction of the major compound of the essential oil, D-
Green mandarin essential oil limonene, was reduced from 0,707 in the raw oil, to 0,218 in the bottom. There was no evidence of
Terpenes thermal degradation in the products of the separation.
Vacuum distillation 2016 Elsevier Ltd. All rights reserved.

1. Introduction mixture of substances in the raw oil (Castro and Escobar, 2014;
Embrapa, 2004; Simo ~es et al., 2004).
The harvest of citrus fruits presents great importance world- The genetics of the plant determines its chemotype. However,
wide, as its production, in 2013, was approximately 111,5 millions of the environmental conditions (climate, soil type, presence of nu-
tons. The main citrus fruits are orange, lemon, mandarin and lime, trients) are capable of provoke considerable variations in the oil
which have a high commercial value as sell in nature or as a raw and in the very chemotype, featuring an ecotype (Dellacassa,
material for food industry (Castro and Escobar, 2014). 2010). Is also important highlight that the composition of the
The peel and the bagasse of citrus represent 40e50% of total essential oil obtained varies considerably between the parts of the
weight of the fruit and in general are waste of the processing of this plant, as well by the extractive process (Gamarra et al., 2006;
raw material, being both used as biomass. The bagasse is also used Simo ~es et al., 2004).
as component in animal feeding. The peel has many bioactive Bonaccorsi et al. (2009), Dugo et al. (2010) and Frizzo et al.
components, as ascorbic acid, terpenes and avonoids, which can (2004) characterized the chemical composition of the Citrus deli-
be extracted and after puried for various applications (Castro and ciosa Tenore essential oil obtained by cold pressing. The mandarin
Escobar, 2014; Lohbauer, 2014). essential oil is a mixture of terpenes and their oxygenated de-
The citrus essential oil is a mixture of terpenes, many of them rivatives. The volatile fraction of the mandarin oil obtained by cold
with important industrial applications, in medicine, pharmacology, pressing is between 96 and 98% of the whole oil. The essential oil
cosmetics and food industry (Bonaccorsi et al., 2009). Tough, to has, as main compounds, D-limonene, g-terpinene, linalool, citral,
have a practical application for the minority compounds (which, in mircene, among others (Bonaccorsi et al., 2009; Favretto et al.,
general, have more value), it is necessary to properly separate the 1999; Teixeira et al., 2013). The major compound is the D-limo-
nene, with a percentage of 60e98% m/m of the essential oil present
in the peel. The other compounds, as g-terpinene, a-pinene, sabi-
* Corresponding author. Laboratory of Chemistry and Soil Fertility, University of nene, mircene, linalol, are present in variable quantities, depending
Caxias do Sul, Road Francisco Getlio Vargas, 1135, Petropolis, 95074-270, Caxias do of the harvest, time of the year, location, among other factors
Sul, RS, Brazil. (Castro and Escobar, 2014; Favretto et al., 1999; Lota et al., 2014;
E-mail address: (W.P. Silvestre).
0260-8774/ 2016 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Silvestre, W.P., et al., Fractionating of green mandarin (Citrus deliciosa Tenore) essential oil by vacuum
fractional distillation, Journal of Food Engineering (2016),
2 W.P. Silvestre et al. / Journal of Food Engineering xxx (2016) 1e5

