Journal of Food Engineering 67 (2005) 21–33 www.elsevier.


Supercritical fluids: 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 fluids (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 decaffeination of green coffee beans, production of hops extracts, recovery of aromas and flavours 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 specific chemical reactions. Costs of SCF extraction (SCFE) processes are competitive. In certain cases SCFE processing is the only way to meet product specifications. Ó 2004 Published by Elsevier Ltd.
Keywords: Supercritical fluid; Carbon dioxide; Food processing; Extraction; Separation

1. Introduction: supercritical fluids 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 different effects on solutes and reactants within neighbouring conditions of state. Similar effects 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.

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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 diffusivity is about two orders of magnitude higher than in typical liquids. In processes with supercritical fluids (SCFs), the driving potential for mass and heat transfer is determined by the difference 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)

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0) · 10À3 0. (v) the extent of the two-phase area. while at ‘‘low’’ pressures loss in solvent power induced by lower density prevails. Furthermore. and yi and yj. density changes with temperature are far more moderate. T = 15–30 °C Supercritical fluid p = pc. (Adapted from Brunner (1994). At ‘‘high’’ pressures.) where xi and xj are the equilibrium concentrations of component i and j. liquid and supercritical state (Brunner. process pressure (segmented lines correspond to equal pressure or isobaric conditions). It is not only cheap and readily available at high purity. 2 shows the solubility of a substance of low volatility.0) · 10À2 (1–3) · 10À4 (3–9) · 10À4 . for instance carbon dioxide (CO2). The same dependence of solubility of the low volatile component in the solvent remains at temperatures higher than Tc. the corresponding equilibrium concentrations of the same components using equivalent units. like a triacylglyceride. Brunner / Journal of Food Engineering 67 (2005) 21–33 Fig. and. and solvent density (doted lines correspond to equal density conditions).2–0. caffeine. Consequently. it is approved for food processing without declaration. 1987) State of the fluid Gas p = 1 atm. Tc) or supercritical fluid (temperature > Tc) as a function of process temperature. Fig. Definition of supercritical state for a pure component (Brunner. The separation factor a is defined by a¼ y i =y j .6–2. a good guess can be made about whether a separation problem can be solved with SCFs. in mole or mass fractions. Variations in the solubility of a low-volatility substance (liquid or solid) in a subcritical (temperature < critical temperature. 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). xi =xj ð1Þ Fig.4 (0. T % Tc p = 4pc. so that the increase of vapor pressure is the dominating factor.0) · 10À5 0. Analogous solubility behaviour can be found in systems of a SCF with a solid substance or a low-volatility liquid.1–0. in the condensed phase.5 0. 1994). when being recycled.7 · 10À3 0. 1. as limiting condition for a two-phase process like gas extraction.2–3. 2.9 Diffusivity (cm2/s) 0. 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.2 · 10À3 Viscosity (g/cm/s) (0. ‘‘High’’ and ‘‘low’’ pressures refer to a ‘‘medium’’ pressure level which for most systems (including the above mentioned) is about 10 MPa.4–0.2–2.22 G. If capacity and selectivity are known. T%Tc Density (g/cm3) (0.and supercritical fluid. At ‘‘low’’ pressures. The solubility in the subcritical (liquid) fluid (solvent) increases at constant pressure up to temperatures slightly below the Tc of the solvent.6–2. Carbon dioxide (CO2) is the most commonly SCF used as a solvent in food applications. or naphthalene in a sub.0) · 10À4 (0. T = 15–30 °C Liquid p = 1 atm.6–1. 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. respectively. it does not contribute to the Table 1 Characteristic values of gas.6 0.

