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The effects of both preparation method and season on the supercritical extraction of ginger
S. Balachandran a , S.E. Kentish a,∗ , R. Mawson b
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 [1–3]. 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 [4–6]. 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
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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 [7–9] 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  observed that the normal moisture content of tobacco had to be increased by up to 25% to affect nicotine extraction. Zosel  reported that pre-soaking coffee beans aids the removal of caffeine. Similar pre-soaking characteristics are reported by Nguyen et al.  to increase the extraction of vanilla from vanilla beans. Leeke et al.  studied the degree of extraction of essential oil from a model herb (Origanum vulgare L. ssp. Virens letswarrt)
1383-5866/$ – see front matter © 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.seppur.2005.07.008
Smyth et al. it is well known that during the industrial drying process. but could not explain the inhibiting effect of water. a longer fast extraction stage and a slow extraction stage. 6-Gingerol(5-hydroxyl-1-(4hydroxy-3-methoxyphenyl)decan-3-one) is the most abundant constituent in the gingerol series . Conversely. the focus has tended to be on analytical aspects such as the amount of moisture required and the composition of the resultant extracts.S. gingerol dehydrates to a series of homologues called shogaols [19.  observed a decrease in extraction of naphthalene from a soil matrix. 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.  studied the effect of modiﬁers (water.26] have considered the extraction of the more pungent fresh ginger. While these workers consider dried ginger.  solved the differential mass balance model with logistic equations to explain their results. 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.  studied the inﬂuence of various process parameters on the extraction rate of Chinese type ginger. but conclude that the increase in solvent density would be dominating rather than the entraining effect of water.  observed an increase in extraction of organochlorines from freeze-dried ﬁsh samples compared to fresh ﬁsh ﬁllet samples. Most works in the scientiﬁc literature consider the supercritical extraction of oleoresin from dried ginger. which contribute to the characteristic ﬂavour of ginger. an inhibiting effect of water on extraction has also been reported. While most of the literature has shown that a high moisture content has a positive effect on extraction processes. / Separation and Puriﬁcation Technology 48 (2006) 94–105 95 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. Information on the effects of moisture content on the intrinsic kinetic parameters is lacking. In this work. which have less pungent properties and lower antioxidant activity. Spiro and Kandiah  studied the extraction kinetics of sun-dried Jamaican ginger at various temperatures and pressures. r/R ξc dimensionless core radius in the particle. q/qo Greek letters θ dimensionless time. Only Bartely et al. the inﬂuence of water on the extraction kinetics. Recently. they identiﬁed the chemical composition of the extract using gas chromatography (GC)–mass spectrometry (MS) and GC–electrospray mass spectrometry (EMS). but obtained higher yield at subcritical conditions. A condition termed “water bridging” which lowers the interfacial areas and increases path length was considered to be controlling the mass transfer process. They showed that solvent density and solute vapour pressure dominate the mass transfer rate. The essential oil consists of monoterpenes and sesquiterpenes. Antunes et al. approximately 50% of the gingerols convert into shogaols . when the moisture content of the matrix was increased from 10 to 20%. They reported the rate constant of the extraction process as a function of three stages: a short washing stage. While they did not collect any kinetic data. Martinez et al. Roy et al. Balachandran et al.  propose a shrinking core model to explain the extraction of ginger oil from freeze-dried ginger. The main pungent compounds are the series of homologues called gingerols. De /R2 t ξ dimensionless radial coordinate of the particle.24]. They note that water appeared to play a role in the extraction kinetics. Its neutraceutical properties have been of interest in food processing and in the pharmaceutical industries . They showed that the swelling properties of water can also enhance the extraction process. Fahmy et al. which belongs to the Zingiberceae family. The more volatile oleoresin is responsible for the pungent ﬂavour of ginger and is a source of anti-oxidants. methanol and acetonitrile) in the extraction of solutes from clay.  reported a lower yield from Stevia rebaudiana containing 5–10% moisture at supercritical conditions. Ci /Csat dimensionless concentration in the solid phase. Yoda et al. [25. Ginger is a food crop used worldwide as a spice and food-ﬂavouring agent. C/Csat dimensionless concentration within the pore volume. which are prominent in fresh ginger. soil and plant matrices. solubility parameters and overall yield of the soluble essence from a typical herb is studied. They show that as a result of the drying process. Yonei et al. The model herb used was Ginger (Zingiber Ofﬁcinale Roscoe).