Simo ~es et al., 2004). kept at 2e5  C, using ice packs. The system and its instrumentation
The aldehydes, alcohols and ketones that generally appear as was controlled by a PLC Altus FBs-24MA (14 digital entrances and
minority compounds or as traces are important in the composition 10 digital exits) and by a computer through the software Winpro-
of the oil's avor, being products of high value when compared to ladder, aiming to automatize the system.
the other terpenes that form the mixture. Its applications go from
food industry to cosmetics and pharmaceutical industry 2.3. Fractionating tests
(Bonaccorsi et al., 2009; Stcker et al., 2011; Teixeira et al., 2013).
Between these compounds, there is methyl-N-methyl anthra- Initially, it was tried to check the separation level of the mixture
nilate, a compound used as a avoring agent and construction block compounds in function of the distillation time and the boiling
in organic chemistry (Opdyke, 1970). Another compound of interest temperature in the bottom of the column (ask), keeping the vac-
by the industry is the aldehyde a-sinensal, used in cosmetics, uum in a constant value of 10 kPa. For this, distillation tests were
perfume and in food industry (Smith et al., 2005). performed, gathering only vapor of the top of the column, with
Most terpenes are thermally unstable, decomposing or oxidizing collection time of 10 min, collecting part of the distillate for analysis
in high temperatures or in presence of light or oxygen (Simo ~ es et al., and discarding the remaining. It was utilized 120 mL of raw
2004). essential oil in each batch. The distillation was performed until the
The fractional distillation is a unit operation that aims the sep- volume of liquid in the ask reduced to near 10 mL. The collected
aration of two or more substances by the volatility difference be- samples were sent to GC/MS analysis.
tween them. This process depends of the pressure and temperature After, it searched to verify the distillate composition in function
of the system, as well the physical and chemical characteristics of of the quantity of stages the vapor passed. The column operated
the components to be separated (Foust et al., 1982). under vacuum (10 kPa) until the vapor reached the top of it. The
The literature is scarce about using the vacuum fractional boiling temperature of the oil at this pressure was between 80 and
distillation for to separate essential oil components. Farah et al. 90  C. Then, the solenoid valves were opened and the vapor in each
(2006) reports the use of the fractional distillation to separate stage was gathered until the volume in the distillation ask reduced
components of Myrtus communis L., with interesting results. to the minimum possible, aiming to obtain circa 25 mL of extract to
Although, vacuum was not applied (Farah et al., 2006). Castilo- each stage (and the minimum possible volume to the bottom
Herrera et al. (2007) reported the use of fractional distillation product), independently of the time necessary. The collected vapor
during the hydrodistillation process to obtain Lippia graveolens was condensed in cooled bottles (2e5  C), and the vapor temper-
H.B.K essential oil and to improve the phenolic fraction. The ature was also monitored. The obtained samples were sent to GC/
distillation column was placed between the distillation ask and MS analysis.
the Clevenger apparatus. The author also reports the phenolic
fraction improved due to the fractional distillation (Castilo-Herrera 2.4. Chromatographic analysis
et al., 2007).
One of the objectives of the vacuum fractional distillation is to The equipment used for the analysis as a gas chromatograph
verify a possible reduction of the degradation of the components of Hewlett Packard, model 6890 Series, equipped with a data pro-
the essential oil by the high temperature, problem also found in the cessor HP-Chemstation and using a HP Innowax column
extraction with water vapor (drag with vapor) and in the hydro- (30 m  320 mm i.d.) with lm thickness of 0,5 mm and a mass
distillation (Soto et al., 2014; Favretto et al., 1999). spectrometer Hewlett Packard, model MSD5973, equipped with a
The objective of this work is to evaluate the use of the vacuum software HP Chemstation and Wiley 275 spectral library, using a
fractional distillation to separate some compounds of the green capillary column of fused silica HP-Innowax (30 m  250 mm) with
mandarin (C. deliciosa Tenore) essential oil, in addition to verify the lm thickness of 0,5 mm.
effect of the pressure reduction in the boiling temperature of the The GC analysis was performed with column temperature of
mixture (raw essential oil). 40  C (8 min) to 180  C at 3  C/min, 180e230/C at 20  C/min and at
230  C for 20 min. Injector temperature was 250  C; split ratio of
2. Material and methods 1:50, ionization detector by ame with temperature of 250  C;
using hydrogen as carrier gas with ux of 1,0 mL/min, at 34 kPa. For
2.1. Obtainment of essential oil the quantication of the chemical compounds, it was utilized an
internal standard of 1-octanol at 30,22 g/mL (25 mL), mixed with
The green mandarin (C. deliciosa Tenore) essential oil was ob- hexane (75 mL) and with the sample to be analyzed (10 mL). The
tained by cold pressing of the peels, provided by EcoCitrus, located used volume for injection in the GC/MS was 1,0 mL.
in the city of Montenegro, in the state of Rio Grande do Sul, Brazil. The MS analysis was performed in a gas chromatograph coupled
The oil was produced in October of 2013, remaining stored in amber to a selective mass detector, as specied before. The used temper-
bottle, closed, in cold chamber (temperature between 1 and 6  C). ature program was the same as of the GC; interface of 280  C; split
ratio of 1:100, using helium as carrier gas at 56 kPa. The gas ux
2.2. Description of the distillation system was kept at 1,0 mL/min; ionization energy of 70 eV; the injected
volume was 1 mL of sample, diluted in hexane (1:10).
The fractionating system consisted of a glass column packed
with Raschig rings with 8 mm of diameter (packing height of 8 cm), 3. Results and discussion
in three stages. The column and extract gathering system were
coupled to a vacuum pump. The pump had a relief valve to adjust 3.1. Results of the fractionating tests
the vacuum of the system. An analogic vacuum gauge, localized in
the top of the column, measured the internal pressure thereof. The raw oil was analyzed to characterize it. Limonene and g-
Between each stage, electronic valves (solenoids) and PT-100 per- terpinene were the major compounds. This is a common chemo-
formed the gathering of the samples and measured the vapor type in the C. deliciosa Tenore essential oil (Dugo et al., 2010)
temperature, respectively. The solenoid valves, controlled by the (Table 1).
PLC, directed the vapor of each stage to the condenser, which was Through the distillation tests with removing only the top