If separation factors are approaching 1. the advantageous possibilities of gaseous solvents should also be applied in chromatographic processes on a preparative and process scale. Smaller scale processes comprise the extraction and concentration of essential oils. The maximum throughput of a single plant for extraction from solids is well above 10 thousand tons per year. which usually is carried out in batch and single stage mode. The solvent is fed to the extractor and evenly distributed to the inlet of the fixed bed. Flow scheme of single stage processing with supercritical fluids (for example for the extraction of solid materials). The loaded solvent is removed from the extractor and fed to the precipitator. pressure vessels of about 40 m3 volume were built for the extraction from solids. and today most are 61 m3 in capacity. the term ‘‘large-scale’’ comprises vessels of P20 m3 for decaffeination and of %5 m3 for extraction of hops. (viii) SC-CO2 is capable of separating compounds that are less volatile. and. since solids are difficult to handle continuously in pressurized vessels and separation factors are high. Brunner / Journal of Food Engineering 67 (2005) 21–33 23 environmental CO2-problem.G. Chromatography is a magnificent tool for separating similar compounds. The solvent power of supercritical CO2 (SC-CO2) can be summarized by a few rules (Brunner. 3). 3. (ii) the solvent power for low molecular weight compounds is high and decreases with increasing molecular weight. the SCF flows through a fixed bed of solid particles and dissolves the extractable components of the solid. 2. The solid material will be depleted from the extractable material in the direction of flow. 1999): (i) it dissolves non-polar or slightly polar compounds. (iv) free fatty acids and their glycerides exhibit low solubilities. (vi) water has a low solubility (<0. 2. Later. del Valle & Aguilera. Concentration of extract components increases in the direction of flow in the SCF and in the solid material. (iii) SC-CO2 has high affinity with oxygenated organic compounds of medium molecular weight. The shape of the concentration curve depends on the kinetic extraction properties of the solid material and the solvent Fig. (vii) proteins. and the removal of pesticides from plant material. Early in the 80 s. 1987. Fluid mixtures often have separation factors which make necessary the application of multi-stage contacting. The SCF flows through the fixed bed and extracts the product components until the substrate is depleted. In the extraction. but as for all commodity products. as pressure increases. The direction of flow of the SCF through the fixed bed can be upwards or downwards. Single stage supercritical fluid 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. In most cases extraction from solids is concerned. .1. This extraction from solids consists of two process steps. namely. vessels became smaller. (v) pigments are even less soluble. polysaccharides. so the economy of the process is the main problem and must be considered separately for each case. The solid substrate in most cases forms a fixed bed. the value-added is not high. The extraction of edible oils would be a large-scale process. Large-scale processes are related to the food industry like the decaffeination of coffee beans and black tea leaves and the extraction of bitter flavours (a-acids) from hops. Although chromatography with SCFs as solvents and mobile phases is presently mostly applied in analytical separations. most other plants consist of pressure vessels in the range of 1 to several cubic meters internal volume. At high solvent ratios (ratio of flow of SCF to the amount of solid) the influence of gravity is negligible. Overview on techniques SCF extraction (SCFE) processes can be carried out in different modes of operation. the extraction. SCFE from solids is carried out by continuously contacting the solid substrate with the supercritical solvent. sugars and mineral salts are insoluble. have a higher molecular weight and/or are more polar.5% w/w) at temperatures below 100 °C. oleoresins and other high-value flavouring compounds from herbs and spices. Here. and the separation of the extract from the solvent (Fig. which is carried out most effective in a counter-current mode. many theoretical stages are necessary for separating the components.

and distribution of the solids. The amount of extract accumulating during the course of the extraction will be typically shaped as any one of the curves in Fig.) power of the SCF which. There may be a total depletion of the substrate of extractible components. 4) is a response curve to the flow of SCF entering the extractor. surface. The response curve depends on process parameters and all the phenomena occurring during the extraction in the fixed bed. a total number of about 100 vessels bigger than 100 l in volume have been ordered for about 50 plants (Fig. there may remain specialty oils or valuable components co-extracted with common oils that could be targeted for commercial application of extraction with SCFs. Total number of pressure vessels >0. (Adapted from Brunner (1994). 4. The extraction of oil from oil seeds should be one of the primary targets of gas extraction. and in Fig. They are mostly distributed in Europe. if the concentration of these compounds in the solvent is zero and there are no irreversible reactions of the extractible compounds with the substrate. the rate of extraction can be enhanced at moderate conditions. The curve for the total amount of extract (Fig. For the solid as well as for the solvent. Moreover. The course of extraction can also be followed by the remaining amount of extractible components in the solid. The course of the extraction process can be followed by determining the amount of extract against the time of extraction or solvent consumption. the USA. 1994). which is given by the total amount of extractible substances in the substrate.) . The extraction rate clearly depends on conditions of state for the extraction. The extract is depleted monotonously in the solid substrate with increasing time of extraction or amount of solvent. the extraction is an unsteady process (Brunner. When the resistance to mass transfer resistance is fully localized in the fluid phase only a straight line results (where the slope of the line represents the extraction rate). Japan. the course of extraction follows an exponential function. Extraction of oil from rape seeds (25 g substrate) using 200 NL/ h of SC-CO2 as the solvent: influence of process temperature and pressure on typical curves of integral extraction yield versus specific solvent consumption. but is lower at relatively low pressures than at higher pressures. Since the early 80 s. like propane). Oils from oil seeds mainly consist of triglycerides of C16-to C20-fatty acids. in turn. depend on operating conditions. The example in Fig. 4 corresponds to the extraction of pretreated rape seeds with supercritical carbon dioxide. Quite a large number of industrials plants (maybe around 100) of different size have been built during the last 20 years for the extraction of solid material with SCFs in a batch mode. Brunner / Journal of Food Engineering 67 (2005) 21–33 Fig. the concentration of extracted substances in the SCF has an axial concentration profile that corresponds to an axial concentration profile in the solid. whereas in the second part the extraction rate decreases as a limiting yield value is approached. but when there exist resistances in both the fluid and solid phase. corresponding to a constant extraction rate. Some of these phenomena include the radial distribution of the solvent at the inlet. The pretreatment of the oil bearing material has also a major influence in total yield. (Data from Gehrig (1998) and Fukuzato (2003). The total yield of oil is generally the same for the conditions of reasonable solubility. a straight line can be caused also by constant resistance to mass transfer.1 m3 for supercritical fluid extraction processes. which determines the solvent power of the SCF. and is no proof that equilibrium conditions are attained during the extraction. 4. which are fairly soluble in SC-CO2. Due to the kinetic of mass transfer. and the self-diffusion of the solvent. However. if the value-added by extraction for most vegetable oils were not too low. the back-mixing of the SCF as it flows through the fixed bed due to the uneven size.24 G. Otherwise the extraction curve approaches an asymptote. The first part of the curve may be a straight line. Although the slope of the first part of the graph can be given by the equilibrium solubility. 5). If solvents are used which are better solvents for triglycerides (for instance short chain paraffines. a radial concentration profile in the solid and in the gaseous phase overlays the axial concentration profile. 5.

