Supercritical Fluid Extraction From Vegetable Materials - Sovova

Rev Chem Eng 27 (2011): 79156 2011 by Walter de Gruyter Berlin Boston. DOI 10.1515/REVCE.2011.
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Supercritical uid extraction from vegetable materials
Helena Sovov1,* and Roumiana P. Stateva2

Institute of Chemical Process Fundamentals of the ASCR, v.v.i., Rozvojova 135, 16502 Prague, Czech Republic, e-mail: sovova@icpf.cas.cz 2 Institute of Chemical Engineering, Bulgarian Academy of Sciences, 1113 Soa, Bulgaria
*Corresponding author
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Abstract
In the 21st century, the mission of chemical engineering is to promote innovative technologies that reduce or eliminate the use or generation of hazardous materials in the design and manufacture of chemical products. The sustainable use of renewable resources, complying with consumer health and environmental requirements, motivates the design, optimisation, and application of green benign processes. Supercritical uid extraction is a typical example of a novel technology for the ecologically compatible production of natural substances of high industrial potential from renewable resources such as vegetable matrices that nds extended industrial application. The present review is devoted to the stage of development of supercritical uid extraction from vegetable material in the last 20 years. Without the ambition to be exhaustive, it offers an extended, in comparison with previous reviews, enumeration of extracted plant materials, discusses the mathematical modelling of the process, and advocates a choice for the appropriate model that is based on characteristic times of individual extraction steps. Finally, the attention is focussed on the elements of a thermodynamic modelling framework designed to predict and model robustly and efciently the complex phase equilibria of the systems solute+supercritical uid. Keywords: kinetic models; plants and herbs; supercritical uid extraction; thermodynamic models.
1. Introduction
A supercritical uid (SCF) is a substance above its critical pressure and temperature (Figure 1). Its properties range between those of liquid and gas. The most important advantages of SCFs applied in extraction are the extreme variability of their solvent power with pressure and temperature, and their low viscosity, enabling much faster mass transfer than in liquids. No other extraction method can claim such exibility. The main drawback of a large-scale SCF application in comparison with conventional methods, namely the high cost of the high-pressure equipment required, can often be
outweighed by superior product properties, lower operating costs, and/or integration of several technological steps into one. SCF extraction (supercritical extraction, SFE) of natural substances from plants is a relatively new process. The discovery of the solvent power of pressurised carbon dioxide was made in the 19th century (Hannay and Hogarth 1879), but its practical application for extraction of vegetable substances was rst studied in the 1960s when more sensitive analytical methods indicated trace amounts of residual organic solvents in food samples and initiated concern about their impact on human health. It was realised that dense carbon dioxide in its supercritical or liquid state (the term supercritical uid extraction often covers the extraction with both supercritical and liquid carbon dioxide) is a non-toxic solvent and thus its traces left in extracts are not harmful. Its critical point (Tc=31.1C, Pc=7.38 MPa) allows application of relatively low operation temperatures so that thermally labile solutes are protected and the extracts better resemble the natural material than the products of steam distillation and conventional extraction where the solvent is usually separated from the extract under increased temperature. Carbon dioxide is non-ammable, non-explosive, cheap, and easily accessible in high purity. To also dissolve more polar substances, supercritical carbon dioxide (SC-CO2) is usually modied by addition of small amounts of polar liquids, such as methanol, ethanol, water, and others. Initially, the experiments with SC-CO2 extraction of natural products were conducted in a limited number of laboratories, most intensively in Germany (Zosel 1964) and in Russia (Pekhov et al. 1965). Since then, many laboratories in different countries have been equipped with SFE units and extensive research has been done in the extraction of avours, spices, essential oils, and other substances from herbs and plants. The rst pilot and full-scale plants were built for SC-CO2 extraction of caffeine from coffee beans and tea leaves, the extraction of acids from hops giving taste to bear, and the extraction of taste and avour compounds from spice. The number and capacity of industrial units for supercritical extraction and the variety of extracted substances are increasing, and today >200 industrial plants are operating all over the world (Perrut 2007). The two most important commercial applications of SFE in the food industry still remain hop extraction and coffee decaffeination (del Valle and Aguilera 1999); however, the production of extracts rich in biologically active substances as antioxidants, lipid-soluble vitamins, and others is fast increasing. Small-scale SFE for analytical application was developed in the mid-1980s in response to the desire to reduce the use of organic solvents in the laboratory environment (King 1995). Extraction equipment with extractor capacity of several cubic centimetres or less enables a fast and efcient isolation
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H. Sovov and R.P. Stateva: SFE from vegetable materials
(sc) Pressure (l) C (s) T Temperature (g)
Figure 1 Phase diagram with ternary point (T), critical point (C), and solid (s), liquid (l), gaseous (g), and supercritical (sc) state.
of substances for chromatographic assay from bulk sample matrix. To achieve complete extraction of analytes, high pressures and temperatures are applied and SC-CO2 is usually modied to increase the solubility of more polar solutes and/or to weaken solute-matrix interaction. SC-CO2 and near-critical water (also known as subcritical water, hot pressurised water, HPW) are regarded as the most promising environmentally benign medium not only for the extraction of natural substances but also for various chemical and related processes. The properties of HPW differ from those of water at ambient conditions. Under pressure and high temperature, it becomes an excellent solvent for not only polar compounds but also non-polar substances. Nevertheless, its critical point (22.1 MPa and 374C) is far above the critical point of CO2, and even though the operation temperature of subcritical water is usually selected closer to the lower limit of the range 100374C, the process is not appropriate for temperature-labile and easily hydrolysable substances. Moreover, HPW is corrosive, in contrast to SC-CO2. Although the focus of the research in SCF applications is moving nowadays to new areas, such as particle design, chemical reactions in supercritical solvents, polymer treatment with SCFs, and fractionation of liquid natural products as edible oils in counter-current extraction columns, still the most extended industrial application of SCFs remains the SC-CO2 extraction from botanic materials. Concerns about the cost and environmental dangers of waste disposal, and the emission of hazardous solvents into the atmosphere motivate the design and application of a green technology such as SFE. Without the ambition to be exhaustive, we have limited the reviewed literature sources almost entirely to original papers. Moreover, during the last few years, several excellent review papers on supercritical extraction from plants have been published, and there is no benet from repetition. However, we believe we can further elaborate several topics and present new information. First, the table of extracted plants, extended in comparison with previous reviews, should help exploit the information contained in the literature. Further, as many papers on mathematical modelling of SFE from plants have been published recently, an attempt is made to review this literature and advocate a classication of the models in relation with characteristic times of individual extraction steps.
We will also focus our attention on the thermodynamic modelling of the complex systems solid solute+SCF. The modelling of systems with an SCF has been comprehensively discussed in two books (McHugh and Krukonis 1994, Prausnitz et al. 1999) and several reviews see, for example, the contributions by Brennecke and Eckert (1989), Johnston et al. (1989), and Ekart et al. (1991), to name just a few. More recent papers and reviews devote particular attention to modelling solid+SCF systems without and with a co-solvent (Ashour et al. 2000, Escobedo-Alvarado et al. 2001, Higashi et al. 2001, Gordillo et al. 2005a) and the main conclusion of the authors can be briey summarised as follows: (i) prediction of SFE is difcult even when experimental data are available to rene the models used, (ii) theoretically based models are forced to t the data better by the introduction of additional adjusted parameters. Needless to say that this area of research is very competitive and fast moving, and we believe there are still some points that need further attention and elucidation.
2. SFE from plants

2.1. The process and the equipment
The extraction is usually carried out as a semicontinuous process (Figure 2). Vegetable material, usually dry and disintegrated, is charged into an extraction vessel of cylindrical shape to obtain a xed bed of particles. The supercritical solvent, fed to the extractor continuously by a high-pressure pump at a xed ow rate, dissolves required substances. The solution ows to a separator where the extracted substances precipitate by temperature and/or pressure changes or by applying a mass-separating agent, and the solvent is continuously regenerated and recirculated. More separation stages are often used to achieve a partial fractionation of the extract (Brunner 1987, Reverchon 1997). The typical volume of extractors is from 0.1 to 2 dm3 on the laboratory scale and from 2 to 5 dm3 on the pilot scale. MicroSFE devices are primarily designed for analytical purposes and are frequently connected to an analyser such as gas chromatograph, gas chromatograph-mass spectrometer, or SCF chromatograph. These instruments use extraction vessels that
Extractor Solution Separator Mixture CO2(g)
CO2(sc)
CO2(l)
Figure 2 Simplied scheme of the extraction equipment with CO2 recycle.
Condenser
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can range from 0.1 cm3 to several hundred cubic centimetres (Reverchon 1997). In micro- and small-scale extraction, the CO2 ow rate is low and therefore the equipment does not require solvent recycle CO2 can be expanded to ambient pressure in the separator and vented. When the SFE plant is equipped with several separators in series, fractionation of the extracts is possible, operating the separators at different pressures and temperatures. The scope of this operation is to induce the selective precipitation of different compound families as a function of their different saturation conditions in the solvent. This procedure has often been applied in the SFE of essential oils to separate them from coextracted cuticular waxes (Reverchon and De Marco 2006). High capital costs of SFE equipment are usually mentioned among the drawbacks of the process. On the other hand, the operating costs are usually lower than those of conventional extraction. Thus, many large-scale units for the SFE of solid natural materials, mainly for food ingredients and phytopharmaceuticals, are operated worldwide and are economically competitive. Perrut (2000) published a correlation of the investment cost of SFE units delivered on a turn-key basis with the product of total volume of extractors and the design ow rate, showing that the cost increases approximately with the square root of the plant capacity. A chapter in a monograph was devoted to the economic evaluation of high-pressure processes by Lack and Seidlitz (2001). The investment and operating costs were also discussed by Brunner (2005). del Valle et al. (2005a) compiled costs of several production-scale SFE plants of 0.68 m3 total extractor capacity and performed a feasibility study of a plant for the extraction of wheat germ oil. They showed how the break-even plant capacity would vary in several countries in Latin America. Simultaneously, Rosa and Meireles (2005a) described the methodology of estimation of the manufacturing costs of SC-CO2 extracts and used the procedure to estimate the costs of clove bud oil and ginger oleoresin. This methodology was applied also in later publications (Pereira and Meireles 2007, Pereira et al. 2007, Prado et al. 2010, Mezzomo et al. 2011). Fiori (2010) performed a study on the possible use of exhausted grape marc for obtaining grape seed oil by means of the SFE based on a thorough analysis of the process, indicating that the proposed industrial application could be economically interesting. Specic costs and incomes linked to the supercritical technology are reported in details for the case study. Perrut (2000) emphasised the importance of regular maintenance of the high-pressure equipment, necessary to eliminate hazards, and mentions the parts of the equipment that must be inspected rst. Cleaning of the equipment was also discussed.
2.2. Review papers
plants but also examine other SCF applications, we mention here only a few. Thus, the potential applications of SCFs in bioprocessing (as non-aqueous media for enzymatic reactions, solvents or anti-solvents in production of micrometre and submicrometre particles, solvents for extraction, rapidly expanding uid for disruption of cells) were reviewed by Jarzebski and Malinowski (1995). The exceptional physical properties of SCFs and their exploitation in environmentally benign separation and reaction processes, as well as in other new kinds of materials processing are described by Eckert et al. (1996). Hauthal (2001) reviewed the results on SCF fundamentals and their applications. Marr and Gamse (2000) reviewed developments in extraction, fractionation of products, dyeing of bres, treatment of contaminated soils, production of powders in micron and submicron range, and reactions in or with SCFs. Perrut (2000) considered the perspectives of production-scale applications of SCFs also in respect to the economic competitiveness of these processes with conventional ones. Beckman (2004) examined the use of CO2 to create greener processes and products, with a focus on research and commercialisation efforts since 1995. The literature on chemical and enzymatic reactions and formation of micro- and nanoparticles revealed that careful application of CO2 technology can result in cleaner and less expensive processes and products of higher quality. In the recent review of Temelli (2009) on processing of fats and oils using SC-CO2, it is shown that SFE of specialty oils has reached commercial scale and that researchers focus on fractionation of complex lipid mixtures, conducting reactions in supercritical uid media, and particle formation for the delivery of bioactive lipid components. A bright future is predicted for new integrated processes to be developed, targeting ingredients for both food and non-food industrial applications. High-pressure uid phase-equilibria, both experimental methods and systems investigated, were reviewed by Fornari et al. (1990) for data published in the period 19781987, Dohrn and Brunner (1995) for the period 19881993, Christov and Dohrn (2002) for the period 19941999, Dohrn et al. (2010) for the period 20002004, and Fonseca et al. (2011) for the period 20052008. The papers also contain solubility data for many substances in supercritical solvents. The reviews listed below focus directly on SFE.
2.2.1. Extraction for food, drug, and perfume industries The state of supercritical extraction of natural prod-
Besides the monographs either devoted to the applications of SCFs generally or directly to SFE (e.g., Stahl et al. 1987, King and Bott 1993, Brunner 1994, Rizvi 1994, Koshevoi and Bliagoz 2000), valuable information on the process has been collected and reported in a number of review papers. From those that are not only limited to supercritical extraction from
ucts in the middle of the 1980s was described by Brunner (1987). Palmer and Ting (1995) discussed the actual and potential applications of SCF technology and presented a summary of commercial applications, patented processes, and published research studies on utilisation of SCFs in food processing. Starmans and Nijhuis (1996) compared different methods, including SFE, for extraction of secondary metabolites from plant material. Sihvonen et al. (1999) summarised some of the advances and the latest developments in the eld of SCF technology focusing on the use of SC-CO2 in food, nutraceutical, and pharmaceutical applications. Wolski and Ludwiczuk (2001) presented fundamentals of high-pressure extraction and reviewed literature related to supercritical
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extraction in different branches of industry. Raventos et al. (2002) focused their review on the applications and potential of SC-CO2 in the food industry. Rozzi and Singh (2002) discussed the use of SCFs in different processes of food industry and in food analysis. A review including general description of SCFs, their physicochemical properties and particularly the solvent power, effect of solid matrices on the extraction, and application areas of SFE was published by Askin and Otles (2005). Brunner (2005) reviewed the state of SCF applications to food processing. Besides other processes, industrialscale extraction from solid materials (decaffeination of green coffee beans, production of hops extracts, recovery of aromas and avours from herbs and spices, extraction of edible oils, and removal of contaminants) was discussed, including the solvent power of SC-CO2, the course of the extraction process, design of commercial plants and modes of their operation, equipment size, and processing costs. Recent advances in SFE were overviewed by Herrero et al. (2010). Hierro and Santamaria (1992) reviewed the SFE techniques for extraction of vegetable and animal fats and particularly those containing polyunsaturated fatty acids, which have important pharmacological applications. The paper written by Kerrola (1995) is focused particularly on the extraction of essential oils and avour compounds. Another excellent review on SFE and fractionation of essential oils and related products was published by Reverchon (1997). The paper presents experimental techniques for SFE from plants, solubility in SC-CO2 of different essential oil components, and mathematical models for the process. Furthermore, the inuence of operating parameters on extraction rate and extract composition is discussed as well as pre-treatment of raw materials and post-processing of the extracted essential oils. The applications of dense carbon dioxide for the extraction of pharmaceuticals from various matrices were reviewed by Dean and Khundker (1997). The SFE process parameters required for a preliminary analysis of the manufacturing costs were compiled from the literature published in 20012003 by Meireles (2003). Brazilian research on SCFs and their application, including the SFE from vegetable materials, was reviewed by Rosa and Meireles (2005b). Herrero et al. (2006) reviewed the SFE of functional ingredients from plants, food products, algae, and microalgae with special attention to antioxidants, both for SC-CO2 and subcritical water as solvents. DiazReinoso et al. (2006) published a comprehensive compilation of data on the SFE of antioxidant compounds from vegetal materials and their purication, with particular attention to the substances of a phenolic nature. Wang and Weller (2006) described and compared the conventional Soxhlet extraction with SFE and other alternative methods and summarised potential uses of these methods for the extraction of nutraceuticals from plant materials. Reverchon and De Marco (2006) critically analysed the research on supercritical extraction and fractionation in the last decade, including the SFE of essential and seed oils, antioxidants, pharmaceuticals, colouring matters and pesticides, as well as mathematical modelling of SFE. Catchpole et al. (2009) reviewed the extraction and fractionation of specialty lipids (high-value seed oils, polyunsaturated fatty acid concentrates, carotenoids, and phospholipids)
with near-critical solvents. Pereira and Meireles (2010) published an extensive review on the SFE of bioactive compounds (essential oils, phenolic compounds, carotenoids, tocopherols, and tocotrienols), taking into account extraction yields, solubility, and manufacturing costs, and operation conditions in the extraction and fractionation. Another overview focused on the application of SFE in recovery of bioactive phenolic compounds from natural sources and effects of extraction conditions on the yield, composition, and antioxidant activity of extracts was published by Marostica et al. (2010). A review of transport properties and solubilities in SCFs, particularly CO2, as well as other underlying factors that are responsible for the kinetics and phase equilibrium in SFE processes, was presented by del Valle and Aguilera (1999). They described the selective CO2 extraction of essential oils, pungent principles, carotenoid pigments, antioxidants, antimicrobials, and related substances to be used as ingredients for the food, drug, and perfume industries from the point of view of the potential applications of SFE in Latin America. Al-Jabari (2002) considered models for various applications of SFE, showed the importance of modelling the initial static extraction (with no solvent ow) preceding the dynamic extraction, and demonstrated the similarity between modelling SFE processes and reversible adsorption/desorption processes. The paper of del Valle et al. (2005a) summarises basic and applied research on phase equilibrium and mass transfer kinetics involved in high-pressure CO2 extraction from solid substrates and particularly the extraction of lipids and essential oils from native Latin American plants. Mass transfer models for SFE of vegetable oils from solid matrix were reviewed by del Valle and de la Fuente (2006). A recent review paper published by Oliveira et al. (2011) includes models for kinetics of SFE from solid particles and for SFE from liquids in counter-current columns.
