Separation and Purification Technology 48 (2006) 94105

The effects of both preparation method and season

on the supercritical extraction of ginger
S. Balachandran a , S.E. Kentish a, , R. Mawson b
a

Co-operative Research Centre for Bioproducts, Department of Chemical and Biomolecular Engineering,
University of Melbourne, Vic. 3010, Australia
b Food Science Australia, Sneydes Road, Werribee, Vic. 3030, Australia

Abstract
Experiments were conducted to study and compare the supercritical extraction of oleoresin from fresh, oven-dried and freeze-dried ginger
samples. When new season water-rich fresh ginger rhizomes were utilised, higher extraction yields resulted relative to both the oven-dried
and freeze-dried samples. Mathematical modelling of experimental data confirmed that this yield enhancement resulted principally from an
enhancement in the effective diffusivity within the ginger particle. However, when a more fibrous and less moist old season ginger supply was
utilised, the mass transfer rate in all samples declined. Further, the reduction in effective diffusivity was most pronounced for the fresh ginger
sample. HPLC analysis showed that the ginger extract obtained from the oven-dried feed contained proportionately less gingerols and more
shogaols due to thermal degradation. This confirms that the utilisation of fresh ginger rhizomes for supercritical extraction would lead to a
more pungent and naturally flavoured extract. However, there are a number of significant disadvantages to this approach from a manufacturing
perspective that would need to be considered.
2005 Elsevier B.V. All rights reserved.
Keywords: Supercritical extraction; Mass transfer; Moisture level; Ginger; Shrinking core model

1. Introduction
The extraction of soluble essences from natural products
using supercritical fluids has significant advantages over conventional methods such as steam distillation and Soxhlet
extraction [13]. Higher solubilities, mass transfer rates and
selectivities make supercritical fluid extraction (SFE) more
attractive. The selectivity of the compound to be extracted
is dependent on the density of the supercritical fluid, which
can be altered by varying process conditions. The low latent
heat of evaporation and high volatility of the solvent makes
the extract free from residual solvent. Moreover, extraction
can be conducted at low temperatures, which helps preserve
thermally degradable food products [46].
Supercritical carbon dioxide (Sc. CO2 ) is considered to
be a particularly useful solvent in the extraction of essential oils from vegetable substrates due to its environmentally

Corresponding author. Tel. +61 3 8344 6682; fax: +61 3 8344 4153.
E-mail address: sandraek@unimelb.edu.au (S.E. Kentish).

1383-5866/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2005.07.008

benign nature. However, one limitation to the use of this fluid

for extraction is its non-polar nature. The use of co-solvents
and modifiers has been studied by various researchers [79]
to overcome this limitation. Water and solvents such as
ethanol, isopropanol, acetone and methanol are among the
more acceptable co-solvents for food grade products. The
advantage of water over organic solvents is that the extraction
process remains clean and non-toxic. Organic solvents are
highly flammable, which further restricts their use in industry.
A number of research groups have also considered the
influence of the substrate moisture level on extraction yield
using Sc. CO2 . Hubert and Vitzthum [10] observed that the
normal moisture content of tobacco had to be increased by up
to 25% to affect nicotine extraction. Zosel [11] reported that
pre-soaking coffee beans aids the removal of caffeine. Similar
pre-soaking characteristics are reported by Nguyen et al. [12]
to increase the extraction of vanilla from vanilla beans. Leeke
et al. [13] studied the degree of extraction of essential oil from
a model herb (Origanum vulgare L. ssp. Virens letswarrt)

S. Balachandran et al. / Separation and Purication Technology 48 (2006) 94105

Nomenclature
ap
Bi
C
Ci
Csat
De
Ds
Kf
m
q
q
q0
r
rc
R
t
u
VCO2
Vg
X
Xi
Y

specific surface area of the particle (m2 /m3 )

Biot number, Kf R/De
solute concentration in the bulk fluid phase
(kg/m3 )
solute concentration in the pore volume of the
solid (kg/m3 )
saturation concentration of the solute in the
CO2 phase (kg/m3 )
effective solid diffusivity (m2 /s)
solid diffusivity (m2 /s)
external mass transfer coefficient (m/s)
partition coefficient (m3 of ginger/m3 of CO2 )
solid phase solute concentration (kg/m3 )
average solid phase solute concentration
(kg/m3 )
initial solid phase solute concentration (kg/m3 )
radial co-ordinate in particle (m)
radius of the core (m)
radius of the solid particle (m)
time (s)
superficial velocity (m/s)
volume of carbon dioxide in the vessel (m3 )
volume of ginger in the vessel (m3 )
dimensionless concentration in the bulk fluid
phase, C/Csat
dimensionless concentration within the pore
volume, Ci /Csat
dimensionless concentration in the solid phase,
q/qo

