Separation and Purication Technology 66 (2009) 322328

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Separation and Purication Technology

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Solubility of lycopene in supercritical CO2 uid as affected by temperature and pressure

John Shi a, , Mehak Khatri a,b , Sophia Jun Xue a , Gauri S. Mittal b , Ying Ma c , Dong Li d
a

Guelph Food Research Center, Agriculture and Agri-Food Canada, Ontario, Canada N1G 5C9 School of Engineering, University of Guelph, Ontario, Canada N1G 2W1 School of Food Science and Engineering, Harbin Institute of Technology, Harbin 150090, China d College of Engineering, China Agricultural University, Beijing 100083, China
b c

a r t i c l e

i n f o

a b s t r a c t
For extraction efciency, it is important to determine the lycopene solubility for optimum extraction technology and highest resulting yield. The temperature range of 5080 C and pressure range of 200400 bars were used to measure the solubility of lycopene from tomato processing residue materials during supercritical uid extraction. Single-pass ow method, off-line solute analysis, and subsequently HPLC quantitative analysis were the procedures followed for the lycopene extraction. The resultant calculated solubilities were on the lower scale as then ranged in the magnitude of 106 . Under supercritical conditions, increasing solubility of lycopene is stimulated by an increase in temperature and pressure. The highest solubility obtained was 1.9 106 mol fraction at a pressure of 250 bars and at a temperature of 80 C. Above these conditions, distinct signs of thermal degradation were observed. The efciency calculated based on the experimental data was compared with the modied PengRobinson Equation of State. The correlated results through modelling show reasonably fair agreement with the experimental data. Through comparison of results produced by experimental methods and modelling, it was determined that the most favourable conditions for high solubility of lycopene in supercritical CO2 , for this particular method of analysis, were at 60 and 70 C. Crown Copyright 2008 Published by Elsevier B.V. All rights reserved.

Article history: Received 29 September 2008 Received in revised form 2 December 2008 Accepted 17 December 2008 Keywords: Extraction Lycopene Solubility Supercritical uid Tomato skin

1. Introduction The extraction process is a unit operation used to obtain targeted food components from natural products such as lycopene from tomatoes. Lycopene extraction from tomatoes, as a promising health-promoting functional food ingredient, is drawing increasing attention by the food industry. The supercritical uid process is being used to extract lycopene from tomatoes as a green technology to meet food safety regulations. Lycopene is an open chain unsaturated carotenoid that imparts red colour, mainly to ripe tomatoes and other fruits such as apricot, pink grapefruit, guava, and watermelon [14]. Lycopene is a 40 carbon open chain polyisoprenoid (C40 H56 ), with 11 conjugated double bonds [4,5] and is considered an acyclic isomer of carotenoids. The structural formula of lycopene is represented in Fig. 1. The colour of lycopene is attributed to its many conjugated double bonds: as the number of conjugated double bonds increases in a compound, less energy is required for the electronic transition to higher energy states.

Corresponding author. Tel.: +1 519 780 8035; fax: +1 519 829 2600. E-mail address: shij@agr.gc.ca (J. Shi).

Of all the carotenoids, lycopene is one of the most effective antioxidants. Antioxidants are able to quench singlet oxygen and peroxyl radicals, both of which are thought to be responsible for damaging DNA in a process that can lead to the initiation of cancer [1,2,4,6]. Thus, extraction and inclusion of lycopene in food products is one of nutritional interests due to its potential health benets. As a result, lycopene is in high demand within the food, pharmaceutical, feed, and cosmetic industries [6]. Studies suggest that tomato processing residues such as tomato skins are ideal for extraction [2,5,7] as the highest amount of lycopene, approximately 120 g/g of wet sample, is found in the pericarp of a tomato [2,5]. Lycopene in the tomato matrix has been found in the cytoplasmic material and the intracellular granuals [2]. Because lycopene is generally sensitive to light, heat, oxygen, and acids [1,5,8], extraction of lycopene from tomatoes by superctritical CO2 uid shows promise for less isomerization and decomposition. CO2 is the ideal supercritical uid solvent for carotenoid extraction as it is non-toxic, non-ammable, safe, and inexpensive [1]. It also has a critical temperature (Tc = 304.1 K) that makes it suitable for the extraction of many natural products under mild conditions [9]. Supercritical CO2 permits highly selective extraction due to its low viscosity, high diffusivity, and wide density ranges [10]. However,