2.2.2. Extraction for analytical purposes
Hawthorne (1990) discussed SFE as a method for extraction of analytes from a bulk sample matrix before their analysis. He considered SFE techniques and hardware and concluded that extraction time is reduced, generation of large volumes of waste solvents is eliminated, and the step of concentration of the extracted analytes is greatly simplied compared with conventional liquid solvent extraction techniques. Castioni et al. (1995) focused attention on near-critical extraction of compounds of plant origin and its on-line coupling with chromatographic methods. Modey et al. (1996a) explored the use of SCFs for analytical extraction of natural products and highlighted applications where SFE might be advantageous. Chester et al. (1996) published a review on SCF chromatography and extraction; 2 years later they continued their review in a new contribution focusing on the most signicant articles concerning the topics (Chester et al. 1998). According to the authors, the enhanced performance characteristics of SFE, such as greater selectivity compared with conventional methods, reduced time, greater quantitative yields, lower cost per extraction, and new capabilities, had driven the technology in the 1990s. The advances in SFE spurred the creation of new extraction techniques known as accelerated solvent extraction, hot (subcritical) water extraction, near-critical
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uid extraction, enhanced-uidity extraction, etc., which are performed below the critical point of the solvent and can be called pressurised uid extraction. Smith (1999) reviewed the development in SCF chromatography and SFE of analytes in the last 20 years and showed that there is unity in separation methods and that a continuum exists from gases to liquids. de Castro and Jimnez-Carmona (2000) emphasised the advantages of SFE, such as preconcentration effect, cleaniness and safety, quantitativeness, expeditiousness, and simplicity. They discussed limitations of the method demonstrated when extracting polar analytes, occurrence of matrix-analyte binding that often makes a complete extraction of analyte from natural samples impossible, and mentioned different ways of clean-up of fat-soluble analytes from unwanted matrix components. Chen and Ling (2000) presented a review on SFE in Chinese herbal medicine. The paper contains lists of application examples of SFE of useful ingredients from herbs and plants, including the operating parameters, concentrations of modiers in CO2, extraction yields, and analytical methods. Similar data were given for SFE of pesticide residues from different botanic materials. The authors concluded that SFE had proven to be a practical and powerful method for the extraction of useful ingredients and pesticide residues from natural products and food plants. They regarded as promising the possibility of extracting both types of solutes separately using the same extraction medium at different operating conditions, and concluded that a systematic and effective means to reach the optimal extraction conditions were yet to come. Lang and Wai (2001) discussed practical aspects of SFE applications in sample preparation, selection of modiers, collection methods, on-line coupling techniques, means for avoiding mechanical problems, and approaches to optimisation of SFE conditions. King (2002) reviewed analytical supercritical extraction with carbon dioxide as the extracting agent from a wide array of sample types. Zougagh et al. (2004) underlined the great analytical potential of SFE, tried to identify reasons for its rare implementation by routine analytical laboratories, and proposed ways to overcome the shortcomings behind them. Several papers were focused on particular topics in analytical SFE. Extensive revue on the use of SFE in food analysis was published by Anklam et al. (1998). The application of SFE and SCF chromatography in forensic investigations was reviewed by Radcliffe et al. (2000). Turner et al. (2001) reviewed the applications of SFE and chromatography for fat-soluble vitamin analysis, and, in the next review paper, Turner et al. (2002) focused on the modes and optimised conditions for the collection of extracted analytes. Smith (2002) published a literature review on extraction with superheated water where the extraction of essential oils, avours, and fragrances from plant materials is mentioned besides other materials. Pourmortazavi and Hajimirsadeghi (2007) discussed the developments, modes, and applications of SFE in the isolation of essential oils from plant matrices; showed how the solubility of the solute in the uid, diffusion through the matrix, and collection process affect their extraction yield; and compared the SFE with conventional extraction methods. Mendiola et al. (2007) reviewed the applications of pressurised solvents,
both supercritical and liquid, in sample preparation for food analysis, and concluded that these extraction techniques could be used for routine analysis as fast, reliable, clean, and cheap methods. There is, however, a clear need for their validation before they can be applied as ofcial methods substituting the most laborious, time-consuming, and classical procedures. The application of SC-CO2 in SFE of lipids and in food processing generally was reviewed by Sahena et al. (2009).
3. Plants and extracts

A hypothetical list of herbs and other plants subjected to SFE in laboratories is getting longer every week, being extended particularly by the plants growing in Asia and Latin America. Table 1 shows the large range of both plants and extracted substances. To keep its size acceptable, we have excluded the extraction of non-native components as pesticides and herbicides (Lehotay 1997, Motohashi et al. 2000, Aguilera et al. 2005), although the research in this eld is promising. Also the extraction with subcritical water (see, e.g., Cacace and Mazza 2006) and with other pressurised solvents than CO2 was not included. Thus, the references concern the extraction of plant components with dense CO2, either pure or modied. Even so, the table could not cover all the papers published on the topic because of their large number. It is based on the data collected in the Institute of Chemical Process Fundamentals, the Czech Republic, for more than two decades and therefore it is not restricted to a certain period of publication or selected literature sources. The knowledge collected in the literature should certainly not be omitted in further research on SFE.
4. Thermodynamic modelling of systems vegetable solute + SC-CO2 + entrainer

The advantages of using SCFs as solvents are numerous and lead to environmental, health and safety, and chemical benets. That is why they are referred to as the green solvents for the future. Furthermore, as discussed previously, the thermophysical properties of SCFs (high diffusivity, low viscosity, density, and dielectric constant) can be ne-tuned by changes of operating pressure and/or temperature, and thus SFE has a great potential as a promising, efcient, and clean alternative method compared with the conventional methods of distillation and extraction. Thus, there is a clear-cut need for obtaining detailed knowledge that will allow the design and optimisation of the environmentally benign SFE processes. Thermodynamics of the phase equilibria is a vital part of this knowledge, as the objects of SFE are usually very complex, and can exhibit intricate phase behaviour. To predict correctly and calculate efciently the equilibria, a robust and reliable thermodynamic modelling framework (TMF) must be available. The TMF comprises three main elements: a library of thermodynamic parameters pertaining to pure substances and binary interactions; thermodynamic models for mixture properties; and methods, algorithms, and numerical techniques for solving the equilibrium relations.
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Table 1 Extract components Volatile oil, lupenol Flavonoids Volatile oil Volatile compounds, repellents Oil, volatile oil Antioxidants: -tocopherol Oil, tocopherols, squalene Alkaloids: phenanthridone class Michellamines Diterpene lactones: andrographolide, etc. Alkaloids: hyoscyamine, scopolamine Volatile oil: anethole Antioxidants Volatile oil Pigments, carotenoid bixin Flavour compounds, polyphenols Oil, -carotene Volatile oil: camphor, 1-8 cineol E-1-propenyl sec-butyl disulde, germacrene B Oil Psoralen, isopsoralen Phenolic compounds Oleoresin Volatile oil Flavonoids: baicalin, baicalein, wogonin Vitamin E: tocopherols, tocotrienols Volatile oil, cuticular waxes, antioxidants References
Plants extracted with pure or modied carbon dioxide.
Plant part
Abajeru (Chrysobalanus icaco) leaves Agrimony (Agrimonia eupatoria, A. procera) leaves Ajowan (Carum copticum) fruit Alfalfa (Medicago sativa) germ, leaf, stem Almond (Prunus dulcis) fruit, seed
Aloe vera (Aloe barbadensis) leaf skin, pulp, rind Amaranth (Amaranthus caudatus, A. cruentus) seed Amaryllidaceae sp. Ancistrocladus korupensis leaves Andrographis paniculata herb, leaves Angels trumpet (Datura candida D. aurea) roots Anise (Pimpinella anisum) fruit Anise hyssop (Lophantus anisatus) Anise verbena (Lippia alba, L. sidoides) Annatto (Bixa orellana) seed
Apple (Malus domestica) fruit, peels, pomace Apricot (Prunus armeniaca) kernels, shells, bagasse, pomace Artemisia herba-alba (Artemisia sieberi) herb Assafoetida (Ferula assa-foetida)
Vargas et al. 2010 Bajer et al. 2007, Venskutonis et al. 2008 Khajeh et al. 2004 Core et al. 1994, 1996, Henning et al. 1994 Calame and Steiner 1982, Passey and Gros-Louis 1993, Lack and Seidlitz 1994, Marrone et al. 1998, Femenia et al. 2001 Hu et al. 2005 Bruni et al. 2001, 2002, He et al. 2003, Westerman et al. 2006 Queckenberg and Frahm 1994 Ashraf-Khorassani and Taylor 1997 Bo et al. 2000, Kumoro and Hasan 2008 Brachet et al. 1999 Stahl and Gerard 1982a, Ondarza and Sanchez 1990, Rodrigues et al. 2003a Dapkevicius et al. 1996 Sousa et al. 2002, Stashenko et al. 2004, Braga et al. 2005 Chao et al. 1991, Degnan et al. 1991, Anderson et al. 1997, Silva et al. 1999, 2008a, Nobre et al. 2006 Bundschuh et al. 1988, Adil et al. 2007 Niewoudt and Botha 1998, Doker et al. 2004, Sanal et al. 2004, 2005, Ozkal et al. 2005, 2005c Ghasemi et al. 2007 Khajeh et al. 2005 Botha and McCrindle 1999 Wang et al. 2004a Piantino et al. 2008 Monteiro et al. 1997 Mi et al. 2005 Lin et al. 1999, Chang et al. 2007 Colombo et al. 1998 Hawthorne et al. 1989, Reverchon et al. 1993a, 1994b, Reverchon and Sesti Osseo 1994b, Lachowicz et al. 1996, 1997, Ehlers et al. 2001, Diaz-Maroto et al. 2002, Gainar et al. 2002, Menaker et al. 2004, Mazutti et al. 2006, Leal et al. 2008 Klejdus et al. 2008 Pourmortazavi et al. 2005 Zhang et al. 1998a Then et al. 1998 Turkay et al. 1996, Fullana et al. 1999, Machmudah et al. 2005, Rao et al. 2007, Kokoska et al. 2008 Kery et al. 1998
Avocado (Persea americana) fruit Babchi (Psoralea corylitolia) seed Baccharis dracunculifolia leaves Bacuri (Platonia insignis) fruit shells Bai zi (Archangelica dahurica) root Baical skullcap (Scutellaria baicalensis) root Barley (Hordeum vulgare) fruit Basil, sweet basil (Ocimum basilicum) leaves
Birch (Betula pendula) leaves Black caraway (Bunium persicum) fruit
Black oil plant (Celastrus paniculatus) seed Blackberry (Rubus fruticosus) seed Blackseed (Nigella sativa) fruit
Blessed thistle (Cnicus benedictus) leaves, owering tops
Amino acids Volatile oil, oil, antioxidants thymoquinone and carvacrol Oil, sesquiterpenes Oil Oil, volatile oil: antioxidants thymoquinone and carvacrol Sesquiterpene lactone cnicin
(Table 1 continued) Extract components Antioxidants Volatile oil: antioxidants; alkaloid boldine Oil, -linolenic acid -ecdysone, antioxidants Volatile oil Oil, carotenoids, tocopherols Sesquiterpenes as petasin, isopetasin, pyrrolizidine alkaloids Volatile oil: acorone, isoacorone, -asarone Isoquinoline alkaloids Bioactive compounds Volatile oil: germacrene d-4-ol, germacrene D, bicyclogermacrene, -cadinene Antioxidants Capillarisin Volatile oil: limonene, carvone; fatty oil Sewram et al. 1998, 2000 Marongiu et al. 2006c Marongiu et al. 2007e Franca et al. 1999a Steiner et al. 1998, Bodensieck et al. 2007 Stahl and Keller 1983, Marongiu et al. 2005c, Dai et al. 2008 Bugatti et al. 1993 References Laroze et al. 2010 Sargenti and Lancas 1997b, del Valle et al. 2004b, 2005b Illes et al. 1994, Sensidoni et al. 1994, Andujar et al. 1999, Dauksas et al. 2002b, Gomez and de la Ossa 2002, Kotnik et al. 2006, Lu et al. 2007, Soto et al. 2008 Leal et al. 2010
Plant part
Blueberry (Vaccinium sp.) residue after pressing Boldo (Peumus boldus) leaves, bark Borage (Borago ofcinalis) seed
