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-

Oranges are grown throughout the Mitidja region of Algeria.
More than 500 Mkg were harvested in 2001 [1]. Such high pro-
duction inevitably saturates the fresh fruit market. An alternative
to consumption of orange as fresh fruit is processing it to other
value-added products. Orange processing yields an increase in
the production of Citrus by-products, the most important of
which is the essential oil extracted from the peel. Orange essen-
tial oil is used to add orange aroma from the orange to products
such as carbonated drinks, ice creams, cakes, air-fresheners, and
perfumes. It is also used for its germicidal, antioxidant, and anti-
carcinogenic properties [2].
Citrus oil is present in oil sacs or oil glands located at different
depths in the peel of the fruit. Recovery of the oil is performed
mostly by cold pressing these peels. However, simultaneous
extraction of juice and oil is considered by many fruit proces-
sors to be economically attractive [3]. None of the mechanical or
manual processes used to extract essential oils from fruit or peel
Corresponding author. Tel.: +262262938182; fax: +262262938183.
E-mail address: chemat@univ-reunion.fr (F. Chemat).
tives. It is in any case essential to have a method to determine the
total essential oil content of the fruit. Such information is funda-
mental to decision on the quality of the fruit and the efficiency
of the machinery employed [4].
The Clevenger apparatus [5] based on distillation is the best
method to determine the essential oil content of the fruit. In
general, an analytical procedure for essential oil from orange
fruits or peels comprises two steps: extraction (hydro-distillation
or steam distillation) and analysis (gas chromatography (GC),
gas chromatography coupled to mass spectrometry (GCMS)).
Although the second step is requires only 1530 min, extraction
takes several hours. Extraction is frequently done by a prolonged
heating and stirring in boiling water.
Microwave energy, with a frequency of 2.45 GHz, is well
known to have a significant effect on the rate of various processes
in the chemical and food industry. Much attention has been given
to the application of microwave dielectric heating in analyti-
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-
mas, pesticides, phenols, dioxins, and other organic compounds
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
Fig. 1. Microwave Clevenger.
soils, sediments, animal tissues, food, and plant materials). All
the reported applications have shown that microwave-assisted
solvent-extraction (MAE) is a viable alternative to conventional
techniques for such matrixes. The main benefits are the reduction
of extraction time and solvent used.
Up to now, however, there are only a few articles in the liter-
ature that have reported the acceleration of essential oil extrac-
tion by microwave irradiation [913]. The advantages of using
microwave energy, a non contact heat source, for the extrac-
tion of essential oils from plant materials, could include: more
effective heating, faster energy transfer, reduced thermal gradi-
ents, selective heating, reduced equipment size, faster response
to process heating control, faster start-up, increased production,
and elimination of process steps [14].
The aim of this work was to present an improved microwave
Clevenger distillation for the extraction of essential oils from
orange peels (Citrus sinensis L. Osbeck, Rutaceae), and compare
the results with those obtained by the conventional technique, in
order to introduce this advantageous alternative in the analysis
of essential oils in the agro-food industry.
2. Experimental
2.1. Plants material
The oranges used in this study were Citrus sinensis L.
Osbeck from Valencia late cultivar. All fruits were gathered
from the same experimental plantation Institut Technique de
lArboriculture Fruitiere (ITAF), located in the Mitidja region
40 km south of Algiers (Boufarik, Algeria). Oranges were peeled
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
fruit. Fresh plant material was employed in all extractions. The
initial moisture content of orange peel was 90%.
2.2. Microwave Clevenger apparatus and procedure
Microwave accelerated distillation MAD was performed
using the DryDist microwave oven illustrated in Fig. 1 [15].
This is a multimode microwave reactor 2.45 GHz with a maxi-
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
water.
In a typical MAD procedure performed at atmospheric pres-
sure, 200 g of fresh orange peels were heated using a fix power
density of 1 W g1 for 30 min without addition of solvents or
water. The extraction was continued at 100 C until no more
essential oil was obtained. The essential oil was collected, dried
over anhydrous sodium sulphate and stored at 4 C until used.
Extractions were performed at least three times, and the mean
values were reported.
2.3. Conventional Clevenger or Hydro-distillation
apparatus and procedure
200 g of fresh orange peels were submitted to hydro-
distillation with a Clevenger-type apparatus [5,16] according
to the European Pharmacopoeia, and extracted with 2 l of water
for 3 h (until no more essential oil was obtained). The essential
oil was collected, dried under anhydrous sodium sulphate and
stored at 4 C until used. Extractions were performed at least
three times, and the mean values were reported.
2.4. Gas chromatography
A Hewlett-Packard 6890 GC system was used for
gas chromatography analysis, fitted with a fused-silica-
capillary column with an apolar stationary phase HP5MSTM
(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
performed at 250 C in the splitless mode; 1 L of sample was
injected. A flow rate of 0.3 ml/min carrier gas (N2 ) was used.