Counter-current operation is therefore useful for separations with high separation factors. an extraction in several stages can yield different extract products. since special effort is necessary for moving the solid. or one fixed bed in a column is used and individual sections are formed by inlets or outlets for the solvent streams. Additional equipment comprises pipes. even for an extract consisting of a pure component this is not the best way to carrying out the process.2. The remaining part of the extract is the top product. and enables higher extract concentrations in the solvent and lower residual concentrations in the raffinate than does single-stage or multi-stage cross-current operation. for recovering product at the lower end of the column. Heat exchangers have to be added to adjust the temperature of process materials. as. These standard designs typically consists of one or several extraction vessel(s). and a cycle gas compressor or cycle pump. loading of the solvent may be enhanced by carrying out the extraction in several stages. In addition. a pressure vessel (separator) for precipitating the extract. for delivering feed to the column.G. devices for feeding reflux to the column. Standard designs are available which can be acquired from various suppliers. Brunner / Journal of Food Engineering 67 (2005) 21–33 25 the South East Asian Countries. Process equipment consists of the separation column where gaseous and liquid phases are contacted counter-currently. 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. the extractions from solid substrates described above. 1994). Solid lines represent fluxes of liquid feed and/or supercritical fluid. in the stripping section the top product compounds are separated from the bottom product compounds and transported to the enriching section. The simplest mode of operation for a fixed bed extraction consists of contacting it until a certain amount of extract has accumulated or a certain mean residual concentration in the solid raffinate is achieved. it is easier keeping the solid material stationary and achieving counter-current contact by other means. But counter-current operation is abso- lutely necessary for achieving a reasonable separation between two substances with a relatively low separation factor. and may be customer tailored to the individual task (Lack & Seidlitz. From the extract a specified part is separated and introduced at the top of the column as reflux. Schematical drawing of a system used for counter-current extraction of ethanol with SC-CO2. measuring and controlling devices. Counter-current multi-stage processing Counter-current operation of a separation device reduces the amount of solvent necessary. At the top of the column the separator removes the extract from the solvent. Each extraction stage may be designed for different process conditions. a separator at the top for separating solvent and extract. Therefore. even the solvent can be different. When the feed is introduced at an intermediate position. For an extract mixture of different compounds. depending whether the solvent (CO2) is recycled in gaseous or liquid state. increases throughput. Either several fixed 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. During the extraction process. 6 the process scheme of a counter-current gas extraction for the separation of two components into practically pure substances is shown (Brunner. In Fig. valves. for recovery of the solvent (usually CO2). and for stepwise extraction simulating a few stages of counter-current extraction. It reduces the amount of solvent and makes possible continuous production of extract. extraction kinetics change due to the depletion of the solid substrate and therefore optimum process conditions change. . for example. sometimes liquefied and again evaporated for removing Fig. and for recycling the solvent. 6. In many cases. However. and dashed lines represent fluxes of gaseous solvent. two or more vessels are used in a plant. Real counter-current contact is not easily established for solids. for recovering top product. The solvent is reconditioned (filtered. 2. 2001). Multi-stage counter-current contacting is the most effective mode. with increased difficulties at elevated pressure.