Brazilian ginseng (Pfafa paniculata, P. glomerata) root Bulnesia sarmientoi wood Buriti (Mauritia exuosa) fruit Butterbur (Petasites hybridus) rhizomes
Calamus (Acorus calamus, A. graminei) rhizomes California poppy (Eschscholtzia californica) aerial part Cape ash (Ekebergia capensis) wood Cape gold (Helichrysum splendidum) leaves
Cape gooseberry (Physalis peruviana) Capillary wormwood (Artemisia capillaris) aerial part Caraway (Carum carvi) seed, fruit
Cardamom (Elettaria cardamomum) seed
Carqueja (Baccharis trimera) aerial part Carrot (Daucus carota L.) root, fruit
Volatile oil, pigments, fatty acids, antioxidants Volatile oil Oil, carotenes, volatile oil, biologically active substances Nut shell liquid, cardanols Oxindole alkaloids Volatile oil, nepetolactone, waxes Volatile oil Alkaloids chelidonine, berberine, coptisine Volatile oil, fatty oil, furanocoumarins, fatty acids Tocopherols, tocotrienols Volatile oil, active components: -bisabolol, matricine, chamazulene; avonoids Oil: free fatty acids, sterol; phenolic compounds
Cashew (Anacardium Occidentale) pericarp Cats claw (Uncaria tormentosa) root Catnip (Nepeta catari, N. transcaucasica) Cedar (Cedrus) wood Celandine (Chelidonium majus) aerial part Celery (Apium graveolens) seed, leaf, root
Cereals Chamomile (Matricaria chamomilla syn. Chamomilla recutita) owers
Cherry (Prunus avium) seed, pomace
Wu et al. 2006 Yang et al. 2007 Stahl and Gerard 1982a, Stahl et al. 1984, Kallio et al. 1994, Sovova et al. 1994b, Then et al. 1998, Baysal and Starmans 1999, Gamse and Marr 2000, Ahro et al. 2001, Cabizza et al. 2001, Sedlakova et al. 2003a Pekhov and Goncharenko 1968, Naik et al. 1989, Gopalakrishnan and Narayanan 1991, Illes et al. 1998, Marongiu et al. 2004a, Hamdan et al. 2008 Vargas et al. 2006, Silva et al. 2009 Subra et al. 1994, 1998, Barth et al. 1995, Vega et al. 1996, Chandra and Nair 1997, Ranalli et al. 2004, Sun and Temelli 2006, Glisic et al. 2007a, Maxia et al. 2009 Shobha and Ravindranath 1991, Smith et al. 2003, Patel et al. 2006 Lopez-Avila et al. 1997a Dapkevicius et al. 1996, Barth et al. 1998, Chotratanadilok and Clifford 1998 Hawthorne et al. 1988 Sarkozi et al. 2000, Then et al. 2000b Moyler 1993, Peplonski et al. 1994, Catchpole et al. 1996a, Jarvenpaa et al. 1997, Nguyen et al. 1998, Della Porta et al. 1998b, Papamichail et al. 2000, Dauksas et al. 2002a Fratianni et al. 2002 Stahl and Schutz 1978, Vuorela et al. 1990, Reverchon and Senatore 1994, Smith and Burford 1994, Pekic et al. 1995, Tolic et al. 1996, Scalia et al. 1999, Zekovic 2000, Povh et al. 2001, Hamburger et al. 2004, Kaiser et al. 2004, Bajer et al. 2007, Kotnik et al. 2007, Zizovic et al. 2007a Bernardo-Gil et al. 2001, Adil et al. 2008
85
86
(Table 1 continued) Extract components Volatile oil, methyl chavicol Cedrelone, phytosterols Podophyllotoxin Alkaloid sinomenine Volatile oil, pyrethrins Volatile oil: cinnamaldehyde Choi et al. 1998b Liu et al. 2005a Senatore et al. 2004, Marongiu et al. 2009 Stahl and Gerard 1982a, Hawthorne et al. 1988, Miller et al. 1995, Marongiu et al. 2007d Simandi et al. 1996 Modey et al. 1996b References
Plant part
Chervil (Anthriscus cerefolium) herb Chinese mahogany, cedrela, toon (Cedrela sinensis syn. Toona sinensis) wood, bark Chinese mayapple (Dysosma pleiantha) roots Chinese moonseed (Sinomenium acutum) vine stem Chrysanthemum (Chrysanthemum cinerariifolium, C. coronarium, C. segetum, C. osculosus) aerial part Cinnamon (Cinnamomum zeylanicum) and cassia (C. cassia) bark
Citruses Bergamot (Citrus bergamia) peels, leaves, seed Grapefruit (Citrus paradisi) avedo, peel, seed Lemon (Citrus limonum) peel Volatile oil: bergapten Volatile oil, avonoid naringin, limonoids Volatile oil
Lime (Citrus aurantifolia, C. latifolia) peel Mandarin (Citrus reticulata) peel Orange (sweet orange) (Citrus sinensis), bitter orange (C. aurantium) peel Satsuma, tangerine (Citrus unshiu) press cake Shaddock (Citrus maxima) peel Lee at al. 2010
Poiana et al. 1994, 1999, Kondo et al. 2000 Poiana et al. 1998, Giannuzzo et al. 2003, Yu et al. 2007 Calame and Steiner 1982, Sugiyama and Saito 1988, Hawthorne et al. 1989, Langenfeld et al. 1992 Hawthorne et al. 1989, Atti-Santos et al. 2005 Illes et al. 1999b Hawthorne et al. 1988, Mira et al. 1996, 1999, Sargenti and Lancas 1998a, Illes et al. 1999b, Berna et al. 2000, Lee et al. 2000, 2001 Lim et al. 2003 Teng et al. 2005
Taiwan tangerine (Citrus depressa) peel
Tangor murcote Citrus sinensis (hybrid) peel Yuzu (Citrus junos) seed Clary sage (Salvia sclarea) herb Clivia (Clivia miniata) root Cloudberry (Rubus chamaemorus) seed Clove (Syzygium aromaticum, Eugenia caryophyllata) buds
Volatile oil Volatile oil, carotenoids, tocopherols Volatile oil, perillyl alcohol, carotenoids, tocopherols -Cryptoxanthin Coumarins imperatorin, meranzin, meranzin hydrate Polymethoxyavones: nobiletin, tangeretin Volatile oil Oil, -sitosterol, squalene Volatile oil: sclareol Bioactive compounds Oil, -carotene, volatile oil, tocopherols Volatile oil: eugenol, caryophyllene, eugenyl acetate
Clove basil (Ocimum gratissimum) leaves Clover, red (Trifolium pratense) leaves, root Coca (Erythroxylum coca) leaves Cocoa (Theobroma cacao) beans/nibs
Coconut palm (Cocos nucifera) copra, meal
Volatile oil Isoavones, volatile oil Cocaine Cocoa butter, theobromine, caffeine; pyrazines from roasted beans Oil
Sargenti and Lancas 1998b Ueno et al. 2008 Ronyai et al. 1999a Sewram et al. 1998, 2001 Manninen and Kallio 1997, Manninen et al. 1997b Stahl and Gerard 1982a, Naik et al. 1989, Gopalakrishnan et al. 1990, Huston and Hong 1991, Hauptschott and Lentz 1993, Moyler 1993, Kollmannsberger and Nitz 1994, Reverchon and Marrone 1997, Della Porta et al. 1998a, Clifford et al. 1999, Rodrigues et al. 2002, Ruetsch et al. 2003, Geng et al. 2007, Guan et al. 2007, Martinez et al. 2007, Takeuchi et al. 2008 Leal et al. 2006 Klejdus et al. 2005, Tapia et al. 2007 Brachet et al. 1999, 2000 Rossi et al. 1993, Li and Hartland 1996, Sanagi et al. 1997, Saldana et al. 2000b,c, 2002, 2002a, Skerget and Knez 2001, Mohamed et al. 2002 Asis et al. 2006
(Table 1 continued) Extract components Caffeine, aroma, diterpenes cafestol and kahweol, lipids, chlorogenic acids References
Plant part
Coffee (Coffea) beans
Cordia verbenacea leaves Coriander (Coriandrum sativum) fruit, seed
Volatile oil: -caryophyllene Volatile oil, fatty oil, antioxidants: tocopherols, avonoides Triterpenes: friedelin, betulin, -sitosterol, sitost-4-en-3-one Oil
Cork oak (Quercus suber) bark
Zosel 1978, Brunner 1984, Sugiyama et al. 1985, Peker et al. 1992, Roethe et al. 1992, Pietsch et al. 1998, Ramos et al. 1998, del Valle and Aguilera 1999, Oliveira et al. 1999, 2001, Sarrazin et al. 2000, Araujo and Sandi 2006, de Azevedo et al. 2008a, 2008b,c Quispe-Condori et al. 2008 Kallio and Kerrola 1992, Kerrola and Kallio 1993, Catchpole et al. 1994, 1996a, 1997, Anitescu et al. 1997, Ribeiro et al. 1998, Then et al. 1998a, Illes et al. 2000, Yepez et al. 2002, Grosso et al. 2008 Castola et al. 2005 List et al. 1983, 1984a, Snyder et al. 1984, Kuk and Hron 1994, Taylor et al. 1997, Bhattacharjee et al. 2007 Calame and Steiner 1982, Cao et al. 2000 Ellington et al. 2003 Laroze et al. 2010 Stashenko et al. 1996b Sewram et al. 1998 Schneider et al. 1995 Sousa et al. 2005 Naik et al. 1989, Eikani et al. 1999a, Heikes et al. 2001 Eller et al. 2011 de Azevedo et al. 2003 Then et al. 1998a Marongiu et al. 2003b, Poli et al. 2003 Vasudevan et al. 1997 Fuh et al. 1996 Peplonski et al. 1994, Gamse and Marr 1999, Simandi et al. 2002 Dean et al. 1998b, Wang et al. 2008a DAndrea et al. 2007 Cao et al. 2007, Xiao et al. 2007 Gamse and Marr 2000 Liu et al. 1995 Sun et al. 2006 Vilegas et al. 1993
Cotton (Gossypium) seed Volatile oil Alkaloids: colchicine, 3-dimethylcolchicine, colchicoside Antioxidants Volatile oil: sesquiterpenes, heavy hydrocarbons, amides, insecticide spilanthol Bioactive compounds Maravuic acid Volatile oil Volatile oil: cuminaldehyde, cymol Fatty oil Fat Oil, linolenic acids Volatile oil: neryl acetate, antioxidants Volatile oil: biocides Volatile oil Oleoresin: -amyrin, -sitosterol Tanshinones Insecticide rotenone Volatile oil Volatile oil Diosgenin Ferulic acid Pimpinelin, isobergapten, furocoumarins psoralen, bergapten, isopimpinelin, triterpenes Wax Volatile oil
Cratoxylum prunifolium leaves Crocus, autumn (Colchicum autumnale) seed
Cranberry (Vacciniumk sp.) residue after pressing Creeping spilanthes (Spilanthes americana) owers, leaves, and stems Crossberry (Grewia occidentalis) wood Croton matourensis bark Croton zehntneri leaves Cumin (Cuminum cyminum) seed Cuphea (Cuphea viscosissmaC. lanceolata) seed Cupuacu (Theobroma grandiorum) seed Currant, red and black (Ribes rubrum, R. nigrum) seed Curry plant (immortelle) (Helichrysum italicum) aerial part Curry tree (Murraya koenigii syn. Chalcas koenigii) leaves Cypress, red (Taxodium distichum) sawdust Dandelion (Taraxacum ofcinale) leaves, roots Danshen (Salvia miltiorrhiza) root, rhizomes Derris (Derris elliptica) root Di qian (Marchantia convoluta) leaves Dill (Anethum graveolens) seed Dioscorea nipponica tuber Dong quai (Archangelica sinensis) root Dorstenia bryoniifolia rhizomes
Douglas-r (Pseudotsuga menziesii) bark Dragonhead (Dracocephalum moldavica) herb
McDonald et al. 1983 Hawthorne et al. 1993, Kakasy et al. 2006
87
88
(Table 1 continued) Extract components Ruberto et al. 1999 Peplonski et al. 1994 Rodrigues et al. 2008 Choi et al. 1996, 1997, 1999b, Kim and Yoo 2000 de Vasconcelos et al. 2000, Mossi et al. 2004, 2010 References
Plant part
Eastern ferulago (Ferulago nodosa L.) Elder (Sambucus nigra) fruit Emburana (Torresea cearensis) seed Ephedra (Ephedra sinica) aerial part
Espinheira santa (Maytenus aquifolium, M. ilicifolia) leaves
Eucalyptus (Eucalyptus globulus, E. camaldulensis, E. citriodora, E. spathulata, E. microtheca) leaves, wood Evening primrose (Oenothera biennis) seed Oil, -linolenic acid Volatile oil, evodiamine, rutaecarpine Volatile oil Volatile oil: anethol, estragol, fenchone; fatty oil; avonoids
Volatile oil: -pinene Oleoresin Coumarin Ephedrine and its derivatives, nonacosan10-ol Triterpenes friedelan-3-ol, friedelin; phytol, squalene, limonene, tocopherols, stigmasterol, dodecanoic acid, geranyl acetate Volatile oil: 1,8-cineole; lipids, antioxidants
Evodia (Evodia rutaecarpa) herb, bre Felty germander (Teucrium polium) leaves, owers Fennel (Foeniculum vulgare) seed
Volatile oil, sesquiterpene lactone parthenolide Oil; wax: nutraceutical octacosanol Volatile oil: incensole acetate, octanol acetate, incensole, phyllocladene Volatile oil, furanocoumarins Allicin Volatile oil Volatile oil: gurjunenes, selinenes Volatile oil, gingerols, oleoresin, antioxidants, anticancer substances
Feverfew (Tanacetum parthenium syn. Chrysanthemum partheniu, syn. Pyrethrum parthenium) owers, seeds Flax (Linum usitatissimum) seed, bre
Hawthorne et al. 1989, Garau and Pittau 1998, Della Porta et al. 1999, Fadel et al. 1999, Gonzales-Vila et al. 2000, Francisco et al. 2001, Rodrigues et al. 2002, Rozzi et al. 2002a, El-Ghorab et al. 2003, Ashtiani et al. 2007 Favati et al. 1991, Catchpole et al. 1994, King et al. 1997, Gawdzik et al. 1998, Zizovic et al. 1998, Kotnik et al. 2006 Ma et al. 1991, Liu et al. 2010 Eikani et al. 1999b Naik et al. 1989, Then et al. 1998a, Reverchon et al. 1999, Simandi et al. 1999, Yamini et al. 2002, Coelho et al. 2003, Damjanovic et al. 2005, Diaz-Maroto et al. 2005, Moura et al. 2005, Bajer et al. 2007, Zizovic et al. 2007a, Takeuchi et al. 2008 Smith and Burford 1992, 1994, Kery et al. 1998, 1999, Kaplan et al. 2002, Cretnik et al. 2005 Then et al. 1998a, Barthet and Daun 2002, Bozan and Temelli 2002, Morrison et al. 2006 Ma et al. 1991, Marongiu et al. 2006e Nykanen et al. 1991, Kerrola and Kallio 1994, Kerrola et al. 1994b, Gawdzik et al. 1996, Doneanu and Anitescu 1998, Paroul et al. 2002 Calvey et al. 1994, 1997, Rybak et al. 2004, del Valle et al. 2008 Reis Machado et al. 1993, Peterson et al. 2006, Gomes et al. 2007 Marongiu et al. 2005a Pekhov and Goncharenko 1968, Krukonis 1985, Chen et al. 1986, Naik et al. 1989, Kandiah and Spiro 1990, Moyler 1993, Bartley and Foley 1994, Bartley 1995, Yonei et al. 1995a, Roy et al. 1996a, Badalyan et al. 1998, Monteiro et al. 1998, Nguyen et al. 1998, Bartley and Jacobs 2000, Rodrigues et al. 2002, Zancan et al. 2002, Catchpole et al. 2003, Leal et al. 2003, Martinez et al. 2003, Liu et al. 2005a, Balachandran et al. 2006, 2007 Choi et al. 2002c, Chiu et al. 2002, Yang et al. 2002, Mannila et al. 2003 Wang et al. 2001, Liu et al. 2005a, Wood et al. 2006, Zhang et al. 2006a, Luo et al. 2007
Frankincense (Boswellia thurifera, B. carterii) resin
Garden angelica (Angelica archangelica, A. dahurica, A. sinensis) root, fruit Garlic (Allium sativum) Geranium (Pelargonium graveolens) owers, leaves, stems, stalk Giant fennel (Ferula communis) owerheads Ginger (Zingiber ofcinalis) Rhizomes