While these batches were purchased in the same calendar month. At the beginning of each experiment. / Separation and Puriﬁcation Technology 48 (2006) 94–105 and the remainder to zingerone and hexanal. Micropump) provides circulation through a stainless steel high-pressure cell with sapphire windows (Graseby Specac. to replicate the industrial drying conditions commonly used in Australia. Conversely. the ﬂow can be directed through a baseline loop that bypasses the sample vessel. The unit was then heated to the desired temperature. Balachandran et al. Each rhizome was peeled and cut into uniform size cylinders using an industrial cutting machine. Experimental 2. Both batches were refrigerated at 4 ◦ C to avoid loss of freshness. As shown in Fig. 1.96 S. the initial moisture content of the original sample was then calculated as 96 wt% for Batch A and 83. CO2 extraction experiments. the residual water content of the oven dried samples was calculated to be <1 wt% for both batches.1. Fig. By adjusting the valve positions. Samples from both A 150 ml stainless steel batch extractor was used in all experiments. UK) which was placed within the spectrophotometer. Batch B was old season ginger from the previous harvest and was characterised by a more ﬁbrous and darker appearance. . This vessel is immersed in a temperature controlled water bath. the extraction vessel is coupled with an online UV–vis spectrophotometer with independent temperature control for kinetic extraction studies.5 wt% for Batch B. the extraction vessel was packed with 3 mm glass beads and the required amount of ginger. or through a sampling loop that includes the extractor. 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. 1. batches were freeze dried using a commercial scale freeze drier which was operated for 48–72 h at −20 ◦ C and high vacuum. Experimental method 2.2. The cylinder height was adjusted to ensure the total volume was equivalent to that of a sphere of identical diameter. Batch A was a new season product with a white-yellow ﬂesh appearance. A magnetic gear drive pump (model 1805/IEC71. It was assumed that the freeze drying process produced a product of negligible water content. Process ﬂow sheet for Sc. 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. 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. Similarly. 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. Further samples from both batches were oven dried in a laboratory oven for 6 h at 60 ◦ C. 2. Based on the total weight loss during freeze drying.
to have a spectral absorbance peak at 280 nm.3.5 2. CO2 was depressurised through a needle valve to a Dreschel bottle containing 30 ml of methanol. a Rheodyne 7125 injector (loop volume of 20 l) and a SPD-10AV VP variable wavelength UV–vis detector was used. which are principally gingerols and shogaols. The pungent compounds can be separated as groups by TLC on silica gel plates.19. It was found that for Batch A. In preliminary experiments. This methanol sample was ﬁltered and used for HPLC analysis.31].06869 × 10−3 7. the quantity of ginger required to give acceptable absorbance readings was estimated. UK) and a gas ﬂow meter (Alexander Wright and Co. The mobile phase ﬂow was 1 ml/min and detection was based on UV absorption at 280 nm.9 × 10−3 Batch B ginger Oven-dried 578 1. temperature and ﬂow rates were checked periodically to ensure consistency.. The extraction vessel was then pressurised with CO2 .33] to quantify particular compounds of similar absorbance that are present in low concentrations within an extract. The exact quantities used are given in Table 1. a baseline scan was performed to conﬁrm that no solute remained.28] have considered the pungent compounds. Balachandran et al. Pressure.71 Fresh 1077 9 1.2 Oven-dried 714 1. The spectral data was recorded at 2 min intervals by the spectrophotometer as extraction proceeded.05 of zero. Experiments were conducted at 160 bar pressure and 40 ◦ C temperature with three different particle sizes of fresh. but individual components cannot be well resolved. In the present work. much less ginger was 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) Batch A ginger Fresh Bulk density (kg/m3 ) Sample mass (g) Sample dry mass (g) Initial gingerol content (wt% of dry solids) 1060 9 0. Analysis was conducted using an isocratic method with a mixture of HPLC grade methanol and water (70:30. Finally. The solvent concentration was calculated using Beer–Lambert’s law  from the absorbance recorded at 280 nm in the spectrophotometer. The unit was cleaned with pure CO2 and organic solvents.2 × 10−9 6 × 10−5 1. a Shimadzu liquid chromatography system equipped with a model LC-10 AT VP solvent delivery pump. Higher temperature can cause gelatinisation of starch. Ltd. The baseline loop was then pressurised to the desired operating pressure. ovendried and freeze-dried ginger samples. With GC–MS.2 Freeze-dried 196 1. / Separation and Puriﬁcation Technology 48 (2006) 94–105 97 Liquid carbon dioxide was delivered to a syringe pump (ISCO 260D.S. gas chromatography–mass spectrometry (GC–MS) and thin layer chromatography (TLC) have all been used in the past to analyse supercritical ginger extract [30. 