Please cite this article in press as: Silvestre, W.P., et al., Fractionating of green mandarin (Citrus deliciosa Tenore) essential oil by vacuum
fractional distillation, Journal of Food Engineering (2016),
W.P. Silvestre et al. / Journal of Food Engineering xxx (2016) 1e5 3

Table 1
Composition (in mass fraction) of the mandarin essential oil obtained by cold pressing. The results obtained are compared to the ones presented by Bonaccorsi et al. (2009);
Frizzo et al. (2004) and Dugo et al. (2010).
a b c
Compound This work Bonaccorsi et al. (2009) Frizzo et al. (2004) Dugo et al. (2010)

a-Pinene 0,019 0,024 0,007 0,019

a-Tujene 0,007 0,009 0,003 0,006
b-Pinene 0,014 0,017 0,009 0,013
Sabinene 0,002 0,003 0,001 0,002
Mircene 0,016 0,017 0,015 0,014
a-Terpinene 0,002 0,004 0,008 0,003
Limonene 0,707 0,705 0,728 0,727
b-Phellandrene 0,002 0,001 e 0,001
g-Terpinene 0,194 0,195 0,180 0,184
p-Cymene 0,009 0,003 e 0,004
D-Terpinene 0,007 0,008 e 0,006
Linalool 0,002 0,002 0,002 0,001
b-Caryophylene 0,002 0,001 0,001 0,001
a-Terpineol 0,003 0,002 0,004 0,002
a-Farnesene 0,003 0,001 0,005 0,001
Methyl-N-methyl anthranilate 0,006 0,004 0,007 0,006
Thymol 0,001 0,001 0,002 0,001
a-Sinensal 0,004 0,004 0,006 0,003
The average value was considered.
The value for cold pressed Cai mandarin were considered, in the month of March (the nearest month to October, the month the oil for this work was obtained).
The corrected average of the peak areas was considered.