Ginkgo, maidenhair tree (Ginkgo biloba) leaves
Ginseng (Panax ginseng) root hair, leaves, seed
Terpene trilactones ginkgolides, bilobalide; avonoids Oil, ginsenosides; saponins
(Table 1 continued) Extract components Fatty oil, linoleic acid, tocopherols, tocotrienols, tannins, glycosides, polyphenols: (+)-catechin, (-)-epicatechin, rutin, quercetin, resveratrol antioxidants References Sovova et al. 1994a, Gomez et al. 1996, Murga et al. 1998, 2000, Palma and Taylor 1999, Palma et al. 1999, 2000, Arce et al. 2001, Pascual-Marti et al. 2001, Palenzuela et al. 2002, 2004, Cao and Ito 2003, Ashraf-Khorassani and Taylor 2004, Louli et al. 2004b, Beveridge et al. 2005, Chafer et al. 2005, Bravi et al. 2007, Fiori 2007, Campos et al. 2008, da Silva et al. 2008a, Fiori et al. 2008, Freitas et al. 2008a, 2008b Choi et al. 1997 Moore and Taylor 1995, 1996, 1997 Ronyai et al. 1999b Vilegas et al. 1997, Celeghini et al. 2001 Mehr et al. 1996, Saldana et al. 2000b,c, 2002b,c Sagrero-Nieves et al. 1994a Fernandez et al. 2006 Li et al. 2009
Plant part
Grape (Vitis vinifera) seed, pulp, skin
Greater duckweed (Spirodela polyrhiza) entire plant Grecian foxglove (Digitalis lanata) leaves Greek sage (Salvia triloba, S. fruticosa) Guaco (Mikania glomerata) leaves
Guaran (Paulinia cupana) seed Guava (Psidium guajava) leaves Guinea pepper (Aframomum melegueta) seed Gutta-percha tree (hardy rubber tree) (Eucommia ulmoides) seed Hawthorn (Crataegus sp.) Hazel (Corylus avellana) nut Hibiscus (Hibiscus esculentus, H. different ssp.) seed Holy basil, tulsi (Ocimum sanctum) leaves Hop (Humulus lupulus) owers Lipophilic compounds Oil, sterols, tocopherols Oil, antioxidants Volatile oil, biocides Volatile oil, resins, bitter acids, waxes, and lipids
Squalene, stigmasterol Digoxin Volatile oil Coumarin, kaurenoic acid, lupeol kipeol acetate Caffeine, methylxanthines Volatile oil Oleoresin Aucubin
Horsetail (Equisetum giganteum) Hu zhang (Polygonum cuspidatum) herb, root Hyssop (Hyssopus ofcinalis) Volatile oil Hydrocarbons Oil, vernolic acid Sanshool compounds Carotenoids Volatile oil Oil Volatile oil, bioactive compounds, antimicrobials
Oleoresin Resveratrol, piceid, emodin, physcion Volatile oil, antioxidants
Hamburger et al. 2004 Bernardo-Gil et al. 2002, Ozkal et al. 2005b,c, Bernardo-Gil and Casquilho 2007 Holser and Bost 2004, Chan and Ismail 2009 Vasudevan et al. 1997 Pekhov and Goncharenko 1968, Hubert and Vitzthum 1978, Laws 1979, Sharpe and Crabb 1980, Sharpe et al. 1980, Gardner 1982, Vollbrecht 1982, Langezaal et al. 1990, Daoud and Kusinski 1992, Verschuere et al. 1992, Moyler 1993, Imbert et al. 1998, del Valle and Aguilera 1999, del Valle et al. 2003b, Zekovic et al. 2007, Roj and Skowronski 2006 Michielin et al. 2005 Wenli et al. 2005, Yu et al. 2005, Lu et al. 2006, Machmudah et al. 2009b Kerrola et al. 1994a, Dapkevicius et al. 1996, Langa et al. 2009, Kazazi et al. 2007, Babovi et al. 2010 Marongiu et al. 2003c Ozcan and Ozcan 2004 King et al. 2001 Machmudah et al. 2009a Takahashi et al. 2006 Raghuram Rao et al. 1992, Sastry and Mukhopadhyay 1994 Friedrich et al. 1984, Friedrich 1988, Salgin et al. 2004, 2007 Moyler 1993, Chatzopoulou 2002, Damjanovic et al. 2003, 2006, Marongiu et al. 2003a, 2004c, 2006c, Park et al. 2004, Pourmortazavi et al. 2004, Barjaktarovic et al. 2005, Glisic et al. 2007b, Medini et al. 2008
Inula (Inula viscosa, I. graveolens) leaves Iranian spurge (Euphorbia macroclada) leaves and stalks (as petro-crops) Ironweed (Vernonia galamensis) seed Japanese pepper, Sichuan pepper (Xanthoxylum piperitum) Japanese persimmon (Diospyros kaki) peels Jasmine (Jasminum ofcinalis, J. grandiorum) owers Jojoba (Simmondsia californica, S. chinensis) seed Juniper (Juniperus communis, J. rigida, J. oxycedrus, J. phoenica) fruit, leaves, wood
89
90
(Table 1 continued) Extract components Oleoresin, kava lactones Caffeine Flavonoids Volatile oil, tocopherols, oil Volatile oil, pasty products, antioxidants, antimicrobials Volatile oil, antioxidants Volatile oil Volatile oil Volatile oil References
Plant part
Kava (Piper methysticum) herb, stems, root
Kola tree (Cola) nuts Kudzu (Pueraria lobata) root Laurel, daphne (Laurus nobilis) leaves, seed
Lavender (Lavandula intermedia, L. stoechas, L. augustifolia) owers
Lemon balm (Melissa ofcinalis) Lemon beebalm (Monardia citriodora) Lemon verbena (Aloysia triphylla) leaves Lemongrass (Cymbopogon citratus) leaves, stems
Licorice (Glycyrrhiza glabra) Lilac (Syringa) owers Lindera strychnifolia Loquat (Eriobotrya japonica) seed Lovage (Levisticum ofcinale) seed, leaves, and roots Love-in-a-mist (Nigella damascena) seed Luohan guo (Siraitia grosvenorii) fruit Lupine (Lupinus) Macadamia (Macadamia integrifolia) nuts Madagascar periwinkle (Catharanthus roseus) Magnolia (Magnolia grandiora, M. virginiana, M. ofcinalis) bar, root
Lopez-Avila and Benedicto 1997, Ashraf-Khorassani et al. 1999, Catchpole et al. 2000, 2002 Ndiomu and Simpson 1988 Wang et al. 2008b Ozek et al. 1998, Caredda et al. 2002, Gomez-Coronado et al. 2004, Beis and Dunford 2006, Santoyo et al. 2006a, Marzouki et al. 2008 Simandi et al. 1993, Adasoglu et al. 1994, Walker et al. 1994b, Reverchon et al. 1995c, Dapkevicius et al. 1996, Fekete et al. 1996, Oszagyan et al. 1996, Akgun et al. 2000, 2001, Flores et al. 2005, Zorca et al. 2006 Ribeiro et al. 2001, Rozzi et al. 2002a, Ziakova et al. 2002, Marongiu et al. 2004d Rozzi et al. 2002a Crabas et al. 2003, Pereira and Meireles 2007 Ndiomu and Simpson 1988, Sargenti and Lancas 1997a, Carlson et al. 2001, Rozzi et al. 2002a, Marongiu et al. 2006a, Ha et al. 2008 Kim et al. 2004, 2005 Calame and Steiner 1982 Li et al. 2002 Kawahito et al. 2008, Machmudah et al. 2008b Dauksas et al. 1998, 1999, 2002a, Menaker et al. 2004 Dauksas et al. 2002c Xia et al. 2008 Stahl et al. 1981, Nossack et al. 2000 Silva et al. 2008a Song et al. 1992, Choi et al. 2002a Castaneda-Acosta et al. 1995, Chandra and Nair 1995, Suto et al. 1997, Dean et al. 1998a, Paltoo et al. 1999, Cheah et al. 2010 Christianson et al. 1984, List et al. 1984b, Wilp and Eggers 1991, Taylor et al. 1993, Fontan et al. 1994, Ronyai et al. 1998a, Taylor and King 2000, 2002, Ambrosino et al. 2004, Nagy et al. 2008 Vilegas et al. 1993 Pereira and Meireles 2007 Sovova et al. 2008
Maize (corn) (Zea mays) bran, germ
Glycyrrhizin Volatile oil, wax Sesquiterpenoids Oil, amygdalin, -sitosterol Volatile oil: ligustilide Oil, volatile oil Sweeteners: mogrosides Oil, alkaloids Oil Indole alkaloids vindoline, vinblastine Sesquiterpene lactones pathenolide, costunolide, sesquiteprene cyclocolorenone, antioxidants, neolignans honokiol, magnolol Oil, sterols, ferulate-phytosterol esters, phospholipids, beauvericin Terpenoids, furocoumarins psoralen, bergapten Oleoresin Ecdysterone, cynaropicrin
Mama cadela (sweet cotton plant) (Brosimum gaudichaudii) bark, roots Mango (Mangifera indica) leaves Maral root (Leuzea carthamoides syn. Rhaponticum carthamoides) root and leaves Maries r (Abies mariesii) leaves Marigold (Calendula ofcinalis) owers
Marjoram (Majorana hortensis syn. Origanum majorana L.) leaves
Maltol (antifungal activity) Oleoresin, volatile oil, triterpenoids: faradiol monoesters, monool taraxasterol, lupeol, -amyrin; lutein Volatile oil, cuticular waxes, pigments, antimicrobials, antioxidants: ursolic acid, carnosic acid, carnosol
Ohira and Yatagai 1993 Ronyai et al. 1998b, Crabas et al. 2003, Baumann et al. 2004, Hamburger et al. 2004, Campos et al. 2005, Danielski et al. 2007, Petrovic et al. 2007, Zizovic et al. 2007a, Nagy et al. 2008 Reverchon 1992, Reverchon et al. 1993, Reverchon and Sesti Osseo 1994b, Dapkevicius et al. 1996, Vagi et al. 2002, 2005a,b, Rodrigues et al. 2003a, El-Ghorab et al. 2004
(Table 1 continued) Extract components Volatile oil, waxes Volatile oil Sesquiterpene lactone tagitinin C Bioactive compounds; fatty oil, cis-vaccenic acid Volatile oil, cuticular waxes, squalene, carotenoids Congiu et al. 2002 Pourmortazavi et al. 2005 Ziemons et al. 2005, 2007 Sewram et al. 1998, Turner and McKeon 2002 Senich et al. 1974, Barton et al. 1992, Goto et al. 1993, Hawthorne et al. 1993, Simandi et al. 1993, Reverchon et al. 1994a, Roy et al. 1996c, Barth et al. 1998, Aleksovski et al. 1999, Ammann et al. 1999, Pino et al. 1999, Reis-Vasco et al. 1999, 2000, Kim and Hong 2000, Qasheh and Barth 2000, Kubatova et al. 2001, Marongiu et al. 2001, Pop and Barth 2001, Diaz-Maroto et al. 2002, Aghel et al. 2004, Zizovic et al. 2005, Al-Marzouqi et al. 2007, Gomez-Prieto et al. 2007, Zekovic et al. 2009 Quitain et al. 2004 Dean and Liu 2000 Joo et al. 1994, Choi et al. 1997 del Valle and Aguilera 1989, Sakaki et al. 1990, Young and Games 1993, Abdulah et al. 1994, Walker et al. 1999, Zhang et al. 2006a, Kitzberger et al. 2007, 2009 Barthet and Daun 2002 Ma et al. 1991, Marongiu et al. 2005c Garau and Pittau 1998 Sun et al. 2002 References
Plant part
Mastic (Pistacia lentiscus) leaves, berries Medlar (Mespilus germanica) seed Mexican sunower (Tithonia diversifolia) aerial part Milkweed (Asclepias fruticosa) root, seed
Mint (Mentha piperita, M. spicata, M. pulegium, Romanian mint hybrid) leaves, owers
Moso-bamboo (Phyllostachys heterocycla)
Moutan (Paeonia suffruticosa) cortex Mulberry tree (Morus alba) bark, leaves, root bark
Mushrooms and fungi
Mustard (Brassica sp.) seed Myrrh herb (Commiphora molmol, C. myrrha) Myrtle (Myrtus communis) leaves Narrow-leaf purple coneower (Echinacea angustifolia) aerial part Neem tree (Azadirachta indica) seed, kernel Insecticides, pharmaceuticals: azadirachtin A, nimbin, salannin, cuticular waxes Oil: unsaturated fatty acids Volatile oil, nutmeg butter Acorn oil, sterols, tocopherols, waxes Oil, fatty acids, -tocopherol, - and -carotene, squalene, sterols Oil, -sitosterol, tocopherols Oil, tocopherols, phenols, squalene
Hydrocarbons, antimicrobials, antioxidants and fungicides Paeonol Triterpene -amyrin acetate, antioxidants -carotene, -tocopherol Oleoresin, oil, ergosterol, carboxylic and fatty acids, antioxidants, substances of antimicrobial activity, polysaccharides Oil Volatile oil Volatile oil Alkylamides
Nitraria tangutorum seed Nutmeg (Myristica fragrans) nutmeg, mace
Oak (Quercus rotundifolia, Q. suber) fruit Oil palm tree (Elaeis guineensis) kernel, leaves, mesocarp bres
Okra (Abelmoschus esculentes syn. Hibiscus esculentes) seed Olive tree (Olea europaea) leaves, husk, pomace
Cernia et al. 1994, Johnson and Morgan 1997, Ambrosino et al. 1999, Tonthubthimthong et al. 2001, 2004, Mongkholkhajornsilp et al. 2005 Wang et al. 2007, Suo and Wang 2010 Pekhov and Goncharenko 1968, Hubert and Vitzthum 1978, Moyler 1993, Nguyen et al. 1998, Spricigo et al. 1999, 2001, Machmudah et al. 2006 Lopes et al. 1998, Lopes and Bernardo-Gil 2005, Bernardo-Gil et al. 2007 Birtigh et al. 1995, Franca and Meireles 2000, Hassan et al. 2000, Rahman et al. 2001, Norulaini et al. 2004a,b, 2008, Lau et al. 2006a,b, 2007, 2008, Zaidul et al. 2006a,b, 2007a,b Andras et al. 2005
Onion (Allium cepa) bulb, skin
Oleoresin, avour, sulphur, quercetin Volatile oil
Orange jasmine (Murraya paniculata) owers
Esquivel and Bernardo-Gil 1993, de Lucas et al. 1998, 2002a,b, 2003, Le Floch et al. 1998, Esquivel et al. 1999b, Ibanez et al. 2000a, Stavroulias and Panayioutou 2005, del Valle et al. 2006 Calvey et al. 1994, 1997, Guyer and Sinha 1995, Dron et al. 1997, Sass-Kiss et al. 1998, Simandi et al. 2000, Martino and Guyer 2004 Marquina-Chidsey et al. 2000
91
92
(Table 1 continued) Extract components Volatile oil, cuticular waxes, resinoid compounds, antioxidants References Ondarza and Sanchez 1990, Dapkevicius et al. 1996, Gaspar et al. 1998, 2000, 2001, 2003, Simandi et al. 1998, Diaz-Maroto et al. 2002, Gaspar 2002, Leeke et al. 2002, Menaker et al. 2004, Rodrigues et al. 2004, Lu et al. 2005, Cavero et al. 2006, Santoyo et al. 2006a Djarmati et al. 1998, da Costa et al. 1999
Plant part
Oregano, wild marjoram (Origanum vulgare, O. virens) leaves, bracts
Osage orange tree (Maclura pomifera) root bark, fruit
Ox knee (Achyranthes bidentata) root Pandan (Pandanus amaryllifolius) leaves Paprika, red pepper (Capsicum annuum), and chillies (Capsicum frutescens) fruit
Xanthones, avanones, isoavonoids: osajin, pomiferin, lupeol, and butyrospermol esters Ecdysterone 2-Acetyl-1-pyrroline, volatile oil Oil, tocopherols, capsaicin alkaloids, carotenoids
Volatile oil: estragole Glycosylated avonoids Polyphenols Oil Oil Oleoresin: volatile oil, piperine
Parsley (Petroselinum crispum, Apium petroselinum) seed, leaves Passion (Passiora edulis) fruit, leaves Peach (Prunus persica) pomace Peanut (Arachis hyprogaea)
