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Journal of Chromatography A, 1112 (2006) 121126

An improved microwave Clevenger apparatus for


distillation of essential oils from orange peel
Mohamed A. Ferhat a , Brahim Y. Meklati a , Jacqueline Smadja b , Farid Chemat b,
a
Centre de Recherches en Analyses Physico Chimiques CRAPC, BP 248 Alger RP 16004, Alger, Algeria
b Laboratoire de Chimie des Substances Naturelles et des Sciences des Aliments Faculte des Sciences et Technologies, Universite de La Reunion, B.P. 7151,
F-97715 Saint Denis messag cedex 9, La Reunion D.O.M., France
Available online 27 December 2005

Abstract
Microwave Clevenger or microwave accelerated distillation (MAD) is a combination of microwave heating and distillation, performed at
atmospheric pressure without added any solvent or water. Isolation and concentration of volatile compounds are performed by a single stage.
MAD extraction of orange essential oil was studied using fresh orange peel from Valencia late cultivar oranges as the raw material. MAD has been
compared with a conventional technique, which used a Clevenger apparatus with hydro-distillation (HD). MAD and HD were compared in term
of extraction time, yields, chemical composition and quality of the essential oil, efficiency and costs of the process. Extraction of essential oils
from orange peels with MAD was better in terms of energy saving, extraction time (30 min versus 3 h), oxygenated fraction (11.7% versus 7.9%),
product yield (0.42% versus 0.39%) and product quality. Orange peels treated by MAD and HD were observed by scanning electronic microscopy
(SEM). Micrographs provide evidence of more rapid opening of essential oil glands treated by MAD, in contrast to conventional hydro-distillation.
2005 Elsevier B.V. All rights reserved.

Keywords: Clevenger; Microwave; Extraction; Hydro-distillation; Essential oil; Orange peel

1. Introduction is able to recover the total quantity of these important deriva-


tives. It is in any case essential to have a method to determine the
Oranges are grown throughout the Mitidja region of Algeria. total essential oil content of the fruit. Such information is funda-
More than 500 Mkg were harvested in 2001 [1]. Such high pro- mental to decision on the quality of the fruit and the efficiency
duction inevitably saturates the fresh fruit market. An alternative of the machinery employed [4].
to consumption of orange as fresh fruit is processing it to other The Clevenger apparatus [5] based on distillation is the best
value-added products. Orange processing yields an increase in method to determine the essential oil content of the fruit. In
the production of Citrus by-products, the most important of general, an analytical procedure for essential oil from orange
which is the essential oil extracted from the peel. Orange essen- fruits or peels comprises two steps: extraction (hydro-distillation
tial oil is used to add orange aroma from the orange to products or steam distillation) and analysis (gas chromatography (GC),
such as carbonated drinks, ice creams, cakes, air-fresheners, and gas chromatography coupled to mass spectrometry (GCMS)).
perfumes. It is also used for its germicidal, antioxidant, and anti- Although the second step is requires only 1530 min, extraction
carcinogenic properties [2]. takes several hours. Extraction is frequently done by a prolonged
Citrus oil is present in oil sacs or oil glands located at different heating and stirring in boiling water.
depths in the peel of the fruit. Recovery of the oil is performed Microwave energy, with a frequency of 2.45 GHz, is well
mostly by cold pressing these peels. However, simultaneous known to have a significant effect on the rate of various processes
extraction of juice and oil is considered by many fruit proces- in the chemical and food industry. Much attention has been given
sors to be economically attractive [3]. None of the mechanical or to the application of microwave dielectric heating in analyti-
manual processes used to extract essential oils from fruit or peel cal chemistry because of the reduced analysis time, simplified
manipulation and work-up, and higher purity of the final product
[68]. Several classes of compounds such as essential oils, aro-
Corresponding author. Tel.: +262262938182; fax: +262262938183. mas, pesticides, phenols, dioxins, and other organic compounds
E-mail address: chemat@univ-reunion.fr (F. Chemat). have been extracted efficiently from a variety of matrices (mainly

0021-9673/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.chroma.2005.12.030
122 M.A. Ferhat et al. / J. Chromatogr. A 1112 (2006) 121126

mum delivered power of 1000 W variable in 10 W increments.


