Journal of Food Engineering 67 (2005) 2133 www.elsevier.

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Supercritical uids: technology and application to food processing

Gerd Brunner
*
Thermal Separation Processes, Technische Universitat Hamburg-Harburg, Eissendorfer Str. 38, D 21073 Hamburg, Germany Received 10 October 2003; accepted 1 May 2004

Abstract Supercritical uids (SCFs) are substances at pressures and temperatures above their critical values. It is characteristic that properties of SCFs can be changed in a wide range. Their solvent power is the highest for non-polar or slightly polar components and decreases with increasing molecular weight. They can easily be removed from the solutes by mere expansion to ambient pressure. Carbon dioxide (CO2) is particularly advantageous for processing food materials. SCFs are used for batch extractions of solids, for multi-stage counter-current separation (fractionation) of liquids, and for adsorptive and chromatographic separations. State of the art design for commercial plants is available, and a number of installed plants are working. Special applications to food processing include decaeination of green coee beans, production of hops extracts, recovery of aromas and avours from herbs and spices, extraction and fractionation of edible oils, and removal of contaminants, among others. The application of SCFs is now extended to new areas like formulation or specic chemical reactions. Costs of SCF extraction (SCFE) processes are competitive. In certain cases SCFE processing is the only way to meet product specications. 2004 Published by Elsevier Ltd.
Keywords: Supercritical uid; Carbon dioxide; Food processing; Extraction; Separation

1. Introduction: supercritical uids and their solvent power A pure component is considered to be in a supercritical state if its temperature and its pressure are higher than the critical values (Tc and pc, respectively). At critical conditions for pressure and temperature, there is no sudden change of component properties. The variation of properties with conditions of state is monotonous, when crossing critical conditions, as indicated in Fig. 1 by the hatched lines. Yet the magnitude of the variation can be tremendous, thereby causing dierent eects on solutes and reactants within neighbouring conditions of state. Similar eects to that of the supercritical state can in some cases be achieved at near critical temperatures in the liquid state of a substance for p > pc and T < Tc.
*

Tel.: +49 40 42878 3040; fax: +49 40 42878 4072. E-mail address: brunner@tu-harburg.de

Characteristic values for the gaseous, liquid, and supercritical state are listed in Table 1. In the supercritical state, liquid-like densities are approached, while viscosity is near that of normal gases, and diusivity is about two orders of magnitude higher than in typical liquids. In processes with supercritical uids (SCFs), the driving potential for mass and heat transfer is determined by the dierence from the equilibrium state. The equilibrium state provides information about: (i) the capacity of a supercritical (gaseous) solvent, which is the amount of a substance dissolved by the gaseous solvent at thermodynamic equilibrium; (ii) the amount of solvent, which dissolves in the liquid or solid phase, and the equilibrium composition of these phases; (iii) the selectivity of a solvent, which is the ability of a solvent to selectively dissolve one or more compounds, expressed by the separation factor a; (iv) the dependence of these solvent properties on conditions of state (p, T)

0260-8774/$ - see front matter 2004 Published by Elsevier Ltd. doi:10.1016/j.jfoodeng.2004.05.060

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Fig. 1. Denition of supercritical state for a pure component (Brunner, 1994).

and, (v) the extent of the two-phase area, as limiting condition for a two-phase process like gas extraction. The separation factor a is dened by a y i =y j ; xi =xj 1

Fig. 2. Variations in the solubility of a low-volatility substance (liquid or solid) in a subcritical (temperature < critical temperature, Tc) or supercritical uid (temperature > Tc) as a function of process temperature, process pressure (segmented lines correspond to equal pressure or isobaric conditions), and solvent density (doted lines correspond to equal density conditions). (Adapted from Brunner (1994).)

where xi and xj are the equilibrium concentrations of component i and j, respectively, in the condensed phase, in mole or mass fractions; and yi and yj, the corresponding equilibrium concentrations of the same components using equivalent units. If capacity and selectivity are known, a good guess can be made about whether a separation problem can be solved with SCFs. Fig. 2 shows the solubility of a substance of low volatility, like a triacylglyceride, caffeine, or naphthalene in a sub- and supercritical uid, for instance carbon dioxide (CO2). The solubility in the subcritical (liquid) uid (solvent) increases at constant pressure up to temperatures slightly below the Tc of the solvent. A further increase in temperature leads at low pressures to a decrease of the dissolved amount of the low-volatility substance in the subcritical liquid solvent and at high pressures still to an increase. High and low pressures refer to a medium pressure level which for most systems (including the above

mentioned) is about 10 MPa. The same dependence of solubility of the low volatile component in the solvent remains at temperatures higher than Tc. At low pressures, solubility of the low-volatility substance in the supercritical and near critical solvent decreases with temperature since density of the supercritical solvent decreases rapidly with increasing temperature at nearcritical pressures. At high pressures, density changes with temperature are far more moderate, so that the increase of vapor pressure is the dominating factor, while at low pressures loss in solvent power induced by lower density prevails. Analogous solubility behaviour can be found in systems of a SCF with a solid substance or a low-volatility liquid. Carbon dioxide (CO2) is the most commonly SCF used as a solvent in food applications. It is not only cheap and readily available at high purity, but also safe to handle and physiologically sound to the very low levels at which it is present in foods (because it is easily removed by simple expansion to common environmental pressure values). Consequently, it is approved for food processing without declaration. Furthermore, when being recycled, it does not contribute to the