Zheng et al. 2008 Laohakunjit and Noomhorm 2004, Bhattacharjee et al. 2005 Hubert and Vitzthum 1978, Coenen 1983, Coenen and Kriegel 1984, Yao et al. 1994, Peusch et al. 1997, Nguyen et al. 1998, Skerget et al. 1998, Illes et al. 1999a, Jaren-Galan et al. 1999, Sato et al. 1999, Weathers et al. 1999, Gnayfeed et al. 2001, Skerget and Knez 2001, Ambrogi et al. 2002, Daood et al. 2002, Catchpole et al. 2003, del Valle et al. 2003a, 2003c, Duarte et al. 2004, Perva-Uzunalic et al. 2004, Uquiche et al. 2004, 2005, Fernandez-Trujillo 2008, Nagy et al. 2008, Nagy and Simandi 2008, Tepic et al. 2009, Richins et al. 2010, Li et al. 2011 Naik et al. 1989, Della Porta et al. 1998b, Then et al. 1998a, Louli et al. 2004a
Pecan (Carya illinoensis) kernels, halves Pepper, black (Piper nigrum) fruit
Physic nut (Jatropha curcas) seed Pepper tree (Schinus molle)
Pimento, allspice, Jamaica pepper (Pimenta dioica) berries, leaves Pine (Pinus palustris, P. sylvestris, P. pinaster, P. nigra) wood, needles, bark Pinecone ginger (Zingiber zerumbet) Pink trumpet tree (Tabebuia avellanedae) wood Pistacia (Pistacia vera, P. lentiscus) nuts, hull Pitanga (Eugenia uniora) fruit pulp Polygala cyparissias root, stems, leaves Pomegranate (Punica granatum) seed Poppy (Papaver bracteatum) seed, straw
Oil Volatile oil: phellandrenes, limonene, elemol, -eudesmol Volatile oil: eugenol Volatile oil, resin, fatty acids; manoyl oxide; phenolic antioxidants Oleoresin Lapachol, lapachones Lipids, antioxidants, volatile oil Carotenoids lycopene, rubixanthin Triterpenes, phytosterols, methyl salicylate Volatile oil, fatty oil, phenolic compounds Oil, tocol, opium alkaloids thebaine, codeine, morphine
Moraes et al. 1997 Adil et al. 2007 Snyder et al. 1984, Goodrum and Kilgo 1987, King and Catchpole 1993, Lancas et al. 1994, Santerre et al. 1994, Goodrum et al. 1996 Maness et al. 1995, Zhang et al. 1995a, Alexander et al. 1997, Li et al. 1999 Hubert and Vitzthum 1978, Calame and Steiner 1982, Vidal and Richard 1987, Ferreira et al. 1993, 1999, Sovova et al. 1995, Nguyen et al. 1998, Skerget and Knez 2001, Ferreira and Meireles 2002, Catchpole et al. 2003, Perakis et al. 2005, Izadifar and Abdolahi 2006, Li et al. 2006 Machmudah et al. 2008b Marongiu et al. 2004b Krukonis 1985, Pino et al. 1997, Marongiu et al. 2005b McDonald et al. 1983, Orav et al. 1998, Ruivo et al. 2000, Duquesnoy et al. 2007, Braga et al. 2008 Ahmad et al. 1994 Viana et al. 2003 Balaban et al. 1998, Palazoglu and Balaban 1998, Goli et al. 2005 Filho et al. 2008 Weinhold et al. 2008 Abbasi et al. 2008a,b Stahl and Willing 1980, Ndiomu and Simpson 1988, Janicot et al. 1990, Then et al. 2000, Bozan and Temelli 2003
(Table 1 continued) Extract components Oil Oil, carotenoids Oil Alkylamides Insecticides pyrethrins Devittori et al. 2000 Bernardo-Gil and Lopes 2004, Yu et al. 2004, Seo et al. 2005, Nagy et al. 2008 Araujo et al. 2000 Catchpole et al. 2000, 2002 Stahl and Schutz 1980b, Bunzenberger et al. 1983, Pan et al. 1995, Otterbach and Wenclawiak 1999, Kiriamiti et al. 2003a,b, OMahony et al. 2003 Bicchi et al. 1991 Muuse et al. 1994, Cuperus et al. 1996 References
Plant part
Proso millet (Panicum miliaceum) bran Pumpkin (Cucurbita cifolia, C. moschata) esh, seed Pupunha (Guilielma speciosa) fruit Purple coneower (Echinacea purpurea) aerial part Pyrethrum (Chrysanthemum cinerariaefolium) owers
Ragwort (Senecio inaequidens, S. cordatus)
Rain daisy (Dimorphotheca pluvialis) seed
Rape, canola (Brasica napus, B. campestris) seed
Pyrrolizidine alkaloids: senecionine, seneciphylline Oil, tocopherols, dimorphecolic acid, tri- and di-dimorphecolin Oil, polyunsaturated fatty acids, phospholipids, phenolic acids
Raspberry (Rubus idaeus) seed, residue after pressing Red cedar (Juniperus virginiana) wood chips Rice (Oryza sativum) bran, corn
Oil, antioxidants Oil (bioactive agent) Oil, triacylglycerols, free fatty acids, oryzanols, tocopherols, sterols, waxes; aroma
Ridola (Ridola segetum) different aerial parts Rock rose (Cistus ladanifer) leaves Rock samphire (Crithmum maritimum) aerial part
Rose: wild dog rose and sweet briar rose (Rosa canina, R. rubiginosa) fruit, seed and peel
Volatile oil Volatile oil, waxes Volatile oil: p-cymene, -phellandrene, -terpinene, thymol methyl ether, dill apiole Oil, carotenoids, tocopherols
Stahl et al. 1980, Bunzenberger et al. 1983, Brunner 1984, Bulley et al. 1984, Eggers et al. 1985, Lee et al. 1986, King et al. 1987, Fattori et al. 1988, Temelli 1992, Taylor et al. 1993, 1997, Walker et al. 1994a, Dunford and Temelli 1995, 1997, Goodrum et al. 1996, Montanari et al. 1996, Bruhl and Matthaus 1999, Matthaus and Bruhl 1999, 2001, Barthet and Daun 2002, Luque-Garcia and de Castro 2004, Germain et al. 2005, del Valle et al. 2006, Jenab et al. 2006, Dong and Walker 2008, Sun et al. 2008 Then et al. 1998a, Laroze et al. 2010 Eller and King 2000, Eller and Taylor 2004 Ramsay et al. 1991, Saito et al. 1991, Garcia et al. 1996, King et al. 1996, Shen et al. 1996, 1997, Kuk and Dowd 1998, Kim et al. 1999a, Xu and Godber 2000, Bhattacharjee et al. 2003, Perretti et al. 2003, Danielski et al. 2005, Sarmento et al. 2006, Sparks et al. 2006, Balachandran et al. 2008, Chen et al. 2008a,b, Wang et al. 2008a Marongiu et al. 2007b de Lucas et al. 1999, Rincon et al. 2000 Marongiu et al. 2007c Illes et al. 1997, del Valle et al. 2000a, 2004, 2006, Eggers et al. 2000, Reverchon et al. 2000, del Valle and Uquiche 2002, Szentmihalyi et al. 2002, Hegel et al. 2007, Machmudah et al. 2007, 2008a,b, Tozzi et al. 2008 Norulaini et al. 2009
Rose of Jericho (Anastatica hierochuntica) aerial part
Rosemary (Rosmarinus ofcinalis) leaves
Hexadecanoic acid, 9,12-octadecadienoic acid, heneicosane, heptacosane Volatile oil, phenolic diterpene antioxidants: carnosic acid, carnosol, favonoids, cuticular waxes, antimicrobials
Rue (Ruta graveolens) aerial part, root Russian sage (Perovskia atriplicifolia) aerial part
Alkaloids Volatile oil
Hawthorne et al. 1988, Reverchon and Senatore 1992, Reverchon et al. 1993, Reverchon and Sesti Osseo 1994b, Walker et al. 1994b, Mendes et al. 1995, Coelho et al. 1997, Tena et al. 1997, Lopez-Sebastian et al. 1998, Bauman et al. 1999, Ibanez et al. 1999, 2000b, Bicchi et al. 2000, Senorans et al. 2000, Leal et al. 2003, Ramirez et al. 2004, Carvalho et al. 2005, Presti et al. 2005, Santoyo et al. 2005, Bajer et al. 2007, Celiktas et al. 2007, Babovi et al. 2010 Stashenko et al. 2000 Pourmortazavi et al. 2003
93
94
(Table 1 continued) Extract components Alkylresorcinols Fatty oil: linoleic acid, linolenic acid, - and -tocopherol Diterpenoids: cis-abienol Oil Safranal Volatile oil, antioxidants, cuticular waxes Francisco et al. 2005 Follegatti-Romero et al. 2009 Ohira and Yatagai 1994 Taylor et al. 1997 Semiond et al. 1996, Lozano et al. 2000 Reverchon et al. 1995c, Catchpole et al. 1996a, 1997, Reverchon 1996, Lemberkovics et al. 1998, Bauman et al. 1999, Dauksas et al. 2001, Marongiu et al. 2001, Menaker et al. 2004, Aleksovski and Sovova 2007, Micic et al. 2008, Babovi et al. 2010 Yamini et al. 2008 Naik et al. 1989, Piggott et al. 1997, Marongiu et al. 2006e Cherchi et al. 2001 Heikes 1994 Hawthorne et al. 1993, Ribeiro et al. 1998, Esquivel et al. 1999a, Kubatova et al. 2001, 2002, Coelho et al. 2007, Zorca et al. 2007, Pavela et al. 2008, Grosso et al. 2009 Marentis 1998, Catchpole et al. 2000, 2002 Lojkova et al. 1997, Slanina et al. 1997, Choi et al. 1998a, Kim et al. 1999b, Dean and Liu 2000, Bartlova et al. 2002, Huyke et al. 2007, Sovova et al. 2007b, Wang et al. 2008a Joo et al. 1994, Choi et al. 1999 References
Plant part
Rye (Secale cereale) bran Sacha inchi (Plukenetia volubilis) seed Sachalin r (Abies sachalinensis) bark Safower (Carthamus tinctorius) seed Saffron (Crocus sativus) owers Sage (Salvia ofcinalis, S. desoleana) leaves
Salvia mirzayanii aerial part Sandalwood (Santalum album, S. spicatum) stems, wood Santolina insularis
Sassafras (Sassafras albidum) root, bark Savory (Satureja hortensis), shrubby savory (S. fruticosa), S. montana leaves Fatty acids, -sitosterol, nutraceuticals Lignans, cinnamic acid
Volatile oil Volatile oil: sesquiterpenes santalol, bisabolol, farnesol, nuciferol Volatile oil, waxes, cytotoxic and antimicrobial substances Allylbenzenes: safrole Volatile oil, antioxidants, insecticides
Saw palmetto (Serenoa serrulata syn. S. repens syn. Sabal serrulata) berries Schizandra (Schisandra chinensis) fruit, seed, stems, leaves Tropane alkaloids: hyoscamine, scopolamine salts Oil, polyunsaturated fatty acids, waxes, carotenoids, tocopherols, phytosterols
Scopolia parviora, Sc. japonica roots, aerial parts
Sea buckthorn (Hippophae rhamnoides) fruit, seed, pulp
Sesame (Sesamum indicum) seed Seseli bocconi leaves Showy rattlebox (Crotalaria spectabilis) seed Smilax, China (Smilax china) tubers Soya (Glycine maximus) beans, akes, our, hypocotyle, cake, pulp
Oil, -tocopherol, antioxidants, lignans Volatile oil Alkaloid: monocrotaline Sapogenins Oil, tocopherols, phospholipids, isoavones daidzein, genistein, phytosterols, phenolic compounds
Spiked thyme (Thymbra spicata)
Volatile oil
Shaftan et al. 1986, Stastova et al. 1996, Manninen et al. 1997a, Yin et al. 2003, 2005a,b, Derevich and Shindyapkin 2004, Yakimishen et al. 2005, Arimboor et al. 2006, Vlase et al. 2006, Cossuta et al. 2007, Li et al. 2007, Olah et al. 2007, Xu et al. 2008a,b, Sajfrtova et al. 2010 Namiki et al. 2002, Odabasi and Balaban 2002, Hu et al. 2004, Xu et al. 2005 Marongiu et al. 2006b Schaeffer et al. 1988, 1989, 1989a Shu et al. 2004 Stahl et al. 1980, Friedrich et al. 1982, Snyder et al. 1984, Eggers et al. 1985, Taylor et al. 1993, Lancas et al. 1994, 1995, Reverchon and Sesti Osseo 1994a, Chandra and Nair 1996, King et al. 1996, Montanari et al. 1996, 1999, Taylor et al. 1997, 2000, Sievers 1998, Bruhl and Matthaus 1999, Matthaus and Bruhl 1999, 2001, Nodar et al. 2002, Rostagno et al. 2002, Luque-Garcia and de Castro 2004, Klejdus et al. 2005, Armando et al. 2006, Quitain et al. 2006, Araujo et al. 2007, Hegel et al. 2007, Kao et al. 2008, Rochova et al. 2008 Sonsuzer et al. 2004
(Table 1 continued) Extract components Volatile oil Volatile oil, alkanes, fatty acids, waxes, phytosterols, phloroglucinols hyperforin, adhyperforin; quercetin, rutin Oil, silymarin, pigments, tocopherols, metals Volatile oil: anethole References
Plant part
Spruce (Picea abies, P. omorica, P. pungens) needle St Johns wort (hyperici herba) (Hypericum perforatum L.) aerial part, owers
St Marys thistle, milk thistle (Silybum marianum) fruit, seed Star anise (Illicium verum) fruit
Stevia (Stevia rebaudiana) leaves
Hawthorne et al. 1988, Orav et al. 1998, Sedlakova et al. 2003b Catchpole et al. 2000, 2002, Cui and Ang 2002, Mannila et al. 2002, 2003, Dimitrieska-Stojkovic and Zdravkovski 2003, Rompp et al. 2004, Seger et al. 2004, Smelcerovic et al. 2004, Wang et al. 2004, Glisic et al. 2008 Szentmihalyi et al. 1998, Gamse and Marr 1999, Skerget et al. 2000, Hadolin et al. 2001, Skerget and Knez 2001 Stahl and Gerard 1982a, Liu 1996, Tuan and Ilangantileke 1997, Della Porta et al. 1998a Liu et al. 1997, Pasquel et al. 1999, 2000, Choi et al. 2002b, Yoda et al. 2003
Stinging nettle (Urtica dioica) leaves, root
Stonebreaker (Phyllanthus niruri) stems, aerial part Strawberry (Fragaria) fruit Sugar cane (Saccharum ofcinarum) leaves, rind Sunower (Helianthus annuus L.) seed
Oleoresin: sesquiterpenes, fatty acids, aliphatic hydrocarbons, steroids, triterpenes; glycosides: stevioside, rebaudioside A Oil, oleoresin: pigments, -sitosterol, scopoletin Gallic acid, ellagic acid, corilagin Aroma Wax, oil, resin Oil, bioactive compounds
Sweet gale (Myrica gale) fruit Sweet grass (Hierochloe odorata)
Rafajlovska et al. 2001, Sovova et al. 2004, Sajfrtova et al. 2005, Hojnik et al. 2007 Markom et al. 2007 Polesello et al. 1993 Garcia et al. 1994, de Lucas et al. 2007 Stahl et al. 1980, Calvo et al. 1994, 1998, Favati et al. 1994, Lancas et al. 1994, Cocero and Calvo 1996, Perrut et al. 1997, Taylor et al. 1997, Bruhl and Matthaus 1999, Matthaus and Bruhl 1999, 2001, Royer and Barth 2000, Andrich et al. 2001, Cocero and Garcia 2001, Bravi et al. 2002, Kiriamiti et al. 2002, Luque-Garcia and de Castro 2004, Salgin et al. 2006, Casas et al. 2007, 2008, Hegel et al. 2007 Sokolova et al. 2005 Grigonis et al. 2005
Sweet iris (Dalmatian iris) (Iris pallida) rhizomes Sweet olive (Osmanthus fragrans) owers Sweet potatoes (Ipomea batatas) root Sweet wormwood (Artemisia annua) aerial part
Tabernaemontana catharinensis branches and leaves Tagetes, marigold (Tagetes lucida, T. erecta, T. patula, T. minuta) ower petals Taiwan plum yew (Cephalotaxus wilsoniana) leaves Tamarind (Tamarindus indica) fruit, pulp, seed coat Tansy (Tanacetum vulgare) owers Tea (Camellia sinensis, C. sasanqua) seed, leaves
