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Research Note
A new process for extraction of essential oil from Citrus peels: Microwave
hydrodiffusion and gravity
Nabil Bousbia a,b, Maryline Abert Vian c, Mohamed A. Ferhat a, Brahim Y. Meklati a, Farid Chemat c,*
a
a r t i c l e
i n f o
Article history:
Received 15 January 2008
Received in revised form 30 May 2008
Accepted 18 June 2008
Available online 3 July 2008
Keywords:
Microwave
Extraction
Hydro-diffusion
Essential oil
Citrus
a b s t r a c t
Attention is drawn to the development of a new and green alternative technique for the extraction of
essential oil from citrus peels. The process uses the hydro-diffusion phenomenon generated by microwaves to extract essential oil from the inside to the outside of the biological material and gravity to collect and separate them. The present apparatus permits fast and efcient extraction, reduces waste, avoids
water and solvent consumption, and allows substantial energy savings.
2008 Elsevier Ltd. All rights reserved.
1. Introduction
Citrus essential oils are the most widely used essential oils in
the world. They are obtained as by-products of the citrus processing. They are used as aroma avor in many food products, including alcoholic and non-alcoholic beverages, candy, gelatins, In
pharmaceutical industries they are employed as avoring agents
to mask unpleasant tastes of drugs. In perfumery and cosmetic,
they are used in many preparations. The traditional way to extract
essential oils is by cold pressing the citrus peels. The oil is present
in oil sacs or oil glands located at different depths in the peel and
the cuticles of the fruit. Peel and cuticle oils are removed mechanically by cold pressing and since cold pressing yields a watery
emulsion, this emulsion is then centrifuged to separate out the
essential oil. Distillation is also used in some countries as an economical way to recover the oils. During distillation, the Citrus peels
exposed to boiling water or steam, release their essential oils
through evaporation. As steam and essential oil vapours are
condensed, both are collected and separated in a vessel
traditionally called the Florentine ask (Guenther, 1948; Dugo
and Di Giacomo, 2002).
The development of new separation techniques for the chemical, food and pharmaceutical industries has lately received a lot
* Corresponding author.
E-mail address: farid.chemat@univ-avignon.fr (F. Chemat).
0260-8774/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2008.06.034
of attention due to the increasing energy prices and the drive to reduce CO2 emissions. These shortcomings have led to considering
the use of new techniques in the extraction of natural substances,
which typically use less solvent and energy, such as supercritical
uid extraction, ultrasound extraction, the controlled pressure
drop process, and sub-critical water extraction. Researchers in
many universities are working on novel techniques that could lead
to compact, safe, efcient, energy saving, and sustainable extraction processes (Luque de Castro et al., 1999; Pollien et al., 1998;
Reverchon, 1997; Vinatoru, 2001; Jimenez-Carmona et al., 1999;
Rezzoug et al., 2000; Ganzler et al., 1986; Lucchesi et al., 2004).
In this study, a new and original process for the extraction of natural substances using microwave hydro-diffusion and gravity
(MHG) was designed and developed (Fig. 1). This green extraction
process is an original combination of microwave heating and gravity working at atmospheric pressure. MHG was conceived for the
extraction of natural substances from different plant materials at
the laboratory and industrial scales. In this relatively simple method, the plant material is directly placed in a microwave reactor
without any added solvent or water. The internal heating of the
in situ water within the plant material distends the plant cells and
leads to rupture of the glands and cell receptacles. Heating under
microwaves thus frees molecules of interest together with in situ
water. This physical phenomenon, known as hydro-diffusion, allows the extract to diffuse outside the plant material and drop by
earth gravity out of the microwave reactor through the perforated
Pyrex disc. A heat exchanger outside the microwave oven cools
410
The potential of the green MHG technique has been investigated for isolation of essential oil and compared with conventional
methods, hydro-distillation (HD) and cold pressing (CP), as the current technique and commercial situation call for research about
new extracts and new extraction techniques. We have applied
MHG, HD and CP techniques to extract essential oil from citrus
peels. Belonging to the Rutaceae family, their essential oils are located in lysigenous secretory reservoirs inside the avedo of the
fruit. Extraction yields and rates, essential oil compositions, and
energy consumption are compared.
2. Experimental
2.1. Plant material
In this study, citrus fruits were gathered from the same experimental plantation Institut Technique de lArboriculture Fruitire
(I.T.A.F.), located in the Mitidja region 40 km south of Algiers (Boufarik, Algeria). The citrus fruits are: Eureka (Citrus limon L.), Villa
Frana (Citrus limon L.), lime (Citrus aurantifolia (Chrism.) Swing),
Marsh Seedless (Citrus paradisi L.), Tarocco (Citrus sinensis L.),
Valencia late (Citrus sinensis L.), Washington Naval (Citrus sinensis
L.), Tengelo Seminole (Citrus paradisi Macf.). Citrus fruits were
peeled to separate the external part of the lemon (avedo), giving
a yield of 20% (w/w) of the peel with respect to the whole fruit.