Table 1 Characteristic values of gas, liquid and supercritical state (Brunner, 1987) State of the uid Gas p = 1 atm, T = 1530 C Liquid p = 1 atm, T = 1530 C Supercritical uid p = pc; T % Tc p = 4pc; T%Tc Density (g/cm3) (0.62.0) 103 0.61.6 0.20.5 0.40.9 Diusivity (cm2/s) 0.10.4 (0.22.0) 105 0.7 103 0.2 103 Viscosity (g/cm/s) (0.62.0) 104 (0.23.0) 102 (13) 104 (39) 104

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environmental CO2-problem. The solvent power of supercritical CO2 (SC-CO2) can be summarized by a few rules (Brunner, 1987; del Valle & Aguilera, 1999): (i) it dissolves non-polar or slightly polar compounds; (ii) the solvent power for low molecular weight compounds is high and decreases with increasing molecular weight; (iii) SC-CO2 has high anity with oxygenated organic compounds of medium molecular weight; (iv) free fatty acids and their glycerides exhibit low solubilities; (v) pigments are even less soluble; (vi) water has a low solubility (<0.5% w/w) at temperatures below 100 C; (vii) proteins, polysaccharides, sugars and mineral salts are insoluble; and, (viii) SC-CO2 is capable of separating compounds that are less volatile, have a higher molecular weight and/or are more polar, as pressure increases. 2. Overview on techniques SCF extraction (SCFE) processes can be carried out in dierent modes of operation. In most cases extraction from solids is concerned, which usually is carried out in batch and single stage mode, since solids are dicult to handle continuously in pressurized vessels and separation factors are high. Fluid mixtures often have separation factors which make necessary the application of multi-stage contacting, which is carried out most eective in a counter-current mode. If separation factors are approaching 1, many theoretical stages are necessary for separating the components. Chromatography is a magnicent tool for separating similar compounds. Although chromatography with SCFs as solvents and mobile phases is presently mostly applied in analytical separations, the advantageous possibilities of gaseous solvents should also be applied in chromatographic processes on a preparative and process scale. 2.1. Single stage supercritical uid extraction (SCFE) The extraction of valuable materials from solid substrates by means of SCFs has been carried out on a commercial scale for more than two decades. Large-scale

processes are related to the food industry like the decaeination of coee beans and black tea leaves and the extraction of bitter avours (a-acids) from hops. Smaller scale processes comprise the extraction and concentration of essential oils, oleoresins and other high-value avouring compounds from herbs and spices, and the removal of pesticides from plant material. The extraction of edible oils would be a large-scale process, but as for all commodity products, the value-added is not high, so the economy of the process is the main problem and must be considered separately for each case. Here, the term large-scale comprises vessels of P20 m3 for decaeination and of %5 m3 for extraction of hops; most other plants consist of pressure vessels in the range of 1 to several cubic meters internal volume. Early in the 80 s, pressure vessels of about 40 m3 volume were built for the extraction from solids. Later, vessels became smaller, and today most are 61 m3 in capacity. The maximum throughput of a single plant for extraction from solids is well above 10 thousand tons per year. SCFE from solids is carried out by continuously contacting the solid substrate with the supercritical solvent. The solid substrate in most cases forms a xed bed. The SCF ows through the xed bed and extracts the product components until the substrate is depleted. This extraction from solids consists of two process steps, namely, the extraction, and the separation of the extract from the solvent (Fig. 3). In the extraction, the SCF ows through a xed bed of solid particles and dissolves the extractable components of the solid. The solvent is fed to the extractor and evenly distributed to the inlet of the xed bed. The loaded solvent is removed from the extractor and fed to the precipitator. The direction of ow of the SCF through the xed bed can be upwards or downwards. At high solvent ratios (ratio of ow of SCF to the amount of solid) the inuence of gravity is negligible. The solid material will be depleted from the extractable material in the direction of ow. Concentration of extract components increases in the direction of ow in the SCF and in the solid material. The shape of the concentration curve depends on the kinetic extraction properties of the solid material and the solvent

Fig. 3. Flow scheme of single stage processing with supercritical uids (for example for the extraction of solid materials).

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Fig. 4. Extraction of oil from rape seeds (25 g substrate) using 200 NL/ h of SC-CO2 as the solvent: inuence of process temperature and pressure on typical curves of integral extraction yield versus specic solvent consumption. (Adapted from Brunner (1994).)