Greek letters

dimensionless time, De /R2 t

dimensionless radial coordinate of the particle,

r/R
c
dimensionless core radius in the particle, rc /R

with varying bed moisture levels. They observed that extraction was enhanced due to changes in the transport properties
of the solvent and a decrease in intraparticle resistance of
the solute inside the particles. Fahmy et al. [14] studied the
effect of modifiers (water, methanol and acetonitrile) in the
extraction of solutes from clay, soil and plant matrices. They
showed that the swelling properties of water can also enhance
the extraction process. Conversely, an inhibiting effect of
water on extraction has also been reported. Antunes et al.
[15] observed an increase in extraction of organochlorines
from freeze-dried fish samples compared to fresh fish fillet samples, but could not explain the inhibiting effect of
water. Smyth et al. [16] observed a decrease in extraction of
naphthalene from a soil matrix, when the moisture content
of the matrix was increased from 10 to 20%. A condition

95

termed water bridging which lowers the interfacial areas

and increases path length was considered to be controlling the
mass transfer process. Recently, Yoda et al. [17] reported a
lower yield from Stevia rebaudiana containing 510% moisture at supercritical conditions, but obtained higher yield at
subcritical conditions.
While most of the literature has shown that a high moisture
content has a positive effect on extraction processes, the focus
has tended to be on analytical aspects such as the amount
of moisture required and the composition of the resultant
extracts. Information on the effects of moisture content on
the intrinsic kinetic parameters is lacking.
In this work, the influence of water on the extraction kinetics, solubility parameters and overall yield of the soluble
essence from a typical herb is studied. The model herb used
was Ginger (Zingiber Ofcinale Roscoe), which belongs to
the Zingiberceae family. Ginger is a food crop used worldwide as a spice and food-flavouring agent. Its neutraceutical
properties have been of interest in food processing and in
the pharmaceutical industries [18]. The essential oil consists of monoterpenes and sesquiterpenes, which contribute
to the characteristic flavour of ginger. The more volatile
oleoresin is responsible for the pungent flavour of ginger
and is a source of anti-oxidants. The main pungent compounds are the series of homologues called gingerols, which
are prominent in fresh ginger. 6-Gingerol(5-hydroxyl-1-(4hydroxy-3-methoxyphenyl)decan-3-one) is the most abundant constituent in the gingerol series [19].
Most works in the scientific literature consider the supercritical extraction of oleoresin from dried ginger. Spiro and
Kandiah [20] studied the extraction kinetics of sun-dried
Jamaican ginger at various temperatures and pressures. They
reported the rate constant of the extraction process as a function of three stages: a short washing stage, a longer fast
extraction stage and a slow extraction stage. They note that
water appeared to play a role in the extraction kinetics, but
conclude that the increase in solvent density would be dominating rather than the entraining effect of water. Roy et al.
[21] propose a shrinking core model to explain the extraction
of ginger oil from freeze-dried ginger. They showed that solvent density and solute vapour pressure dominate the mass
transfer rate. Yonei et al. [22] studied the influence of various
process parameters on the extraction rate of Chinese type ginger. Martinez et al. [23] solved the differential mass balance
model with logistic equations to explain their results.
While these workers consider dried ginger, it is well
known that during the industrial drying process, gingerol
dehydrates to a series of homologues called shogaols [19,24],
which have less pungent properties and lower antioxidant
activity. Only Bartely et al. [25,26] have considered the
extraction of the more pungent fresh ginger. While they did
not collect any kinetic data, they identified the chemical composition of the extract using gas chromatography (GC)mass
spectrometry (MS) and GCelectrospray mass spectrometry
(EMS). They show that as a result of the drying process,
approximately 50% of the gingerols convert into shogaols

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S. Balachandran et al. / Separation and Purication Technology 48 (2006) 94105

and the remainder to zingerone and hexanal. They argue that

the compositional changes that occur during drying would
be perceived by the consumer as a decrease in the pungency
and that supercritical fluid extraction could produce a flavour
extract that preserved the natural characteristics of the fresh
product.
The main objective of this work is thus to further investigate the effect of the moisture content and drying method on
the supercritical extraction of a pungent oleoresin from ginger. We aim to determine whether the use of a fresh ginger
substrate could improve both the quality and quantity of the
extract and the efficacy with which it could be produced.

batches were freeze dried using a commercial scale freeze

drier which was operated for 4872 h at 20 C and high
vacuum. Further samples from both batches were oven dried
in a laboratory oven for 6 h at 60 C, to replicate the industrial
drying conditions commonly used in Australia.
It was assumed that the freeze drying process produced a
product of negligible water content. Based on the total weight
loss during freeze drying, the initial moisture content of the
original sample was then calculated as 96 wt% for Batch A
and 83.5 wt% for Batch B. Similarly, the residual water content of the oven dried samples was calculated to be <1 wt%
for both batches.
2.2. Experimental method

2. Experimental
2.1. Materials and sample preparation
Two different batches of fresh ginger rhizomes were
bought from Queensland through a local market during
February of 2003 and 2005. While these batches were purchased in the same calendar month, Batch A was a new season
product with a white-yellow flesh appearance. Conversely,
Batch B was old season ginger from the previous harvest and
was characterised by a more fibrous and darker appearance.
Both batches were refrigerated at 4 C to avoid loss of
freshness. Each rhizome was peeled and cut into uniform size
cylinders using an industrial cutting machine. The cylinder
height was adjusted to ensure the total volume was equivalent
to that of a sphere of identical diameter. Samples from both