1383-5866/$ see front matter. Crown Copyright 2008 Published by Elsevier B.V. All rights reserved. doi:10.1016/j.seppur.2008.12.012

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2. Materials and methods Nomenclature Subscripts 1 solvent 2 solute List of symbols a parameter of attractive interactions between molecules b parameter of volume of exclusion and repulsive interactions n1 moles of solvent n2 moles of solute P absolute pressure vp P2 vapour pressure of pure solute Pc critical pressure volumetric ow rate Q1 R gas constant t time required for the collection of solute T absolute temperature Tc critical temperature Tr reduced temperature V1 molar volume of the solvent s V2 molar volume of pure solid molar fraction of lycopene y2 Z1 compressibility factor for the solvent Greek letters 2 fugacity coefcient of pure solute molar density of solvent 1 acentric factor 2.1. Sample preparation and chemicals Air-dried tomato skins and seeds (93% dry matter) from tomato processing residue were provided by a tomato processing plant of Heinz Company (Leamington, Ontario, Canada). The raw materials were ground with a grinder (SmartGrind Deluxe, Black & Decker, Mirama, FL, USA) to a ne particle size of about 1 mm, corresponding to 18 mesh, and stored in dark brown polyethylene bottles at 30 C to avoid any degradation by light and air. Lycopene standard (>95% purity) was purchased from SigmaAldrich Co. (St. Louis, MO, USA). HPLC grade solvents, including methyl t-butyl ether, methanol, and ethyl acetate were from Caledon Laboratories (Georgetown, Ontario, Canada). The liquid carbon dioxide (>90%) was purchased from Praxair Product Inc. (Kitchener, Ontario, Canada). 2.2. Supercritical uid extraction The powdered tomato skin sample was used for supercritical CO2 uid extraction using an automated Spe-ed Supercritical Fluid Extraction unit (NP model 7100) equipped with a pump (Module 7100) and a 10-mL stainless cylindrical extractor vessel (Applied Separations, Allentown, PA, USA). Pressurized liquid CO2 was pumped into the system. The ow meter (Applied Separations Inc., Allentown, PA, USA) was manually adjusted to the desired ow rate. The extraction vessel contained aliquots of 5 g tomato skin samples. Defatted cotton was placed at both ends of the extraction vessel to prevent CO2 from transporting any solids out of the system. The extraction time and the ow rate were set to 1.5 mL/min for 90 min to avoid losing any extracts. The samples were collected in 25 mL brown vials to prevent any UV activated degradation of lycoepne. Collected extracts were dissolved in 4 mL hexane and transferred into 5 mL brown vials. Extracts were dried under nitrogen and stored in the freezer at 30 C until time for analysis. 2.3. HPLC analysis The resulting lycopene-rich extracts were analyzed by an HPLC system, utilising an Agilent 1100 Hewlett Packard Computing System (Agilent Technologies, Waldbronn, Germany) equipped with a quaternary pump (Module 1100), a diode array detector (set to 475 nm), and a reversed phase analytical polymeric C30 column (4.6 m i.d., 3 mm 250 mm) (YMC, Inc. Wilmington, NC, USA). The mobile phase of methyl t-butyl ether/methanol/ethyl acetate (40:50:10, v/v) was used at 2 mL/min ow rate. Before HPLC analysis, the lycopene-rich samples were dissolved in 2 mL hexane. A sample volume of 20 L was injected into the column. The column temperature was maintained at 298 K. To identify the targeted compound in the analysis, the results from the tomato derived lycopene standard were used for comparison. This analysis was performed under a dim light to prevent any degradation by photo-oxidation. The resulting chromatogram was used to determine the lycopene concentration of each sample by using peak area measurements. 2.4. Analytical methods and solubility measurements The solubilities were determined at temperatures of 50, 60, 70, and 80 C and pressures of 200, 250, 300, 350, and 400 bars with at least three replications. A schematic diagram of the extraction apparatus is shown in Fig. 2. After lycopene concentration was determined by HPLC analysis, the concentrations were converted into mol/L. According to the physical characteristics of materials solubility in supercritical CO2 [21], solubility of the solute (lycopene), y2 , in