power of the SCF which, in turn, depend on operating conditions. For the solid as well as for the solvent, the extraction is an unsteady process (Brunner, 1994). The course of the extraction process can be followed by determining the amount of extract against the time of extraction or solvent consumption. The amount of extract accumulating during the course of the extraction will be typically shaped as any one of the curves in Fig. 4. The rst part of the curve may be a straight line, corresponding to a constant extraction rate, whereas in the second part the extraction rate decreases as a limiting yield value is approached, which is given by the total amount of extractible substances in the substrate. Although the slope of the rst part of the graph can be given by the equilibrium solubility, a straight line can be caused also by constant resistance to mass transfer, and is no proof that equilibrium conditions are attained during the extraction. The example in Fig. 4 corresponds to the extraction of pretreated rape seeds with supercritical carbon dioxide. Oils from oil seeds mainly consist of triglycerides of C16-to C20-fatty acids, which are fairly soluble in SC-CO2. The extraction rate clearly depends on conditions of state for the extraction, which determines the solvent power of the SCF. The total yield of oil is generally the same for the conditions of reasonable solubility, but is lower at relatively low pressures than at higher pressures. The pretreatment of the oil bearing material has also a major inuence in total yield. If solvents are used which are better solvents for triglycerides (for instance short chain paranes, like propane), the rate of extraction can be enhanced at moderate conditions. The extraction of oil from oil seeds should be one of the primary targets of gas extraction, if the value-added by extraction for most vegetable oils were not too low. However, there may remain specialty oils or valuable components co-extracted with common oils that could

be targeted for commercial application of extraction with SCFs. The curve for the total amount of extract (Fig. 4) is a response curve to the ow of SCF entering the extractor. The response curve depends on process parameters and all the phenomena occurring during the extraction in the xed bed. Some of these phenomena include the radial distribution of the solvent at the inlet, the back-mixing of the SCF as it ows through the xed bed due to the uneven size, surface, and distribution of the solids, and the self-diusion of the solvent. Due to the kinetic of mass transfer, the concentration of extracted substances in the SCF has an axial concentration prole that corresponds to an axial concentration prole in the solid. Moreover, a radial concentration prole in the solid and in the gaseous phase overlays the axial concentration prole. The course of extraction can also be followed by the remaining amount of extractible components in the solid. The extract is depleted monotonously in the solid substrate with increasing time of extraction or amount of solvent. When the resistance to mass transfer resistance is fully localized in the uid phase only a straight line results (where the slope of the line represents the extraction rate), but when there exist resistances in both the uid and solid phase, the course of extraction follows an exponential function. There may be a total depletion of the substrate of extractible components, if the concentration of these compounds in the solvent is zero and there are no irreversible reactions of the extractible compounds with the substrate. Otherwise the extraction curve approaches an asymptote. Quite a large number of industrials plants (maybe around 100) of dierent size have been built during the last 20 years for the extraction of solid material with SCFs in a batch mode. Since the early 80 s, a total number of about 100 vessels bigger than 100 l in volume have been ordered for about 50 plants (Fig. 5). They are mostly distributed in Europe, the USA, Japan, and in

Fig. 5. Total number of pressure vessels >0.1 m3 for supercritical uid extraction processes. (Data from Gehrig (1998) and Fukuzato (2003).)

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the South East Asian Countries. Standard designs are available which can be acquired from various suppliers, and may be customer tailored to the individual task (Lack & Seidlitz, 2001). These standard designs typically consists of one or several extraction vessel(s), a pressure vessel (separator) for precipitating the extract, and a cycle gas compressor or cycle pump, depending whether the solvent (CO2) is recycled in gaseous or liquid state. Heat exchangers have to be added to adjust the temperature of process materials. Additional equipment comprises pipes, valves, measuring and controlling devices. In many cases, two or more vessels are used in a plant, for recovery of the solvent (usually CO2), and for stepwise extraction simulating a few stages of counter-current extraction. The simplest mode of operation for a xed bed extraction consists of contacting it until a certain amount of extract has accumulated or a certain mean residual concentration in the solid ranate is achieved. However, even for an extract consisting of a pure component this is not the best way to carrying out the process. During the extraction process, extraction kinetics change due to the depletion of the solid substrate and therefore optimum process conditions change. In addition, loading of the solvent may be enhanced by carrying out the extraction in several stages. For an extract mixture of dierent compounds, an extraction in several stages can yield dierent extract products. Each extraction stage may be designed for dierent process conditions, even the solvent can be dierent. Multi-stage counter-current contacting is the most eective mode. It reduces the amount of solvent and makes possible continuous production of extract. Real counter-current contact is not easily established for solids, since special eort is necessary for moving the solid, with increased diculties at elevated pressure. Therefore, it is easier keeping the solid material stationary and achieving counter-current contact by other means. Either several xed beds can be applied and contacted in such a way that the bed with the highest extract concentration is contacted with the gas with the highest loading of extract and vice versa, or one xed bed in a column is used and individual sections are formed by inlets or outlets for the solvent streams. 2.2. Counter-current multi-stage processing Counter-current operation of a separation device reduces the amount of solvent necessary, increases throughput, and enables higher extract concentrations in the solvent and lower residual concentrations in the ranate than does single-stage or multi-stage cross-current operation. Counter-current operation is therefore useful for separations with high separation factors, as, for example, the extractions from solid substrates described above. But counter-current operation is abso-

lutely necessary for achieving a reasonable separation between two substances with a relatively low separation factor. In Fig. 6 the process scheme of a counter-current gas extraction for the separation of two components into practically pure substances is shown (Brunner, 1994). Process equipment consists of the separation column where gaseous and liquid phases are contacted counter-currently, a separator at the top for separating solvent and extract, devices for feeding reux to the column, for recovering top product, for delivering feed to the column, for recovering product at the lower end of the column, and for recycling the solvent. When the feed is introduced at an intermediate position, the separation column consists of two separation cascades: in the enriching section (the upper part) the bottom product compounds are separated from the top product compounds and rejected to the lower or stripping section; in the stripping section the top product compounds are separated from the bottom product compounds and transported to the enriching section. At the top of the column the separator removes the extract from the solvent. From the extract a specied part is separated and introduced at the top of the column as reux. The remaining part of the extract is the top product. The solvent is reconditioned (ltered, sometimes liqueed and again evaporated for removing