25 cm × 4.74 1. UK).71 .4 0. other researchers [26. which may block the cell walls and disturb mass transport of the solute . Osaka. 5 m) was purchased from SGE.. 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.5 2. 160 313 796. This pressurization takes approximately 8–10 min and spectral data collection commenced only at the end of this stage. Baseline spectral measurements for pure CO2 were recorded in the spectrophotometer.74 1. which was used to verify the amount of CO2 used in the experiment. Previous work has indicated that these conditions are the most suitable for ginger extraction . Ltd. 2.5 1.6 mm. Chromatographic analysis High-performance liquid chromatography (HPLC).4 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. These duplicate runs suggested that concentration data could be replicated to within ±10% deviation.4 Freeze-dried 74 1 1 2.32] have successfully used GC–MS to analyse the concentration of the essential oil components. Experiments only proceeded if this baseline reading was within ±0. This assumption is used in this work to record kinetic data.45 2. After completion of the extraction process. pungent compounds can undergo spontaneous thermal degradation and dehydration. Japan (99% purity). Connell  has concluded that GC is an unsatisfactory tool to examine gingerol and shogaol levels. v/v). Some runs are repeated in duplicate to conﬁrm the accuracy of the experimental method. The CO2 was vented to atmosphere through a rotameter (MFG Co. Most researchers [18. The analysis time was 30 min. Conversely. A reversed phase column (Exil ODS RP-18. using an extinction coefﬁcient of 3000 l/(mol cm) . HPLC is considered to be the best analytical tool by many researchers [30. USA) and pressurised to the desired pressure.
. but adapted to a batch extraction process. we assume that the gingerol solute is already contained within the water-rich matrix. (1)–(3) are C[t = 0] = 0 (0 ≤ r ≤ R) q[r. This is followed by mass transfer through the bulk ﬂuid phase with a mass transfer coefﬁcient (Kf ). characterised by a diffusion coefﬁcient (Ds ) and external mass transfer. (2). However. Similarly. 0] = q0 ∂q =0 (r = 0. CO2 are constant.1 software package. the solute is evenly dispersed through a water-ﬁlled matrix. . (c) There is a continuous low ﬂow through the extractor because of the ﬂow loop through the spectrophotometer. the rate of solute mass transfer from the solid phase can also be written in terms of the gas phase mass transfer coefﬁcient (Kf ): d¯ q = ap Kf [C − Ci (R)] dt Diffusion in the pore is given by: De ∂ r2 ∂r r2 ∂Ci ∂r =0 (6) (5) The differential mass balance in the bulk ﬂuid phase surrounding each particle is Vg ap Kf [C(R) − C] dC = dt VCO2 (2) The average solid phase concentration (¯ q) is described as a function of particle diameter: q ¯ rc = qo R 3 (7) In Eq. any residual air content within the pores may retard this solvent penetration. followed by migration through Sc. Shrinking core model for freeze-dried ginger For freeze-dried ginger we use the shrinking core model developed by Goto et al. With this model. in a dried particle. (d) The system is isothermal and isobaric. (b) Several compounds will be simultaneously extracted from the ginger. That is: (a) The extraction vessel is considered to be ﬁlled with homogeneous spherical particles of uniform size. 3. Solute is desorbed from the boundary of the non-extracted core. this solute will migrate through this water-rich phase to the particle surface where it will desorb into the supercritical ﬂuid phase. Conversely. / Separation and Puriﬁcation Technology 48 (2006) 94–105 3. 3. Desorption of solute into the solvent will then occur within the particle pores. (2) and (4) are similar. t ≥ 0) ∂r ∂q = Kf [C − C(R)] (r = R.19. the extractor is otherwise considered as a well-mixed reactor with minimal axial and radial concentration gradients and negligible pressure drop. the model considers the behaviour only of a single pseudo-component. Balachandran et al. resulting in a sharp dissolution front with a saturated ﬂuid concentration (Csat ) at this point.28]. ap = 3/R is the speciﬁc surface area of the particle.1. The solute then diffuses through the pore structure with an effective diffusivity (De ). 