Temperature was monitored by an external Infrared (IR) sensor.
Based on a relatively simple principle, this method involves
placing orange peels in the microwave reactor, without any
added solvent or water. The internal heating of the in situ water
within the orange peels distends the oil glands and sacs and leads
to rupture of the glands and oleiferous receptacles. This process
thus frees essential oil, which is evaporated by the in situ water
of the plant material. A cooling system outside the microwave
oven condenses the distillate continuously. Excess water was
refluxed to the extraction vessel in order to restore the water to
the plant material. The MAD is neither a modified microwave
assisted extraction (MAE), which use organic solvents, nor a
modified hydro-distillation (HD) which use a large quantity of
Fig. 1. Microwave Clevenger.
water.
In a typical MAD procedure performed at atmospheric pres-
sure, 200 g of fresh orange peels were heated using a fix power
soils, sediments, animal tissues, food, and plant materials). All density of 1 W g1 for 30 min without addition of solvents or
the reported applications have shown that microwave-assisted water. The extraction was continued at 100 C until no more
solvent-extraction (MAE) is a viable alternative to conventional essential oil was obtained. The essential oil was collected, dried
techniques for such matrixes. The main benefits are the reduction over anhydrous sodium sulphate and stored at 4 C until used.
of extraction time and solvent used. Extractions were performed at least three times, and the mean
Up to now, however, there are only a few articles in the liter- values were reported.
ature that have reported the acceleration of essential oil extrac-
tion by microwave irradiation [913]. The advantages of using 2.3. Conventional Clevenger or Hydro-distillation
microwave energy, a non contact heat source, for the extrac- apparatus and procedure
tion of essential oils from plant materials, could include: more
effective heating, faster energy transfer, reduced thermal gradi- 200 g of fresh orange peels were submitted to hydro-
ents, selective heating, reduced equipment size, faster response distillation with a Clevenger-type apparatus [5,16] according
to process heating control, faster start-up, increased production, to the European Pharmacopoeia, and extracted with 2 l of water
and elimination of process steps [14]. for 3 h (until no more essential oil was obtained). The essential
The aim of this work was to present an improved microwave oil was collected, dried under anhydrous sodium sulphate and
Clevenger distillation for the extraction of essential oils from stored at 4 C until used. Extractions were performed at least
orange peels (Citrus sinensis L. Osbeck, Rutaceae), and compare three times, and the mean values were reported.
the results with those obtained by the conventional technique, in
order to introduce this advantageous alternative in the analysis 2.4. Gas chromatography
of essential oils in the agro-food industry.
A Hewlett-Packard 6890 GC system was used for
2. Experimental gas chromatography analysis, fitted with a fused-silica-
capillary column with an apolar stationary phase HP5MSTM
2.1. Plants material (30 m 0.25 mm 0.25 m film thickness). The column tem-
perature progress from 60 to 280 C at 2 C min1 . Injection was
The oranges used in this study were Citrus sinensis L. performed at 250 C in the splitless mode; 1 L of sample was
Osbeck from Valencia late cultivar. All fruits were gathered injected. A flow rate of 0.3 ml/min carrier gas (N2 ) was used.
from the same experimental plantation Institut Technique de Flame ionisation detection was performed at 320 C.
lArboriculture Fruitiere (ITAF), located in the Mitidja region
40 km south of Algiers (Boufarik, Algeria). Oranges were peeled 2.5. Gas chromatographymass spectrometry identication
by hand, separating the external part of the orange (flavedo), giv-
ing a yield of 20% (w/w) of orange peel with respect to the whole The essential oils were analysed by gas chromatography
fruit. Fresh plant material was employed in all extractions. The coupled to mass spectrometry (GCMS) (Hewlett-Packard com-
initial moisture content of orange peel was 90%. puterized system comprising a 6890 gas chromatograph cou-
pled to a 5973A mass spectrometer) using a fused-silica-
2.2. Microwave Clevenger apparatus and procedure capillary column with an apolar stationary phase HP5MSTM
(30 m 0.25 mm 0.25 m film thickness). GCMS spectra
Microwave accelerated distillation MAD was performed were obtained using the following conditions: carrier gas He;
using the DryDist microwave oven illustrated in Fig. 1 [15]. flow rate 0.7 mL min1 ; split 1:20; injection volume 0.1 L;
This is a multimode microwave reactor 2.45 GHz with a maxi- injection temperature 250 C; oven temperature progress from
M.A. Ferhat et al. / J. Chromatogr. A 1112 (2006) 121126 123