Fig. 6. Schematical drawing of a system used for counter-current extraction of ethanol with SC-CO2. Solid lines represent uxes of liquid feed and/or supercritical uid, and dashed lines represent uxes of gaseous solvent.

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trace substances, pressure and temperature are adjusted) and recycled by the cycle pump as the supercritical solvent at the bottom of the column. The feed is introduced at an intermediate location in the column by the feed pump; for a mixture of two components of about the same concentration, this location is at about the middle of the column. Although multi-component mixtures prevail, it is common practice to try to reduce multi-component separations to two-component separations, because these still retain the main features of a multi-component separation but are simpler to analyze as described above. Fig. 7 presents an example of a multi-component separation, corresponding to the separation of fatty acid ethyl esters (C16- and C18-compounds from C20- and C22-compounds) (Riha, Meyer, Birtigh, & Brunner, 1996; Tiegs, Steiner, Riha, & Brunner, 1996). Concentration proles are typical for a multi-component and multi-stage separation of key compounds (C18 and C20) and accompanying compounds (C14, C16 on the high-solubility or extract side and C22 on the low-solubility or ranate side). Key compounds exhibit typical

Fig. 7. Counter-current separation in a column of fatty acid ethyl esters according to the length of the carbon backbone, using SC-CO2 as the solvent. Concentration proles along a column are presented for (h, j) C14, ( , ) C16, (n, m) C18, (,, .) C20, and ( , ) C22 fatty acid ethyl esters (closed symbols and solid lines represent compositions of the liquid phase, whereas open symbols and dotted lines those of the gaseous phase). The bottom product contained >97% C20/C22fraction, whereas the top product contained >90% of C16/C18fraction. The dashed horizontal line for theoretical plate 23 represents the feed plate.

maximum values in concentration near the ends of the column, while accompanying compounds are transported to the column ends and depleted rapidly in the other direction. In an analogue manner, C20 can be separated from C22 in dierent runs. The process in Fig. 7 is developed for industrial application (Fleck, Tiegs, & Brunner, 1998). Due to the relative high solubility of the fatty acid ethyl- or methyl-esters in SC-CO2, the process is competitive to distillation. In addition, distillation cannot produce the highly enriched fractionsup to 90%which are possible with SCF counter-current separation. Capacity and diameter of a column for counter-current multi-stage separation must be determined from the planned throughput for the design of industrial scale plants. Costs of counter-current separation are also determined by maximum possible throughput. In a gravity driven counter-current column, the parameter to know is the ooding point. The experimental determined ooding diagram for SCFliquid counter-current columns is essentially the same as for gasliquid columns operating at normal pressures. At high pressures, however, the eect of not only the type of mass transfer equipment should be taken into account, but also the inuence of density on the gaseous phase. The capacity of SCFliquid counter-current columns often is much higher than anticipated. Low viscous systems will allow a relatively large linear gas velocity of about 4050 mm/s. Thus, relatively high quantities of SC-CO2 are needed for optimum mass transfer: the throughput of SC-CO2 in a counter-current column increases from 49 kg/h for a 25 mm-diameter column to 785 kg/h for a 100 mm-column, for a measured ooding point of 100 ton CO2/(m2 h) and a linear gas velocity of 46 mm/s (Fleck, 2000). Scale-up of column diameter is possible maintaining similar separation performance. Yet capacity is essentially determined by the type of mass transfer equipment. With Sulzer CY regular packing, capacity is in the range of 80100 ton CO2/(m2 s). The diameter of a column will then increase from about 200 mm for a capacity of 200 ton per year, to 450 mm for 1000 ton per year (Fig. 8). Industrial scale applications have been developed for the fractionation of the n-3 fatty acid esters, and for the enrichment of tocopherols and tocotrienols. Other possible applications include: (i) separation of alcohol and water; (ii) separation of aroma compounds (essential oils); (iii) fractionation of citrus oils; (iv) recovery of squalene from edible oils; (v) de-acidication of edible oils; and, (vii) enrichment of carotenoids. Columns of 100 and 200 mm diameter have been successfully operated for counter-current separation, which have allowed a throughput of about 10 ton per year. However, columns of up to 500 mm diameter with a throughput of several hundred tones per year can safely be designed, if demand shows up.