Fresh plant material was employed in all extractions.
2.2. Extraction apparatus and procedures
Hydro-distillation with a Clevenger-type apparatus was used to
extract 500 g of fresh citrus peels with 3 l of water for 3 h (until no
more essential oil was obtained). For cold pressing, essential oil
was collected from 1 kg of whole lemon fruit using an automated
cold pressing machine from Schwaub. The epidermis and oil glands
were lacerated by a needle, creating areas of compression in the
peel, surrounded by areas of lower pressure, across which the oil
owed to the exterior. The oil is carried down to a decantation
vessel in a stream of water, the emulsion being collected and then
separated by centrifugation. Microwave extrcation has been performed in a Milestone microwave laboratory oven (Milestone
srl). In a typical procedure at atmospheric pressure, 500 g of fresh
citrus peels was heated using a xed microwave power 500 W for
15 min. 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.
The extraction apparatus are illustrated in Fig. 1.
2.3. Gas chromatography and gas chromatographymass
spectrometry identication
Fig. 1. Extraction methods of essential oils from citrus fruits (MHG, HD, and CP).
the extract continuously. Crude juice or extract (in situ water and
metabolites) is collected and separated in receiving asks. It is
important to note that this green method allows extracting natural
substances without distillation or solvent extraction which are the
most energy- and solvent-consuming unit operations.
The essential oils were analyzed by gas chromatography coupled to mass spectrometry (GCMS) (HewlettPackard computerized system comprising a 6890 gas chromatograph coupled to a
5973A mass spectrometer) using two fused-silica-capillary columns with different stationary phases. The non-polar column
was HP5MSTM (30 m 0.25 mm 0.25 lm lm thickness) and
the polar one was a StabilwaxTM consisting of CarbowaxTM-PEG
(60 m 0.2 mm 0.25 mm lm thickness). GCMS spectra were
obtained using the following conditions: carrier gas He; ow rate
0.3 mL/min; split-less mode; injection volume 1 ll; injection temperature 250 C; the oven temperature programme was 60 C for
8 min increased at 2 C/min to 250 C and held at 250 C for
15 min; the ionisation mode used was electronic impact at 70 eV.
The relative percentage of the components was calculated from
GC-FID peak areas. Most constituents were tentatively identied
411
by comparison of their GC Kovats retention indices (RI), determined with reference to an homologous series of C5C28 n-alkanes
and with those of authentic standards available in the authors laboratory. Identication was conrmed 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 (de lEurope. Pharmacope Europenne, 1996; Adams, 1995;
Arctander, 1994; Recueil des normes franaises, 2000).
45.00
40.00
35.00
30.00
25.00
20.00
15.00
10.00
5.00
0.00
0
200
400
600
800
1000
1200
Yield (% )
8
7
6
5
4
3
time (min.)
0
0
20
40
60
80
100
120
140
160
180
200
Fig. 3. Yield (g EO/g lime peel) prole of lime essential oil obtained by MHG (d) and
HD (s) as function of the extraction time.
412
Table 1
Chemical compositions of essential oils obtained by SFME, HD, and CP extraction from citrus peels
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Compoundsa
R.I.b
Monoterpenes
Pinene<Alpha->
Pinene<Beta->
Myrcene<Beta->
Carene<Delta-3->
Limonene
Terpinene<Gamma->