CO2 lacks polarity and the ability to form specic solventsolute interaction [9]. The addition of a small amount of polar solvent for a modier role, such as water, ethanol, methylene chloride, and hexane, can greatly enhance its solvent power [1,2,11]. The solvating power of supercritical uids such as CO2 is sensitive to temperature and pressure. Therefore, extraction parameters can be adjusted to obtain the highest possible yields [11]. With the increase in density, the solvating power of a supercritical uid also increases [12,13]. Thereby, the choice of temperature and pressure are the two most crucial parameters for the extraction of a given component [14]. Generally, solubility increases with an increase in temperature and pressure [9,1418]. However, lycopene solubility has shown to be much lower in CO2 than that of other fat-soluble vitamins; this could be due to its high molar mass and the elongated shape of the lycopene molecule [17,19,20]. Experimental data pertaining to the solubility of lycopene in supercritical CO2 is limited, although an investigation in combination with astaxanthin [9] has been reported. Therefore the objective was to study the solubility of lycopene in supercritical CO2 . The effects on solubility at various pressure and temperature were studied through experimental analysis and modelling. For the greatest yield, lycopene was extracted from tomato skins. The solubility studies were conducted over a temperature range of 5080 C and a pressure range of 200400 bars, which are generally considered to be suitable operating conditions for carotenoid extractions.

Fig. 1. Molecular structure of lycopene.

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J. Shi et al. / Separation and Purication Technology 66 (2009) 322328 Table 1 Density and solubility of lycopene in supercritical CO2 at 50, 60, 70, and 80 C, and for pressures 200, 300, and 400 bar. Temperature ( C) 50 Pressure (bars) 200 250 300 350 400 200 250 300 350 400 200 250 300 350 400 200 250 300 350 400 CO2 density (kg/m3 ) 785.0 834.8 871.0 897.4 923.8 724.5 787.2 830.3 860.5 890.6 660.0 737.6 788.6 822.9 857.2 595.4 687.1 746.3 785.0 823.7 27.3 21.6 32.9 41.2 39.2 28.4 19.6 30.2 33.5 29.3 19.8 21.6 23.5 33.1 29.7 16.7 18.9 21.3 22.7 31.2 Solubility (y2 106 ) 0.651 0.776 0.802 0.821 0.845 0.902 0.989 1.014 1.057 1.056 1.150 1.231 1.290 1.304 1.340 1.790 1.872 1.847 1.799 1.712 0.17 0.12 0.09 0.13 0.09 0.11 0.09 0.12 0.09 0.13 0.11 0.09 0.13 0.11 0.12 0.09 0.13 0.15 0.09 0.19

60

Fig. 2. Schematic diagram of the supercritical uid extraction apparatus: (1) Liquid CO2 Cylinder, (2) Cooler (Refrigerated Bath), (3) Cooling Coil, (4) SF Pump, (5) Oven, (6) Heating Coil, (7) Extraction Cell, (8) Gas Flow Meter, (9) Carbon Dioxide Release Valve, (10) Product Release Valve, (11) Sample Collection Vial.