A 150 ml stainless steel batch extractor was used in all

experiments. This vessel is immersed in a temperature controlled water bath. As shown in Fig. 1, the extraction vessel is
coupled with an online UVvis spectrophotometer with independent temperature control for kinetic extraction studies. A
magnetic gear drive pump (model 1805/IEC71, Micropump)
provides circulation through a stainless steel high-pressure
cell with sapphire windows (Graseby Specac, UK) which
was placed within the spectrophotometer. By adjusting the
valve positions, the flow can be directed through a baseline
loop that bypasses the sample vessel, or through a sampling
loop that includes the extractor.
At the beginning of each experiment, the extraction vessel
was packed with 3 mm glass beads and the required amount of
ginger. The unit was then heated to the desired temperature.

Fig. 1. Process flow sheet for Sc. CO2 extraction experiments.

S. Balachandran et al. / Separation and Purication Technology 48 (2006) 94105

Liquid carbon dioxide was delivered to a syringe pump (ISCO

260D, USA) and pressurised to the desired pressure.
The baseline loop was then pressurised to the desired
operating pressure. Baseline spectral measurements for pure
CO2 were recorded in the spectrophotometer. Experiments
only proceeded if this baseline reading was within 0.05 of
zero. The extraction vessel was then pressurised with CO2 .
This pressurization takes approximately 810 min and spectral data collection commenced only at the end of this stage.
The spectral data was recorded at 2 min intervals by the spectrophotometer as extraction proceeded. Pressure, temperature
and flow rates were checked periodically to ensure consistency.
After completion of the extraction process, CO2 was
depressurised through a needle valve to a Dreschel bottle containing 30 ml of methanol. This methanol sample was filtered
and used for HPLC analysis. The CO2 was vented to atmosphere through a rotameter (MFG Co. Ltd., UK) and a gas
flow meter (Alexander Wright and Co. Ltd., UK), which was
used to verify the amount of CO2 used in the experiment.
The unit was cleaned with pure CO2 and organic solvents.
Finally, a baseline scan was performed to confirm that no
solute remained.
Experiments were conducted at 160 bar pressure and 40 C
temperature with three different particle sizes of fresh, ovendried and freeze-dried ginger samples. Previous work has
indicated that these conditions are the most suitable for ginger
extraction [26]. Higher temperature can cause gelatinisation
of starch, which may block the cell walls and disturb mass
transport of the solute [27]. Most researchers [18,19,28] have
considered the pungent compounds, which are principally
gingerols and shogaols, to have a spectral absorbance peak
at 280 nm. This assumption is used in this work to record
kinetic data. The solvent concentration was calculated using
BeerLamberts law [29] from the absorbance recorded at
280 nm in the spectrophotometer, using an extinction coefficient of 3000 l/(mol cm) [28].
In preliminary experiments, the quantity of ginger
required to give acceptable absorbance readings was estimated. It was found that for Batch A, much less ginger was

97

required (on a dry solids basis) for the fresh ginger than for
the oven-dried ginger and the freeze-dried sample required
an intermediate quantity. The exact quantities used are given
in Table 1.
Some runs are repeated in duplicate to confirm the accuracy of the experimental method. These duplicate runs suggested that concentration data could be replicated to within
10% deviation.
2.3. Chromatographic analysis
High-performance liquid chromatography (HPLC), gas
chromatographymass spectrometry (GCMS) and thin layer
chromatography (TLC) have all been used in the past to analyse supercritical ginger extract [30,31]. The pungent compounds can be separated as groups by TLC on silica gel plates,
but individual components cannot be well resolved. With
GCMS, pungent compounds can undergo spontaneous thermal degradation and dehydration. Connell [19] has concluded
that GC is an unsatisfactory tool to examine gingerol and
shogaol levels. Conversely, other researchers [26,32] have
successfully used GCMS to analyse the concentration of
the essential oil components. HPLC is considered to be the
best analytical tool by many researchers [30,33] to quantify
particular compounds of similar absorbance that are present
in low concentrations within an extract.
In the present work, a Shimadzu liquid chromatography
system equipped with a model LC-10 AT VP solvent delivery pump, a Rheodyne 7125 injector (loop volume of 20 l)
and a SPD-10AV VP variable wavelength UVvis detector was used. A reversed phase column (Exil ODS RP-18,
25 cm 4.6 mm, 5 m) was purchased from SGE. Analysis
was conducted using an isocratic method with a mixture of
HPLC grade methanol and water (70:30, v/v). The analysis time was 30 min. The mobile phase flow was 1 ml/min
and detection was based on UV absorption at 280 nm. The
compounds were identified and quantified based on retention times using both published data from the literature and a
6-gingerol HPLC standard purchased from Wako Pure Chemical Industries, Osaka, Japan (99% purity).