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 equation for the diffusion within the spherical particle ∂2 q 2∂q ∂q = Ds + ∂t ∂r 2 r∂r (3) The initial and the boundary conditions for Eqs. The rate determining steps are diffusion to the particle surface. A similar assumption has been made by a number of workers [18. t ≥ 0) Ds ∂r These equations were converted into a dimensionless format and then solved using a ﬁnite difference approach with the Mathematica© 4. characterized by 6-gingerol with a spectrophotometric absorbance peak at 280 nm. Further development of mathematical models requires consideration of the speciﬁc microscopic structure of the solid. Solid diffusion model for fresh ginger For fresh ginger. except that the mass transfer is from the solid bulk in the ﬁrst case and from the pore volume in the latter case. CO2 ﬂuid phase to the particle surface and beyond to the bulk phase. 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.2.98 S. characterised by a ﬂuid phase mass transfer coefﬁcient (Kf ). Mathematical model development is The basic assumptions made in developing a mathematical model replicate those used by other researchers. the supercritical ﬂuid must ﬁrst diffuse into the particle pore structure. (e) The physical properties of Sc. an inner non-extracted core shrinks as extraction progresses. As the extraction vessel is not evacuated prior to experiments. In the case of the fresh ginger particle. During extraction. While this ﬂow is assumed to enhance the external mass transfer coefﬁcient through standard correlations.
Of greater interest in the present work is that the water abundant fresh ginger from Batch A shows a signiﬁcant Fig.  have shown that contrary to oven drying.  for solids and liquids or gases at low pressure regions.1 g of ground freeze-dried ginger was mixed with 30 ml of methanol in a conical ﬂask and stirred using a shaker table. Estimation of properties for theoretical analysis In order to utilise the above models. 0] = q0 Ci [r. freeze-drying does not result in a signiﬁcant loss of gingerol. which was within the range of our experimental conditions. the respective gingerol contents in the fresh ginger of Batch A and Batch B are qo = 1.2 wt% for the old season Batch B ginger. respectively.24] that vary from 1. On a total solids basis. The bulk density of individual ginger particles is calculated from the ratio of mass to volume.3. It was difﬁcult to use this approach to determine the quantity of gingerol in the fresh ginger samples. it is best to calculate the bed void fraction based on the packing of these beads. This bed void fraction was used to calculate the interstitial velocity of solution through the bed. 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. was estimated from the empirical correlation reported by Wakao et al. Generally. On this basis. The binary diffusion coefﬁcient for gingerol–carbon dioxide at supercritical conditions was calculated by the method proposed by Takahashi . θ = 0] = 1 ∂X = Bi[bX − Xi (1)] (ξc = 1.9 kg/m3 . Concentration of pungent compounds in the bulk ﬂuid phase for different particle sizes of Batch A fresh ginger. t ] = Csat (r = rc . Zhang et al. Samples were taken every 24 h and the spectrophotometric absorbance recorded at 280 nm. Results and discussion Figs. the initial amount of gingerols/pungent compounds was calculated as 2. 2. the gingerol is signiﬁcantly higher in Batch B. the Batch B ginger had probably been stored for a number of months.1 software package. The correlation is valid for 3 < Re < 3000. This data tended to be less reproducible than that obtained for fresh and freeze-dried samples. It is normally found that the gingerol in old season ginger is higher than that in the new season product. we elected not to model the oven-dried results. θ ≥ 0) ∂ξc (0 ≤ ξc ≤ 1. Amount of ginger used (dry basis) = 0. Results with all ginger samples showed a signiﬁcant dependence upon particle size which is consistent with the work of other researchers [21.S. because of the lower water content of this material.22]. . θ = 0) Xi = 1 The above dimensionless differential equations and their respective initial and boundary conditions were solved numerically using a fourth order Runge–Kutta method within the Mathematica© 4.4 wt% (on a dry solids basis) for the new season Batch A ginger and 2. 