& Brunner. using SC-CO2 as the solvent. The process in Fig. The bottom product contained >97% C20/C22fraction. (iii) fractionation of citrus oils. the effect of not only the type of mass transfer equipment should be taken into account. because these still retain the main features of a multi-component separation but are simpler to analyze as described above. However. Costs of counter-current separation are also determined by maximum possible throughput. 8). pressure and temperature are adjusted) and recycled by the cycle pump as the supercritical solvent at the bottom of the column.and C18-compounds from C20. . ) C16. 7 is developed for industrial application (Fleck. Brunner / Journal of Food Engineering 67 (2005) 21–33 trace substances. & Brunner. In a gravity driven counter-current column. whereas open symbols and dotted lines those of the gaseous phase). With Sulzer CY regular packing. j) C14. 2000). for a measured flooding point of 100 ton CO2/(m2 h) and a linear gas velocity of 46 mm/s (Fleck. (n. the parameter to know is the flooding point. while accompanying compounds are transported to the column ends and depleted rapidly in the other direction. Tiegs. 1996). Although multi-component mixtures prevail. Industrial scale applications have been developed for the fractionation of the n-3 fatty acid esters. The capacity of SCF–liquid counter-current columns often is much higher than anticipated. (v) de-acidification of edible oils. 7. . The feed is introduced at an intermediate location in the column by the feed pump. At high pressures. 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. ) C22 fatty acid ethyl esters (closed symbols and solid lines represent compositions of the liquid phase. it is common practice to try to reduce multi-component separations to two-component separations. Riha. ( . and for the enrichment of tocopherols and tocotrienols. 1998). (vii) enrichment of carotenoids. Fig. to 450 mm for 1000 ton per year (Fig. capacity is in the range of 80–100 ton CO2/(m2 s). distillation cannot produce the highly enriched fractions––up to 90%––which are possible with SCF counter-current separation. In addition. 7 presents an example of a multi-component separation. C16 on the high-solubility or extract side and C22 on the low-solubility or raffinate side).or methyl-esters in SC-CO2. if demand shows up. Counter-current separation in a column of fatty acid ethyl esters according to the length of the carbon backbone.) C20. (iv) recovery of squalene from edible oils. In an analogue manner. Yet capacity is essentially determined by the type of mass transfer equipment. Columns of 100 and 200 mm diameter have been successfully operated for counter-current separation. Other possible applications include: (i) separation of alcohol and water. The dashed horizontal line for theoretical plate 23 represents the feed plate. Steiner. maximum values in concentration near the ends of the column. for a mixture of two components of about the same concentration. Low viscous systems will allow a relatively large linear gas velocity of about 40–50 mm/s. m) C18. Concentration profiles along a column are presented for (h. whereas the top product contained >90% of C16/C18fraction. and. Tiegs.and C22-compounds) (Riha. 1996. The experimental determined flooding diagram for SCF–liquid counter-current columns is essentially the same as for gas–liquid columns operating at normal pressures.. Due to the relative high solubility of the fatty acid ethyl. Concentration profiles are typical for a multi-component and multi-stage separation of key compounds (C18 and C20) and accompanying compounds (C14. The diameter of a column will then increase from about 200 mm for a capacity of 200 ton per year.26 G. columns of up to 500 mm diameter with a throughput of several hundred tones per year can safely be designed. Scale-up of column diameter is possible maintaining similar separation performance. Key compounds exhibit typical Fig. C20 can be separated from C22 in different runs. but also the influence of density on the gaseous phase. Meyer. (. & Brunner. Thus. (ii) separation of aroma compounds (essential oils). corresponding to the separation of fatty acid ethyl esters (C16. which have allowed a throughput of about 10 ton per year. the process is competitive to distillation. Birtigh. however. and ( . this location is at about the middle of the column. 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.