Table 1
Physical property data used as input to the models
Pressure (bar)
Temperature (K)
CO2 density (kg/m3 )
CO2 viscosity (kg/(m s))
CO2 -gingerol diffusivity in supercritical phase (m2 /s)
External mass transfer coefficient Kf (m/s)
Superficial velocity in bed (m/s)

160
313
796.4
0.06869 103
7.2 109
6 105
1.9 103

Batch A ginger

Bulk density (kg/m3 )

Sample mass (g)
Sample dry mass (g)
Initial gingerol content (wt% of dry solids)

Batch B ginger

Fresh

Freeze-dried

Oven-dried

Fresh

Freeze-dried

Oven-dried

1060
9
0.45
2.4

74
1
1
2.4

578
1.74
1.71

1077
9
1.5
2.2

196
1.5
1.5
2.2

714
1.74
1.71

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S. Balachandran et al. / Separation and Purication Technology 48 (2006) 94105

3. Mathematical model development

The equation for the diffusion within the spherical particle

is

The basic assumptions made in developing a mathematical

model replicate those used by other researchers. That is:
(a) The extraction vessel is considered to be filled with
homogeneous spherical particles of uniform size.
(b) Several compounds will be simultaneously extracted
from the ginger. However, the model considers the
behaviour only of a single pseudo-component, characterized by 6-gingerol with a spectrophotometric absorbance
peak at 280 nm. A similar assumption has been made by
a number of workers [18,19,28].
(c) There is a continuous low flow through the extractor
because of the flow loop through the spectrophotometer. While this flow is assumed to enhance the external
mass transfer coefficient through standard correlations,
the extractor is otherwise considered as a well-mixed
reactor with minimal axial and radial concentration gradients and negligible pressure drop.
(d) The system is isothermal and isobaric.
(e) The physical properties of Sc. CO2 are constant.
Further development of mathematical models requires
consideration of the specific microscopic structure of the
solid. In the case of the fresh ginger particle, the solute is
evenly dispersed through a water-filled matrix. During extraction, this solute will migrate through this water-rich phase to
the particle surface where it will desorb into the supercritical
fluid phase. Conversely, in a dried particle, the supercritical
fluid must first diffuse into the particle pore structure. As
the extraction vessel is not evacuated prior to experiments,
any residual air content within the pores may retard this solvent penetration. Desorption of solute into the solvent will
then occur within the particle pores, followed by migration
through Sc. CO2 fluid phase to the particle surface and beyond
to the bulk phase.
3.1. Solid diffusion model for fresh ginger
For fresh ginger, we assume that the gingerol solute is
already contained within the water-rich matrix. The rate
determining steps are diffusion to the particle surface, characterised by a diffusion coefficient (Ds ) and external mass
transfer, characterised by a fluid phase mass transfer coefficient (Kf ). Desorption from the water-rich phase into the
supercritical phase is assumed not to be rate controlling but
characterised by an equilibrium relationship:
C(R) = mq(R)

(1)

The differential mass balance in the bulk fluid phase surrounding each particle is
Vg ap Kf [C(R) C]
dC
=
dt
VCO2

(2)

In Eq. (2), ap = 3/R is the specific surface area of the particle.

2

q 2q
q
= Ds
+
t
r 2
rr

(3)

The initial and the boundary conditions for Eqs. (1)(3) are
C[t = 0] = 0
(0 r R)
q[r, 0] = q0
q
=0
(r = 0; t 0)
r
q
= Kf [C C(R)] (r = R; t 0)
Ds
r
These equations were converted into a dimensionless format
and then solved using a finite difference approach with the
Mathematica 4.1 software package.
3.2. Shrinking core model for freeze-dried ginger
For freeze-dried ginger we use the shrinking core model
developed by Goto et al. [34], but adapted to a batch extraction process. With this model, an inner non-extracted core
shrinks as extraction progresses. Solute is desorbed from the
boundary of the non-extracted core, resulting in a sharp dissolution front with a saturated fluid concentration (Csat ) at
this point. The solute then diffuses through the pore structure
with an effective diffusivity (De ). This is followed by mass
transfer through the bulk fluid phase with a mass transfer
coefficient (Kf ).
The rate of solute mass transfer into the bulk fluid phase
can be expressed in terms of the gas phase mass transfer
coefficient (Kf )
Vg
dC
=
ap Kf [Ci (R) C]
dt
VCO2

(4)

Eqs. (2) and (4) are similar, except that the mass transfer is
from the solid bulk in the first case and from the pore volume
in the latter case.
Similarly, the rate of solute mass transfer from the solid
phase can also be written in terms of the gas phase mass
transfer coefficient (Kf ):
dq
= ap Kf [C Ci (R)]
dt
Diffusion in the pore is given by:


De
2 Ci
r
=0
r2 r
r

(5)

(6)

The average solid phase concentration (q) is described as a

function of particle diameter:
 r 3
q
c
=
qo
R

(7)

S. Balachandran et al. / Separation and Purication Technology 48 (2006) 94105

The initial and boundary conditions are given by:

