Utilization of citrus peel by sub- and supercritical fluid technology

Motonobu Gotoa, Siti Machmudaha, Mitsuru Sasakib, Masahiro Tanakac

a
Bioelectrics Research Center, Kumamoto University, Kumamoto, Japan (mgoto@kumamoto-u.ac.jp)
b
Graduate School of Science and Technology, Kumamoto University, Kumamoto, Japan
c
Ascii Co. Ltd., Fukuoka, Japan

ABSTRACT
In the citrus juice production process, a large amount of by-product is generated. We have been developing
effective utilization processes to produce high value products by using sub- and supercritical fluids.
Supercritical CO2 was used as a green solvent to extract components such as essential oil, flavonoids, oil
from citrus peel and seeds. Subcritical water was used for reactive extraction of pectin and flavonoids from
citrus peel. We also developed a hybrid process to use supercritical CO 2 and subcritical water for the
efficient extraction process. In this work, yuzu (Citrus junos) was used as a citrus fruit.
Essential oil was extracted with supercritical CO2 from dry or wet citrus peel. Since yuzu contains a large
amount of seed, supercritical CO2 was used to extract N-methylanthranyl acid methyl, fatty acid, -sitosterol,
squalene, and vitamin E, as well as seed oil. Fractionation using a countercurrent extraction tower is a
promising process for deterpenation where aroma components of citrus oil is concentrated. Essential oil
obtained from yuzu peel was fractionated and oxygenated and sesquiterpene components are enriched.
By hydrothermal extraction where subcritical water was flowed through a packed bed of citrus peel after
extraction of essential oil, hydrophilic component, pectin, and minerals were eluted. As the temperature was
increased step-wise up to 200oC, pectin was extracted accompanied by molecular weight reduction.
Hybrid extraction was carried out using various type of extractor. By the mixed flow of supercritical carbon
dioxide and water, hydrophobic components were selectively extracted into carbon dioxide phase, whereas
hydrophobic components were extracted into water phase. By increasing the process temperature, pectin was
also extracted.

Keywords: Citrus fruit; supercritical carbon dioxide; subcritical water; extraction

INTRODUCTION
Citrus fruits have been widely used to produce juice and the other food products. In the juice production
process, a large number of wastes are generated. Since the waste contains valuable materials, they should be
utilized to produce high-value products. In this paper, the
development of extraction or reactive-extraction technologies
using supercritical fluid for the treatment of citrus waste is
described.
The objective of this research is to develop high pressure
technology to produce valuable materials from by-product of
citrus juice processing as shown in Fig. 1. By using supercritical
carbon dioxide, essential oil and pigments were extracted from
the citrus peel. After that process, subcritical water was used to
extract pectin and the flavonoids. Various citrus fruits were
used as the raw materials. We also proposed hybrid process
using simultaneously supercritical carbon dioxide and water to
extract hydrophobic and hydrophilic compounds from citrus
peel.

MATERIALS & METHODS

Yuzu (Citrus junos) was used as a citrus fruit. Citrus peel and
citrus juice production residue were used. A semi-batch
supercritical CO2 extraction apparatus (extractor: 500 ml, Figure 1 Total citrus utilization process.
AKICO Co., Japan) was used to extract
3.5E-04
essential oil and pigment. Fractionation of N-methylanthranylacid methyl
citrus essential oil was carried out by a

Extracted compounds (mg/g extract)

3.0E-04
-sitosterol
countercurrent extractor with a column of 20 Squalene
2.5E-04
mm i.d. and 1.8 m long packed with Dixon
Packing Subcritical water extraction was 2.0E-04

carried out (Toyo Koatsu Co., Japan). 1.5E-04

Subcritical water extraction from citrus peel
after supercritical CO2 extraction was carried 1.0E-04

out by a semi-batch extractor (8.7 mm i.d., 118 5.0E-05

mm long). A hybrid extraction apparatus
consists of an extractor with cocorrent or 0.0E+00
60 120 180 240 300 360
countercurrent flow of supercritical CO2 and Time (min)
water through packed bed of citrus peel.
Figure 2. Extracted compounds from seed at 343K and
RESULTS & DISCUSSION 20 MPa
Supercritical CO2 extraction from citrus peel
Essential oil was extracted with supercritical
CO2 at temperatures of 40 60 oC and Sample 40 60 80
pressures of 10 30 MPa. The highest 40-60 40-80 40-100
8
extraction yield of 91 % was obtained at 40
Oxygenated compounds content

o
C and 10 MPa. The monoterpene content in 7
the extract was 89.9 % and oxygenated 6
compounds were 7.7 %.
(GC area %)

