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,

1. Introduction Oranges are grown throughout the Mitidja region of Algeria. More than 500
Mkg were harvested in 2001. Such high production 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 essential 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
anticarcinogenic properties. 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 processors
to be economically attractive. None of the mechanical or manual processes used to extract
essential oils from fruit or peel is able to recover the total quantity of these important
derivatives. It is in any case essential to have a method to determine the total essential oil
content of the fruit. Such information is fundamental to decision on the quality of the fruit and
the efficiency of the machinery employed . The Clevenger apparatus 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 analytical
chemistry because of the reduced analysis time, simplified manipulation and work-up, and
higher purity of the final product. Several classes of compounds such as essential oils, aromas,
pesticides, phenols, dioxins, and other organic compounds have been extracted efficiently
from a variety of matrices (mainly 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 literature that have reported the acceleration of essential oil extraction by
microwave irradiation. The advantages of using microwave energy, a non contact heat source,
for the extraction of essential oils from plant materials, could include: more effective heating,
faster energy transfer, reduced thermal gradients, selective heating, reduced equipment size,
faster response to process heating control, faster start-up, increased production, and
elimination of process steps . 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),
giving 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 maximum
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 pressure, 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 hydrodistillation 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-silicacapillary column with an apolar stationary phase HP5MSTM (30 m 0.25 mm
0.25m film thickness). The column temperature progress from 60 to 280 C at 2 C min1.
Injection was performed at 250 C in the splitless mode; 1L 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 identification

The essential oils were analysed by gas chromatography coupled to mass spectrometry (GC
MS) (Hewlett-Packard computerized system comprising a 6890 gas chromatograph coupled to
a 5973A mass spectrometer) using a fused-silicacapillary column with an apolar stationary
phase HP5MSTM (30 m 0.25 mm 0.25m film thickness). GCMS spectra were obtained
using the following conditions: carrier gas He; flow rate 0.7 mL min1; split 1:20; injection
volume 0.1L; injection temperature 250 C; oven temperature progress from 60 to 280 C at 2
C min1; the ionisation mode used was electronic 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 reference to a homologous series of C5C28 n-alkanes and with
those of authentic standards available in the authors laboratory. Identification 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

he 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.

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 extraction 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 extractions. To reach this extraction temperature (100 C) and thus obtain
the distillation of the first essential oil droplet, it is necessary 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 essential
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 essential oil per 100 g of orange fruit. These results mean a
substantial saving of time, energy and plant material.

3.2. Composition of essential oil

The comparison of yields, extraction times, oxygenated fraction, 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
monoterpene 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%, respectively 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 comparison
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
oxygenated 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 constants 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 difference 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 possibility 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
significant 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 dehydrating 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, and Chen and Spiro [21] for the microwave extraction of rosemary leaves in hexane.
When the glands were subjected to more severe thermal stresses and localized high pressures,
as in the case of microwave heating, the pressure build-up within the glands could have
exceeded their capacity for expansion, and caused their rupture more rapidly than in
conventional extraction.

3.5. Cost, cleanliness and up-scaling

The reduced cost of extraction is clearly advantageous for the proposed MAD method in terms
of time and energy. Hydrodistillation required an extraction time of 30 min for heating 2 l of
water and 200 g of orange peels to the extraction temperature, followed by evaporation of
water and essential oil for 150 min. The MASD method required heating for 3 min only and
evaporation for 27 min of the in situ water and essential oil of the orange peels. The energy
required to perform the two extraction methods are respectively 4.33 kWh for HD, and 0.25
kWh for MAD (Table 4). The power consumption has been determined with a Wattmeter at
the microwave generator entrance and the electrical heater power supply. Regarding
environmental impact, the calculated quantity of carbon dioxide rejected in the atmosphere is
higher in the case of 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 will be rejected in the atmosphere during combustion of fossil fuel.
In this study, we present MAD as an environmentally friendly extraction method suitable for
sample preparation prior to essential oil analysis. MAD is a very clean method, which avoids
the use of large quantity of water and voluminous extraction vessels (HD). MAD could also be
used to produce larger quantities of essential oils by using existing big scale microwave
extraction reactors. These microwave reactors are suitable for the extraction of 10, 20 or 100
kg of fresh plant material per time. Theses reactors could be easily modified and used for MAD
extractions.

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
serious 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 knowledgeable
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; environmentally 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.