C[t = 0] = 0
(0 r R)
q[r, 0] = q0
Ci [r, t] = Csat
(r = rc ; t 0)
Ci
De
= Kf [C Ci (R)] (r = R; t 0)
r
The above equations and the initial and boundary conditions
can be expressed in terms of the following dimensionless
variables as:



3BiVg
1X
dX
=
(8)
d
VCO2 1 Bi(1 1/c )
Y = c3

(9)

The respective initial and boundary conditions are:

X[ = 0] = 0
(0 c 1)
Y [c , = 0] = 1
X
= Bi[bX Xi (1)] (c = 1; 0)
c
(0 c 1; = 0)
Xi = 1
The above dimensionless differential equations and their
respective initial and boundary conditions were solved
numerically using a fourth order RungeKutta method within
the Mathematica 4.1 software package.
While the freeze-dried ginger was modelled using this
approach, we elected not to model the oven-dried results.
This data tended to be less reproducible than that obtained
for fresh and freeze-dried samples. We believe this increased
variability arose from the less uniform particle shapes and
size distributions that resulted from the oven drying process.
3.3. Estimation of properties for theoretical analysis
In order to utilise the above models, the viscosity of Sc.
CO2 was estimated using the empirical correlation of Jossi et
al. [35]. The binary diffusion coefficient for gingerolcarbon
dioxide at supercritical conditions was calculated by the
method proposed by Takahashi [36]. The estimated values
are shown in Table 1.
As a major portion of the extractor bed was dominated by
glass beads, it is best to calculate the bed void fraction based
on the packing of these beads. A value of 0.5 was calculated
from the ratio of the volume occupied by glass beads to that
of the total volume of bed. This bed void fraction was used
to calculate the interstitial velocity of solution through the
bed. The external mass transfer coefficient Kf , was estimated
from the empirical correlation reported by Wakao et al. [37]
for solids and liquids or gases at low pressure regions. The
correlation is valid for 3 < Re < 3000, which was within the
range of our experimental conditions. The bulk density of
individual ginger particles is calculated from the ratio of mass
to volume.

99

To determine the initial concentration of gingerol compounds in each batch, about 0.1 g of ground freeze-dried ginger was mixed with 30 ml of methanol in a conical flask and
stirred using a shaker table. Samples were taken every 24 h
and the spectrophotometric absorbance recorded at 280 nm.
Sampling continued until this absorbance reached a constant
value. Generally, extraction was complete in 24 h. On this
basis, the initial amount of gingerols/pungent compounds was
calculated as 2.4 wt% (on a dry solids basis) for the new season Batch A ginger and 2.2 wt% for the old season Batch
B ginger. These values are consistent with literature values
[18,24] that vary from 1.9 to 3 wt%. It is normally found that
the gingerol in old season ginger is higher than that in the
new season product. While on a dry ginger basis this is not
reflected in the present results, on a total solids basis, the gingerol is significantly higher in Batch B, because of the lower
water content of this material. On a total solids basis, the
respective gingerol contents in the fresh ginger of Batch A
and Batch B are qo = 1.3 kg/m3 and 3.9 kg/m3 , respectively.
Further, the Batch B ginger had probably been stored for a
number of months, and such storage is also known to lead to
a reduction in gingerol content [24].
It was difficult to use this approach to determine the
quantity of gingerol in the fresh ginger samples. However,
Zhang et al. [24] have shown that contrary to oven drying,
freeze-drying does not result in a significant loss of gingerol.
Consequently, we utilised the freeze-dried values in our fresh
ginger modelling.

4. Results and discussion

Figs. 2 and 3 show the concentration of pungent compounds (the pseudo-component gingerol) as a function of
both time and particle size for fresh and freeze-dried ginger samples from Batch A. Results with all ginger samples
showed a significant dependence upon particle size which is
consistent with the work of other researchers [21,22].
Of greater interest in the present work is that the water
abundant fresh ginger from Batch A shows a significant

Fig. 2. Concentration of pungent compounds in the bulk fluid phase for

different particle sizes of Batch A fresh ginger. Continuous curves from
model. Amount of ginger used (dry basis) = 0.45 g.

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S. Balachandran et al. / Separation and Purication Technology 48 (2006) 94105

Fig. 3. Concentration of pungent compounds in the bulk fluid phase for different particle sizes of Batch A freeze-dried ginger. Continuous curves from
model. Amount of ginger used (dry basis) for 4.02 mm particle size = 1.5 g,
and for 5.8 and 7.7 mm particle size = 1 g.

increase in the extraction of oleoresin over that of the dried

ginger. In these experiments, it was observed that extraction was higher from fresh ginger even though the extractor
was loaded with 23 times less solids on a dry weight basis.
Fig. 4 shows the extraction yield (i.e. the grams of pungent
compounds extracted divided by the grams of dry solids in
the feed) as a function of time for fresh, freeze-dried and
oven-dried ginger of around 6 mm particle size. This relative
increase can be related to three possible factors:
(a) the dissolution of water into the supercritical phase
enhancing the solubility of gingerol through an entrainer
type mechanism. Under the experimental conditions,
0.074 g of water would be expected to dissolve in the
working volume of Sc. CO2 (110 ml) at equilibrium [38].
This is less than 1% of the total water present in the fresh
ginger feed;
(b) the water-swollen ginger providing less mass transfer
resistance to the intra-particular movement of gingerol
to the particle surface;
(c) a significant loss of gingerol from the oven dried feed as
a consequence of the drying process itself.