70

mole fraction was calculated by the following equation: y2 = n2 n2 = n1 + n2 Q1 1 t + n2 (1)

80

where n1 and n2 are the moles of CO2 and lycopene collected in time t, respectively, Q1 is volumetric ow rate of CO2 (1.5 mL/min), and 1 is the molar density of CO2 . The molar mass (n1 ) of CO2 is 44.0 g/mol. To determine the moles of CO2 in the solution, it is necessary to determine the density of CO2 for each condition. By using data from the literature, the density was obtained for a required temperature and pressure. Moles of lycopene were calculated from the concentration determined from HPLC analysis. The mole mass of lycopene is 536.873 g/mol. 2.5. Statistical analysis Differences between variables were tested for signicance using the one-way analysis of variance (ANOVA) procedure (SPSS for Windows 13.0, SPSS Inc., Chicago, IL; Design Expert 6.0.5 trial, Stat-Ease Inc., Minneapolis, MN, USA). Signicant differences were accepted at P 0.05. 3. Results and discussions 3.1. Effects of temperature and pressure on CO2 density The changes in density (kg/m3 ) as a function of various pressures (bar) of a supercritical CO2 uid are illustrated in Fig. 3. The calcu-

lated density values of CO2 in the experimental condition ranges are present in Table 1. The density increased dramatically as the pressure was raised to approximately 150 bars, but decreased thereafter. Density decreases with increasing temperature at a constant pressure. These trends are true not only for CO2 , but for other supercritical gases as well. When the pressure for CO2 reaches approximately 74 bars, there is a rather sharp incline on the slope in the vicinity of the critical pressure (Fig. 3). Around this pressure, a small increase in pressure would result in a substantial incline in the CO2 solvent density. However, above approximately 150 bars, there is a gradual decline in increase in the density. The zone above the critical point provides the greatest density changes, and thus even the slightest changes in pressure and temperature, the density of CO2 will effectively change the operating variables in this zone. The slope immediately below the critical point also shows an increase, but not as steep as in the supercritical region. Hence, the density of CO2 varies substantially with pressure changes. The solubility of any uid depends on its density. The density of the supercritical uid can be manipulated easily by changing the temperature, pressure, or both (Table 1). When pressures are low at constant temperature, there is a dissolution of non-polar and weakly polar analytes. However, there will be more polar and high-molecular weight solutes at higher pressures [22]. This point is further emphasized by Calvey and Page [23]. Since an increase in temperature decreases the threshold density, increasing the vapour pressure of the gas to increase solubility is a very important factor. Thus the vapour pressure of a compound affects the solubility more than the solvent strength (density) at higher temperatures [23]. 3.2. Lycopene solubility in CO2 The solubility data for lycopene in CO2 were determined at the temperatures of 5080 C, in ten-degree intervals, and in the pressure range from 200 to 400 bar. The experimental conditions were chosen in a region where both temperature and pressure could greatly affect the solubility of lycopene in supercritical uid. Table 1 lists the corresponding experimental values of solubilities (y2 , in mole fractions) of lycopene in supercritical CO2 , with the density of CO2 at each operating condition. Since CO2 is a non-polar solvent,

Fig. 3. Density of CO2 as a function of pressure at various temperatures. () 50 C ( ) 60 C ( ) 70 C ( ) 80 C

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325

Fig. 4. Solubility isotherms for lycopene: ( ) 50 C ( ) 60 C ( ) 70 C ( ) 80 C. Lines represent trends, and symbols represent experimental data points.