60 to 280 C at 2 C min1 ; the ionisation mode used was elec-


tronic impact at 70 eV.

2.6. Qualitative and quantitative analyses

Most constituents were tentatively identified by comparison


of their GC Kovats retention indices (RI), determined with refer-
ence to a homologous series of C5 C28 n-alkanes and with those
of authentic standards available in the authors laboratory. Iden-
tification was confirmed when possible by comparison of their
mass spectral fragmentation patterns with those stored in the MS
database (National Institute of Standards and Technology and
Wiley libraries) and with mass spectra literature data [17,18].
Component relative concentrations were obtained directly from
GC peak areas obtained with GC-FID.
Fig. 2. Temperature profiles ( MAD  HD) and yields ( MAD  HD) as a
function of time for the MAD and HD extractions of essential oil from orange
2.7. Olfactory evaluation
peels.

The two essential oils were evaluated olfactorically by Jean


essential oil per 100 g of orange fruit. These results mean a sub-
Claude ELLENA (Perfurmer from Symrise, France).
stantial saving of time, energy and plant material.

2.8. Physical constants 3.2. Composition of essential oil

Orange essential oils have been analysed according to the The comparison of yields, extraction times, oxygenated frac-
standard method AFNOR. The usual physical constants defining tion, composition of chemical families, and detailed composition
the essential oil have been determined at 20 C: specific gravity, for each extract is reported in Table 1. Limonene, -myrcene,
refractive index, optical rotation, and solubility in 95% ethanol linalool, -sisensal and decanal were the main components in the
[19]. essential oil extracted from orange peels but the relative amounts
differed for the two extraction methods. Limonene, a monoter-
2.9. Scanning electron micrographs (SEM) pene hydrocarbon, is the most abundant component present at
76.7% and 78.5%, respectively for MAD and HD. Linalool, an
The specimens were freeze-dried, fixed on the specimen oxygenated monoterpene, is present at 3.1% and 2.0%, respec-
holder with aluminium tape and then sputtered with gold. All tively for MAD and HD.
the specimens were examined by a TOPCON ABT60, under Substantially higher amounts of oxygenated compounds and
vacuum condition and accelerating voltage of 15 kV, with a spot lower amounts of monoterpenes hydrocarbons are present in
size 5 and a working distance of 15 mm. the essential oil of orange peels extracted by MAD in compari-
son with HD. The oxygenated fraction in essential oil samples
3. Results and discussion from MAD (11.7%) was higher than HD (7.9%). Monoterpenes
hydrocarbons are less valuable than oxygenated compounds in
3.1. Extraction yield and time terms of their contribution to the fragrance of the essential oil.
Conversely, the oxygenated compounds are highly odoriferous
MAD is clearly quicker than conventional HD. The extrac- and, hence, the most valuable. The greater proportion of oxy-
tion takes 30 min, whilst 3 h were required by hydro-distillation. genated compounds in the MAD essential oils is probably due
For HD or MAD, the extraction temperature is equal to boiling to the diminution of thermal and hydrolytic effects, compared
temperature of water at atmospheric pressure (100 C). Fig. 2 with hydro-distillation, which uses a large quantity of water and
shows the temperature profiles during MAD and HD extrac- is time and energy consuming. Water is a polar solvent, which
tions. To reach this extraction temperature (100 C) and thus accelerates many reactions, especially reactions via carbocation
obtain the distillation of the first essential oil droplet, it is nec- as intermediates.
essary to heat for only 3 min with MAD compared with 30 min
for HD. 3.3. Physical constants and olfactory evaluation
As is shown in Table 1 and Fig. 2, an extraction time of 30 min
with MAD provides yields comparable to those obtained after Orange essential oils have been analysed according to the
180 min by means of HD, which is the one of the reference standard method AFNOR to determine the usual physical con-
methods in essential oil extraction. The ultimate yield of essen- stants defining the essential oil extracted either by MAD or HD:
tial oil obtained from orange peels was 0.42 0.02% by MAD specific gravity, refractive index, optical rotation, and solubility
and 0.39 0.02% by HD. Yields are expressed as in grams of in 95% ethanol at 20 C (Table 2). There is no significant differ-
124 M.A. Ferhat et al. / J. Chromatogr. A 1112 (2006) 121126