Fig. 4. Yield of pungent compounds vs. extraction time for Batch A, based
on the on-line spectrophotometer results.

Fig. 5. Yield of pungent compounds vs. extraction time for Batch B, based
on the on-line spectrophotometer results.

To confirm whether these results persisted across a range

of ginger rhizome conditions, and in order to obtain HPLC
results, the above experiments were repeated with Batch B.
However, as shown in Fig. 5, in this case, the results are
reversed with freeze-dried ginger providing a higher yield
than the fresh product. All yields are also significantly lower
with Batch B.
4.1. Modelling results
The best fit to the fresh ginger data was obtained by varying the effective diffusivity (Ds ) and partition coefficient (m)
in the solid diffusion model until the sum of squared errors
was minimised. In dimensionless format, the data for different particle sizes collapse onto a single curve, making this
optimisation relatively straightforward. Fig. 2 shows the best
fit curves obtained while Table 2 summarises the optimised
Ds and m values and the standard errors obtained for both
batches.
The predicted effective diffusivity for Batch A is two
orders of magnitude higher than that of Batch B ginger. This
indicates that the resistance to solute diffusivity is significantly higher in Batch B, which would lower the yield at
any given time relative to Batch A experiments. Further, it
appears that the optimised partition coefficient is also lowered for Batch B experiments. This decrease in the partition
coefficient may reflect the lower water level in this batch.
As there is less water available, and the mass transfer rate of
water into the supercritical phase will also decline, this water
may not be as available to act as an entrainer and enhance the
equilibrium concentration of gingerol. However, the change
in the partition coefficient may also indicate that the use of a
linear equilibrium relationship is too simplistic. As shown in
Table 4, once the gingerol concentrations in the solid phase
are taken into account, the model predicts comparable saturation concentrations in the supercritical phase.
In modelling the freeze-dried ginger the unknown parameters are the effective diffusivity (De ) and saturation concentration value (Csat ). The best fit was again obtained by
varying these parameters until the sum of squared errors was

S. Balachandran et al. / Separation and Purication Technology 48 (2006) 94105

101

Table 2
Predicted effective diffusivity and partition coefficient values for different batches of fresh ginger
Fresh ginger

(m3

ginger/m3

Partition coefficient m
of
Effective Diffusivity Ds (m2 /s)
Particle size (mm)

of CO2 )
4.7

Standard error in concentration (kg/m3 )

0.0023

Batch A

Batch B

2.5
1.6 1011
6

7.9

1.0
4.8 1013
6.5

0.0010

0.0011

0.0016

Table 3
Predicted effective diffusivity and saturation concentration value for different batches of freeze-dried ginger
Freeze-dried ginger
Batch A

Batch B

4.02

3.0
1.4 1012
9.5 1013
5.7

7.5

5.0
9.2 1013
4.4 1013
6.3

3.9 103

9.3 104

6.7 104

1 103

(kg/m3 )

Saturation concentration Csat

Effective first stage
Diffusivity De (m2 /s) second stage
Particle size (mm)
Standard error in concentration

(kg/m3 )

minimised. Fig. 3 shows the best fit curves obtained while

Table 3 summarises the optimised De and Csat values and the
standard errors obtained.
While it was possible to fit the experimental data for
freeze-dried ginger with a single diffusivity value, a much
better data fit could be obtained by using one value of De
for the initial period of the experiments and a lower value in
latter stages. This slowing in mass transfer rate has been discussed by Sovova et al. [39] while modelling the extraction
of vegetable oil. They consider particles to have two different
regions; one region which is broken during sample preparation and the other which has intact cells. Marrone et al. [40]
also considered a similar approach to model the extraction of
almond seeds. They considered two different solute concentrations that have different mass transfer resistances inside the
solid particles. This hypothesis was confirmed by performing
scanning electron microscopy of the particles.
In this work, the model shows that the transition of effective diffusivity occurred at a constant penetration depth inside
all particles. This confirms that the solute is initially extracted
from ruptured cells and is unhindered by the cell membranes
and walls. In the later stages, extraction occurs from intact
cells and hence the diffusional resistance increases.
The predicted effective diffusivity for Batch A is again
larger than for Batch B ginger but the difference is less dramatic than in the fresh ginger case. Further, the optimised
saturation concentration Csat is in this case higher for Batch
B than Batch A ginger.

versely, in the freeze-dried ginger model, these pungent components partition into the supercritical phase, internally at the
core radius rc . The diffusivity therefore represents diffusion
through a supercritical phase. To compare these two diffusivities directly, it is necessary to convert the fresh ginger
diffusivity to a parameter based on the supercritical phase.
As discussed by Do and Rice [41] the appropriate conversion
is:
De =

Ds
m

(10)