the solidgas equilibrium behaviour is dependent on physical interactions between CO2 and lycopene. When establishing a plot from the results of Table 1 (Fig. 4), the expected trends of supercritical uids were observed. At temperatures of 5070 C, the solubility of lycopene in supercritical CO2 increased with increasing pressure and temperature. However, at 80 C, there were notable decreases in the lycopene solubility. At least three experiments were run at each condition, and the discrepancies between measurements were reasonable, with relative error mainly ranging from 7 to 10%. The uncertainties may have resulted from various sources such as the calibration procedure and the uctuation of the set temperature and pressure that determines the density estimation. At lower pressures, the relative error was comparatively higher at approximately 1315%. This may be because, at low pressures, only a small amount of sample was collected and analyzed, thus discrepancies are higher in these conditions. Consequently, limitations occur on the experimental system, meaning that solubility for low temperature and low pressure conditions could not be adequately evaluated. The mole fractions of lycopene dissolved in the supercritical phase were much lower for the ranges of pressure and temperature tested (Table 1). The mole fraction of lycopene, for every condition, was at a magnitude of 106 . The highest value of solubility, of approximately 1.9 106 mol mol1 , was obtained with a pressure of 250 bars and 80 C. The reason that the solubilities remain low was explained by Subra et al. [16]. The lack of polar fractions within the lycopene structure indicates that the solubility should be relatively high. However, in our results, lycopene solubilites were actually low. This can be further explained by considering the molecules molecular weight. The higher molecular weight of a solute lowered its solubility in the solvent. Lycopene has a relatively large molecular weight (MW = 536.9 g mol1 ), hence limiting solubility in supercritical uids. Subra et al. [16] also compared it to the solubility of phenanthrene (C14 H10 ), whose molecular weight (MW = 178.2 g mol1 ) is signicantly lower than lycopene, and therefore has a higher solubility value. The solubility of lycopene in supercritical CO2 as a function of system pressure is presented in Fig. 4. The effect of pressure on the solubility indicates expected trends. Increasing the operating pressure from 200 to 400 bars at 50 bar intervals resulted in a gradual increase in lycopene recovery up to 70 C. As the pressure is raised at a constant temperature, the CO2 density also increases, thereby decreasing the intermolecular space between the CO2 molecules, and hence increasing the interactions between the lycopene and CO2 molecules [4]. Therefore, solubility increases with pressure, especially at lower pressures as demonstrated by the

slightly steeper slope (Fig. 4). This is due to the fact that supercritical CO2 uid density is more sensitive to pressure, especially at lower pressures, as can be shown in Fig. 3. Another factor affecting the solubility of lycopene is the system temperature. The temperature inuences the solute vapour pressure, the solvent density, and the intermolecular interactions in the uid phase. The solubility data of lycopene at 70 C is larger than at 50 C or 60 C due to the high interactions of the lycopene and CO2 molecules [13]. Gomez-Prieto et al. [11] observed that lycopene has the highest solubility of all carotenoids. At higher temperatures, for example at 80 C, there is a decline in the solubility curve with increasing pressure. This can be explained by considering thermally induced lycopene degradation. MayerMiebach et al. [24] concluded that lycopene begins degradation at temperatures above 70 C. As noted in many reports [2426], thermal treatment promotes lycopene isomerization to convert the all-trans form to the cis-isomer lycopene in tomato matrices. When the temperature is raised too high, thermal treatment is probably the cause of lycopene degradation in this case. This could explain the reason that some lycopene was lost and not all was extracted, hence the decrease on the solubility curve was observed. Usually, an isobaric increase in temperature decreases the density of the supercritical solvent and hence decreases solubility due to the density effect. However, the same increase in temperature increases the volatility of the solute, resulting in an increase in solubility due to the volatility effect [4]. Therefore, at high pressures, as the solvent density is less dependent on temperature, the resultant solubility increase is mainly due to the higher vapour pressure of the solute [13]. The solubility data is also plotted as a function of solvent density in Fig. 5. The plots in both Figures (Figs. 4 and 5) are similar identical, as explained by the reasons above. As the graphs are plotted for high pressures, density does not play as signicant a role with temperature. To conrm the consistency of results and the efciency of the solubility apparatus and technique employed in this study, the solubility data of lycopene in CO2 is compared with the data from De la Fuente et al. [9]. Both data sets expand the horizon of 106 magnitude. However, De la Fuente et al.s [9] data curve has a steeper incline than the results acquired in this investigation. The solubility values in the study only increased a couple of units. To our knowledge, there has been no other data produced as of yet for the solubility of lycopene. Therefore it is difcult to compare

Fig. 5. Mole fraction solubility, y2 , of lycopene in supercritical CO2 as a function of density of pure CO2 : ( ) 45 C ( ) 55 C ( ) 65 C ( ) 75 C. Lines represent trends, and symbols represent experimental data points.