Oxygenated Monoterpenes
Linalool
Citron ellal
Terpin-4-ol
Terpineol<Alpha->
Nerol
Neral
Geraniol
Geranial
Sesquiterpenes
Elemene<Beta->
Caryophellene<E->
Bergamotene<Alpha-Trans->
Humulene<Alpha->
Farnesene<(E)-Beta->
Germacrene D
Valencene
Bisabolene<(Z)-Alpha->
Bisabolene(Beta-)
Oxygenated Sesquiterpenes
Elemol
Nerolidol<E->
Bisabolol<Alpha->
Nootkatone
Other oxygenated compounds
Nonanal<N->
Citronellyl Acetate
Neryl Acetate
R.I.c
926
974
988
1101
1030
1103
1023
1109
1165
1290
1206
1285
1125
1167
1191
1203
1237
1268
1271
1284
1538
1478
1590
1677
1781
1670
1828
1714
1373
1391
1437
1450
1453
1477
1488
1498
1508
1583
1594
1577
1657
1650
1696
1705
1761
1718
1540
1555
1684
1799
1381
2026
2212
2250
1126
1342
1351
1400
1645
1706
Eureka
Villa Frana
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
Monoterpenes
Pinene<Alpha->
Pinene<Beta->
Myrcene<Beta->
Carene<Delta-3->
Limonene
Terpinene<Gamma->
Oxygenated Monoterpenes
Linalool
Citronellal
Terpin-4-ol
Terpineol<Alpha->
Nerol
Neral
Geraniol
Geranial
Sesquiterpenes
Elemene<Beta->
Caryophellene<E->
Bergamotene<Alpha-Trans->
Humulene<Alpha->
Farnesene<(E)-Beta->
Germacrene D
Valencene
Bisabolene<(Z)-Alpha->
Bisabolene(Beta-)
Oxygenated Sesquiterpenes
Elemol
Nerolidol<E->
Bisabolol<Alpha->
Nootkatone
CP
MHG
HD
CP
MHG
HD
CP
MHG
HD
CP
92.10
1.60
10.20
1.57
0.11
69.65
8.25
3.01
0.20
0.1
0.08
0.21
0.26
0.76
0.24
1.08
0.85
0.13
0.26
0.03
0.01
0.02
0.38
0.02
0.01
0.95
0.08
0.02
0.30
92.76
1.75
15.35
1.33
0.20
65.25
8.08
3.89
0.18
0.05
0.42
0.56
0.49
0.68
0.60
0.89
1.06
93.73
1.62
14.00
1.42
0.15
68.81
7.04
2.65
0.10
0.08
0.03
0.22
0.77
92.50
1.94
13.09
1.46
63.44
11.17
4.91
0.36
0.05
0.19
0.37
0.13
1.55
0.07
2.05
1.92
0.24
0.50
0.06
0.02
0.17
0.29
0.03
0.31
0.54
0.06
0.06
0.17
0.03
0.01
0.03
0.43
0.1
0.05
0.81
0.02
0.03
0.03
0.09
0.02
0.02
0.86
0.09
0.03
0.26
0.65
0.06
0.04
0.19
0.75
0.10
0.02
0.34
1.19
0.04
0.87
0.82
0.02
0.60
97.93
0.41
1.73
95.05
0.01
0.45
0.17
0.05
0.02
0.06
0.04
0.02
0.03
0.49
0.06
0.17
0.04
0.10
0.01
0.01
0.07
0.52
0.04
0.01
0.01
0.04
0.05
0.75
0.03
0.56
1.00
0.13
0.03
0.05
0.10
1.51
0.02
95.80
1.62
14.00
1.42
68.81
8.90
3.71
0.22
0.08
0.03
0.23
0.09
1.06
0.07
1.82
1.98
0.35
0.58
0.09
0.02
0.07
0.87
0.03
0.03
0.59
0.04
0.19
97.03
0.45
1.81
94.21
0.03
0.51
0.18
0.02
0.09
0.08
0.03
0.02
0.04
0.50
0.04
0.20
0.04
0.03
0.44
0.03
93.60
1.02
9.24
1.55
0.15
71.86
8.90
3.65
0.22
0.07
0.02
0.23
0.09
1.06
0.07
1.82
2.12
0.35
0.58
0.09
0.02
0.11
0.07
0.87
0.04
0.04
0.69
0.08
0.04
0.32
88.70
1.86
11.60
1.40
60.56
11.91
5.11
0.25
0.05
0.08
0.38
0.20
1.66
0.12
2.23
3.56
0.18
0.28
0.04
0.02
88.39
1.18
7.08
1.52
0.15
71.22
6.58
3.75
0.35
0.06
0.37
0.53
0.44
0.53
0.56
0.85
0.88
0.16
0.20
0.05
0.01
0.07
0.02
0.31
0.24
0.15
0.71
0.02
0.02
0.36
97.27
0.27
1.55
94.54
0.01
0.36
0.07
0.03
0.02
0.05
1.30
1.65
89.68
1.53
6.99
1.51
0.16
70.92
7.70
3.72
0.20
0.09
0.09
0.29
0.30
0.94
0.32
1.37
0.99
0.16
0.01
0.01
0.13
0.74
0.04
0.01
0.01
0.26
0.04
0.02
0.15
0.38
0.05
0.05
180
0.8
4.78
93.82
60
0.1
3.33
95.38
15
1.6
4.57
90.57
180
1.7
4.70
89.27
60
0.2
4.38
95.72
15
0.8
6.32
92.26
180
0.8
5.75
94.42
60
0.2
4.33
97.78
15
1.0
1.07
98.42
180
1.1
1.41
97.53
60
0.2
1.00
99.15
15
0.7
3.98
92.95
926
974
988
1101
1030
1103
1023
1109
1165
1290
1206
1285
1125
1167
1191
1203
1237
1268
1271
1284
1538
1478
1590
1677
1781
1670
1828
1714
1373
1391
1437
1450
1453
1477
1488
1498
1508
1583
1594
1577
1657
1650
1696
