Scaling-up effects on supercritical CO2 extraction kinetics of pelletized tomato

Gonzalo A. Neza, Lorena I. Mdingera, Jos M. del Vallea,*, & Rudolf Eggersb
a

Dept. Chemical & Bioprocesses Engineering, Pontificia Universidad Catlica de Chile, Santiago, Chile
(*email: delvalle@ing.puc.cl)
b
Inst. Thermal Separation Processes, Technische Universitt Hamburg-Harburg, Hamburg, Germany

ABSTRACT
Tomato is a natural source of carotenoids, mainly lycopene, that contribute colour (yellow-to-red) and
functional properties (antioxidant) to foods. Supercritical CO2 extraction is an interesting alternative to
recover lycopene from tomato because CO2 is highly selective and harmless, and leaves no traces in extracts
or treated substrates. Because scale-up is important for process design purposes, we set the objective of
quantifying the effect of a change in scale, from a one-pass, 50-cm3 laboratory unit to a 4-dm3 pilot plant
with solvent recycling capabilities, on the extraction rate and yield of oleoresin from pelletized tomato using
supercritical CO2 as the solvent. Screening experiments in the laboratory unit were carried out at 40 or 60 C
and 30 or 50 MPa. Extraction appeared to be a diffusion-controlled process, with yields (percentage of total
available oleoresin recovered) increasing more than twice with an increase in temperature from 40 to 60 C,
and increasing in excess of 5 times with an increase in pressure from 30 to 50 MPa. Highest oleoresin yield
was 25.1% of all available oleoresin following 7-h extraction at 60 C and 50 MPa, and unexpectedly,
decreased to 17.6% in a 500-cm3 pilot plant, and increased to 30.7% in 4-dm3 pilot plant. Because
experiments used different substrates, differences between the 500-cm3 and 4-dm3 plants were possible due
to differences in initial moisture (18 versus 3.7%, respectively) and bulk density (550 versus 760 kg/m3,
respectively) between the substrates. Packing high-moisture pellets densely possible results in agglomeration
of the substrate and undesirable channelling in the packed bed.
Keywords: Extraction; pelletization; scaling-up; supercritical carbon dioxide; tomato oleoresin.

INTRODUCTION
Consumers are currently aware of the increase in diseases associated with poor nutrition and bad eating
habits of modern life, which has resulted in increased demand for healthier foods. In this scenario, the food
industry is continuously looking for new ways to develop healthy, value-added foods containing functional
ingredients (e.g., antioxidants, antimicrobials). All this explains the growing interest in natural antioxidants
such as carotenoids as food additives. Carotenoids are natural pigments that give yellow, orange, or red
colour to fruits, vegetables, and plants, among others [1]. Moreover, the antioxidant activity of carotenoids
helps preventing cardiovascular diseases and cancer [2]. Among carotenoids, lycopene is of special interest
because of its particular functional properties [3].
Tomato is the main source of lycopene in foods. Lycopene content ranges widely between 0.088 and 0.42
mg/kg of fresh tomato [4], depending on genetic (tomato variety), environmental (light and temperature), and
culturing (irrigation, soil nutrients) factors [5]. Finally, the lycopene content is five times higher in tomato
skin than tomato pulp [6]. Lycopene is a 40-carbon, lineal, highly unsaturated, hydrophobic molecule that is
soluble in organic solvents [4]. It is normally in a trans- configuration in biological products, being easily
degraded by isomerisation and oxidation. Lycopene is sensitive to light, heat, and oxygen, which causes
losses of bioactivity, decolouration, and off-odours in foods [7].
The recovery of bioactive compounds in foods requires appropriate extraction technologies, being
SuperCritical (SC) Fluid (SCF) Extraction (SCFE) an excellent alternative. A SCF is a substance that is
above its critical temperature and pressure, having a density (related to power solvent) that changes widely
with state conditions [8]. Transport properties of CO2 are comparatively better than those of conventional
organic solvents; that is, they exhibit a high self-diffusivity and low viscosity. Finally, the SCF (a gas under
normal conditions, for all practical purposes) can be easily removed from extracts and solid matrices by mere
expansion to environment pressure. Thus, SCF extracts are virtually solvent-free [8]. Within SCFs carbon
dioxide (CO2) is the most advantageously used for food processing because is innocuous for human health.
CO2 is not corrosive in the presence of water, is not flammable, is not toxic, and can be obtained from

