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Scaling-up effects on supercritical CO 2 extraction kinetics of pelletized tomato

Gonzalo A. Núñez a , Lorena I. Mödinger a , José M. del Valle a,* , & Rudolf Eggers b

a Dept. Chemical & Bioprocesses Engineering, Pontificia Universidad Católica de Chile, Santiago, Chile (*email: delvalle@ing.puc.cl) b Inst. Thermal Separation Processes, Technische Universität 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 CO 2 extraction is an interesting alternative to recover lycopene from tomato because CO 2 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-cm 3 laboratory unit to a 4-dm 3 pilot plant with solvent recycling capabilities, on the extraction rate and yield of oleoresin from pelletized tomato using supercritical CO 2 as the solvent. Screening experiments in the laboratory unit were carried out at 40 or 60 ºC 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 w ith 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-cm 3 pilot plant, and increased to 30.7% in 4-dm 3 pilot plant. Because experiments used different substrates, differences between the 500-cm 3 and 4-dm 3 plants were possible due to differ ences in initial moisture (18 versus 3.7%, respectively) and bulk density (550 versus 760 kg/m 3 , 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 contain ing 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 caroten oids 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 high er in tomato skin than tomato pulp [6]. Lycopene is a 40-carbon, lineal, highly un saturated, hydrophobic molecule that is soluble in organic solvents [4]. It is n ormally 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 CO 2 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 en vironment pressure. Thus, SCF extracts are virtually solvent-free [8]. Within SCFs carbon dioxide (CO 2 ) is the most advantageously used for food processing because is innocuous for human health. CO 2 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 CO 2 (T c = 31 °C, P c = 73.8 bar ) is its effectiveness at typical environmental temperatures, which preven ts thermal damage to heat-labile compounds.

There are several reports in literature on SCFE of tomato using SC CO 2 as solvent at a laboratory scale [3,9- 14], but none at pilot-plant or larger scale. Most works use tomato processing by-products as raw materia ls, and grinding and drying as pre-treatment s (Table 1). Top extraction pressures tested rarely reach as high as ca. 50 MPa [9-11], despite clear indication s 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]. Extraction s improve with temperature [3,9-11,13] ; the single exception is a study that has an intermediate temperature (60 ºC) 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

Pre-treatment

T (°C)

P (MPa)

Optimal conditions

Ref.

   

– 80

25

– 30

  • 60 °C; 30 MPa

80

[3]

Skin and seeds (by-product) Dried skin

Grinding and drying none

– 100

20

– 50

  • 70 °C; 40 MPa

100

[9]

Skin and seeds (by-product)

none

– 86

13.8 – 48.3

  • 32 °C; 34. 5 MPa

    • 86 [10 ]

 

Pulp, skin and seeds (by-product)

Grinding and drying

– 80

30

– 46

  • 40 °C; 46 MPa

    • 80 [11]

 
 

Grinding and drying

 

7.7 – 28.2

  • 40 °C; 28.2 MPa

    • 40 [12]

 

Pulp and skin Dried skin and seeds

 
  • 40 – 100

20

– 40

100

°C; 40 MPa

[13]

Skin and seeds (by-product)

Grinding Grinding and drying

– 80

20

– 30

  • 40 °C, 30 MPa

60

[14]

The objective of this work was to study the scaling-up of SCFE of tomato pellets using SC CO 2 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 tran sfer (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 Bühler extruder model DNDL-44 ( Uzwil, Switzerland), for extractions in a one-pass, screening unit, and 0.5-dm 3 and 1.3-dm 3 pilot plants. For the purpose of this manuscript we will refer to th ese pellets as sample MP1. Sample MP2 was pelletized in Amandus Kahl GmbH & Co. (Reinbek, Germany) for SCFE in a 4-dm 3 pilot plant. In all cases, pellets were stored under refrigeration (5 ºC) 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 CO 2 mass flow rate was kept by a 50-gram-per -min ute, computer -controlled pump. Desired extraction temperature was kept by a computer-controlled convection oven holding a 50-cm 3 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 CO 2 to 20-cm 3 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 CO 2 , and heat exchangers and heating and cooling systems to adjust extraction and separation temperature, condense ga seous CO 2 from the separator(s) prior to the work-tank, and pre-cool CO 2 to prevent cavitation in the pump. The pilot plant PP1 in Chile processed MP1 in 500-cm 3 extraction vessel and collected oleoresin in two 200-cm 3 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-cm 3 basket of a 1.3- dm 3 (volume of extraction vessel) pilot plant (PP2) in which oleoresin was collected in two 500-cm 3