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Fig. 8. Column diameter for a separation column separation C18 to C22 fatty acid ethyl esters. In all cases, the loading of the gas phase was 4% (w/w) and the separation factor was 1.3, so that 52 theoretical stages, each 0.3 m in height, were required to reach a product purity of 99% (w/w) when employing a reux ratio of 10. Curves indicate maximum throughput for two regular packings, namely Sulzer EX for the lower throuphput (Q = 27.5 ton/m2/h), and Sulzer CY for the higher throughputs (Q = 86.2100 ton/m2/h). (Figure adapted from Riha et al. (1996).)

2.3. Preparative chromatographic separation Another separation technique where SCFs may be applied is chromatography. In chromatographic separation, the supercritical solvent is used as mobile phase. Analytical packed columns have diameters up to 4.6 mm. Columns can be directly scaled-up in diameter if measures are taken that the xed bed of the packed column with particle diameters in the range of 2040 lm remains unchanged during operation and start-up and shut-o operations. One way to achieve this is by axial compression, where a piston compresses the xed bed in the cylindrical column to keep it under higher pressure conditions than operational levels all the time the device is in use. This has allowed long operational time use of months in our laboratories (Depta, 2000). The separation of phytol isomers is shown in Fig. 9 as an example of preparative chromatographic separation. Analytical and preparative separations were carried out in the elution mode which is a batch separation process. However, a continuous chromatographic separation can be designed, for example as a simulated moving bed (SMB). (The ow scheme of such an apparatus was reported by Depta, Giese, Johannsen, & Brunner (1999), who arranged eight columns in a circle, to allow a switching in their function by a multi-port rotating valve.) The advantages of SMB-chromatography are lower solvent ratio, higher throughput, and higher product concentration. With 30 mm-diameter columns about 10 ml/h of phytol isomers can be separated to more than 95% purity.

Fig. 9. Chromatograph for preparative-scale separation of phytol isomers. The process conditions were as follows: Column = Li chrospher Si 60 (10 lm); temperature = 40 C; pressure (before column) = 240 bar; ow rate = 3 NL/min of CO2; modier = 3% w/w isopropanol; injection volume = 20 ll of phytol pure (dotted line 17 mg/ml of crude phytol sample) or diluted in n-hexane (dashed line 0.85 mg/ml of crude phytol sample); UV-detection wavelength = 221 nm. Peaks for retention time <2 min correspond to samples impurities, whereas peaks in the 46.5 min range correspond to the isomers of phytol (Figure adapted from Depta et al. (1999).)

Applications of chromatographic separations comprise analytical and preparative separations. There are many publications available on analytical separations. Advantages of this type of analysis is that compounds spanning a wide range in terms of volatility and polarity can be separated in a single run. The analysis of edible oil compounds is particularly advantageous. Preparative separations can be used to separate enantiomers (ibuprofen, phytol), produce standards (tocotrienols), and purify pharmaceuticals (vitamin D). Chromatographic separations have been carried out so far using columns of up to about 100 mm-diameter, allowing throughputs which are far below 1 ton per year. The maximum diameter employed in our laboratory was 70 mm, but it is technically possible to scale-up these processes.

3. Special applications of supercritical uids to food processing Some products possibly produced by SCF technology may be found on our everydays table. Some examples of products are listed in Fig. 10, which can be obtained by the methods discussed above. Processes to obtain vitamin additives, de-alcoholize beverages, de-fat potato

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Fig. 11. Percent oil removed from salted and unsalted potato chips as a function of solvent usage when employing SC-CO2 at 55 1 C and 40.8 0.7 MPa as the solvent. The separation conditions were 30 3 C and 0.1 MPa in both the cases. (Figure adapted from Vijayan et al. (1994).)

Fig. 10. Supercritical uid technology applied to everydays food.

ships, and encapsulate liquids will be discussed in more detail below. For more information on the other examples the reader is referred to the literature, in particular King and Bott (1993), Brunner (1994, 2000), McHugh and Krukonis (1994), Bertucco and Vetter (2001), and Arai, Sako, and Takebayashij (2002). 3.1. Removal of fat from foods Edible oils and their components have been the target of SCF processing since the early 70 s. Although triacylglycerides are only fairly soluble in SC-CO2, the advantages of organic solvent-free processing have stimulated research and development in various areas. One of these is the removal of fat from food. As an example in Fig. 11 the extraction curves for fat from potato chips is shown. The process has been fully designed for commercial application, using the aforementioned standard design. The process has the advantage of producing fat-free or fat-reduced potato chips. According to the expected taste the amount of remaining fat in the potato chips can easily be controlled. 3.2. Enrichment of vitamin E from natural sources SCFE oers several advantages for the enrichment of tocochromanols over conventional techniques such as vacuum distillation, in particular a lower operating temperature (Brunner, 1994). As starting material one can