3. . t ≥ 0) δr The above equations and the initial and boundary conditions can be expressed in terms of the following dimensionless variables as: 3BiVg 1−X dX = dθ VCO2 1 − Bi(1 − 1/ξc ) 3 Y = ξc (8) (9) The respective initial and boundary conditions are: X[θ = 0] = 0 (0 ≤ ξc ≤ 1) Y [ξc . While on a dry ginger basis this is not reﬂected in the present results. we utilised the freeze-dried values in our fresh ginger modelling. t ≥ 0) δCi De = Kf [C − Ci (R)] (r = R. the viscosity of Sc. However. Further. The external mass transfer coefﬁcient Kf . We believe this increased variability arose from the less uniform particle shapes and size distributions that resulted from the oven drying process.45 g. extraction was complete in 24 h. A value of 0.3 kg/m3 and 3. While the freeze-dried ginger was modelled using this approach. 4. Consequently. The estimated values are shown in Table 1. Balachandran et al.9 to 3 wt%. about 0. These values are consistent with literature values [18. Continuous curves from model. / Separation and Puriﬁcation Technology 48 (2006) 94–105 99 The initial and boundary conditions are given by: C[t = 0] = 0 (0 ≤ r ≤ R) q[r. on a total solids basis. and such storage is also known to lead to a reduction in gingerol content . As a major portion of the extractor bed was dominated by glass beads. Sampling continued until this absorbance reached a constant value. To determine the initial concentration of gingerol compounds in each batch. CO2 was estimated using the empirical correlation of Jossi et al.5 was calculated from the ratio of the volume occupied by glass beads to that of the total volume of bed.
Amount of ginger used (dry basis) for 4. In these experiments. (b) the water-swollen ginger providing less mass transfer resistance to the intra-particular movement of gingerol to the particle surface. Fig. 5. However. which would lower the yield at any given time relative to Batch A experiments. 3. To conﬁrm whether these results persisted across a range of ginger rhizome conditions. However. Further. As there is less water available. it was observed that extraction was higher from fresh ginger even though the extractor was loaded with 2–3 times less solids on a dry weight basis.5 g. Concentration of pungent compounds in the bulk ﬂuid phase for different particle sizes of Batch A freeze-dried ginger. This is less than 1% of the total water present in the fresh ginger feed. 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. and for 5. 5.8 and 7. extraction time for Batch B. This decrease in the partition coefﬁcient may reﬂect the lower water level in this batch. Balachandran et al. As shown in Table 4. Fig. and in order to obtain HPLC results. This indicates that the resistance to solute diffusivity is signiﬁcantly higher in Batch B. freeze-dried and oven-dried ginger of around 6 mm particle size.7 mm particle size = 1 g. (c) a signiﬁcant loss of gingerol from the oven dried feed as a consequence of the drying process itself. 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 Fig. it appears that the optimised partition coefﬁcient is also lowered for Batch B experiments. 0. the change in the partition coefﬁcient may also indicate that the use of a linear equilibrium relationship is too simplistic. making this optimisation relatively straightforward.02 mm particle size = 1. increase in the extraction of oleoresin over that of the dried ginger. the results are reversed with freeze-dried ginger providing a higher yield than the fresh product.100 S. once the gingerol concentrations in the solid phase are taken into account. the above experiments were repeated with Batch B. Under the experimental conditions. based on the on-line spectrophotometer results. 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. The predicted effective diffusivity for Batch A is two orders of magnitude higher than that of Batch B ginger. 4. this water may not be as available to act as an entrainer and enhance the equilibrium concentration of gingerol. Continuous curves from model. Yield of pungent compounds vs.1.e. and the mass transfer rate of water into the supercritical phase will also decline. In dimensionless format. 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.074 g of water would be expected to dissolve in the working volume of Sc. Yield of pungent compounds vs. . based on the on-line spectrophotometer results. the grams of pungent compounds extracted divided by the grams of dry solids in the feed) as a function of time for fresh. extraction time for Batch A. in this case. as shown in Fig. / Separation and Puriﬁcation Technology 48 (2006) 94–105 Fig. the model predicts comparable saturation concentrations in the supercritical phase. CO2 (110 ml) at equilibrium . the data for different particle sizes collapse onto a single curve. 4 shows the extraction yield (i. All yields are also signiﬁcantly lower with Batch B. Fig. 4.