1705
1761
1718
1540
1555
1684
1799
1381
2026
2212
2250
Marsh Seedless
HD
Tarocco
1
2
3
4
5
6
Lime
MHG
Valencia late
Washington Naval
0.04
1.88
0.08
0.72
Tengelo Seminole
MHG
HD
CP
MHG
HD
CP
MHG
HD
CP
MHG
HD
CP
98.02
0.46
1.85
0.02
95.19
0.01
1.11
0.88
0.04
0.06
0.05
0.05
0.19
0.01
0.01
0.12
98.11
0.49
1.87
0.06
94.68
0.05
0.60
0.17
0.02
0.12
0.05
0.06
0.01
0.03
0.45
0.02
0.01
0.03
0.28
0.05
98.10
0.50
1.89
0.01
94.94
0.01
0.61
0.49
0.02
0.04
0.02
97.57
0.43
1.64
0.09
94.64
0.05
0.99
0.62
0.06
0.03
0.09
0.05
98.71
0.51
1.85
0.15
95.48
0.06
0.56
0.30
0.03
0.06
0.06
0.03
98.33
0.45
1.78
0.25
95.20
0.67
0.41
0.03
0.01
0.06
0.07
96.24
0.53
1.76
0.23
93.16
0.64
0.27
0.02
0.12
0.09
0.03
98.45
0.50
1.90
0.28
95.00
0.29
0.15
0.04
0.02
0.02
97.24
0.91
0.37
1.88
90.34
3.78
1.16
0.62
0.04
0.08
0.16
0.01
89.38
3.90
0.57
0.27
0.08
0.01
0.10
0.01
0.09
0.11
0.01
0.02
0.01
0.01
0.02
0.05
0.12
0.01
0.01
0.02
0.01
0.04
0.07
0.18
0.01
0.01
0.01
0.13
0.03
0.29
0.02
0.01
0.01
0.13
0.04
0.38
0.02
0.03
0.01
0.26
0.24
0.03
0.01
0.02
0.02
0.12
0.35
0.04
0.01
0.01
0.04
0.08
0.10
0.08
0.01
0.02%
0.02
0.01
0.03
0.01
0.02
0.01
97.48
0.52
0.36
1.83
90.25
3.65
0.81
0.29
0.08
0.05
0.18
0.01
0.23
0.01
0.01
0.01
0.01
0.01
0.15
0.02
0.01
97.80
0.83
0.38
1.79
0.03
0.26
0.01
0.02
0.01
0.02
0.12
98.55
0.52
1.89
0.20
95.06
0.01
0.64
0.34
0.05
0.02
0.05
0.06
0.09
0.13
0.02
0.01
0.03
0.01
0.02
0.07%
0.04
0.01
0.05
0.01
0.01
413
28
29
30
1126
1342
1351
Valencia late
Washington Naval
Tengelo Seminole
MHG
HD
CP
MHG
HD
CP
MHG
HD
CP
MHG
HD
CP
0.24
0.02
0.01
0.30
0.05
0.33
0.01
0.26
0.03
0.38
0.05
0.43
0.06
0.31
0.04
0.18
0.02
0.06
0.01
0.01
0.07
0.03
1400
1645
1706
0.23
0.06
0.01
0.03
0.01
0.01
180
1.3
0.89
98.36
60
0.3
0.91
97.68
60
0.2
1.09
98.51
15
0.9
1.12
96.53
15
1.2
0.89
98.04
180
1.3
1.26
97.59
60
0.3
0.65
98.21
15
1.2
1.34
98.56
15
1.0
1.40
98.83
180
1.1
0.84
98.68
180
1.0
0.98
98.83
60
0.2
0.49
97.71
Essential oil compounds sorted by chemical families and percentages calculated by GC-FID on non-polar HP5MSTM capillary column.
Retention indices calculated on non-polar HP5MSTM capillary column.
Retention indices calculated on polar CarbowaxTM-PEG capillary column.
4. Conclusion
This is the rst time that microwave heating has been used in
combination with earth gravity to devise a fast and efcient extraction technique. Both the re-design of the glassware and the application of microwaves afford a development of a method that serves
as an example of its usefulness. Microwave hydro-diffusion and
gravity (MHG) makes use of physical and chemical phenomena
that are fundamentally different from those applied in conventional solvent extraction and distillation techniques. Using this novel process, fully reproducible extractions can now be completed in
minutes without adding solvent or water. Its additional advantages
are simplied manipulation and work-up, a higher purity of the nal product, no need for a post-treatment of waste water and the
consumption of only a fraction of the energy normally required
by conventional food extraction methods.
F2 (12.47 %)
-1
-2
-3
-5
-4
-3
-2
-1
F1 (87.53 %)
Fig. 4. Canonical discriminant analysis (CDA) measured on eight different citrus
fruits considering extraction methods MHG (d), HD () and CP (D) as dependent
variable and concentrations of 10 volatile compounds as explanatory variables.
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