renewable resources in large quantities, with high purity, and at low cost [8]. Another advantage of using
CO2 (Tc = 31 C, Pc = 73.8 bar) is its effectiveness at typical environmental temperatures, which prevents
thermal damage to heat-labile compounds.
There are several reports in literature on SCFE of tomato using SC CO2 as solvent at a laboratory scale [3,914], but none at pilot-plant or larger scale. Most works use tomato processing by-products as raw materials,
and grinding and drying as pre-treatments (Table 1). Top extraction pressures tested rarely reach as high as
ca. 50 MPa [9-11], despite clear indications of a positive effect of pressures on extraction [3,11-14]. The
effect of temperature on extraction is evaluated in all cases but one [12]. Extractions improve with
temperature [3,9-11,13]; the single exception is a study that has an intermediate temperature (60 C) as the
optimal [14]. As an aside, it is relevant mentioning that claims of optimal conditions (cf. Table 1) are
questionable in cases where the so-called optimum is in the border of the experimental region tested, as in the
case of most studies in Table 1.
Table 1. Summary of SCFE of lycopene from tomato at laboratory scale in literature.
Substrate
Skin and seeds (by-product)
Dried skin
Skin and seeds (by-product)
Pulp, skin and seeds (by-product)
Pulp and skin
Dried skin and seeds
Skin and seeds (by-product)

Pre-treatment
Grinding and drying
none
none
Grinding and drying
Grinding and drying
Grinding
Grinding and drying

T (C)
60 80
70 100
32 86
40 80
40
40 100
40 80

P (MPa)
25 30
20 50
13.8 48.3
30 46
7.7 28.2
20 40
20 30

Optimal conditions
80 C; 30 MPa
100 C; 40 MPa
86 C; 34. 5 MPa
80 C; 46 MPa
40 C; 28.2 MPa
100 C; 40 MPa
60 C, 30 MPa

Ref.
[3]
[9]
[10]
[11]
[12]
[13]
[14]

The objective of this work was to study the scaling-up of SCFE of tomato pellets using SC CO2 at high
pressure, considering a one-pass, screening unit and three pilot plants with solvent-recycling capabilities and
different sizes. Scale-up experiments are important for the design and evaluation of industrial processes.
Moreover, pelletizing is an excellent pre-treatment alternative because it breaks down inner barriers to the
mass transfer (shear efforts) and increases bulk density (compaction efforts) thus potentially allowing an
increase in volumetric productivity of the plant (ton extract per cubic-meter of extraction vessel and hour of
processing time) [15].
MATERIALS & METHODS
Raw materials and pre-treatments. We extracted dehydrated commercial tomato flakes (Invertec Foods,
Rengo, Chile) containing 6% water. Pelletization of tomato flakes occurred in Centro de Estudios de la
Universidad de Santiago (CEUS, Llanquihue, Chile) using a Bhler extruder model DNDL-44 (Uzwil,
Switzerland), for extractions in a one-pass, screening unit, and 0.5-dm3 and 1.3-dm3 pilot plants. For the
purpose of this manuscript we will refer to these pellets as sample MP1. Sample MP2 was pelletized in
Amandus Kahl GmbH & Co. (Reinbek, Germany) for SCFE in a 4-dm3 pilot plant. In all cases, pellets were
stored under refrigeration (5 C) in kraft paper into polyethylene bags up to analysis, to protect them from
light-catalyzed oxidation.
Extraction at screening unit. Screening studies were done in a computer controlled one-pass laboratory unit
(LU). Desired CO2 mass flow rate was kept by a 50-gram-per-minute, computer-controlled pump. Desired
extraction temperature was kept by a computer-controlled convection oven holding a 50-cm3 extraction
vessel. Finally, desired extraction pressure was kept by a computer-controlled Back Pressure Regulator
(BPR) placed after the extractor. A 6-port, 2-way valve placed after the BPR diverted SC CO2 to 20-cm3
amber vials (placed in a bath at 50 C) where oleoresin came out of solution for collection and quantification.
The vials were covered with aluminum paper to minimize light-catalyzed oleoresin degradation.
Extraction at pilot plant scale. Pilot plants had the following components: a pump, an extraction vessel, an
automated expansion valve to control system pressure, two separation vessels, a work-tank for liquid CO2,
and heat exchangers and heating and cooling systems to adjust extraction and separation temperature,
condense gaseous CO2 from the separator(s) prior to the work-tank, and pre-cool CO2 to prevent cavitation in
the pump. The pilot plant PP1 in Chile processed MP1 in 500-cm3 extraction vessel and collected oleoresin in
two 200-cm3 cyclone separator connected in parallel (flow was diverted to either vessel by a 6-port, 2-way
valve). SCFE was done also in two pilot plants in Germany. MP1 was placed in the 480-cm3 basket of a 1.3dm3 (volume of extraction vessel) pilot plant (PP2) in which oleoresin was collected in two 500-cm3