Flame ionisation detection was performed at 320 C.
2.5. Gas chromatographymass spectrometry identication
The essential oils were analysed by gas chromatography
coupled to mass spectrometry (GCMS) (Hewlett-Packard com-
puterized system comprising a 6890 gas chromatograph cou-
pled to a 5973A mass spectrometer) using a fused-silica-
capillary column with an apolar stationary phase HP5MSTM
(30 m 0.25 mm 0.25 m film thickness). GCMS spectra
were obtained using the following conditions: carrier gas He;
flow rate 0.7 mL min1 ; split 1:20; injection volume 0.1 L;
injection temperature 250 C; oven temperature progress from
 M.A. Ferhat et al. / J. Chromatogr. A 1112 (2006) 121126
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.
2.7. Olfactory evaluation
The two essential oils were evaluated olfactorically by Jean
Claude ELLENA (Perfurmer from Symrise, France).
2.8. Physical constants
Orange essential oils have been analysed according to the
standard method AFNOR. The usual physical constants defining
the essential oil have been determined at 20 C: specific gravity,
refractive index, optical rotation, and solubility in 95% ethanol
[19].
2.9. Scanning electron micrographs (SEM)
The specimens were freeze-dried, fixed on the specimen
holder with aluminium tape and then sputtered with gold. All
the specimens were examined by a TOPCON ABT60, under
vacuum condition and accelerating voltage of 15 kV, with a spot
size 5 and a working distance of 15 mm.
3. Results and discussion
3.1. Extraction yield and time
MAD is clearly quicker than conventional HD. The extrac-
tion takes 30 min, whilst 3 h were required by hydro-distillation.
For HD or MAD, the extraction temperature is equal to boiling
temperature of water at atmospheric pressure (100 C). Fig. 2
shows the temperature profiles during MAD and HD extrac-
tions. To reach this extraction temperature (100 C) and thus
obtain the distillation of the first essential oil droplet, it is nec-
essary to heat for only 3 min with MAD compared with 30 min
for HD.
As is shown in Table 1 and Fig. 2, an extraction time of 30 min
with MAD provides yields comparable to those obtained after
180 min by means of HD, which is the one of the reference
methods in essential oil extraction. The ultimate yield of essen-
tial oil obtained from orange peels was 0.42 0.02% by MAD
and 0.39 0.02% by HD. Yields are expressed as in grams of
123
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
peels.
essential oil per 100 g of orange fruit. These results mean a sub-
stantial saving of time, energy and plant material.
3.2. Composition of essential oil
The comparison of yields, extraction times, oxygenated frac-
tion, composition of chemical families, and detailed composition
for each extract is reported in Table 1. Limonene, -myrcene,
linalool, -sisensal and decanal were the main components in the
essential oil extracted from orange peels but the relative amounts
differed for the two extraction methods. Limonene, a monoter-
pene hydrocarbon, is the most abundant component present at
76.7% and 78.5%, respectively for MAD and HD. Linalool, an
oxygenated monoterpene, is present at 3.1% and 2.0%, respec-
tively for MAD and HD.
Substantially higher amounts of oxygenated compounds and
lower amounts of monoterpenes hydrocarbons are present in
the essential oil of orange peels extracted by MAD in compari-
son with HD. The oxygenated fraction in essential oil samples
from MAD (11.7%) was higher than HD (7.9%). Monoterpenes
hydrocarbons are less valuable than oxygenated compounds in
terms of their contribution to the fragrance of the essential oil.
Conversely, the oxygenated compounds are highly odoriferous
and, hence, the most valuable. The greater proportion of oxy-
genated compounds in the MAD essential oils is probably due
to the diminution of thermal and hydrolytic effects, compared
with hydro-distillation, which uses a large quantity of water and
is time and energy consuming. Water is a polar solvent, which
accelerates many reactions, especially reactions via carbocation
as intermediates.
3.3. Physical constants and olfactory evaluation
Orange essential oils have been analysed according to the
standard method AFNOR to determine the usual physical con-
stants defining the essential oil extracted either by MAD or HD:
specific gravity, refractive index, optical rotation, and solubility
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
by MAD or HD.
The organoleptic properties of essential oils extracted by
MAD and HD are shown in Table 3. According to Mr. J.C.
Ellena, a Nose or perfumer, the MAD method offers the pos-
sibility for a better reproduction of natural aroma of the orange
essential oil than the hydro-distilled essential oil.