Supercritical CO2 extraction from citrus seed 4

Since the fraction of seed in yuzu is 3
considerable, utilization of the seed is 2
important. Supercritical CO2 extraction from
1
ground seed was carried out at temperatures
o
of 40 70 C and pressures of 20 50 MPa. 0
The highest extraction yield was obtained at 0 1 2 3 4 5 Residue
6
Fraction number
higher pressure and temperature (50 MPa and
70 oC). The main components in the extracts were
N-methylanthranyl acid methyl as volatile Figure 3. Effect of temperature on oxygenated
compound, fatty acid, -sitosterol, squalene, and compounds content of the fractions and residue obtained
by SCCO2 column fractionation at 8.8 MPa
vitamin E as shown in Fig. 2.
The fatty acids in the oil extracted using
60 2.5
supercritical CO2 are palmitic, linoleic and Mg 2+

oleic acid as major componets and the minor Ca 2+

50 K +
Galacturonic acid [mg/ml]

compounds are palmitoleic, stearic and 10- 2

Galacturonic acid
octadecenoic acid. 160
40
Cation [mg/L]

1.5
Fractionation of citrus essential oil using
countercurrent extractor with supercritical 30 120

CO2 1
For a semi-batch operation of yuzu oil was 20
80
carried out at conditions of temperatures of 40
o 0.5
100 C and pressures of 8.8 20 MPa. 10
Enrichment of oxygenated compounds and
sesquiterpene is the objective of the 0 0
fractionation. In yuzu oil, typical 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29
characteristic aroma compounds are linalool Fraction NO.
and- and -elemene. As terpenes are
extracted selectively, these components are Figure 4. Hydrothermal extraction behavior of pectin
(galacturonic acid) and cations.
enriched in later fraction or residue as shown in Fig. 3. High recovery of these aroma components in the
residue was obtained at the extraction at 60 oC. Temperature gradient along the extraction column improved
the separation. Higher enrichment of sesquiterpene could be obtained at 8.8 MPa with temperature gradient
of 40 100 oC. The higher yield of extract was found at 20 MPa and 40 oC. 94% of -elemene was recovered
at 88 MPa and 60 oC.

Subcritical water extraction

Pectin was separated from the yuzu flavedo with subcritical water using a semi-continuous extractor. Water
was continuously delivered into the extractor while gradually increasing the temperature from 60 to 160 oC at
20 MPa. Pectin was rapidly extracted when the temperature of the extractor reached 160 oC as shown in Fig.
4. The yield of pectin reached as high as 80%. Large amount of potassium was extracted just prior to the
extraction of pectin, because extraction of potassium indicates destruction of the cell wall and membrane.
Calcium and magnesium was also extracted.

Hybrid extraction with supercritical CO2 and water SCCO2 + non-polar compound
We have proposed a hybrid extraction process with supercritical
CO2 and water. As shown in Fig. 5, supercritical CO2 and water
are flowing counter-currently over a packed bed of solid sample.
Water
Hydrophobic and hydrophilic compounds are selectively
extracted into CO2 and water phase, respectively.
Extraction of pectin and flavonoids were extracted by using a
semi-continuous flow extractor with a mixed flow of subcritical
water and supercritical CO2 at temperatures of 40 120 oC and
pressures of 10 30 MPa. Increasing pressure accelerated pectin
extraction and dissolved CO2 showed acidic effect. 90% of
pectin was obtained in water phase at 120 oC and 30 MPa as
shown in Fig. 6. Supercritical CO2 with small amount of
dissolved water was suitable solvent for extracting weakly polar
flavones such as naringin and hesperidin.
SCCO2

CONCLUSION Water + polar compound

By using supercritical CO2 and subcritical water, wide
Figure 5. Concept of simultaneous extraction and
spectrum of components from essential oil to pectin. separation process.
CO2 and water were used separately or simultaneously = Water; = SCCO2; = polar compound; =
as a mixed solvent. Synergetic effect of CO2 and water non-polar compound
was observed.

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