whereas peaks in the 4–6. However.3. phytol). Chromatographic separations have been carried out so far using columns of up to about 100 mm-diameter. In all cases. (1999). Johannsen. The maximum diameter employed in our laboratory was 70 mm. 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. produce standards (tocotrienols).5 min range correspond to the isomers of phytol (Figure adapted from Depta et al. (The flow scheme of such an apparatus was reported by Depta. Brunner / Journal of Food Engineering 67 (2005) 21–33 27 Fig. namely Sulzer EX for the lower throuphput (Q = 27.85 mg/ml of crude phytol sample––). injection volume = 20 ll of phytol pure (dotted line À17 mg/ml of crude phytol sample––) or diluted in n-hexane (dashed line À0. Fig. The separation of phytol isomers is shown in Fig. Analytical packed columns have diameters up to 4. 8. Chromatograph for preparative-scale separation of phytol isomers. Analytical and preparative separations were carried out in the elution mode which is a batch separation process. Column diameter for a separation column separation C18 to C22 fatty acid ethyl esters. 10. each 0. so that 52 theoretical stages. de-alcoholize beverages. modifier = 3% w/w isopropanol. where a piston compresses the fixed bed in the cylindrical column to keep it under higher pressure conditions than operational levels all the time the device is in use. the loading of the gas phase was 4% (w/w) and the separation factor was 1. The process conditions were as follows: Column = Li chrospher Si 60 (10 lm). In chromatographic separation.) 2. There are many publications available on analytical separations. & Brunner (1999). but it is technically possible to scale-up these processes. the supercritical solvent is used as mobile phase.3 m in height.5 ton/m2/h). Peaks for retention time <2 min correspond to samples impurities. flow rate = 3 NL/min of CO2.3.) Applications of chromatographic separations comprise analytical and preparative separations. allowing throughputs which are far below 1 ton per year. This has allowed long operational time use of months in our laboratories (Depta.6 mm. and Sulzer CY for the higher throughputs (Q = 86. and higher product concentration. UV-detection wavelength = 221 nm.) The advantages of SMB-chromatography are lower solvent ratio. and purify pharmaceuticals (vitamin D). Columns can be directly scaled-up in diameter if measures are taken that the fixed bed of the packed column with particle diameters in the range of 20–40 lm remains unchanged during operation and start-up and shut-off operations. Preparative separations can be used to separate enantiomers (ibuprofen. 9. (1996). 9 as an example of preparative chromatographic separation. With 30 mm-diameter columns about 10 ml/h of phytol isomers can be separated to more than 95% purity. pressure (before column) = 240 bar. 2000). were required to reach a product purity of 99% (w/w) when employing a reflux ratio of 10. de-fat potato . for example as a simulated moving bed (SMB).2–100 ton/m2/h). Preparative chromatographic separation Another separation technique where SCFs may be applied is chromatography. which can be obtained by the methods discussed above. to allow a switching in their function by a multi-port rotating valve. The analysis of edible oil compounds is particularly advantageous. temperature = 40 °C. Giese. (Figure adapted from Riha et al.G. Special applications of supercritical fluids to food processing Some products possibly produced by SCF technology may be found on our everydayÕs table. higher throughput. Curves indicate maximum throughput for two regular packings. a continuous chromatographic separation can be designed. 3. Processes to obtain vitamin additives. Some examples of products are listed in Fig. One way to achieve this is by axial compression. who arranged eight columns in a circle.

The process has been fully designed for commercial application. phase equilibrium data have to be considered first. 1994). 2000). and Takebayashij (2002). For more information on the other examples the reader is referred to the literature. 3. and Arai. meaning that these components stay in the liquid oil phase. the triglycerides are subject to an esterification with methanol to form fatty acid methyl esters. In this method. 12 the distribution coefficients 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. For a discussion of enriching tocochromanols. together with other unsaponifiable matter (squalene. whereas that for the carotenes is much smaller than one. tocochromanols can be extracted as the top phase product in a separation column. 3. SODD may contain (after several conventional concentration steps) about 50% tocopherols. in particular King and Bott (1993). Removal of fat from foods Edible oils and their components have been the target of SCF processing since the early 70 s. Supercritical fluid technology applied to everydayÕs food.2. it is better to produce esters of the triglycerides in order to be able to more easily separate these compounds from the tocochromanols. Free fatty acids (FFA) and tocochromanols exhibit a much higher solubility in CO2 than the triglycerides. In Fig. One of these is the removal of fat from food. Brunner (1994. This attempt is described in more detail by Jungfer (2000). Sako. According to the expected taste the amount of remaining fat in the potato chips can easily be controlled.28 G. Hence. 10.) Fig. Brunner / Journal of Food Engineering 67 (2005) 21–33 Fig. Although triacylglycerides are only fairly soluble in SC-CO2. Both materials can be used for the production of enriched fractions of tocochromanols.7 MPa as the solvent. As starting material one can use various edible oils or their distillates. etc. Bertucco and Vetter (2001). 11. in particular a lower operating temperature (Brunner. Percent oil removed from salted and unsalted potato chips as a function of solvent usage when employing SC-CO2 at 55 ± 1 °C and 40.1 MPa in both the cases. the advantages of organic solvent-free processing have stimulated research and development in various areas.1. which are easily extractable with CO2. Thus. As an example in Fig. these components are enriched in the gaseous phase. 11 the extraction curves for fat from potato chips is shown. (Figure adapted from Vijayan et al. McHugh and Krukonis (1994). sterols. Most promising as feed materials are crude palm oil (CPO) and soybean oil deodorizer distillate (SODD). Although it is possible to recover tocochromanols directly from CPO. For recovering the carotenes together with the tococromanols the above mentioned esterification to volatile (CO2 soluble) methyl . Enrichment of vitamin E from natural sources SCFE offers several advantages for the enrichment of tocochromanols over conventional techniques such as vacuum distillation.8 ± 0.) are enriched in the bottom phase of an extraction column. (1994). The separation conditions were 30 ± 3 °C and 0. using the aforementioned standard design. ships. whereas carotenes remain in the bottom phase product together with triglycerides. That means that the tocochromanols. and encapsulate liquids will be discussed in more detail below. The process has the advantage of producing fat-free or fat-reduced potato chips. expressed by a distribution coefficient being higher than one. CPO contains several tocotrienols and tocopherols at a total concentration of approximately 500 ppm. The distribution coefficient of the triglycerides is smaller than one.