3.4. Structural changes after extraction
The various extraction methods produced distinguishable
physical changes in the orange peels. Fig. 3a is a micrograph of
the untreated peels, which can be compared with structures of the
treated orange peels in Fig. 3b (MAD) and Fig. 3c (HD). Fig. 3b
shows the typical structure after MAD extraction; cells are empty
but still intact. In the case of HD extraction, we observed signif-
icant damage on the external surface of the orange peel together
with some dispersed cellular material. This indicates that the
mechanical strain induced by the rapid decompression and the
violent vaporization of water have two main effects: the dehy-
drating effect due to vaporization and a subsequent change in
the surface tension of the glandular wall, causing it to crumble
or rupture more readily (Fig. 3).
Similar effects were pointed out by Pare and Belanger [20],
and Chen and Spiro [21] for the microwave extraction of rose-
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
3.6. Safety considerations
Microwave extraction process is simple and can be readily
understood in terms of the operating steps to be performed.
However, the application of microwave energy can pose seri-
ous hazards in inexperienced hands. A high level of safety and
attention to details when planning and performing experiments
must be used by all the persons dealing with microwaves. They
have to ensure that they seek proper information from knowl-
edgeable sources and that they do not attempt to implement this
technique unless proper guidance is provided. Only approved
equipment and scientifically sound procedures should be used.
4. Conclusion
Microwave Clevenger or microwave accelerated distillation
(MAD) technique has been compared with the conventional
hydro-distillation method, for the extraction of essential oil
from fresh orange peels. This microwave extraction method
offers important advantages over traditional hydro-distillation,
namely; water and solvent free process, shorter extraction times
(30 min against 3 h for hydro-distillation); better yields (0.42%
against 0.39% for HD); higher oxygenated compounds; environ-
mentally friendly; lower production of by-products (as no water
or solvent is used); lower cost; and the possibility for a better
reproduction of natural aroma of the orange essential oil than
the hydro-distilled essential oil. SEM images of orange peels
untreated or subjected to MAD or HD emphasize the difference
between the two extraction methods used. Microwaves seem to
cause the rupture of the cells and the glands more rapidly than
in conventional hydro-distillation.
Acknowledgements
The authors gratefully acknowledge Mme Esme Spicer from
the University of Stellenbosch for SEM micrographs, and Pr
Steven Bradshaw for his valuable comments.
References
[1] A. Ferhat, Lagrumiculture Algerienne, Internal Report, CRAPC,
Algiers, Algeria, 2004.
[2] E. Guenther, The Essential Oils, 3, R.E. Kreiger Publishing, New York,
1974.
[3] M. Mukhopadhyay, Natural Extracts Using Supercritical Carbon Diox-
ide, CRC Press, New York, 2000.
[4] G. Dugo, A. Di Giacomo, The Genus Citrus, Taylor & Francis Publish-
ing, London, 2002.
[5] J.F. Clevenger, Am. Perfumer Essential Oil Rev. (1928) 467.
[6] H.M. Kingston, L.B. Jassie, Introduction to Microwave Sample Prepa-
ration, American Chemical Society, Washington, 1988.
[7] H.M. Kingston, S.J. Haswell, Microwave Enhanced Chemistry: Fun-
damentals, Sample Preparation and Applications, American Chemical
Society, Washington, 1997.
[8] A. Zlotorzynski, Crit. Rev. Anal. Chem. 25 (1995) 43.
[9] M.D. Luque de Castro, M. Jiminez Carmona, V. Fernandez-Prez, Trends
Anal. Chem. 18 (1999) 708.
[10] A.A. Craveiro, F.J.A. Matos, J.W. Alencar, Flavour Frag. J. 4 (1989) 43.
[11] J.R.J. Pare, European Patent, EP 0,485,668, 1992.
[12] P. Mengal, B. Mompon, European Patent, EP 2,705,035, 1993.
[13] F. Chemat, J. Smadja, M.E. Lucchesi, United Stated Patent, US
0,187,340, 2004.
[14] A.C. Metaxas, R.J. Meredith (Eds.), Industrial Microwave Heating, Pere-
grinus Ltd., London, 1993.
[15] Milestone, Bergamo, Italy, www.miestonesrl.com.
[16] Conseil de lEurope, Pharmacopee Europeenne 1, Maisonneuve S.A.
Editions, Sainte Ruffine, 1996.
[17] R.P. Adams, Identification of Essential Oil Components By Gaz Chro-
matography/Mass Spectroscopy, Allured Publishing Corporation, Carol
Stream, 1995.
[18] S. Arctander, Perfume and Flavor Chemicals, Allured Publishing Cor-
poration, Carol Stream, 1994.
[19] Recueil des normes francaises, Huiles essentielles, Editions AFNOR,
Paris, 2000.
[20] J.R.J. Pare, J.M.R. Belanger, Instrumental Methods in Food Analysis,
Elsevier, Amsterdam, 1997.
[21] S.S. Chen, M. Spiro, Flavour Frag. J. 10 (1995) 101.
[22] J. Bernard, Sciences et vie 214 (2001) 68.
[23] Archimex, Quimper, France, www.archimex.com.