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J. Shi et al. / Separation and Purication Technology 66 (2009) 322328

experimental results. It has been observed that the solubilities of -carotene produced from different sources are quite dissimilar. Although lycopene is very similar to -carotene in terms of molecular similarities, it is unreasonable to assume that lycopene will generate the same trends as -carotene. The aforementioned discrepancies in solubilities of lycopene can have several origins, such as the experimental method, the method for measuring solubility, the degradation of the compound, and the degree of purity of the starting materials. It is difcult to identify a reason for the discrepancies among the data sets. The complexity of measuring such small solubilities must be one factor. Even minute losses of extracts during collection could make a signicant impact on the solubility values, especially at lower pressures (e.g. at 200 bars and 50 C). It is also difcult to obtain lycopene of such high purity, as impurities may have affected some or all of the data. Subra et al. [16] conrms that even using the pure degree of a carotenoid, the measured solubility could still be lower than the one with a lesser degree of purity. Results are extremely sensitive to the experimental method. In literature, various techniques have been employed for the determination of mole fractions. Experimental methods can vary in ow system (equilibrium cell, one-pass ow or multi-pass circulating ow), the method of sampling (on-line or collection procedure), and the method of quantitation (gravimetric, spectroscopic, or chromatographic analysis). However, Subra et al. [16] did conclude that the best method for measuring extremely low solubility was through a multi-pass circulating ow, which is enhanced by on-line sampling, and to ensure that all solutes are collected. Supercritical uid chromatography should be used to enhance sensitivity of detection. However, we were not equipped with on-line sampling equipment; therefore the collection procedure was utilised with an attempt to limit relative error between results at every particular condition. This difference in the experimental procedure may also explain the high dissimilarities between our results and those of De la Fuente et al. [9]. It is known that degradation results in thermal arrangements of -carotene isomers. Since the lycopene and -carotene have almost identical molecular structure, this may apply to lycopene as well. Though we did try to minimize exposure to light, heat, and air to the best of our abilities, regardless, it does add some uncertainty to our data, and therefore it is improbable that all the thermal and photochemical degradation had ceased. Finally, the method for calculating solubility also differed from that used by De la Fuente et al. [9] that employed the model of Mndez-Santiago and Teja [27], whereas the modied version of PengRobinsons Equation of State was used in our study. Although there is not enough data produced on the solubility of lycopene in the literature, all of the above could be possible reasons to explain why there were reasonably high discrepancies between our data and those of De la Fuente et al. [9]. 3.3. Modelling To predict the solubility of lycopene in supercritical CO2 at various conditions, the compressed gas model is based on the phase equilibrium model, a modied PengRobinson method in this study. This equation has been derived from the equifugacity condition between the solute (lycopene) and solvent (CO2 ) where it is used to predict phase performance for solutes with an extensive range of volatility [28]. It is assumed that the system pressure is signicantly greater than the vapour pressure of the solute, the saturated vapour of the pure solute at sublimation behaves like an ideal gas, the solute is incompressible, and it is also vital to assume that the solubility of the solvent in the solute is negligible. Then lycopene solubility in mole fraction is calculated according to Eq.

(2) [29]. y2 = P2 P
vp

1 2

exp

s V2

RT

(2)

where y2 is the mole fraction of the solute (lycopene) at equilibrium in the supercritical phase, P is the pressure, 2 is the fugacity vp coefcient of the species in the supercritical phase, P2 is the s vapour pressure of pure solute, V2 is the molar volume of the solute (assumed to be independent of pressure), R is the gas constant, and vp s T is the given temperature. P2 and V2 were acquired from experimental and literature data. The molar volume of solid lycopene is 604.2 cm3 mol1 . To determine the fugacity coefcient, the simplied version of Schmitt and Reid [29] was used as Eq. (3). They conrmed that certain variables could be neglected because they were found to be sufciently small. ln 2 b2 b1 (Z1 1) ln a2 a1
0.5

P(V1 + b1 ) RT ln

a1 2.828RTb1 (3)

b2 b1

(V1 + 2.414b1 ) (V1 0.414b1 )

where T is critical temperature, the relation of T and Tr and Tc is as Tr = T Tc

where Tr is the reduced temperature that is equivalent to the fraction of absolute temperature, Tc where the subscript c denotes critical parameters, Z1 is the compressibility factor that could be determined by using the Nelson-Obert generalized compressibility charts [30] where Pr = P/Pcr , V1 is the molar volume of CO2 and is determined by the compressibility equation [30,31], V1 = Z1 RT P