Investigations employing SODD as feed material for the extraction were performed at temperatures of 353 Fig. (n) triglycerides. all phytosterols have a rather low solubility in CO2 (and remain in the oil phase). occasionally to more than 50% (w/w). and the reflux ratio was set between 1 and 38. and tocochromanols exhibit an intermediate solubility between the two. it could not be found in the bottom phase. as expected. tocopherols and sterols in a column using SC-CO2 as the solvent. When the glycerides (in case of the esterification) or the FFAs from deodorizer distillates have been removed. Experiments showed that.4% (w/w) in the bottom product was obtained (Gast. The sterols were completely enriched in the bottom phase. Starting from a tocochromanol concentration of 48. or in reflux mode.6 kg/h of SC-CO2.) and 363 K and at pressures of 23 and 26 MPa. Jungfer. as intermediatesoluble components.G. ( . 13. Saure. Brunner / Journal of Food Engineering 67 (2005) 21–33 29 Fig. 353 K.) carotenes of crude palm oil (700 ppm tocochromanols. 95–99% (w/w) triglycerides. Counter-current separation of squalene. The dashed horizontal line for theoretical plate 3 represents the feed plate. the sterols and the tocochromanols have to be separated first.) esters makes possible to recover tocochromanols and carotenes (together with squalene and sterols) as bottom product from this natural source. the separation of squalene and tocochromanols was now possible. This separation was performed at 23 MPa. m) sterols (closed symbols and solid lines represent compositions of the liquid phase.8% (w/w) in the top phase product. the products become too viscous and clog the packing mash and the column (Saure. In this feed material. The gaseous solvent is recycled. 2003). with the solvent introduced at the bottom and the feed at the top of the column. (Figure adapted from Saure (1996). For further purification. having a S/F ratio of 110 and a reflux ratio of 4. 3. the top phase product of some experiments was collected and introduced as feed a second time. In a second separation step tocochromanols are separated from phytosterols. such as squalene and sterols. Concentration profiles along a column are presented for (h. Of these compounds.5 mm and can be operated either in a true stripping mode. The inner diameter of the column is 17. The contained squalene could be completely enriched in the top phase product. and 55 g/h of reflux. whereas open symbols and dotted lines those of the gaseous phase). The tocochromanols. Distribution coefficients for (h) tocochromanols. ) tocopherols. The experiment was carried out at 353 K and 23 MPa by employing 86 g/h of feed. it was enriched from 3. 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 flow. and (n. were neither distinctly enriched in the top nor in the bottom phase product. (Figure adapted from Jungfer (2000). 1–5% (w/w) free fatty acids. The segmented line separates the less volatile components that are enriched in the raffinate (below the line) from the more volatile compounds that are enriched in the extract. If the concentration approaches 50% (w/w).1% (w/w) in the feed to 18. 12.6. The core of this apparatus is an extraction column having an effective separation height of 6 m equipped with Sulzer EX packing. then there is a feed material available for obtaining enriched fractions of tocochromanols and carotenes of much higher concentration. Consequently. tocochromanols and carotenes (in case of palm oil) are the main components and have to be separated from other unsaponifiable substances present. and 800 ppm carotenes) in SC-CO2 as a function of pressure. In order to simulate a taller extraction column. j) squalene. squalene has the highest solubility in SC-CO2. 1996). In fact. and (. & Brunner. The solvent-to-feed (S/F) ratio was varied in the range between 33 and 171. 13) that were conducted in a pilot scale plant described in more detail by Gast and Brunner (2001). For the first step concentration profiles of an experiment are shown (Fig. ( ) free fatty acids. Products with a tocotrienol and/or a tocopherol concentration in the range of 70–90% are obtainable with . With this sterol-free feed material. squalene was enriched in the top phase product.3% (w/w) an enrichment to 94.