separation vessels connected in series. MP2, on the other hand, was placed in the 2.28-dm3 basket of a 4-dm3
pilot plant in which extracted oleoresin was collected in two 1-dm3 separation vessels connected in series.
Experimental design. In all experiments the extraction pressure was reached by pumping liquid CO2 at
constant mass flow rate. Recovered oleoresin was weighed as a function of extraction time. Extraction yield
was expressed as percent oleoresin recovered of total available in the substrate. LU extracted 40-g samples of
MP1 (bulk density, b, of 800 kg/m3) using of 12 g/min of CO2 (superficial velocity, U = 0.6-0.8 mm/s) at 40
or 60 C and 30 or 50 MPa (22 factorial design). Eight-to-ten samples of oleoresin were collected in the vials
during 420-to-450 min extractions. Pilot plant extractions were all carried out at 60 C and 50 MPa (best
conditions in screening extractions). PP1 extracted 380-g samples of MP1 (b = 760 kg/m3) using 90 g/min of
CO2 (U = 0.7 mm/s), PP2 extracted 340-g of samples of MP1 (b = 708 kg/m3) using 288 g/min of CO2 (U =
2.9 mm/s), and PP3 extracted 1260-g samples of MP2 (b = 553 kg/m3) using 156 g/min of CO2 (U = 0.4
mm/s).
Analyses. Diameter and length of pellets were estimated using image analysis. True density (s) was
measured by He picnometry. Bulk density values informed above were estimated by weighting pellets loaded
in extraction vessels and accounting for their effective (basket) volumes. Moisture was measured
gravimetrically by drying samples in a convection oven at 105 C to constant weight (12-17 h). Oleoresin
content was measured by comprehensive (until substrate exhaustion, ca. 24 h) Sohxlet extraction using
hexane. Finally, lycopene content in acetone-extracted and saponified pellet samples was measured by HPCL
using the method of Rodriguez-Amaya [16].
RESULTS & DISCUSSION
There were small differences between tomato pellets done in Chile and Germany. In average, tomato pellets
MP1 had ca. 4.0 mm in diameter (dp) and ca. 5.5 mm in length (lp), whereas dp 3.4 mm and lp 5.0 mm in
pellets MP2. Pelletization of tomato flakes (b = 196 kg/m3) increased bulk density of the substrate from 2.4fold in the case of MP2 to 4.1-fold for MP1. Real densities ranged 1420-1435 kg/m3. Oleoresin contents were
1.16 in MP1 and 1.47% in MP2, whereas lycopene content was 0.25% in both cases. Main difference
between pellet samples was in moisture, which was 18% (w.b.) in sample MP1, and 3.7% (w.b.) in sample
MP2. This difference could be due to post-pelletizing and storage in the second case because dried tomato is
hygroscopic material and picks up water easily in moistened environment.
Figure 1 shows cumulative extraction curves for screening studies of tomato pellets in LU. Extraction yields
after 7 h (420 min) increased with temperature and, to a greater extent, with pressure. Indeed extraction yield
was 2.4% at 40 C and 30 MPa, 8.3% at 60 C and 30 MPa, 17.8% at 40 C and 50 MPa, and 25.1% at 60 C
and 50 MPa, meaning an average improvement of 2.4 times when increasing temperature from 40 to 60 C,
and a 5.2-fold improvement (average) when increasing pressure from 30 to 50 MPa. As part of these
screening experiments, we measured the final moisture of treated pellets, which were 18.3% at 40 C and 30
MPa, 17.9% at 60 C and 30 MPa, 17.5% at 40 C and 50 MPa, and 19.8% at 60 C and 50 MPa. These
values are comparable to the initial moisture content (18 %) which means water was not co-extracted with
tomato oleoresin, or else, despite our precautions, treated samples picked-up water from the environment
during post-process storage. Both explanations are plausible because of the low solubility of water in CO2
[17] and hygroscopicity of dried tomato.
The cumulative extraction curve at 60 C and 50 MPa that maximized oleoresin recovery clearly shows (cf.
Fig. 1) that 7 h are not enough to fully extract tomato pellets MP1 in LU. Yield can be improved by
increasing extraction temperature above 60 C, increasing extraction pressure above 50 MPa, and increasing
extraction time above 7 h. Increasing temperature above 60 C may be questionable considering the
possibility of thermal damage of lycopene above 60-70 C [14]. Several authors [3,9-11,13] claimed that the
optimal temperature to extract lycopene from tomato products is above 70 C (cf. Table 1). Increasing
pressure above 50 MPa requires special equipment that is not readily available, being this the main reason for
optimal pressures <46 MPa in some studies in Table 1 (single exceptions being those of Topal et al. [9]
and Rozzi et al. [10]). Finally, increasing extraction time above 7 h may be impractical at an industrial scale
from a commercial standpoint.
The 60 C and 50 MPa curve in Figure 1 was compared with cumulative extraction curves in PP1, PP2, and
PP3 (unreported results). Results were unexpected in that the initial slopes of the curves varied widely