use various edible oils or their distillates. Most promising as feed materials are crude palm oil (CPO) and soybean oil deodorizer distillate (SODD). CPO contains several tocotrienols and tocopherols at a total concentration of approximately 500 ppm. SODD may contain (after several conventional concentration steps) about 50% tocopherols. Both materials can be used for the production of enriched fractions of tocochromanols. Although it is possible to recover tocochromanols directly from CPO, it is better to produce esters of the triglycerides in order to be able to more easily separate these compounds from the tocochromanols. In this method, the triglycerides are subject to an esterication with methanol to form fatty acid methyl esters, which are easily extractable with CO2. That means that the tocochromanols, together with other unsaponiable matter (squalene, sterols, etc.) are enriched in the bottom phase of an extraction column. This attempt is described in more detail by Jungfer (2000). For a discussion of enriching tocochromanols, phase equilibrium data have to be considered rst. In Fig. 12 the distribution coecients Ki (distribution between liquid and gaseous phase) of the components of interest are shown for the example of CPO with SC-CO2 at 67 C. Free fatty acids (FFA) and tocochromanols exhibit a much higher solubility in CO2 than the triglycerides. Hence, these components are enriched in the gaseous phase, expressed by a distribution coecient being higher than one. The distribution coecient of the triglycerides is smaller than one, whereas that for the carotenes is much smaller than one, meaning that these components stay in the liquid oil phase. Thus, tocochromanols can be extracted as the top phase product in a separation column, whereas carotenes remain in the bottom phase product together with triglycerides. For recovering the carotenes together with the tococromanols the above mentioned esterication to volatile (CO2 soluble) methyl

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Fig. 12. Distribution coecients for (h) tocochromanols, ( ) free fatty acids, (n) triglycerides, and (,) carotenes of crude palm oil (700 ppm tocochromanols, 15% (w/w) free fatty acids, 9599% (w/w) triglycerides, and 800 ppm carotenes) in SC-CO2 as a function of pressure. The segmented line separates the less volatile components that are enriched in the ranate (below the line) from the more volatile compounds that are enriched in the extract. (Figure adapted from Jungfer (2000).)

esters makes possible to recover tocochromanols and carotenes (together with squalene and sterols) as bottom product from this natural source. When the glycerides (in case of the esterication) or the FFAs from deodorizer distillates have been removed, then there is a feed material available for obtaining enriched fractions of tocochromanols and carotenes of much higher concentration. In this feed material, tocochromanols and carotenes (in case of palm oil) are the main components and have to be separated from other unsaponiable substances present, such as squalene and sterols. Of these compounds, squalene has the highest solubility in SC-CO2, all phytosterols have a rather low solubility in CO2 (and remain in the oil phase), and tocochromanols exhibit an intermediate solubility between the two. In a second separation step tocochromanols are separated from phytosterols. For the rst step concentration proles of an experiment are shown (Fig. 13) that were conducted in a pilot scale plant described in more detail by Gast and Brunner (2001). The core of this apparatus is an extraction column having an eective separation height of 6 m equipped with Sulzer EX packing. The inner diameter of the column is 17.5 mm and can be operated either in a true stripping mode, with the solvent introduced at the bottom and the feed at the top of the column, or in reux mode. In the latter mode of operation the feed is introduced at the middle of the column and part of the extract is reintroduced at the top of the column to ensure counter-current ow. The gaseous solvent is recycled. Investigations employing SODD as feed material for the extraction were performed at temperatures of 353

Fig. 13. Counter-current separation of squalene, tocopherols and sterols in a column using SC-CO2 as the solvent. Concentration proles along a column are presented for (h, j) squalene, ( , ) tocopherols, and (n, m) sterols (closed symbols and solid lines represent compositions of the liquid phase, whereas open symbols and dotted lines those of the gaseous phase). The dashed horizontal line for theoretical plate 3 represents the feed plate. The experiment was carried out at 353 K and 23 MPa by employing 86 g/h of feed, 3.6 kg/h of SC-CO2, and 55 g/h of reux. (Figure adapted from Saure (1996).)

and 363 K and at pressures of 23 and 26 MPa. The solvent-to-feed (S/F) ratio was varied in the range between 33 and 171, and the reux ratio was set between 1 and 38. Experiments showed that, as expected, squalene was enriched in the top phase product. In fact, it could not be found in the bottom phase. Consequently, it was enriched from 3.1% (w/w) in the feed to 18.8% (w/w) in the top phase product. The sterols were completely enriched in the bottom phase, occasionally to more than 50% (w/w). If the concentration approaches 50% (w/w), the products become too viscous and clog the packing mash and the column (Saure, 1996). For further purication, the sterols and the tocochromanols have to be separated rst. The tocochromanols, as intermediatesoluble components, were neither distinctly enriched in the top nor in the bottom phase product. In order to simulate a taller extraction column, the top phase product of some experiments was collected and introduced as feed a second time. With this sterol-free feed material, the separation of squalene and tocochromanols was now possible. Starting from a tocochromanol concentration of 48.3% (w/w) an enrichment to 94.4% (w/w) in the bottom product was obtained (Gast, Jungfer, Saure, & Brunner, 2003). This separation was performed at 23 MPa, 353 K, having a S/F ratio of 110 and a reux ratio of 4.6. The contained squalene could be completely enriched in the top phase product. Products with a tocotrienol and/or a tocopherol concentration in the range of 7090% are obtainable with