Csat . Balachandran et al.0023 2.7 0. internally at the core radius rc .2 × 10−13 4.8 × 10−13 5. This slowing in mass transfer rate has been discussed by Sovova et al.3 1 × 10−3 4. the model shows that the transition of effective diffusivity occurred at a constant penetration depth inside all particles.5 1. Comparison of kinetic parameters The diffusivity calculated from the fresh ginger simulations represents the ﬂow of pungent compounds through the water-saturated solid phase. Again. / Separation and Puriﬁcation Technology 48 (2006) 94–105 Table 2 Predicted effective diffusivity and partition coefﬁcient values for different batches of fresh ginger Fresh ginger Batch A Partition coefﬁcient m of Effective Diffusivity Ds (m2 /s) Particle size (mm) (m3 ginger/m3 of CO2 ) 4. Con- Fresh ginger Freeze-dried ginger De (m2 /s) Csat (kg/m3 ) De (m2 /s) Csat (kg/m3 ) The effective diffusivity (De ) and saturation concentration (Csat ) values for the fresh ginger are estimated from Eqs.5 6. these pungent components partition into the supercritical phase.4 × 10−13 6. The diffusivity therefore represents diffusion through a supercritical phase. one region which is broken during sample preparation and the other which has intact cells.  while modelling the extraction of vegetable oil. with the partition into the supercritical phase occurring at the outer solid surface. This conﬁrms that the solute is initially extracted from ruptured cells and is unhindered by the cell membranes and walls. Fig.0 4. the optimised saturation concentration Csat is in this case higher for Batch B than Batch A ginger.4 × 10−12 3.9 0.5 × 10−13 5.0 Batch B 4. They considered two different solute concentrations that have different mass transfer resistances inside the solid particles. 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. They consider particles to have two different regions.7 × 10−4 (kg/m3 ) minimised. In this work. 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 6. Csat = mqo (11) Table 4 summarises the parameters for both fresh and freeze-dried ginger on this basis.2.5 0.8 × 10−13 3. 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. This high diffusivity may be explained on the basis of the structure of the matrix.0016 Batch B 101 7.02 3.0010 1. versely. Further. extraction occurs from intact cells and hence the diffusional resistance increases. i.e.S. This hypothesis was conﬁrmed by performing scanning electron microscopy of the particles. In the later stages. Marrone et al. 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.0 4.9 × 10−3 7.3 × 10−4 Batch B 5.0 9. the partition coefﬁcient is not explicitly calculated.2 × 10−12 3. . While it was possible to ﬁt the experimental data for freeze-dried ginger with a single diffusivity value.2 1. in the freeze-dried modelling.0 1. 3 shows the best ﬁt curves obtained while Table 3 summarises the optimised De and Csat values and the standard errors obtained. rather only the equilibrium saturation concentration.8 × 10−13 6.9 6. As discussed by Do and Rice  the appropriate conversion is: De = Ds m (10) Similarly.  also considered a similar approach to model the extraction of almond seeds. To compare these two diffusivities directly. this can be compared to the saturation concentration that would be in equilibrium with fresh ginger. it is necessary to convert the fresh ginger diffusivity to a parameter based on the supercritical phase.7 9.4 × 10−12 9.6 × 10−11 6 0. (10) and (11).0011 Standard error in concentration (kg/m3 ) Table 3 Predicted effective diffusivity and saturation concentration value for different batches of freeze-dried ginger Freeze-dried ginger Batch A Saturation concentration Csat Effective ﬁrst stage Diffusivity De (m2 /s) second stage Particle size (mm) Standard error in concentration (kg/m3 ) 3. for comparison purposes. in the freeze-dried ginger model.