Volatile oil Antioxidants 5,8-dihydroxycoumarin, 5-hydroxy-8-O--d-glucopyranosylbenzopyranone Irones, iridals Essential oil Carotenoids, -tocopherol Artemisinin (antimalaric compound), artemisinic acid, scopoletin Indole alkaloids, antioxidants Volatile oil: insecticides; lutein Cephalotaxine Volatile oil, antioxidants: epicatechin Volatile oil Oil, volatile oil, catechins, caffeine, gallic acid Volatile oil: terpinen-4-ol
Tea tree (Melaleuca alternifolia) leaves, terminal branchlets
Bicchi et al. 1993 Yao et al. 1998 Spanos et al. 1993, Okuno et al. 2002 Kohler et al. 1997a,b, Hao et al. 2002, Quispe-Condori et al. 2005, Tzeng et al. 2007 Pereira et al. 2004, 2005, 2007 Wells et al. 1992, Vasudevan et al. 1997, Bicchi et al. 1999, Ma et al. 2008, Gao et al. 2009, 2010, Skerget et al. 2010 Choi et al. 2000 Sagrero et al. 1994, Tsuda et al. 1995, Luengthanaphol et al. 2004 Smith and Burford 1994 Swift et al. 1994, Braren and Kurzhals 1998, Chang et al. 1999, 2000, Rajaei et al. 2005, Huang et al. 2007, Kim et al. 2007, 2008, Lee et al. 2007, Park et al. 2007a,b, Shalmashi et al. 2008 Garau and Pittau 1998, Wong et al. 2001
95
96
(Table 1 continued) Extract components Volatile oil: thymol, pasty products, antioxidants References
Plant part
Thyme (Thymus vulgaris, T. zygis, T. herba-barona) leaves, owering tops
Tirphal (Zanthoxylum rhesta) fruit Tobacco (Nicotiana tabacum)
Volatile oil, fatty acids, hydrocarbons Tar precursors, nicotine, N-nitrosamines, volatile oil, tetra-acyl sucrose esters Oil, carotenoids: lycopene, -carotene; tocopherols, sitosterols
Tomato (Solanum lycopersicum, syn. Lycopersicon esculentum) seed, fruit pulp, skin
Bestmann et al. 1985, Hawthorne et al. 1988, Hartonen et al. 1992, Dapkevicius et al. 1996, Fekete et al. 1996, Oszagyan et al. 1996, Ribeiro et al. 1998, de Melo et al. 2000, Moldao-Martins et al. 2000, 2002, Zekovic et al. 2000, 2001, 2003, De Gioannis et al. 2001, Simandi et al. 2001, Diaz-Maroto et al. 2005, Dawidowicz et al. 2009, Babovi et al. 2010 Rout et al. 2007 Hubert and Vitzthum 1978, Donsi et al. 1990, Prokopczyk et al. 1992, 1995, Uematsu et al. 1994, Yonei et al. 1995b, Fischer and Jefferies 1996, Rincon et al. 1998, Stojanovic et al. 2000, Palic et al. 2002, Ashraf-Khorassani et al. 2005 Roy et al. 1994a, 1996a, Favati et al. 1997, Inakuma et al. 1998, Baysal et al. 2000, Cadoni et al. 2000, Ollanketo et al. 2001, Gomez-Prieto et al. 2002, 2003, Rozzi et al. 2002b, del Castillo et al. 2003, Sabio et al. 2003, Vasapollo 2004, Topal et al. 2006, Blanch et al. 2007, Vagi et al. 2007, Kassama et al. 2008, Nobre et al. 2009 Ehlers et al. 1996 Marongiu et al. 2006c
Tonka bean tree (Dipteryx odorata, Coumarouna odorata) beans Tree wormwood (Artemisia arborescens) aerial part
Lipophilic top phase, crystalline base phase, coumarin Volatile oil: trans-thujone, camphor, chamazulene Wax: fatty acids, primary alcohols, alkanes, sterols, diketones Volatile oil, antioxidants, antimutagens Oil, carotenoids Volatile oil, curcuminoids, turmerones Athukorala and Mazza 2010
Triticale (Triticosecale) straw
Tropical almond (Terminalia catappa) leaves, seed Tucuma palm (Astrocaryum vulgare) pulp Turmeric (Curcuma longa, C. zedoaria) rhizomes
Valerian (Valeriana wallichii, V. ofcinalis) root
Volatile oil, valepotriates, valerenic acid, sesquiterpenes Oleoresin Volatile oil - and -Carotene Volatile oil: khusinol, khusilal Oil Lycopene Volatile oil: biocides, antibacterial and antifungal substances Fatty oil: non-polar lipids, glycolipids, phospholipids, tocopherols
Vanilla (Vanilla planifolia) beans Vassoura (Baccharis dracunculifolia) Vegetables various Vetiver (Vernonia zizanioides) root
Walnut tree (Juglans nigra) nuts
Watermelon (Citrullus lanatus) fruit West Indian lantana (Lantana camara)
Ko et al. 2002, 2003, Mau et al. 2003 Franca et al. 1999b Sanagi et al. 1993, Ma et al. 1995, Baumann et al. 2000, Began et al. 2000, Chassagnez-Mendez et al. 2000a,b, Gopalan et al. 2000, Machado et al. 2000, Braga et al. 2003, Leal et al. 2003, Chang et al. 2006, Kao et al. 2007 Muravlev and Smetanin 1974, Stahl and Schutz 1980a, Gamse and Marr 1999, Shohet and Wills 2006, Zizovic et al. 2007b, Safaralie et al. 2008, 2010, Salimi et al. 2008, Huang et al. 2009 Vitzthum and Hubert 1971, Nguyen et al. 1991, Anklam and Muller 1995 Cassel et al. 2000 Marsili and Callahan 1993 Naik et al. 1989, Blatt and Ciola 1991, Martinez et al. 2004, 2007, Takeuchi et al. 2008, Talansier et al. 2008 Crowe et al. 2002, Oliveira et al. 2002, Crowe and White 2003, Salgin and Salgin 2006, Bernardo-Gil and Casquilho 2007 Vaughn et al. 2008 Vasudevan et al. 1997, Marongiu et al. 2007a Taniguchi et al. 1985, Saito et al. 1989, Artz and Sauer 1992, Lancas et al. 1994, King et al. 1996, Gomez et al. 1997, Zhang et al. 1998a, Munoz et al. 1999, Gomez and de la Ossa 2000, Ge at al. 2002a,b, Panli et al. 2003, Hubbard et al. 2004, Eisenmerger et al. 2006, Zacchi et al. 2006, Lucas et al. 2007, Eisenmerger and Dunford 2008, Shao et al. 2008, Piras et al. 2009
Wheat (Triticum vulgare, T. aestivum) germ, our, plumule
97
Stahl and Gerard 1982b, 1983 Peplonski et al. 1994, Gamse and Marr 1999, Bocevska and Sovova 2007, Barghamadi et al. 2009 Saldana et al. 1999, 2000a,b,c, 2002b, Esmelindro et al. 2004, Cardozo et al. 2007, Jacques et al. 2007
Jennings et al. 1992, Heaton et al. 1993, Chun et al. 1994, 1996, Vandana and Teja 1995, Vandana et al. 1996 Stashenko et al. 1996a Ebrahimzadeh et al. 2003
In the particular case of designing and development of supercritical processes for extraction of valuable botanic substances, the TMF should be able to model and predict mainly the solubility of solid solutes in supercritical solvents, and to a lesser extent the solubility of liquids. However, as discussed in detail by Fornari et al. (2010), this is not a simple task because the modelling of the solubility of condensed nonvolatile solutes in supercritical solvents involves a number of difculties not usually encountered in other phase equilibrium calculations. In particular (i) The vapour pressure is the most important indicator of solubility: However, together with additional purecomponent data, it is often unavailable and cannot be measured experimentally for relatively non-volatile complex solids, which are most of the solutes of interest. (ii) The proximity to the critical point: The rapid density changes and the anomalous behaviour displayed in the critical region is a challenge to any model applied near the critical point, which is mathematically singular. (iii) SCF solutions are often highly asymmetric: The solute and solvent molecules generally differ greatly in molecular size and in their interaction strengths, leading to highly non-ideal mixtures. As a result, binary interaction constants must be correlated from data using conventional corresponding states theory based on critical properties. (iv) SCF solutions are highly compressible: This leads to solvent condensation or clustering about the solute even in non-polar systems. In what follows we will briey outline the thermodynamics of the phase equilibria exhibited by the systems SCF+botanic substance without/with an entrainer, followed by a concise description of the different elements of a TMF: namely thermodynamic mixture models; the methods that are used to estimate the properties of the extracts when they are not available; and the methods, algorithms, and numerical techniques to calculate the phase equilibria.
4.1. The thermodynamics of phase equilibria of SCF+botanic substances systems 4.1.1. Vapour-liquid equilibria The extraction with SC-CO2 of valuable vegetable oils consisting mainly of triglycerides, with a low fraction of diglycerides, free fatty acids, and a number of minor components (sterols, tocopherols, phospholipids, etc.) that have added value as pharmaceuticals and food additives, and the extraction and fractionation of essential oils with SC-CO2 requires detailed knowledge of the of the vapour-liquid (and vapour-liquid-liquid) equilibria of the systems under consideration (Franceschi et al. 2004). For vapour-liquid equilibrium, the general equilibrium relation is
References
Volatile oil: -thujone, artabsin, absinthin Volatile oil, oleoresin
Extract components
Purine alkaloids: caffeine, xanthines, squalene, tocopherols, sterols, fatty acids, hydrocarbons, alcohols Paclitaxel (Taxol), taxicin, baccatin III Yerba mate (Ilex paraguarensis) herbs, leaves
Wormwood (Artemisia absinthium) Yarrow (Achillea millefolium) aerial part, owers
Yew (Taxus brevifolia, T. cuspidata, T. baccata) needles, bark Ylang-ylang (Cananga odorata) owers Zataria multiora
(Table 1 continued)
Volatile oil Volatile oil
Plant part
fi L = fi V
(1)
where fi L and fi V are the fugacities of component i in the liquid and vapour phases, respectively.
98
Fugacities are related as fi L = xi iL P fi V = yi iV P (2)
where P is the pressure, and xi and yi are mole fractions, and iL and iV are fugacity coefcients of the i-th component in the liquid and vapour phase, respectively. Thus, the solubility (mole fraction) of component i in the vapour (SC uid) phase can be expressed as follows: yi = xi iL iV (3)
Thus, the problem is how to calculate the fugacity coefcient of the i-th component in the liquid and vapour phases.
4.1.2. Solid-SCF
The majority of the systems that we focus on involve medium- and large-sized solutes at ambient or slightly elevated temperatures where they are typically pure solids. Four different modelling approaches are typically used to describe the solubility of solids in SCFs. These approaches are density based, dense gas, expanded liquid, and solubility parameter. The density-based approach is an empirical or semiempirical modelling approach that relies on developing a relationship between the solubility and the density of the SCF. The dense gas and expanded liquid approaches are both equationof-state (EoS) approaches that differ in the way in which the SCF phase is treated. At high pressures and liquid-like densities common in SFE, the distinction between a gas and a liquid is difcult. SCFs can therefore be treated either as a gas or as a liquid (McHugh et al. 1988, McHugh and Krukonis 1994). The dense gas approach treats the SCF as a gas while the expanded liquid approach treats the SCF as a liquid. The solubility parameter approach is an expanded liquid approach that uses the regular solution theory and the solubility parameter concept to develop a model for the solubility of solids in SCFs. The density-based approach for modelling solubilities of solids in SCFs attempts to explain the common observation that the logarithm of the solubility is linearly dependent on the density or the logarithm of the density of the SCFs (Kumar and Johnston 1988). This approach has been studied by many authors, including Chrastil (1982), Schmitt and Reid (1985), Kumar and Johnston (1988), Harvey (1990), Bartle et al. (1991a), Mitra and Wilson (1991), and Liu and Nagahama (1996). Chrastil (1982) proposed the following relationship between the solubility and the density: (4)
Chrastil (1982) identied the constant a with the heat of reaction as the solute associates with the solvent and the constant b with a relationship between the molecular weights of the solute and solvent, and used Eq. (4) to successfully correlate solubilities of a variety of different compounds in SC-CO2. Adachi and Lu (1983) used Chrastils equation to correlate the solubilities of 37 systems. To obtain reasonable performance, they made the parameter k density dependent and added two additional parameters. Yun et al. (1991) correlated cholesterol solubilities in SC-CO2 using Chrastils equation and obtained a performance ranging from 1.5% to 9%. Skerget et al. (1995) correlated solubilities of carotene, oleic acid, and capsaicin in SC-CO2 using Chrastils equation. The performance of the correlation for these compounds varied from 10% to 34%. Kumar and Johnston (1988) proposed two new relationships to relate the solubility to the SCF density. The relationships were derived using a dense gas-type approach, expressing the fugacity coefcient of the supercritical phase in terms of density rather than pressure. Chrastils equation was used to describe the solubility behaviour of fatty acids; mono-, di-, and triglycerides; and fatty acid esters in SC-CO2 (Guclu-Ustundag and Temelli 2000). The authors point out that mono- and diglycerides are the least studied classes of lipids, although information on their phase behaviour is essential for the design of processes such as fractionation of glyceride mixtures or rening of vegetable oils, which are of great commercial importance. Brennecke and Eckert (1989) state that Chrastils equation has been the most successful density-based model, but due to its empirical nature, it is unable to predict phase equilibria. Additional detailed enumeration of the empirical models most often applied for modelling of the solubilities of solids in SCFs can be found in the recent review by Skerget et al. (2011).