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SCF separation techniques. A further purication of these compounds is possible, e.g. with adsorptive or chromatographic techniques, again using SCFs. 3.3. Removal of alcohol from wine and beer, and related applications De-alcoholized wine or beer is achieved by removing ethanol from water. Distillation is well known for this purpose with the disadvantage that aroma compounds will also be removed. New techniques like membrane separation (pervaporation) emerge, and in between these is SCFE with CO2. Starting from an aqueous solution with about 10% (w/w) ethanol, ethanol can be removed by SC-CO2 in a stripping column as shown in Fig. 14. The rate of ethanol removal depends strongly on temperature. Reducing the alcohol content to values well below 0.5% (w/ w) requires about 2.5 h at 45 C under non-optimized conditions. Much shorter times for the ethanol removal can be obtained if ow rates and mass transfer equipment are carefully selected. With the information available in the literature, for instance from Budich (1999), a column for dealcoholizing aqueous solutions can be designed. Recovery of aroma compounds is achieved by a side column in which a separation from ethanol is carried out. A related process that can be mentioned is the recovery of absolute alcohol. Many studies were carried out at conditions of complete miscibility of ethanol and CO2 in order to get a high solubility of ethanol in the vapor phase (Gilbert & Paulaitis, 1986; Kreim, 1983). At these conditions, anhydrous ethanol cannot be produced. However, ethanol can be concentrated above

azeotropic composition whenever the pressure in the ternary mixture CO2 + ethanol + water is below the critical pressure of the binary mixture CO2 + ethanol (Budich & Brunner, 2003; Furuta, Ikawa, Fukuzato, & Imanshi, 1989; Nagahama, Suzuki, & Suzuki, 1988). Fig. 15 illustrates the separation factor of ethanolwater as a function of the concentration of ethanol in the solventfree liquid phase. The separation factor decreased from around 30 at innite dilution of ethanol in water to approximately 1.25 at innite dilution of water in ethanol. No azeotrope was formed at the conditions investigated. Separation factors are larger compared to data at atmospheric conditions. Counter-current multi-stage extraction was carried out in an extraction column of 6 m total height (25 mm ID, equipped with of Sulzer EX packing). The experimental set-up is shown in Fig. 6. Extraction conditions were set to 333 K and 10 MPa. Solvent and extract were separated by pressure reduction down to 5 MPa and washing the extract phase with liquid CO2 in counter-current ow. With a feed of 94% (w/w) ethanol, an extract with 99.5% (w/w) ethanol was produced at a reux ratio of 4 and a S/F ratio of 60 (using 9 kg CO2/h and 150 g feed/h). Twelve equilibrium stages were achieved, with a height equivalent of a theoretical stage (HETS) of 0.33 m. Liquid solvent reux was not required during this experiment because the ranate was still very rich in ethanol (87% w/w). S/F ratios are relatively small (30 kg/kg) compared to other counter-current gas extraction processes (Budich, 1999). This is due to large separation factors and a solubility of pure ethanol in CO2 of 5% w/w at the conditions investigated.

Fig. 14. Eect of process temperature and extraction time on the removal of ethanol from an aqueous solution using SC-CO2 at 15.5 MPa (supercial solvent velocity = 0.12 cm/s). (Figure adapted from Brunner and Kreim (1985).)

Fig. 15. Equilibrium diagram for the separation of ethanolwater with SC-CO2 at 333 K and 10 MPa. The plot includes experimental values of the separation factor determined using both ( ) a conventional and ( ) a modied sampling method, as well as ( ) reference values experimentally assessed at normal pressure (0.1 MPa). The line represents the trend for experimental data at high pressure. (Figure adapted from Budich and Brunner (2003).)

G. Brunner / Journal of Food Engineering 67 (2005) 2133

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3.4. Encapsulation of liquids for engineering solid products A liquid product can be entrapped by adsorption onto solid particles (liquid at the outside of solid particles), by agglomeration (liquid in the free volumes between the solid particles), or by impregnation (liquid within the pore system of the solid particles). Microspheres or larger capsules can be formed, totally encapsulating the liquid. The solid material provides a coating for the liquid inside. Such particulate products can be achieved by means of SCF processing also. An example is the so-called concentrated powder form-process, wherein CO2 is mixed (dissolved) in the liquid feed by static mixing. The CO2liquid feed mixture is then sprayed into a spray chamber at ambient conditions together with the substrate material. The CO2 is suddenly released from the liquid, and the liquid forms small droplets. During the spraying process, solid substrate and liquid droplets are intensively mixed and combined to a solid particulate product of the type described above. The product is nally removed from the chamber as a free owing powder and separated from the outgoing gas stream by a cyclone. With this type of process, a wide variety of solid substrates can be applied to uptake liquids of dierent kind and up to about 90%. As advantages can be claimed the easier handling and storage, prevention of oxidation processes, and easier dosage. Solid products can also be formed under high pressure conditions. As an example for such a type of process, the encapsulation or adsorption of tocopherol acetate on silica gel. Here, about 50% of tocopherol acetate can be incorporated onto the silica gel without apparent change of morphology and ow properties of the powder. The powder with 50% loading is still free

owing. The amount which can be adsorbed at high pressures is comparable to that of normal pressure. Only at very high densities, the equilibrium loading decreases (Fig. 16). In the experiments that are reported in Fig. 16, the autoclave was used to saturate the SC-CO2 current with tocopherol acetate, and the density of the solvent was changed in the nozzle where the loaded SC-CO2 phase was fed to the adsorber. This adsorption at high pressures makes possible the direct product formation in the SCF, with the advantageous eect that the supercritical solvent can easily be recycled without substantial compression.