40 ◦ C) a Literature value De (m2 /s) 2.  and the present work measure gingerol concentration using only the absorbance at 280 nm. 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 Yield (wt% of dry solids) Fresh ginger Oven-dried Ginger Freeze-dried Ginger Tube wash Separator Tube wash Separator Tube wash Separator 0.  and Roy et al. so there is low tortuosity and limited obstruction to the ﬂow path.  have pointed out that such differences can be due to different mass transfer mechanisms. Reverchon et al. However. 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. separator: solvent from Dreschel bottle. marjoram (100 bar. High-performance liquid chromatography In order to validate the concentration data. the results obtained by Roy et al. CO2 is exhausted into a methanol solution after extraction. Predicted effective diffusivity values are two orders of magnitude lower than the values predicted by Roy et al.16 0. Further.  were at a signiﬁcantly higher CO2 pressure and this will affect the composition of the extract.65 2. . Balachandran et al. : extraction with freeze dried ginger (245 bar.047 0.5 – Adjusted value to 160 bar.7 × 10−13 Csat (kg/m3 ) 1. Csat values are adjusted using the empirical model suggested by Chrastll .19 HPLC analysis of 6-gingerol Yield (wt% of dry solids) 0. As indicated in the experimental procedure.12 0. The predicted kinetic parameters have been compared to literature values and are summarised in Table 5. 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.7 × 10−10 2.028 Total yield (wt% of dry solids) 0.0 De values are adjusted using the method of Takahashi . basil. the decline for the fresh ginger product is larger. Fig. .051 0.2 × 10−10 1. we found that much of the ﬁnal extract also deposited in the tubing between the depressurising valve and the methanol collection vessel.25 2. However.4 × 10−12 1. When the more ﬁbrous old season ginger is used in place of Batch A.2 3.3.  who consider the higher solute diffusivity and the swelling of the matrix as reasons for the enhancement of extraction yield from water ﬁlled matrices.  but an order of magnitude higher than the values predicted by Goodarznia and Eikani  and Reverchon et al. This is consistent with the results of other workers who ﬁnd that high water contents are necessary to enhance mass transfer rates.013 0. 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. cell structure. This is a crude concentration measurement and changes in the composition of the pungent extractives will inﬂuence the concentration equilibria. .16 0. / Separation and Puriﬁcation Technology 48 (2006) 94–105 Table 5 Comparison of predicted effective diffusivity (De ) value and saturation concentration (Csat ) values with literature values Reference works (process conditions) Roy et al. We consequently collected this material by washing the tubing with a further quantity of methanol.012 0.4 × 10−12 Csat (kg/m3 ) 0. HPLC analysis was also completed on the supercritical extracts from Batch B. the Sc.025 0.0011 0. leading to the reversal in the relative yields from these products. the diffusivity for both fresh and freeze-dried ginger falls.5 – 3.  and Goto et al.0026 Total yield (wt% of dry solids) 0. 96% water. 6 shows the different compounds eluted from fresh. This may again be caused by sample variation. 40 ◦ C) This work: fresh ginger (160 bar.05 20 16 26 Percentage of 6-gingerol in pseudo component Tube wash: solvent from washing the tubings with methanol. indicating that the entraining effect of water is marginal.048 0. these spectrophotometer results indicated that we had recovered between 60 and 75% of the extract based on the ﬁnal on-line spectrophotometric results. The saturation concentrations in the four cases modelled are comparable.102 S.5 × 10−10 4.5 × 10−10 1.11 0. 40 ◦ C) This work: freeze-dried ginger (160 bar. : extraction studies with rapeseed (205 bar. 4.070 0. 40 ◦ Ca De (m2 /s) 4.025 0. 51 ◦ C) Goodarznia and Eikani : extraction with rapeseed. Both Roy et al. mechanisms of solute extraction and molecular sizes and hydrophilic properties of the solute.026 0.6 × 10−13 6. 40 ◦ C) Goto et al. The saturation concentration for Batch B is slightly larger and this may be the result of changes in the pungent compound composition between batches. A number of compounds are eluted during HPLC analysis. This is in good agreement with the mechanism discussed by Leeke et al.