Similarly, in the freeze-dried modelling, the partition coefficient is not explicitly calculated, rather only the equilibrium
saturation concentration, Csat . Again, for comparison purposes, this can be compared to the saturation concentration
that would be in equilibrium with fresh ginger, i.e.
Csat = mqo

(11)

Table 4 summarises the parameters for both fresh and

freeze-dried ginger on this basis. The predicted effective diffusivity for the fresh ginger from the water-rich new season
Batch A is five times higher than the value for the freezedried ginger samples. This high diffusivity may be explained
on the basis of the structure of the matrix. Batch A contains
Table 4
Comparison of kinetic parameters of fresh and freeze-dried ginger of Batch
A and Batch B
Kinetic
parameters

Batch A

Batch B

4.2. Comparison of kinetic parameters

Fresh ginger

De (m2 /s)
Csat (kg/m3 )

6.4 1012
3.2

4.8 1013
3.9

The diffusivity calculated from the fresh ginger simulations represents the flow of pungent compounds through
the water-saturated solid phase, with the partition into the
supercritical phase occurring at the outer solid surface. Con-

Freeze-dried ginger

De (m2 /s)
Csat (kg/m3 )

1.2 1012
3.0

6.8 1013
5.0

The effective diffusivity (De ) and saturation concentration (Csat ) values for
the fresh ginger are estimated from Eqs. (10) and (11).

S. Balachandran et al. / Separation and Purication Technology 48 (2006) 94105

102

Table 5
Comparison of predicted effective diffusivity (De ) value and saturation concentration (Csat ) values with literature values
Reference works (process conditions)
Roy et al. [21]: extraction with freeze dried ginger (245 bar, 40 C)
Goto et al. [34]: extraction studies with rapeseed (205 bar, 51 C)
Goodarznia and Eikani [42]: extraction with rapeseed, basil,
marjoram (100 bar, 40 C)
This work: fresh ginger (160 bar, 40 C)
This work: freeze-dried ginger (160 bar, 40 C)
a

Adjusted value to 160 bar, 40 Ca

Literature value
De (m2 /s)

Csat (kg/m3 )

De (m2 /s)

Csat (kg/m3 )

2.5 1010
1.5 1010
4.7 1013

1.25
2.5

4.2 1010
1.7 1010
2.6 1013

0.65
2.5

6.4 1012
1.4 1012

3.2
3.0

De values are adjusted using the method of Takahashi [36]. Csat values are adjusted using the empirical model suggested by Chrastll [44].

96% water, so there is low tortuosity and limited obstruction

to the flow path. This is in good agreement with the mechanism discussed by Leeke et al. [13] who consider the higher
solute diffusivity and the swelling of the matrix as reasons for
the enhancement of extraction yield from water filled matrices. When the more fibrous old season ginger is used in place
of Batch A, the diffusivity for both fresh and freeze-dried ginger falls. However, the decline for the fresh ginger product is
larger, leading to the reversal in the relative yields from these
products. This is consistent with the results of other workers
who find that high water contents are necessary to enhance
mass transfer rates.
The saturation concentrations in the four cases modelled
are comparable, indicating that the entraining effect of water
is marginal. The saturation concentration for Batch B is
slightly larger and this may be the result of changes in the
pungent compound composition between batches. Changes
in the relative proportions of the gingerols and shogaols that
absorb at 280 nm will affect the partition coefficient for the
overall pseudo-component modelled in this work.
The predicted kinetic parameters have been compared to
literature values and are summarised in Table 5. Predicted
effective diffusivity values are two orders of magnitude lower
than the values predicted by Roy et al. [21] and Goto et al. [34]
but an order of magnitude higher than the values predicted
by Goodarznia and Eikani [42] and Reverchon et al. [43].
Reverchon et al. [43] and Roy et al. [21] have pointed out
that such differences can be due to different mass transfer
mechanisms, cell structure, mechanisms of solute extraction
and molecular sizes and hydrophilic properties of the solute.

We further predict a significantly higher saturation concentration of gingerol in the supercritical phase for the freezedried ginger model relative to the values provided by Roy
et al. [21]. This may again be caused by sample variation.
Further, the results obtained by Roy et al. [21] were at a
significantly higher CO2 pressure and this will affect the
composition of the extract. Both Roy et al. [21] and the
present work measure gingerol concentration using only the
absorbance at 280 nm. This is a crude concentration measurement and changes in the composition of the pungent
extractives will influence the concentration equilibria.
4.3. High-performance liquid chromatography
In order to validate the concentration data, HPLC analysis
was also completed on the supercritical extracts from Batch
B. As indicated in the experimental procedure, the Sc. CO2
is exhausted into a methanol solution after extraction. However, we found that much of the final extract also deposited in
the tubing between the depressurising valve and the methanol
collection vessel. We consequently collected this material by
washing the tubing with a further quantity of methanol. Both
samples were analysed using the UV spectrophotometer in
order to quantify the total recovery of oleoresin before analysis with HPLC. As shown in Table 6, these spectrophotometer
results indicated that we had recovered between 60 and 75%
of the extract based on the final on-line spectrophotometric
results.
A number of compounds are eluted during HPLC analysis. Fig. 6 shows the different compounds eluted from fresh,