Table 1
Chemical compositions, grouped compounds, oxygenated fractions, and yields of essential oils obtained by MAD and HD extractions from fresh orange peels
No. Compounds RI MAD (%) HD (%) Method of identification

Monoterpene hydrocarbons 85.7 89.8


1 -Pinene 918 0.5 1.6 GC, GCMS
2 Sabinene 961 1.2 1.2 GC, GCMS
3 -Pinene 983 2.4 2.7 GC, GCMS
4 -Myrcene 1003 4.3 5.3 GC, GCMS
5 Limonene 1075 76.7 78.5 GC, GCMS
6 3-Carene 1098 0.2 0.1 GC, GCMS
7 -Terpinene 1099 0.3 0.2 GC, GCMS
8 Terpinolene 1110 0.2 0.2 GC, GCMS
Oxygenated monoterpenes 7.0 4.8
9 Linalool 1132 3.1 2.0 GC, GCMS
10 trans-Limonene oxide 1144 0.3 0.1 GC, GCMS
11 Citronellal 1159 0.4 0.3 GC, GCMS
12 Terpin-4-ol 1178 0.3 0.5 GC, GCMS
13 -Terpineol 1192 0.8 0.4 GC, GCMS
14 trans-Carveol 1217 0.2 0.3 GC, GCMS
15 Nerol 1228 0.6 0.3 GC, GCMS
16 Neral 1239 0.4 0.3 GC, GCMS
17 Geraniol 1254 0.3 0.1 GC, GCMS
18 Geranial 1268 0.5 0.5 GC, GCMS
19 Perilla Alcohol 1284 0.1 0.0 GC, GCMS
Sesquiterpene hydrocarbons 1.0 1.3
20 -Copaene 1357 0.1 0.1 GC, GCMS
21 -Cubebene 1371 0.1 0.1 GC, GCMS
22 -Elemene 1373 0.1 0.1 GC, GCMS
23 (E)-Caryophyllene 1391 0.2 0.2 GC, GCMS
24 -Gurjunene 1406 0.1 0.1 GC, GCMS
25 (E)--Farnesene 1442 0.1 0.1 GC, GCMS
26 Germacrene D 1465 0.1 0.1 GC, GCMS
27 Valencene 1479 0.2 0.4 GC, GCMS
28 -Cadinene 1513 0.1 0.2 GC, GCMS
Oxygenated sesquiterpenes 0.9 0.3
29 -Sinensal 1647 0.2 0.2 GC, GCMS
30 -Sinensal 1675 0.7 0.1 GC, GCMS
Other oxygenated compounds 4.0 2.7
31 1-Hexanol 852 0.2 0.0 GC, GCMS
32 1-Octanol 1102 1.1 0.5 GC, GCMS
33 n-Nonanal 1118 0.2 0.1 GC, GCMS
34 Decanal 1210 1.9 1.7 GC, GCMS
35 Octanol Acetate 1212 0.1 0.1 GC, GCMS
36 1-Decanol 1266 0.3 0.0 GC, GCMS
37 Undecanal 1299 0.1 0.1 GC, GCMS
38 Dodecanal 1391 0.2 0.2 GC, GCMS
Extraction time (min) 30 180
Yield (%) 0.42 0.02 0.39 0.02
Oxygenated fraction 11.7 7.9