Secondly. 6. Balachandran et al. there are some disadvantages to this approach that must also be con- sidered. in comparison with literature results [30.33]. Other issues While the results presented above show signiﬁcant positive beneﬁts from the use of a fresh ginger feed. . 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. as can be seen from Table 6. and (e) not identiﬁed. The yield enhancement described above for fresh ginger would increase as the particle size is reduced. In commercial practice much smaller particle sizes are utilised. Peaks are: (a) 6-gingerol. This is probably due to thermal degradation of 6-gingerol to shogaols during the oven drying process. oven-dried and freeze-dried ginger extract. Finally.4. the volume of ginger that can be accommodated in a given run must also be considered.  and Zhang et al. However. 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. Given the high capital cost associated with supercritical extraction vessels. as also observed by Bartley et al. The proportion of 6-gingerol in the oven-dried sample is lower than that for both the freezedried and fresh samples. which are identiﬁed based on retention times. (c) 6-shogaol. (b) 8-gingerol. Given this higher load. which are richer in shagoals. while the yield may be higher on a dry solids basis. it is easier to store and transport a dried product relative to a fresh one. and (C) freeze-dried ginger extract. 4. forming discrete particles of very small size from fresh ginger would be difﬁcult and . However.S. If fresh ginger was to be utilised the extraction facility would need to be located close to the harvesting site. Quantiﬁcation of all these compounds is not possible as 6-gingerol is the only standard available commercially. (B) oven-dried ginger extract. around 10 times as much oven or air-dried ginger could be accommodated within such a vessel relative to the fresh product. Firstly. HPLC chromatograms of: (A) fresh ginger extract. on a volume basis. there would indeed be a greater yield per run from the dried product than from the fresh product. Thus. 6-gingerol indeed only represents around 20% of the total quantity of compounds that absorb at this wavelength. the volume of fresh ginger relative to the oven-dried product is also higher. / Separation and Puriﬁcation Technology 48 (2006) 94–105 103 Fig. this work was based on relatively large particle sizes in order to extract kinetic data. (d) 8-shogaol.
Lahiere. Hazard.J. which could be of signiﬁcant marketing advantage commercially. P. 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.  B. Res. second ed. Yonei. The use of liquid carbon dioxide for extracting natural products. Food Agric. Reynolds. Heidi. W.H. Santos. Zytner.E. J. Tomasko. 42 (2002) 61–65. A.  D.E. 35 (1996) 607–612. .A. Yoshida. The interfacial area for mass transfer between this fresh ginger slurry and the supercritical ﬂuid could be reduced relative to the dried ginger case. Int.W. Foster. O. Ohinata. 1. A. Gaspar. Chem. Huang. 66 (1994) 365–371. Jacobs. Marques.S. Supercrit.M. Boston. 41 (2002) 2033–2039. Int. Food Aust. there are also some manufacturing disadvantages relating to the use of a high volume and perishable feed stream that would need to be considered.  K. J. J.M. Applications of supercritical ﬂuid extraction in the Japanese food industry. J.O. Ind. J.G. Rosa. indeed a pulp or slurry is likely to result. Spiro.O.R.A.A.T. Rev. 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. Smyth. M. Int. 32 (1993) 1471–1481. Antunes. soil and plant materials.T. S. spices and tobacco with supercritical gases.V. 59 (6) (1994) 1338–1343. M. The pungent principles of ginger and their importance of ginger product. Monteiro. Ting. Supercrit. Hirose. Paulaitis. Meireles. J. 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. Supercritical ﬂuid extraction of organochlorines from ﬁsh muscle with different sample preparation. Govindarajan. V. Krukonis.  G. Meireles. Petenate. J..V. J. Ind. Johnston. 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