15 illustrates the separation factor of ethanol–water as a function of the concentration of ethanol in the solventfree liquid phase. Extraction conditions were set to 333 K and 10 MPa. 14. 1988). Brunner / Journal of Food Engineering 67 (2005) 21–33 SCF separation techniques. The separation factor decreased from around 30 at infinite dilution of ethanol in water to approximately 1. Separation factors are larger compared to data at atmospheric conditions. With a feed of 94% (w/w) ethanol. (Figure adapted from Brunner and Kreim (1985). Recovery of aroma compounds is achieved by a side column in which a separation from ethanol is carried out. again using SCFs.5 h at 45 °C under non-optimized conditions. for instance from Budich (1999). With the information available in the literature. At these conditions. 1999). & Suzuki.12 cm/s). The plot includes experimental values of the separation factor determined using both ( ) a conventional and ( ) a modified sampling method. 6. The rate of ethanol removal depends strongly on temperature. The experimental set-up is shown in Fig. & Imanshi. Fig.5% (w/w) ethanol was produced at a reflux ratio of 4 and a S/F ratio of 60 (using 9 kg CO2/h and 150 g feed/h). S/F ratios are relatively small (30 kg/kg) compared to other counter-current gas extraction processes (Budich.3. with adsorptive or chromatographic techniques. and in between these is SCFE with CO2. (Figure adapted from Budich and Brunner (2003).30 G. Suzuki.5% (w/ w) requires about 2. with a height equivalent of a theoretical stage (HETS) of 0.) .g. equipped with of Sulzer EX packing). 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. Liquid solvent reflux was not required during this experiment because the raffinate was still very rich in ethanol (87% w/w). 1983). Furuta. Starting from an aqueous solution with about 10% (w/w) ethanol.5 MPa (superficial solvent velocity = 0.25 at infinite dilution of water in ethanol. A further purification of these compounds is possible. Solvent and extract were separated by pressure reduction down to 5 MPa and washing the extract phase with liquid CO2 in counter-current flow. 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. Fig. an extract with 99. Distillation is well known for this purpose with the disadvantage that aroma compounds will also be removed. Nagahama.) Fig. Twelve equilibrium stages were achieved. and related applications De-alcoholized wine or beer is achieved by removing ethanol from water. This is due to large separation factors and a solubility of pure ethanol in CO2 of 5% w/w at the conditions investigated. No azeotrope was formed at the conditions investigated. Reducing the alcohol content to values well below 0. 14. a column for dealcoholizing aqueous solutions can be designed. 2003. Removal of alcohol from wine and beer. A related process that can be mentioned is the recovery of absolute alcohol.1 MPa). However. Ikawa. Fukuzato. as well as ( ) reference values experimentally assessed at normal pressure (0. New techniques like membrane separation (pervaporation) emerge.33 m. 1989. e. 15. 1986. Much shorter times for the ethanol removal can be obtained if flow rates and mass transfer equipment are carefully selected. 3. The line represents the trend for experimental data at high pressure. Counter-current multi-stage extraction was carried out in an extraction column of 6 m total height (25 mm ID. Equilibrium diagram for the separation of ethanol–water with SC-CO2 at 333 K and 10 MPa. Kreim. Effect of process temperature and extraction time on the removal of ethanol from an aqueous solution using SC-CO2 at 15. anhydrous ethanol cannot be produced. ethanol can be removed by SC-CO2 in a stripping column as shown in Fig.

Costs of separation processes with supercritical fluids Reported costs for production rates around 1000 ton/ year of solid feed are in the range of 3 US$/kg feed.0%. The fixed adsorber was operated at 353 K using a feed of 20 g/min of SC-CO2. administration = 1. labour = 24. the encapsulation or adsorption of tocopherol acetate on silica gel. Solid products can also be formed under high pressure conditions.5 U$/kg for batch operation. and was fed with ( ) 73% (w/w) TA or (h) 97% (w/w) TA. and the liquid forms small droplets. In the experiments that are reported in Fig. Fig. 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). about 50% of tocopherol acetate can be incorporated onto the silica gel without apparent change of morphology and flow properties of the powder. Economy of scale for SC-CO2-extraction of solids. a recovery pressure for the extracts of 45 bar and 20 processing weeks they calculated processing costs of 1 €/kg of feed material. The amount which can be adsorbed at high pressures is comparable to that of normal pressure. solid substrate and liquid droplets are intensively mixed and combined to a solid particulate product of the type described above. The autoclave was operated at 333 K and 20 MPa.5%. and easier dosage. Microspheres or larger capsules can be formed. Lack and Seidlitz (2001) published data for the production of extracts from hops. wherein CO2 is mixed (dissolved) in the liquid feed by static mixing.4. Continuous operation would further reduce costs. utilities = 17. 16. This adsorption at high pressures makes possible the direct product formation in the SCF. An example is the so-called concentrated powder form-process.5%. with the advantageous effect that the supercritical solvent can easily be recycled without substantial compression. The lower curve in Fig. 17. by agglomeration (liquid in the free volumes between the solid particles). For extraction pressure of 350 bar. Another interesting feature is the cost structure for SCF processing.G. Here. 16. the autoclave was used to saturate the SC-CO2 current with tocopherol acetate. The CO2 is suddenly released from the liquid. or by impregnation (liquid within the pore system of the solid particles). 4. Adsorption isotherms for tocopherol acetate (TA) in SC-CO2 on silica gel (Fleck. It has also to be considered that cost estimates of such a type have an agreed variability of ±30%. totally encapsulating the liquid. taxes = 20. the equilibrium loading decreases (Fig. The product is finally removed from the chamber as a free flowing powder and separated from the outgoing gas stream by a cyclone. some data of different authors and processes are shown in Table 2. and the density of the solvent was changed in the nozzle where the loaded SC-CO2 phase was fed to the adsorber. Yet continuous extraction has been so far carried out only on laboratory scale. prevention of oxidation processes. Such particulate products can be achieved by means of SCF processing also. As advantages can be claimed the easier handling and storage.2%.1%. The powder with 50% loading is still free flowing. Brunner / Journal of Food Engineering 67 (2005) 21–33 31 3. As an example for such a type of process. a wide variety of solid substrates can be applied to uptake liquids of different kind and up to about 90%. Only at very high densities. . 16). 17 represents an anticipated fivefold increase in productivity (mostly due to shorter use of high pressure volume for extraction) reducing operating costs in the same proportion. Economy of scale may bring costs down to less than 0. During the spraying process. 2000). Therefore. The CO2–liquid feed mixture is then sprayed into a spray chamber at ambient conditions together with the substrate material. The solid material provides a coating for the liquid inside. With this type of process. The cost breakdown without considering the cost of the raw material is as follows: interest and depreciation = 36. Investment costs in this case are about Fig.