Figure 1. Cumulative extraction curves in screening experiments show that extraction temperature and pressure improve
SC CO2 extraction of tomato pellets MP1 at laboratory scale.

depending on the extraction plant, being the same (and highest) in PP1 and PP3, and lowest in PP2 (LU had
an intermediate value of operational solubility). The initial slope of cumulative extraction curves define an
operational solubility (439, 174, 44.8, and 11.0 mg oleoresin/kg CO2 in PP3, PP1, LU, and PP2,
respectively), which does not depend on extraction conditions in solubility-controlled extraction process,
Cumulative extraction curves differed between PP1 and PP3 after a low specific solvent consumption (ca. 5
kg CO2/kg substrate), when the cumulative extraction curve in PP3 moved above the one in PP1. This can be
explained by differences in superficial solvent velocity; when U increases the residence time in the extractor
(6 min in PP1 versus 13 min in PP3) is no enough to warrant saturation of SC CO2 with oleoresin. (The
residence times in LU and PP2 were 4 and 1.5 min, respectively.) This applies when solubility controls
extraction rate, which typically occurs in the early stages of the extraction process. Yield in LU and PP1
coincided (ca. 175 mg oleoresin/kg substrate) for a specific solvent consumption of ca. 50 kg CO2/kg
substrate. Given the cross between cumulative extraction curves in LU and PP1, it is apparent that there was
a problem during extraction of MP1 in PP1 causing an abrupt decrease in extraction rates. Besides the
compaction problem we describe below, there was a systematic difference in the collection and weighing of
oleoresin samples between PP1 and the other plants in that solvent was used to clean tubing, fittings, and
vessels so as to remove all oleoresin coming out of solution in the separation stage. This procedure allowed
accounting for all oleoresin extracted in each time interval during the extraction process.
When cumulative extraction curves plotted as oleoresin yield versus specific CO2 consumption do not
coincide for different superficial CO2 velocities, it can be claimed that the process is not controlled by
solubility phenomena but rather by inner mass transfer phenomena. Inner-mass-transfer or diffusioncontrolled processes are better analyzed by plotting oleoresin yield versus time as presented in Figure 2.
Figure 2 suggest that there are differences in the extraction behaviour of samples MP1 and MP2 in that there
are clear differences between extraction curves in LU, PP1, and PP2, on one side, and in PP3, on the other.
Indeed the extraction yield following 7-h extractions are 30.7% using MP2 (in PP3) and 17.6-to-25.1% using
MP1 (in LU and PP1). In fact, extraction curves in LU (7-h extraction) and PP2 (3.2-h extraction) virtually
coincided despite differences between superficial solvent velocities (0.68 mm/s in LU versus 2.9 mm/s in
PP2) which brings support to the hypothesis that the extraction of MP1 is a diffusion-controlled process. It is
relevant stressing that extraction in LU was better than in PP2 when comparing cumulative extraction curves,
which means a wasteful use of energy in the solvent cycle of PP2. Indeed, PP2 used more CO2 than LU (163
versus 123 kg CO2/kg substrate) in 2.2 times less time (190 versus 420 min). Regarding use of energy in the
solvent cycle, the best unit was PP3, which used 7.39 kg CO2 per kg substrate per hour as compared to 17.6
kg kg-1 h-1. On the other hand, differences subsist between LU and PP2, on one hand, and PP1, on the other,
which could be due to the oleoresin recovery procedure, as explained before.
We informed above differences in shape, moisture, and oleoresin content between MP1 and MP2 that may
partially explain differences in extraction curves in Figure 2 between MP1 (using LU, PP1, or PP2) and MP2
(using PP3). We believe relevant differences between the substrate that explain our results are the moisture
content (18% in MP1 versus 3.7% in MP2) and the bulk density (700-800 kg/m3 in MP1 versus 550 kg/m3 in
MP2). As the substrate packs more densely and/or as the water content increases, the susceptibility to
agglomeration phenomena increases that could favour undesirable channelling phenomena when using MP1.