4.1.3. The dense gas approach The dense gas approach for modelling solute solubilities in SCFs begins with equating the fugacities of the solid and SCF phase and the standard formulation of this problem is based on the equi-fugacity condition for the solute; that is, assuming an EoS model for the uid phase and denoting by the superscript S the solid solute and by the superscript F the uid phase:
f S(T, P) = f F(T, P, y, V)
(5)
a c = k exp + b T
where c is the concentration of the solid in the SCF in g l-1, is the SCF density, T is the temperature, k is the association number, and a and b are empirical constants. The parameters k, a, and b are obtained performing a multiple linear regression on the experimental solubility data.
where f S is the fugacity of the solute in the pure solid phase, f F is fugacity of the solute in the uid-phase solution, y=(y1, y2, ,yNc)T is the vector of uid-phase mole fractions, and V is the molar volume of the uid from an EoS model. Additional relationships that must be satised are the summation to one of the uid-phase mole fractions. As discussed by Fornari et al. (2010), there have been a number of efforts at introducing mathematical artices for solid-phase fugacity within traditional uid-phase equilibrium EoS descriptions. Some investigators have attempted to modify the EoS so that it may predict the existence of a solid phase. However, it has been more common to take a popular EoS and use it directly in solid-uid equilibrium
99
calculations by introducing a solid-phase fugacity function dened in terms of a uid-phase reference state. Two different approaches are popular. According to the rst approach, originally proposed by McHugh et al. (1988), the solid vapour pressure is used as the reference fugacity of the solid. Thus, for the simple case of binary solid-gas equilibria, and if the solid solute in the system is denoted by subscript 2, then: f2S = P2s s exp 2
S v2 dP RT Ps
2
(6)
where P2s (T) is the sublimation (vapour) pressure of the pure solid, S is the fugacity coefcient at sublimation pressure, and 2 S v2 is the molar volume of the solid, all at temperature T. The fugacity of the solute in the supercritical phase is f2G = y2 PG 2 (7)
G where 2 is the fugacity coefcient and y2 is the solubility (mole fraction) of the solute in the SCF. For phase equilibrium between a high-boiling compound and a SCF whose critical temperature is low, the following three assumptions are usually introduced: (i) the solid solute remains pure since the size and shape of solute and solvent molecules are ordinarily sufciently different and hence solid solutions do not form; (ii) the molar volume of the solid solute can be treated as a constant with respect to pressure; and (iii) the saturated vapour of the solid solute-vapour (pure) system behaves as an ideal gas. The fugacity coefcient takes into account deviations of the saturated vapour from ideal gas behaviour and the Poynting factor (the exponential term) takes into account the effect of pressure. Furthermore, since the solid phase is pure (assumption 1), the fugacity of the solute in the solid state is equal to the pure solid fugacity and Eq. (6) can be rewritten as follows: S vS P -Psub1 (T ) S S f2S = Psubl (T )subl exp RT
of pressure on the fugacity of the pure solid; and G. Of all 2 three correction terms, the last one is by far the most important. In most practical cases, the sublimation pressure of the solid is quite small and thus s is nearly equal to unity 2 (assumption 3). The Poynting correction is not negligible, but it generally accounts for an enhancement factor <2 or 3. However, G is always far removed from unity and can 2 produce very large enhancement factors. The solubility in an Ps ideal gas is y2 = 2 ; hence, the large solubility enhancements P in SCFs relative to an ideal gas are due to exceptionally small values of G. The above equation represents the basis 2 for the dense gas approach for modelling solubilities in SCFs. G This equation relies on the adequate evaluation of 2 , at the specied conditions of P and T. Therefore, the solute solubility is primarily a function of the solid solute pure compound physical properties, the system temperature and pressure, and the fugacity coefcient of the solid solute in the SCF. The fugacity coefcient is the property calculated by a thermodynamic model. The second approach, introduced originally by Kikic et al. (1997), implements the fugacity of a hypothetical subcooled liquid phase, as the reference of the solid phase fugacity. Thus, the solid-phase fugacity function, for a pure solute solid phase at temperature T and pressure P, dened in terms of a hypothetical liquid-phase fugacity as a reference state, and disregarding the change in specic heat because of its negligible effect, is given as follows: P V S -V SCL Hfus 1 1 dP + f S = f SCL ( P, T )exp - R Tm T s Psubl RT (10)
Implicitly assuming that there are no solid-solid phase transitions and provided the solid specic volume at the subcooled liquid state V SCL is weakly dependent on pressure, Eq. (10) can be written as follows: f S = f SCL ( P, T )exp V S -V SCL Hfus 1 1 S - P -Psubl (T ) + RT R Tm T
(6a)
)(
Applying further assumption 2 and the thermodynamic equilibrium condition [Eq. (5)], the mole fraction of the solid component in the supercritical phase can be expressed as y2 = P2s E P (8)
(10a)
In Eq. (10), f SCL is the fugacity of the pure subcooled liquid, Hfus is the enthalpy of fusion, Vfus=V S-V SCL is the change in volume, all taken for the solute at its triple point. Often the second approach should be preferred because of the following reasons: (i) With the use of Eq. (6a) for the calculation of solid fugacity, it is not usually possible to t the normal melting point (Tfus) of the solid compound. On the other hand, use of Eq. (10a) reproduces the normal melting point of the solid compound since it is an input parameter for this approach. (ii) The rst part of the exponential term in Eq. (10a), Vfus=V S-V SCL, is important at higher pressures and should not be eliminated.
where s exp 2
S v P -P v2 dP s exp 2 RT RT P2s = G G 2 2 P S 2 s 2
(9)
The enhancement factor E contains three correction terms: s , which takes into account non-ideality of the pure satu2 rated vapour; the Poynting correction, which gives the effect
100 H. Sovov and R.P. Stateva: SFE from vegetable materials
In Eq. (10a), the data that are required for calculating the fugacity of the pure solid phase are as follows: the fugacity of the pure solute in the subcooled liquid phase (calculated from a thermodynamic model), the enthalpy of fusion at the triple point (HTP), the triple point temperature (TTP), the triple point pressure (PTP), and the change in molar volume assumed to be a constant upon fusion (VTP). The theory behind lattice gas models is based on the fact that the molecules are distributed over a three-dimensional lattice (Brennecke and Eckert 1989) and that these molecules interact with a mean-eld-type intermolecular potential (McHugh and Krukonis 1994). A number of holes are placed at specic lattice sites to obtain the correct density (McHugh and Krukonis 1994). Lattice gas models are reviewed by Johnston et al. (1989), Brennecke and Eckert (1989) and McHugh and Krukonis (1994). Brennecke and Eckert (1989) conclude in their review that, although the lattice gas equations are theoretically based, their performance in terms of modelling solubilities is poorer than the performance of cubic and perturbed EoSs.
4.1.4. Lattice gas models 4.1.5. Expanded liquid approach The expanded liquid approach for modelling solute solubilities in SCFs begins with equating the fugacities of the solid and SCF phase. Assuming the solid is pure, the fugacity of the solid is calculated using the same equation as in the dense gas approach. The fugacity of the SCF phase, treated as an expanded liquid, is written as follows:
SCF f2SCF = y2 2 f pure
solvent, V1 is the molar volume of the liquid solvent, and 1 and 2 are, respectively, the solvent and solute solubility parameters, dened by: U i = i Vi
1/ 2
i =1, 2
(14)
where Ui is the vapourisation energy and Vi is the liquid molar volume. Thus, Eqs. (12) and (13) represent the functional form of the RST, using solubility parameters to calculate the solubility. Ekart et al. (1991) and Brennecke and Eckert (1989), in summarising the efforts that have been made to use the RST in correlating solubilities in SCFs, point out that semiempirical modications of the theory have been required.
4.2. Thermodynamic models
(11)
where 2 is the activity coefcient of the solute in the liquid phase. The expanded liquid approach has an advantage over the dense gas approach in that it does not require integration through the critical region. The expanded liquid approach, however, requires the evaluation of two parameters, the activity coefcient and the partial molar volume of the solute at innite dilution, versus one parameter in the dense gas approach. Mackay and Paulaitis (1979) found that the expanded liquid approach did not provide better solubility correlation performance than the dense gas approach and therefore the introduction of a second parameter is not warranted.
4.1.6. Solubility parameter approaches
Reliable thermodynamics mixture models that are able to describe the extremely complex phase behaviour of the systems studied are a vital element of the TMF. An ideal thermodynamic model is a model that uses easily measured physical properties to predict phase equilibria at all conditions and is theoretically based. Still, up to the present time, no current model ts these criteria. Existing correlations of phase equilibria data contain many regressed parameters, are semiempirical at best, and may succeed in tting the data in portions of the phase diagram with some accuracy (Ekart et al. 1991). The dense gas approach is an EoS approach that treats the supercritical phase as a gas and is currently the most widely used for representing the phase equilibria of asymmetric systems at high pressures. It requires the evaluation of the fugacity coefcient using an EoS valid over the entire density range studied, and hence an adequate relationship to describe the P-V-T behaviour of the SCF phase. The dense gas approach requires the evaluation of the fugacity coefcient and hence a variety of different relationships exist to describe this relationship. The most commonly used are the cubic equations of state.
4.2.1. Equations of state Both cubic and noncubic EoSs have been used to model the solubility of solids in SCFs, and a summary of the models and methods used can be found inAshour et al. (2000). Cubic EoSs are derived from the equation, which takes attractive and repulsive forces into account, and was proposed for the rst time by van der Waals. Currently, cubic EoSs, in combination with different mixing rules, are the most widely used models for the calculation of solubilities of solid solutes in SCF. The recent contribution of Fornari et al. (2010) is devoted entirely to the application of cubic EoSs to correlating the solubility of solid compounds in SCFs. The authors offer a detailed critical analysis of the cubic EoSs advantages and shortcomings in fullling the above tasks and stress that to model adequately SC uid-solid phase equilibria or SCF+liquid equilibria using an EoS approach, the EoSs employed must be able to describe both the uid-phase and
The solubility parameter approach is an expanded liquid approach that uses the regular solution theory to determine the solubility and activity coefcient, according to the following relations: ln y2 = H fus Tm2 RT T
m2
-1 - ln 2
(12)
ln 2 =
V2 2 ( - )2 RT 1 1 2
(13)
where V2 is the solute molar volume in a hypothetical liquid state, 1=(x1V1)/(x1V1+x2V2) is the volume fraction of the
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the solid (liquid) phase behaviour reliably. To realize that, two avenues are usually pursued improvement of mixing rules and improvement of the existing EoS and development of new models and Fornari et al. (2010) present an analysis of van der Waals one-uid mixing rule and its modications. Haselow et al. (1986) evaluated seven cubic EoSs and two non-cubic EoSs for the prediction of SFE. They suggested that there is a need to develop new mixing rules, otherwise no existing cubic EoS with the traditional van der Waals mixing rules can yield good predictions. Yamamoto et al. (1987) evaluated two EoSs, namely the perturbed hard sphere (PHS) EoS that comprises the Carnahan-Starling equation repulsive term and the Soave attractive term, and the Soave-Redlich-Kwong (SRK) EoS (Soave 1972) for the prediction of the solubilities of high-boiling compounds in SCFs. They reported that the performance of the SRK-EoS seems slightly better than that of the PHS-EoS, and it was pointed out that the selection of mixing rules is more important than the equation itself. Lee et al. (1989) conducted a similar study to examine three cubic EoSs for the prediction of solid solubilities in SCFs with co-solvent. Weber et al. (1999) modelled the solubility of tristearin, tripalmitin, and triolein with the Redlich-KwongAspen EoS and the Mathias-Klotz-Prausnitz mixing rule: the relative deviation of calculated and experimental solubility in the gas-phase was high, whereas the absolute deviation was considerably small. Yamamoto et al. (2000) correlated solubilities and entrainer effects for fatty acids and higher alcohols in SC-CO2 using SRK EoS with association model. Ismadji and Bhatia (2003) demonstrated that the one- or twoparameter van der Waals mixing rule with the Peng-Robinson (PR) EoS model failed to predict the solubility of some esters in SC-CO2, but the Stryjek-Vera mixing rules were able to correlate the experimental data fairly well. One empirical approach to eliminate the shortcomings of the van der Waals one-uid model for a cubic EoS has been to provide additional composition dependence by adding parameters to the combining rule for the parameter amix, generally leaving the mixing rule for the parameter bmix unchanged. Some examples are the combining rules of Panagiotopoulos et al. (1986), Adachi and Sugie (1986), Sandoval et al. (1989) and Schwartzentruber and Renon (1989a,b). However, there are several problems associated with this multiparameter combining rules that limit their use. One is that because of added composition dependence in the parameter amix, this group of combining rules fails to satisfy the theoretical quadratic composition dependence of the second virial coefcient. Ashour et al. (2000) have shown that incorporating additional parameters in the cubic EoS does not signicantly improve the prediction of the solubility of the solid in the SCF. However, this study did not take into account the dependence of the interaction EoS parameters with respect to temperature. Nicolas et al. (2005) considered different mixing rules associated with the Sanchez-Lacombe EoS, and the results were compared with those obtained with the PR equation. For this purpose, binary mixtures of solids with SC-CO2, ethane, ethylene, and xenon were investigated. Several mixing rules were considered, among which classical kij and lij
and the generalised composition-dependent mixing rule originally proposed by Adachi and Sugie (1986) and generalised by Hernandez-Garduza et al. (2001), to avoid the invariance problem pointed out by Michelsen and Kistenmacher (1990).