4. Costs of separation processes with supercritical uids Reported costs for production rates around 1000 ton/ year of solid feed are in the range of 3 US$/kg feed. Economy of scale may bring costs down to less than 0.5 U$/kg for batch operation. Continuous operation would further reduce costs. The lower curve in Fig. 17 represents an anticipated vefold increase in productivity (mostly due to shorter use of high pressure volume for extraction) reducing operating costs in the same proportion. Yet continuous extraction has been so far carried out only on laboratory scale. It has also to be considered that cost estimates of such a type have an agreed variability of 30%. Therefore, some data of different authors and processes are shown in Table 2. Another interesting feature is the cost structure for SCF processing. Lack and Seidlitz (2001) published data for the production of extracts from hops. For extraction pressure of 350 bar, a recovery pressure for the extracts of 45 bar and 20 processing weeks they calculated processing costs of 1 /kg of feed material. The cost breakdown without considering the cost of the raw material is as follows: interest and depreciation = 36.1%; labour = 24.5%; utilities = 17.2%; taxes = 20.5%; administration = 1.0%. Investment costs in this case are about

Fig. 16. Adsorption isotherms for tocopherol acetate (TA) in SC-CO2 on silica gel (Fleck, 2000). The autoclave was operated at 333 K and 20 MPa, and was fed with ( ) 73% (w/w) TA or (h) 97% (w/w) TA. The xed adsorber was operated at 353 K using a feed of 20 g/min of SC-CO2.

Fig. 17. Economy of scale for SC-CO2-extraction of solids.

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Table 2 Cost estimates for processing of solids with supercritical carbon dioxide (Lack and Seidlitz, 2001) Type of process Decaeination of coee beans (batch, non-isobaric) Decaeination of coee beans (batch, isobaric) Solids extraction, general Removal of pesticides (from ginseng) Capacity (ton/year) 3500 4500 7000 3500 4500 7000 10,000 600 1000 2000 Cost estimate (/kg feed) 1.1 0.9 0.75 0.85 0.7 0.55 0.7 14 9 5

Another possibility for reducing costs is a low pressure drop along the solvent cycle. To achieve this, separation of the solute from the supercritical solvent by membranes would be an ideal means (Sartorelli & Brunner, 2000). In cooperation with the Institute of Chemistry of GKSS in Hamburg, Germany, our group succeeded in nding a polymer membrane which can be applied (Sartorelli, 2001). An active multiple layer of poly-tetra-uoro-ethylene supported by a ceramic or organic material proved to be applicable at high CO2pressures (tested up to 35 MPa). The solute is retained and SC-CO2 permeates through the membrane at high rates. Still the membrane has to be tested in a module, and the integration into a process cycle has to be proven.

5. Conclusions one third of total processing costs. This value is still higher than for equipment operated at ambient pressure but lower than the 50% mostly cited. Fleck, Brunner, and Karge (2000) and Fleck (2000) have carried out a cost analysis for counter-current processing raw tocopherol acetate to industrial grade tocopherol acetate (about 92% pure) using SC-CO2 with the addition of some propane (1020%). For a plant with a 300 mm ID column the production rate per year was determined to 450 ton (20% propane) with resulting production costs (without costs for the raw material) of 1.4 /kg product. For a plant with 500 mm ID column the respective values for capacity and cost have been estimated as 10901250 ton/year (for 10% or 20% propane) and 1.05 /kg product. Table 3 summarizes the eects of using propane-CO2 mixtures as the solvent on operating costs. The base case is high vacuum distillation (p < 1 mbar). Costs are twice as high with SC-CO2 and solvent recovery by pressure reduction. If propane is added, costs can be reduced to 20% of the base case. If the favourable case occurs that the solute can be adsorbed, and the adsorbate used as product, cycle costs are only 50% of the base case, even with pure CO2. If, in addition, propane is added, costs may be less than 10% of the base case. Processing materials with SCFs is a proven and industrially applied technology. It is readily available for extraction from solids (also in simulated countercurrent mode) and multi-stage counter-current separation. Chromatographic techniques with SCFs as a mobile phase are primarily used for analytical purposes by now. Some plants for preparative scale are available as for SMB chromatography. Processing costs can be very competitive to other processes but sometimes supercritical processes are unique in their ability to produce solvent-free products and handle high viscous material. New technologies are emerging, for instance for particle design, sterilization, and separation of enantiomers.

Acknowledgments Useful discussions with Jose M. del Valle are gratefully acknowledged as is the funding by FONDECYT (International Cooperation project 703-0033) from Chile, DFG (Deutsche Forschungsgemeinschaft) from Germany, and F. Homann-La Roche AG (Basel, Switzerland).

Table 3 Operating costs for the purication of tocopherol acetate for dierent solvent mixtures and dierent methods for precipitating the extract (Fleck, 2000) Method of precipitation Pressure reduction Adsorption Supercritical solvent CO2 CO2 + C3H8 CO2 CO2 + C3H8 Operating costa (%) 200 20 50 8

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a Values are expressed as a percentage of the base case (operating cost = 100% for high vacuum distillation).

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