product (in intervals of 10 min between each sample collecting) the top product, with exception of the mircene, who stayed in the
and the bottoms (at the end of the batch), it was capable to make a ask (although the mass fraction was very low).
qualitative analysis of the more volatile compounds and of the However, the distillation time, as well as the batch regime can
products that stayed in the distillation ask. This was done to cause differences between the results (Nadais and Bernardo-Gil,
determine which compounds left the mixture rst and what of 1993). It is observed again the separation in terpenes and other
them were xed. The quantitative and qualitative evaluation aimed chemical classes, due to the physical and chemical properties of the
to verify the degree of separation in each distillate and its relation compounds in the same class be similar. In qualitative level, it was
with the raw essential oil (Table 2). not observed great deviations in relation to the prior tests, occur-
In relation to distillates gathered by column stage, the degree of ring a large presence of limonene and g-terpinene in the bottoms
separation is similar to the separation obtained by collecting only products (Table 3).
the top product. It is observed that the qualitative separation of the Beyond individual analysis, it was also aimed to observe the
compounds by stages is similar to the distillation tests removing composition of the fractions in terms of chemical functions to both

Table 2
Average mass fractionsa of the compounds in the raw oil, distillates and in the ask obtained in the distillation tests collecting only the top of the column and analyzed by GC/
MS. The grouping of the compounds in chemical classes is also presented.

Compound Raw oil Mass in raw oil (g) Distillate Bottom Mass in bottom (g) Recovery (%)b

1 2 3 4 5 6

a-Pinene 0,019 1,938 0,108 0,028 0,007 0,004 e e e e e

a-Tujene 0,007 0,714 0,046 0,009 0,002 e e e e e e
b-Pinene 0,014 1,428 0,036 0,031 0,013 0,007 0,003 0,004 e e e
Sabinene 0,002 0,204 0,019 0,005 0,003 e e e e e e
Mircene 0,016 1,632 0,037 0,032 0,020 0,013 0,008 0,005 e e e
a-Terpinene 0,002 0,204 0,200 0,005 0,005 0,004 0,003 0,002 e e e
Limonene 0,707 72,114 0,418 0,760 0,785 0,759 0,748 0,684 0,201 0,718 1,00
b-Phellandrene 0,002 0,204 0,041 0,002 0,002 0,002 0,002 0,002 e e e
g-Terpinene 0,194 19,788 0,089 0,119 0,152 0,195 0,218 0,279 0,217 0,775 3,91
p-Cymene 0,009 0,918 0,004 0,006 0,007 0,007 0,008 0,009 0,003 0,011 1,17
D-Terpineno 0,007 0,714 0,002 0,003 0,004 0,007 0,008 0,012 0,027 0,096 13,50
Linalool 0,002 0,204 e e e 0,002 0,002 0,003 0,013 0,046 22,75
b-Caryophylene 0,002 0,204 e e e e e e 0,059 0,214 99,75
a-Terpineol 0,003 0,306 e e e e e e 0,085 0,303 99,17
a-Farnesene 0,003 0,306 e e e e e e 0,085 0,303 99,17
Methyl-N-methyl anthranilate 0,006 0,612 e e e e e e 0,170 0,607 99,17
Thymol 0,001 0,102 e e e e e e 0,028 0,100 98,00
a-Sinensal 0,004 0,408 e e e e e e 0,114 0,407 99,75
Chemical classes
Hydrocarbon terpene 0,984 100,368 1,000 1,000 1,000 0,998 0,998 0,997 0,59 2,106 2,10
Alcohol 0,005 0,510 e e e 0,002 0,002 0,003 0,098 0,350 68,60
Phenol 0,001 0,102 e e e e e e 0,028 0,100 98,00
Aldehyde 0,004 0,408 e e e e e e 0,114 0,407 99,75
Amine/ether 0,006 0,612 e e e e e e 0,170 0,607 99,17
The marker e indicates absence of the substance in the fraction.
Of the bottom relative to the raw oil.

Please cite this article in press as: Silvestre, W.P., et al., Fractionating of green mandarin (Citrus deliciosa Tenore) essential oil by vacuum
fractional distillation, Journal of Food Engineering (2016),
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Table 3
Average mass fractionsa obtained in each of the stages of the column.