The variable a is the parameter that describes attractive interactions between molecules, and the variable b is the parameter for volume exclusion and repulsion interactions. Therefore the pure component parameters could either be of subscript 1 or 2, where subscript 1 represents the solvent and subscript 2 represents the solute. a1 =0.457
2 R2 TC

Pc

0.5 [1+(0.3746+1.5423 0.26992 )(1 Tr )]

(4) (5)

b1 = 0.07780

RTc Pc

The parameters a2 and b2 are determined by nonlinear regression models of the experimental data. The supercritical temperature and pressure of CO2 are 304.21 K and 73.825 bars, respectively, and were taken from TRC Thermodynamic TablesHydrocarbon [32]. The acentric factor, , of a substance is dened as Balasubramanian [33]:(6) = log Pr at Tr = 0.7To obtain the values of , the reduced vapour pressure Pr at Tr = 0.7 is required. The values of and some other literature data are tabulated in many thermodynamic tables. The lycopene solubility was measured under different pressure and temperature conditions as listed in Table 1. The lycopene solubility increase with isothermal and pressure effects was due to the increase in density. It was noticed in modelling calculations that the vapour pressure of lycopene showed signicant signs of increase as the temperature rose from 50 to 70 C, which correlates well with other published data [9]. According to the modied PengRobinson equation, model lines for the solubility of lycopene in supercritical CO2 are presented in Fig. 6. The determination of solubility through the modied

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Acknowledgements The authors gratefully acknowledge the contribution of the Guelph Food Research Center, Agriculture and Agri-Food Canada (AAFC Journal Series No. S598). References
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Fig. 6. Plot of mole fraction vs. pressure for the solubility in supercritical CO2 a comparison between experimental and calculated values: ( ) 50 C; ( ) 60 C; ( )70 C; () calculated results from modied PengRobinson equation.

PengRobinson equation was in reasonably close agreement with the experimental data albeit with some obvious scattering. The scattering of data was more prominent under low-density conditions. The plot portrays that the experimental and the calculated plotted curves follow the same trend, where it is more apparent that solubility increases with both the system pressure and the temperature. Both curves differ slightly and do not follow each other closely at 50 C. This discrepancy could be caused by the very low solubility of lycopene at 50 C, where accurate results are extremely sensitive to the method of analysis for low solubility conditions. In addition, Subra et al. [16] also indicated that the ambiguity of solubility measurements becomes higher at lower pressures, and achieving solubility at the lowest temperatures also amplies the uncertainty. The 60 C curve for the experimental values ts very closely to the calculated values. Therefore, for this particular experimental procedure, it can be concluded that the most favourable conditions for lycopene solubility are at 60 and 70 C. 3.4. Conclusions and discussion The solubilities of lycopene at 50, 60, 70, and 80 C were determined in supercritical CO2 for pressures ranging from 200 to 400 bars. The low solubility was determined by a single-pass ow apparatus, where off-line solute analysis was performed. For this reason, it was necessary to ensure that all the solute was collected. Though the solubilities were very low, the reproducibility of results was reasonably good. Three replications were conducted for each condition, and the deviation between measurements ranged from 7 to 10%, except at some lower conditions where it ranged from 13 to 15%. The solubility values show the usual trend for solubility increase with both pressure and temperature. An isothermal increase in solubility with pressure was observed. Increasing the density of CO2 showed a distinct increase in solubility. The measurement of lycopene solubility is affected possible by factors such as the experimental method, sampling method, method of quantitation, method of measurement of solubility, degradation of lycopene, and the degree of purity of the starting material. The presented solubility data was correlated using the modied PengRobinson equation. The proposed model ts reasonably close to the experimental curve and provides reliable solubility estimates. It is concluded that the most favourable conditions for lycopene solubility are at 60 and 70 C. At 80 C, noticeable signs of thermal degradation were observed.

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