separation vessels connected in series. MP2, on the other hand, was placed in the 2.28 -dm 3 basket of a 4-dm 3 pilot plant in which extracted oleoresin was collected in two 1-dm 3 separation vessels connected in series.

Experimental design. In all experiments the extraction pressure was reached by pumping liquid CO 2 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, ρ b , of 800 kg/m 3 ) using of 12 g/min of CO 2 (superficial velocity, U = 0.6-0.8 mm/s) at 40 or 60 °C and 30 or 50 MPa (2 2 factorial design ). Eight -to-ten samples of oleoresin were collected in the vials during 420-to-450 min extractions. Pilot plant extraction s were all carried out at 60 °C and 50 MPa (best conditions in screening extractions). PP1 extracted 380-g samples of MP1 (ρ b = 760 kg/m 3 ) using 90 g/min of CO 2 (U = 0.7 mm/s), PP2 extracted 340-g of samples of MP1 (ρ b = 708 kg/m 3 ) using 288 g/min of CO 2 (U = 2.9 mm/s), and PP3 extracted 1260-g samples of M P2 ( ρ b = 553 kg/m 3 ) using 156 g/min of CO 2 (U = 0.4 mm/s).

Analyses. Diameter and length of pellets were estimated using image analysis. True density (ρ 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 measur ed gravimetrically by drying samples in a convection oven at 105 °C to constant weight (12 -17 h). Oleoresin content was measur ed by comprehensive (until substrate exhaustion, ca. 24 h) Sohxlet extraction using hexane. Finally, l ycopen e content in acetone-extracted and saponified pellet samples was measured by HPCL using the method of Rodr iguez-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 (d p ) and ca. 5.5 mm in length (l p ), whereas d p 3.4 mm and l p 5.0 mm in pellets MP2. Pelletization of tomato flakes (ρ b = 196 kg/m 3 ) increased bulk density of the substrate from 2.4- fold in the case of MP2 to 4.1-fold for MP1. Real densities ranged 1420-1435 kg/m 3 . Oleoresin content s 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. Th ese 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 explanation s are plausible because of the low solubility of water in CO 2 [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 ºC, increasing extraction pressure above 50 MPa, and increasing extraction time above 7 h. Increasing temperature above 60 ºC may be questionable considering the possibility of thermal damage of lycopene above 60-70 ºC [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 ºC 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

Figure 1. Cumulative extraction curves in screening experiments show that extraction temperature and pressure improve SC CO 2 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 CO 2 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 CO 2 /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 CO 2 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 CO 2 /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 oleor esin extracted in each time int erval during the extraction process.

When cumulative extraction curves plotted as oleoresin yield versus specific CO 2 consumption do not coincide for different superficial CO 2 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 diffusion - controlled 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 CO 2 than LU (163 versus 123 kg CO 2 /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 CO 2 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 bet ween 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/m 3 in MP1 versus 550 kg/m 3 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

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 un extracted 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 CO 2 .

Another factor that may affect extraction rate and yield is the superficial velocity of CO 2 than in this work ran ged from 0.38 mm/s in PP3 (the unit having the best performance) to 2. 86 mm/s in PP2 (that one with the wor st performance). Increasing superficial velocity (a consequently interstitial velocity, which is proportiona lly high er 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 CO 2 [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-cm 3 pilot plant decreased to 17.6% but increased to 30.7% in 4-dm 3 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, multi- vessel 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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