Average mass fraction

Compound Raw oil Mass in raw oil (g) Top Second stage First stage Bottom Mass in bottom (g) Recovery (%)

a-Pinene 0,019 1,938 0,037 0,005 e e e e

a-Tujene 0,007 0,714 0,013 0,003 e e e e
b-Pinene 0,014 1,428 0,033 0,011 0,005 e e e
Sabinene 0,002 0,204 0,006 0,002 e e e e
Mircene 0,016 1,632 0,032 0,018 0,008 0,003 0,019 1,17
a-Terpinene 0,002 0,204 0,005 0,004 0,003 e e e
Limonene 0,707 72,114 0,753 0,771 0,706 0,380 2,384 3,31
b-Phellandrene 0,002 0,204 0,002 0,002 0,002 0,001 0,006 3,13
g-Terpinene 0,194 19,788 0,110 0,172 0,256 0,284 1,811 9,15
p-Cymene 0,009 0,918 0,006 0,006 0,005 0,004 0,026 2,78
D-Terpineno 0,007 0,714 0,003 0,006 0,012 0,023 0,147 20,54
Linalol 0,002 0,204 e e 0,003 0,011 0,070 34,38
b-Caryophylene 0,002 0,204 e e e 0,031 0,198 96,88
a-Terpineol 0,003 0,306 e e e 0,031 0,306 100,00
a-Farnesene 0,003 0,306 e e e 0,052 0,306 100,00
Methyl-N-methyl anthranilate 0,006 0,612 e e e 0,101 0,606 98,96
Thymol 0,001 0,102 e e e 0,017 0,102 100,00
a-Sinensal 0,004 0,408 e e e 0,062 0,395 96,88
Chemical classes
Hydrocarbon terpene 0,984 100,368 1,000 1,000 0,997 0,778 4,896 4,88
Alcohol 0,005 0,510 e e 0,003 0,042 0,376 73,75
Phenol 0,001 0,102 e e e 0,017 0,102 100,00
Aldehyde 0,004 0,408 e e e 0,062 0,395 96,88
Amine/ether 0,006 0,612 e e e 0,101 0,606 98,96
The marker e indicates absence of the substance in the fraction.