Table 6
Concentration of 6-gingerol in different samples of Batch B ginger analysed by a HPLC technique
Ginger type

Spectrophotometeric analysis of
total pseudo-component

HPLC analysis of 6-gingerol

Yield (wt% of
dry solids)

Total yield (wt%

of dry solids)

Yield (wt% of
dry solids)

Total yield (wt%

of dry solids)

Tube wash
Separator

0.070
0.051

0.12

0.013
0.012

0.025

20

Oven-dried
Ginger

Tube wash
Separator

0.11
0.048

0.16

0.025
0.0011

0.026

16

Freeze-dried
Ginger

Tube wash
Separator

0.16
0.028

0.19

0.047
0.0026

0.05

26

Fresh ginger

Tube wash: solvent from washing the tubings with methanol; separator: solvent from Dreschel bottle.

Percentage of 6-gingerol
in pseudo component

S. Balachandran et al. / Separation and Purication Technology 48 (2006) 94105

103

Fig. 6. HPLC chromatograms of: (A) fresh ginger extract; (B) oven-dried ginger extract; and (C) freeze-dried ginger extract. Peaks are: (a) 6-gingerol; (b)
8-gingerol; (c) 6-shogaol; (d) 8-shogaol; and (e) not identified.

oven-dried and freeze-dried ginger extract, which are identified based on retention times, in comparison with literature
results [30,33]. A qualitative analysis of these chromatograms
shows that the fresh ginger extract has a higher proportion of
gingerols compared to both the oven-dried and freeze-dried
ginger extracts, which are richer in shagoals.
Quantification of all these compounds is not possible as
6-gingerol is the only standard available commercially. However, as can be seen from Table 6, 6-gingerol indeed only
represents around 20% of the total quantity of compounds
that absorb at this wavelength. The proportion of 6-gingerol
in the oven-dried sample is lower than that for both the freezedried and fresh samples. This is probably due to thermal
degradation of 6-gingerol to shogaols during the oven drying
process, as also observed by Bartley et al. [26] and Zhang et al.
[24].
4.4. Other issues
While the results presented above show significant positive benefits from the use of a fresh ginger feed, there are
some disadvantages to this approach that must also be con-

sidered. Firstly, while the yield may be higher on a dry solids

basis, the volume of fresh ginger relative to the oven-dried
product is also higher. Given the high capital cost associated
with supercritical extraction vessels, the volume of ginger
that can be accommodated in a given run must also be considered. Thus, on a volume basis, around 10 times as much
oven or air-dried ginger could be accommodated within such
a vessel relative to the fresh product. Given this higher load,
there would indeed be a greater yield per run from the dried
product than from the fresh product.
Secondly, it is easier to store and transport a dried product relative to a fresh one. If fresh ginger was to be utilised
the extraction facility would need to be located close to the
harvesting site. It may also be necessary to add preservatives
to any fresh product being stored for long periods and this
would negate the fresh product marketing advantage.
Finally, this work was based on relatively large particle
sizes in order to extract kinetic data. In commercial practice
much smaller particle sizes are utilised. The yield enhancement described above for fresh ginger would increase as the
particle size is reduced. However, forming discrete particles
of very small size from fresh ginger would be difficult and

104

S. Balachandran et al. / Separation and Purication Technology 48 (2006) 94105

indeed a pulp or slurry is likely to result. The interfacial

area for mass transfer between this fresh ginger slurry and
the supercritical fluid could be reduced relative to the dried
ginger case.

5. Conclusion
This work has shown that the use of fresh ginger for supercritical extraction provides a greater yield than the oven or
air-dried feed currently employed commercially. When the
moisture levels within the fresh ginger are high as is the case
in new season rhizomes, the extract yield is also enhanced
relative to a freeze-dried feed. However, the yield enhancement falls significantly when the drier and more fibrous old
harvest ginger is utilised. Mathematical modelling of the
experimental data shows that these changes are principally
related to changes in the effective diffusivity of the extract
within the solid matrix. Further work might consider whether
mass transfer rates in old season ginger could be enhanced
by pre-soaking this material to increase the water load.
The use of fresh ginger for supercritical extraction also
leads to a product that is richer in the pungent gingerols
than the oven dried feed commonly used. The literature suggests that this extract could be better flavoured and more
pungent, which could be of significant marketing advantage
commercially. However, there are also some manufacturing
disadvantages relating to the use of a high volume and perishable feed stream that would need to be considered.

Acknowledgements
Financial support for this project from the Co-operative
Research Centre for Bioproducts is gratefully acknowledged.
Mr. Balachandran receives an International Postgraduate
Research Scholarship from the Australian government and a
Melbourne Research Scholarship from the University of Melbourne and this support is further gratefully acknowledged.
The infrastructure support for this project from the Particulate Fluid Processing Centre, a Special Research Centre of
the Australian Research Council, is also gratefully acknowledged.

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