G. & Vetter. propane is added.85 0. It is readily available for extraction from solids (also in simulated countercurrent mode) and multi-stage counter-current separation. Bertucco. cycle costs are only 50% of the base case. Gas extraction. (2002). Stofftrennung mit uberkritischen Gasen (Gasext¨ raktion). To achieve this. Hoffmann-La Roche AG (Basel. 2001) Type of process Decaffeination of coffee beans (batch. Conclusions one third of total processing costs. and the integration into a process cycle has to be proven. a Values are expressed as a percentage of the base case (operating cost = 100% for high vacuum distillation). This value is still higher than for equipment operated at ambient pressure but lower than the 50% mostly cited. Berlin. (Eds.9 0. and separation of enantiomers. .. Costs are twice as high with SC-CO2 and solvent recovery by pressure reduction. isobaric) Solids extraction. 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 (10–20%). G. non-isobaric) Decaffeination of coffee beans (batch. NY: Springer. our group succeeded in finding a polymer membrane which can be applied (Sartorelli.7 14 9 5 Another possibility for reducing costs is a low pressure drop along the solvent cycle. 5. Switzerland). separation of the solute from the supercritical solvent by membranes would be an ideal means (Sartorelli & Brunner. Germany: Springer.75 0. Molecular interactions. 12–22. Brunner. del Valle are gratefully acknowledged as is the funding by FONDECYT (International Cooperation project 703-0033) from Chile. Y. If. A. sterilization. (Eds.05 €/kg product. G. If propane is added. Brunner. Some plants for preparative scale are available as for SMB chromatography. 2000). The Netherlands: Elsevier. and new applications. (1987).000 600 1000 2000 Cost estimate (€/kg feed) 1. The base case is high vacuum distillation (p < 1 mbar). general Removal of pesticides (from ginseng) Capacity (ton/year) 3500 4500 7000 3500 4500 7000 10. High pressure process technology: Fundamentals and applications. costs may be less than 10% of the base case. Still the membrane has to be tested in a module. 2000) Method of precipitation Pressure reduction Adsorption Supercritical solvent CO2 CO2 + C3H8 CO2 CO2 + C3H8 Operating costa (%) 200 20 50 8 References Arai. Fleck. New York.). and F. DFG (Deutsche Forschungsgemeinschaft) from Germany. Y.. Chromatographic techniques with SCFs as a mobile phase are primarily used for analytical purposes by now. costs can be reduced to 20% of the base case. 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. If the favourable case occurs that the solute can be adsorbed. Supercritical fluids. Brunner / Journal of Food Engineering 67 (2005) 21–33 Table 2 Cost estimates for processing of solids with supercritical carbon dioxide (Lack and Seidlitz. for instance for particle design.1 0. In cooperation with the Institute of Chemistry of GKSS in Hamburg.). Germany. 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.7 0. in addition. Chemie-Ingenieur-Technik. For a plant with 500 mm ID column the respective values for capacity and cost have been estimated as 1090–1250 ton/year (for 10% or 20% propane) and 1. (1994). The solute is retained and SC-CO2 permeates through the membrane at high rates.32 G. (2001).55 0. T. Table 3 summarizes the effects of using propane-CO2 mixtures as the solvent on operating costs. 2001). An active multiple layer of poly-tetra-fluoro-ethylene supported by a ceramic or organic material proved to be applicable at high CO2pressures (tested up to 35 MPa).4 €/kg product. even with pure CO2. and the adsorbate used as product. Table 3 Operating costs for the purification of tocopherol acetate for different solvent mixtures and different methods for precipitating the extract (Fleck. Brunner. physical properties.. & Takebayashij. An introduction to fundamentals of supercritical fluids and the application to separation processes. Sako. Amsterdam. 59. New technologies are emerging. Acknowledgments ´ Useful discussions with Jose M. Processing materials with SCFs is a proven and industrially applied technology.

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