tests and what would be the separation pattern. As noted earlier, is as we can see the recovery of linalool was poor (22,75%) when
visible the separation of the oil in hydrocarbon terpenes and in the compared to the other compounds, with recoveries greater than
other chemical functions which, due to intermolecular interactions, 95%.
tend to have higher boiling points (Soto et al., 2014), staying in the
distillation ask. It is remarkable that, both in the rst distillations
than in the superior stages, the distillates were composed exclu-
sively by hydrocarbon terpenes. The only chemical function that
was detected outside the bottoms product was the alcohol function 3.2. Evaluation of the oil thermal stability
(linalool), being detected in the nal stages of the separation
process. Both distillates and bottom products were analyzed by GC/MS.
The main difference between the raw oil and the distillates was None of the distillates presented evidences of thermal degradation
the visual appearance. The raw oil extracted by pressing has a dark nor oxidation of its compounds when compared to the raw oil, with
green coloration, characteristic of the fruit's peel. The distillate is no different compound appeared in these fractions.
colorless, presenting no visual relation to the oil of origin. The The bottom products, when analyzed by MS, also did not pre-
bottom product, due to the increase in the concentration of colored sent oxidation and decomposition evidences. Oxides of limonene
compounds and due to the temperature, has a dark color and a high and terpinene were detected in considerably low concentrations
viscosity. (mass fraction lesser than 0,01) in some bottom products. In these
The visual appearance gives to the distilled oil a better appli- products, it was observed the appearing of these substances, which
cability in the industry, because it prevents an unwanted coloration were not detected by the GC/MS analysis in the raw oil, neither in
of the products who use the oil as a raw material (Gamarra et al., the tests of gathering top product (Table 5).
2006). In sensory context, the distillates present a considerably The low mass fraction of these compounds can indicate a small
different aroma compared to the raw oil, while the bottom product degradation of the oil, or can be trace compounds, which, due to the
has a very sharp odor (Oliveira et al., 2011; Stcker et al., 2011). low concentration, could not be detected in the raw oil. Bonaccorsi
The presence of aldehydes, alcohols and phenols in the bottoms et al. (2009) and Dugo et al. (2010) report these compounds as trace
products, compounds who are responsible to the nuance of the raw compounds in cold pressed mandarin peel oil. Librando and
oil aroma, ends to sharp the aroma of the concentrated product in Tringali (2005), in a work regarding the oxidation of a-pinene,
the ask. This concentrated product, due to its composition, is of presents the role of ozone, hydroxyl radical and UV light in the
the interest of the industry, despite its color, which, depending on oxidation of terpenes, more than moderate heating. The concen-
its application, must be removed (Favretto et al., 1999; Gamarra tration of the bottom product by removing the light terpenes,
et al., 2006; Simo~es et al., 2004). decreasing more than 90% of the initial volume of the raw oil, al-
Among the compounds who stayed in the ask, it was observed lows that trace compounds, before undetectable by the GC/MS,
that the mass fractions of some of them were increased up to 25 could be detected, making it difcult to analyze the results
times in relation to the mass fraction in the raw essential oil, (Favretto et al., 1999; Lota et al., 2014; Stcker et al., 2011).
indicating the potentialities of the process (Table 4). Among these It is more probable that these compounds were already in the
compounds, it is remarkable an increase of the mass fraction of the raw oil as trace compounds than being products of the exposition of
methyl-N-methyl anthranilate, thymol and a-sinensal, when the raw oil to heat and oxygen during the operation of the column.
compared to the raw oil. Despite of the large increase in the mass If degradation exists, it is very low, not harming the quality of the
fraction, the concentration effect can provoke interpretation errors, products obtained by vacuum fractional distillation.

Please cite this article in press as: Silvestre, W.P., et al., Fractionating of green mandarin (Citrus deliciosa Tenore) essential oil by vacuum
fractional distillation, Journal of Food Engineering (2016),
W.P. Silvestre et al. / Journal of Food Engineering xxx (2016) 1e5 5

Table 4
Comparison between the mass fraction of some compounds in the bottom product compared to the raw essential oil.

Substance Average mass fraction (raw Mass in raw oil Average mass fraction Mass in bottom Relative increase to the raw oil Recovery
oil) (g) (bottom) (g) (times) (%)

Methyl-N-methyl 0,006 0,612 0,170 0,607 28,33 99,17

a-Sinensal 0,004 0,408 0,114 0,407 28,50 99,75
Thymol 0,001 0,102 0,028 0,100 28,00 98,00
Linalool 0,002 0,204 0,013 0,046 6,50 22,75
a-Terpineol 0,003 0,306 0,085 0,303 28,33 99,17

Table 5
Summary of the compounds detected in the GC/MS analysis of the bottom products and were not detected in the raw oil.

Substance Average mass fraction (bottom) Mass (g) Chemical class Possible origin

Terpinen-4-ol 0,005 0,018 aliphatic alcohol isomerization of a-terpineol

Perillaldehyde 0,008 0,029 aldehyde oxidation of limonene
Trans-carveol 0,004 0,014 aliphatic alcohol oxidation of limonene
Cis-b-terpineol 0,003 0,011 aliphatic alcohol isomerization of a-terpineol
a-Caryophylene 0,003 0,011 sesquiterpene isomerization of b-caryophylene

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la ora aroma tica latinoamericana: proyecto CYTED IV.20. EDIPUCRS, Porto
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Alegre (org.).
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Please cite this article in press as: Silvestre, W.P., et al., Fractionating of green mandarin (Citrus deliciosa Tenore) essential oil by vacuum
fractional distillation, Journal of Food Engineering (2016),