Figure 2. Kinetics of the SCFE of tomato pellets at 60 C and 50 MPa. Comparison of the extraction yield in function of
time for three different-sized pilot plants and laboratory scale.

Channelling leaves pockets of unextracted substrate within the packed bed. Agglomeration, on the other
hand, increases average particle size, thus decreasing extraction rate in a diffusion-controlled process.
Besides differences in raw materials, results in Figure 2 can be also explained on the basis of differences
between the extraction units, being PP3 more efficient than LU, PP1, or PP2 specifically with regards to
oleoresin recovery. Also, the separation step PP3 was better than in PP1 or PP2 which helped minimizing
oleoresin content in recycled CO2.
Another factor that may affect extraction rate and yield is the superficial velocity of CO2 than in this work
ranged from 0.38 mm/s in PP3 (the unit having the best performance) to 2.86 mm/s in PP2 (that one with the
worst performance). Increasing superficial velocity (a consequently interstitial velocity, which is
proportionally higher in densely packed beds having small porosities) may also contribute to sample
compaction and undesirable channelling phenomena in packed beds. Other authors report a decrease in
extraction rate and yield when increasing the superficial velocity of CO2 [9,10].
CONCLUSIONS
Pressure had a larger positive effect than temperature in the extraction of tomato pellets at the laboratory
scale. Oleoresin yield increased more than twice when increasing temperature from 40 to 60 C, and more
than five times when increasing pressure from 30 to 50 MPa. The highest yield in LU was 25.1% at 60 C
and 50 MPa. Scaling-up experiments under these conditions produced unexpected results. Extraction yield in
a 500-cm3 pilot plant decreased to 17.6% but increased to 30.7% in 4-dm3 pilot plant. These experiments
used two different substrates, and we believe differences were due to changes in initial moisture and bulk
density between them. Packing high-moisture pellets densely possible resulted in agglomeration of the
substrate and undesirable channelling within the packed bed.
Ongoing work is aimed at optimizing sample pre-treatment and packing of tomato pellets in the extraction
vessel at the pilot plant scale, and modelling the data. Mathematical models are to simulate large-scale, multivessel plants, which is in turn required for the design and estimation of production costs of industrial plants
[18]. Our final goal is to estimate the cost of production of tomato oleoresin in an industrial SCFE plant.
ACKNOWLEDGEMENTS
This work was funded by Fondecyt (project 108-0211) from Chile.
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