ence between the physical constants of essential oils obtained treated orange peels in Fig. 3b (MAD) and Fig. 3c (HD). Fig. 3b
by MAD or HD. shows the typical structure after MAD extraction; cells are empty
The organoleptic properties of essential oils extracted by but still intact. In the case of HD extraction, we observed signif-
MAD and HD are shown in Table 3. According to Mr. J.C. icant damage on the external surface of the orange peel together
Ellena, a Nose or perfumer, the MAD method offers the pos- with some dispersed cellular material. This indicates that the
sibility for a better reproduction of natural aroma of the orange mechanical strain induced by the rapid decompression and the
essential oil than the hydro-distilled essential oil. violent vaporization of water have two main effects: the dehy-
drating effect due to vaporization and a subsequent change in
3.4. Structural changes after extraction the surface tension of the glandular wall, causing it to crumble
or rupture more readily (Fig. 3).
The various extraction methods produced distinguishable Similar effects were pointed out by Pare and Belanger [20],
physical changes in the orange peels. Fig. 3a is a micrograph of and Chen and Spiro [21] for the microwave extraction of rose-
the untreated peels, which can be compared with structures of the mary leaves in hexane. When the glands were subjected to more
M.A. Ferhat et al. / J. Chromatogr. A 1112 (2006) 121126 125

Table 2 Table 4
Physical properties of essential oils obtained by MAD and HD extraction from Energy consumption of MAD and HD methods
fresh orange peels
MAD HD
Physical properties MAD HD
Extraction time (min) 30 180
20 Electric consumption (kWh) 0.25 4.33
Specific gravity d20 0.86 0.86
Refractive index n20
D +1.475 +1.477 CO2 rejected (g) 200 3464
Optical rotation in degree []20
D 38 39
Solubility (v/v) in 95% ethanol 0.4 0.4

followed by evaporation of water and essential oil for 150 min.


Table 3 The MASD method required heating for 3 min only and evap-
Organoleptic properties of essential oils obtained by MAD and HD extraction oration for 27 min of the in situ water and essential oil of the
from fresh orange peels orange peels. The energy required to perform the two extraction
Organoleptic MAD HD methods are respectively 4.33 kWh for HD, and 0.25 kWh for
properties MAD (Table 4). The power consumption has been determined
Colour Colourless Pale yellow
with a Wattmeter at the microwave generator entrance and the
Odour Fresh, light and Fresh, pungent but electrical heater power supply.
sweet citrusy different from fresh Regarding environmental impact, the calculated quantity of
odour fruit carbon dioxide rejected in the atmosphere is higher in the case of
Aspect Mobile liquid Mobile liquid HD (3464 g CO2 /g of essential oil) than for MASD (200 g CO2 /g
of essential oil). These calculations have been made according
to literature: to obtain 1 kWh from coal or fuel, 800 g of CO2
severe thermal stresses and localized high pressures, as in the will be rejected in the atmosphere during combustion of fossil
case of microwave heating, the pressure build-up within the fuel [22].
glands could have exceeded their capacity for expansion, and In this study, we present MAD as an environmentally
caused their rupture more rapidly than in conventional extrac- friendly extraction method suitable for sample preparation prior
tion. to essential oil analysis. MAD is a very clean method, which
avoids the use of large quantity of water and voluminous extrac-
3.5. Cost, cleanliness and up-scaling tion vessels (HD). MAD could also be used to produce larger
quantities of essential oils by using existing big scale microwave
The reduced cost of extraction is clearly advantageous for extraction reactors [23]. These microwave reactors are suitable
the proposed MAD method in terms of time and energy. Hydro- for the extraction of 10, 20 or 100 kg of fresh plant material
distillation required an extraction time of 30 min for heating 2 l per time. Theses reactors could be easily modified and used for
of water and 200 g of orange peels to the extraction temperature, MAD extractions.

Fig. 3. Electron micrograph of orange peels: untreated (a); after MAD extraction (30 min) (b); and after HD extraction (3 h) (c).
126 M.A. Ferhat et al. / J. Chromatogr. A 1112 (2006) 121126

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