( With Sanchez-Lacombe EoS, two versions were studied: kij0 ) , ( ( kij1) mixing rule associated with a linear co-volume b, and kij0 ), ( kij1), lij mixing rule where b is a quadratic function of molar fractions. It was shown that, in many cases, the range of solu( bility data was too narrow to allow estimating meaningful kij0 ), ( kij1) values. The correlation of data in a large range of temperatures by means of classical mixing rules requires taking into account a temperature dependence of binary interaction parameters. It was observed that, with the proposed temperature function, only three parameters associated with the kij (T) and lij, or kij and lij(T) mixing rules allow to predict solubility data with an accuracy comparable to that of isothermal correlation. The PR-EoS results at the same conditions were of the same accuracy, provided a temperature dependence of EoS parameters was considered. Another interesting approach was advocated by Ruckenshtein and Shulgin (2001) who suggested a family of mixing rules for the cubic EoS in which the empirical binary interaction parameter k12 in the van der Waals mixing rule was replaced by a physically more meaningful parameter. In the new mixing rules, some mole fractions in the expressions of parameters amix and bmix in the van der Waals mixing rules were replaced with various expressions for the local mole fractions. The family of the new mixing rules can contain one, two, or even three parameters, and thus they are quite exible regarding the number of adjustable parameters. In particular, it was shown that the new mixing rules with two or three adjustable parameters provided better correlations of the experimental data for the solubilities of the antibiotic penicillin in SCF CO2 than the conventional mixing rules or the empirical expressions containing many more parameters. To avoid the two principal limitations of the dense-gas/ cubic EoS approach and in an attempt to improve the modelling success that is, in some cases, only semiquantitative, researchers have focused on developing more sophisticated mixing rules and EoS (Colussi et al. 1992), e.g., Rao and Mukhopadhyay (1989), Sheng et al. (1992), Bartle et al. (1992a) and Carleson et al. (1993). Rao and Mukhopadhyay (1989) and Sheng et al. (1992) proposed new mixing rules to attempt to improve correlation results. Nishiumi et al. (1988), Bartle et al. (1992a), and Carleson et al. (1993) developed new relationships for the binary interaction parameter that avoid the need for experimental data. Schmitt and Reid (1986) therefore adopt a new approach that still remains a dense gas approach, which uses the PR-EoS to evaluate the fugacity coefcient but the EoS parameters of the mixture are not calculated in the conventional manner. Another alternative to van der Waals one-uid mixing rules and a very attractive route to developing better mixing rules is to combine EoS with activity coefcient models thus combining the advantages of successful cubic EoS and GE models, such as the Universal Functional Activity Coefcient (UNIFAC) model (Fornari et al. 2010). A number of models
that are essentially all mixing rules for the energy parameter of cubic EoS has appeared (see, e.g., Huron and Vidal 1979, Mollerup 1986, Dahl and Michelsen 1990, Michelsen 1990a, Dahl et al. 1991, Holderbaum and Gmehling 1991, Wong and Sandler 1992). EoS/GE models have been applied mainly to modelling vapour-liquid systems and only to a limited extent to solidgas systems (see, e.g., Sheng et al. 1992, Spiliotis et al. 1994, Chen et al. 1995, Escobedo-Alvarado et al. 2001, Huang et al. 2001, Sovova et al. 2001a, to name a few). Tochigi et al. (1998) applied the PR-EoS with the analytical solutions of group (PRASOG) method to estimate solid solubilities in SC-CO2 and indicated its applicability. Coutsikos et al. (2003) evaluate the linear combination of Vidal and Michelsen mixing rules (LCVM) EoS model (Boukouvalas et al. 1994, Voutsas et al. 1996), which combines the PR-EoS with original UNIFAC using an EoS/GE type mixing rule, for solid-gas equilibria applications including systems with co-solvents, and studied the inuence of using vapor-liquid equilibria (VLE)based parameters for making SGE predictions. The LCVM model has a large parameter table including gases and it has been shown to yield quantitatively satisfactory predictions for binary solid+gas systems involving aromatic hydrocarbons, aliphatic acids, and some alcohols. Poor results were obtained, however, for complex solids, e.g., naproxen and cholesterol. Another model that can be used successfully to calculate and predict the solubility of a solid solute in SCFs is the predictive SRK (PSRK) EoS (Holderbaum and Gmehling 1991). PSRK has also a large parameter table available enabling the representation of a wide variety of complex natural products. Jaubert et al. (1999) performed phase equilibria calculations of mixtures involving SC-CO2 and fatty acid esters (FAE) by combining at a constant packing fraction the PR-EoS and the Van Laar GE model. A new group O=C-O was added, and the fully predictive model thus obtained was used to predict the phase behaviour of a real sh oil containing 30 different fatty acid ethyl esters. In a further study, Jaubert et al. (2001) compared the phase equilibria predictions for systems of carbon dioxide and two different fatty acid ethyl esters eicosapentaenoic acid and docosahexaenoic acid ethyl esters of the Jaubert et al. (1999) model with that developed by Coniglio et al. (1995), namely the MHV1-QB approach. The MHV1-QB approach combines the SRK-EoS with a quadratic expression for the mixture b parameter, and a constant value for the binary interaction parameter lij = 0.3, with the rst order modied Huron-Vidal mixing rule (MHV1) proposed by Michelsen (1990b). It was demonstrated that the MHV1-QB model lead to very good results at low pressures but overestimated the bubble point pressures in the vicinity of the critical point and all the dew point pressures. Jaubert et al. (1999) model performed better in the vicinity of the critical point and for the dew point prediction, which was explained by some intrinsic features of the two models. Araujo and Meireles (2000) applied the PR equation with van der Waals mixing rules and combining rules with two parameters and three binary parameters of Kwak and Mansoori (1986) and Park et al. (1987) to the systems containing fatand oil-related compounds in SC-CO2. Preference was given
to correlating experimental data for both phases, which is perhaps the most difcult form of correlating vapour-liquid equilibrium data with cubic EoS considering the importance of this information for the design of supercritical fractionation systems. On the basis of the absolute mean deviation for mole fractions, it was concluded that the PR equation with van der Waals mixing rules for the three different combining rules described qualitatively all the important characteristics of the vapour-liquid equilibrium of the systems studied. The differences among the results obtained with the analysed combining rules were not signicant. On the other hand, the absolute mean deviations for the vapour phase obtained were smaller compared with the Soave equation and the mixing rules of MHV1 and MHV2, and the LCVM model for the majority of the binary and ternary systems studied. Therefore, concluded the authors, if experimental data are available, a simple model as the one discussed predicts the phase equilibrium of complex system within the required accuracy for project design. On the other hand, in the absence of experimental data, the entirely predictive EoS/GE models are very useful. Huang et al. (2001) applied the PR-EoS and a modied Huron-Vidal type mixing model with a volume correction term to calculate the solid solubilities of aromatic, fatty acid, and heavy alcohol compounds in SC-CO2. The UNIFAC activity coefcient model with its optimally tted binary interaction parameters was used and a volume correction term was employed, and its parameters were correlated as functions of the solid molar volume for both non-polar and polar systems. Escobedo-Alvarado et al. (2001) used the Wong-Sandler mixing rule and the PR-EoS to model the solubility of solid phases in SCFs. More recently, Vieira de Melo et al. (2005) applied the PR-LCVM-UNIFAC model to model the solubility of caffeic acid and l-dopa in the SC-CO2-rich phase. Gracin et al. (2002) examined the ability of the original UNIFAC method to predict solubilities of very different solid organic ne and specialty chemicals, organic intermediates, and pharmaceutically important compounds in 15 industrially important solvents. Valderrama et al. (2003) proposed a model that includes an EoS and an excess Gibbs free energy model and applied it to the correlation of phase equilibria in gas+solid systems containing SC-CO2. A modied regular solution model for the excess Gibbs free energy that considers nonpolar, polar, and hydrogen-bonding contributions and a generalised threeconstant EoS was advocated. The mixing rule derived for the model includes a concentration-dependent interaction parameter and an interaction parameter into one of the volume constants of the EoS. Literature data for nine binary gas+solid systems containing SC-CO2 were used for testing the proposed model. Espinosa et al. (2002) applied the group contribution (GC) EoS proposed by Skjold-Jorgensen (1988) to model highpressure phase equilibria in mixtures of fatty oils and acid alkyl esters with SCFs. The GC-EoS is based on the generalised van der Waals partition function and a group contribution principle. The repulsive term is a Carnahan-Starling-type expression, which is characterised by the critical hard-sphere
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diameter, and it is considered a function of the molecular size of the pure component. The attractive term is calculated using the non-random two liquid (NRTL) model with density-dependent mixing rules. Espinosa et al. (2002) represented the fatty oil by a pseudo-triacylglyceride with the same molecular weight and degree of unsaturation of the natural oil. The critical hard sphere diameter of the oil, i.e., the size-related parameter, was determined from the correlation of innite dilution activity coefcients of n-alkanes in high molecular weight triacylglycerides and hydrocarbons. Good predictions of vapour-liquid, liquid-liquid, and vapour-liquid-liquid equilibria in mixtures of supercritical solvents (propane, ethane, and CO2) with pure triacylglycerides, natural vegetable oils, and fatty acid alkyl esters were obtained. The authors conclude that the results obtained show the capability of the GC-EoS model to describe the phase equilibria of size-asymmetric mixtures and its potential for modelling supercritical processes involving oils and derivatives. In new developments, Chafer et al. (2004, 2005) and de la Fuente et al. (2005) also applied the GC-EoS to model the solubility of quercetin and carnosic acid, and capsaicin in SC-CO2 and compared its capabilities with those of SRK. Still, the use of this group contribution approach can be considered to be quite demanding while dealing with the amount of necessary regressed parameters and with the calculation of the association contributions for multiple associating groups. At this stage, we feel that the following should be underlined: the key assumption of all group contribution approaches such as UNIFAC is that molecules can be broken down into functional groups that can be treated as being independent of the rest of the molecule. Interaction parameters between groups are determined by correlation of the model to experimental data. For UNIFAC parameters, for example, more than 60 different functional groups are determined simultaneously in an extensive optimisation where the total deviation between the UNIFAC model and huge amounts of experimental data is minimised. Because of the complexity of this optimisation, parameter values are primarily correlation values rather than describing the actual physics in each particular interaction, and of course this limits the possibility to extrapolate the use into new situations. Furthermore, the values of the UNIFAC parameters to be used have been determined from vapour-liquid equilibrium data because these are the most extensive data that are available. From a physical point of view these interaction parameters should be equally useful for solid-liquid equilibria. However, because of deviations from the underlying assumptions and because of the complexity of the parameter determination, the extrapolation to solid-liquid systems is not necessarily valid. The practical problems associated with the application of the UNIFAC-based mixing rules are that many solid solute compound molecules extracted from natural matrices are more complex than the molecules normally encountered in gas-liquid equilibria. In addition, these molecules sometimes contain functional groups for which UNIFAC parameters are unavailable. Also, even if all group denitions exist, a subset of the relevant parameters is unavailable. These problems can
be eliminated with sufcient and accurate experimental data. Frequently, however, this involves a rather large number of parameters compared with the amount of data available. Finally, all group contribution methods discussed thus far treat the light gases, such as CO2, as individual groups, and hence the volume and surface area parameters for these groups must be determined. In some cases, as pointed out by Fornari et al. (2010), these structural parameters are estimated using semitheoretical methods like those of Bondi (1964) and Apostolou et al. (1995) but their values are essentially arbitrary and differ from those given by Dahl et al. (1991), the size parameters of the latter being about twice the size of the gases of Apostolou et al. (1995). There has not been a thorough analysis of which values are the best. In addition, these values must be set before the optimum values of the group interaction parameters of the UNIFAC model can be found, and hence any deciency that exists in the selection of these structural parameters will inevitably affect the group interaction parameters (Orbey and Sandler 1998).
4.2.2. Other models Cubic EoSs are exceedingly simple and have been remarkably successful in modelling SCFphase behaviour and are probably the most widely used in analysing experimental data. Moreover, the cubic EoS must be the equation of choice for process design of any complex system because the interactions are too involved to justify the use of a more fundamentally based equation. However, all of the cubic EoSs were originally developed to characterise hydrocarbons, and they embody a very wrong component of the corresponding state theory. This theory assumes similarity of molecular size and force constant an assumption that does not work for the highly asymmetric in force constant and size SC systems. Furthermore, cubic EoSs are least precise in the region near the critical point, and are completely inapplicable right at the critical point, which is mathematically singular. This is because many cubic EoSs predict common value for the critical compressibility factor for all uids, Zc = 0.303, while real values vary from 0.2 to 0.5 (Valderrama 2003, Valderrama and Alvarez 2004). Furthermore, the rapid density changes and the anomalous behaviour displayed in the critical region are a further challenge for EoS models. Thus, attempts to modify mixing rules, making them variable in density, temperature, or composition may be useful, but are stopgap solutions. The real need is to develop better EoSs. One response to this challenge is the application of the statistical associating uid theory (SAFT) to model SFE. To overcome the use of empirical corrections to cubic EoSs or G E mixing rules, the breakthrough in the modelling of polar and highly non-ideal systems came with the development of more rigorous explicit association models. A semiempirical EoS that was developed in the late 1980s and has gained considerable popularity in both the academic and industrial communities is the SAFT. SAFT is derived from the rst-order thermodynamic perturbation theory of Wertheim (1984a,b, 1986a,b), where the reference uid is a hard sphere and the perturbation consists of the relatively weak dispersive attractions. In SAFT, the Helmholtz free energy is written as the
sum of contributions due to hard-sphere repulsive interactions, due to chain formation through bonding of a number of hard spheres, and due to association and dispersion. From the several successful modications of SAFT that have been advocated, the one suggested by Huang and Radosz (1990, 1991) should be mentioned in particular. Although the approach is very successful in modelling the phase equilibria of complex systems, research dealing with its application to the modelling of the solubility of solids in SCFs is rather scarce (Muller and Gubbins 2001). Economou et al. (1992) used the SAFT EoS to correlate the solubility of polynuclear aromatics in supercritical ethylene and ethane, where a total of six systems were adopted and the correlated results showed that good agreement with experimental data can be obtained with the SAFT EoS. Zhong and Yang (2002) carried out a comprehensive investigation of the capability of the SAFT approach for modelling the solubility of solids in SCFs. They adopted an extended SAFT EoS combined with eight mixing rules to evaluate the capability of the SAFT approach. The results show that the SAFT approach gives good correlative accuracy in general, and that it can be used to model solid-SCF equilibria, which gives slightly better correlative accuracy than the cubic EoSs. In their further work, the authors apply the SAFT approach to model the solubility of solid aromatic compounds in SCFs with co-solvents (Yang and Zhong 2005). Efforts to develop new models and improve the existing ones with the view to represent in a more comprehensive manner the complex interaction between the solid+SCF are continuing. We will briey discuss some of them without either the ambition to be exhaustive or that all new models are covered. Vetere (1998) presented an empirical correlation with two parameters, namely molecular weight and melting point for the prediction of solid solubility. In a similar development, Mendez-Santiago and Teja (1999) showed that a simple linear expression, based on the theory of dilute solutions, can be used to correlate solid solubility data. The linear relationship may also be used to check the consistency of experimental data. The proposed equation for solid solubility requires knowledge of the sublimation pressure of the solid of interest, and the authors advocated another relationship for the solid solubility that incorporates a Clausius-Clapeyron equation for the sublimation pressure. Although the resulting expression contains three parameters, it was demonstrated that these parameters are independent of temperature and pressure. The proposed expression may therefore be used to extrapolate data to temperatures where experimental information may not be available. The molecular interactions near the critical point and high pressures have recently been studied intensively. The solutesolvent interactions near the critical point are strong. The studies that show these phenomena observed clusters in solutions aggregates of solvent around solute of dilute organics in SCFs (see, e.g., Walsh et al. 1987, Eckert and Knutson 1993, Zhang et al. 1995a). Cheng et al. (2003) calculated solid solubility by applying the equilibrium criteria for the cluster formation process. The simplied cluster-solvation model has two temperature-independent binary parameters, and it was observed that the overall deviation in solid solubility
calculations from this model is comparable to that from other semiempirical models with more optimally tted parameters. Solute-solute interactions are also important, as observed by Kurnik and Reid (1982) and Kwiatkowski et al. (1984). Brennecke and Eckert (1989) presented evidence for both solute-solvent and solute-solute interactions, due to the formation of dimers, even at very low concentrations using spectroscopic studies. They recommended using solute-solute interactions to develop EoSs. Zhong et al. (1998) suggested a model for correlating the solubility of solids in SCFs. This model is based on the fact that the free solute molecules, the solvent molecules, and the solventsolute clusters in such solid-SCF systems are in chemical equilibrium. The local density of the solvent surrounding a solute is used as a one parameter. The model can correlate the solubility data that are not in immediate region to the critical point of the solvent. Jiang et al. (1998) presented an equation for solubility behaviour representation derived from the solvation concept. Cheng et al. (2002) also explored the application of a modied regular solution model as an alternative method without the need of critical constants to the modelling of solid solubility of complex biological compounds, including steroids, antioxidants, xanthines, drugs, and heavy aromatic in SC-CO2. They compared their results with those obtained using semiempirical equations and EoS approaches. It was demonstrated that with two or with a single parameter in the solution model, satisfactory results are obtained that are comparable to those from other methods with more parameters. The optimally tted parameters in the solution model method are presented and the generalisation of the solution model parameters as a function of pure solid property is illustrated. Ruckenstein and Shulgin (2002) developed a predictive method for the solubility of a solid in a SCF containing an entrainer at any concentration. They presented a method based on the Kirkwood-Buff formalism, and expressions for the derivatives of the fugacity coefcient of the solute in a ternary mixture with respect to the mole fractions were obtained. On the basis of these expressions, an algebraic equation, which allowed one to predict the solubility of a solid solute in terms of its solubilities in the SCF and in the entrainer, was derived. The equation was compared with the experimental results available in the literature regarding the solubility in a mixture of SCFs and good agreement was obtained. Li et al. (2003) studied the solubility of solids in SCFs by chemical association reaction method, and both cases of with and without co-solvent were considered. On the basis of the thermodynamic and association reaction equilibrium theories, a model for the solubility of solids in SCFs under association reactions was developed. It reduces to normal solubility calculation model when there are no co-solvent and association reactions. The model was tested with the experimental data collected from the literature, and the results show that it is more accurate than other models.
4.3. Solute properties estimation
The systems that we focus on involve medium- and largesized solutes at ambient or slightly elevated temperatures
105
where they are typically pure solids. Such substances usually have the following characteristics: molar mass >100 g mol-1; polyfunctionality (two or more functional groups); multiple molecular conformations; complex molecular interactions, such as large dipoles, high polarisability, hydrogen bonding, and charge-transfer complexes; and, very importantly, limited amounts of reliable measured data, as their critical parameters and/or melting properties cannot be determined experimentally (Fornari et al. 2010). Correlation of solubility requires not only robust thermodynamic models but reliable methods to estimate the values of the solid compounds thermophysical properties (e.g., critical and melting properties) because inaccuracy in the properties plays a major role in the quality of the SFE predictions. This is a very challenging task on its own, moreover that there are very big deviations between the values estimated and reported by the different authors applying different methods. In view of this, a range of effective methods to estimate the solute properties should be available within the TMF. The two groups of properties of the pure solid solute required for modelling its solubility in SCF are its critical parameters and melting properties. For a liquid solute (such as essential oils, and di- and triglycerides), only critical parameters are required, while for a solid solute both the critical and the melting properties are needed.
4.3.1. Critical parameters
although for a different type of solid solutes, namely dyes. The authors employ several methods to estimate the critical parameters of blue 14, a disperse anthraquinone dye, and demonstrate that the choice of a particular group contribution method was more important than the choice of the EoS; for example, for the SRK cubic EoS, the Lydersen (1955) method, combined with Meissner group contribution method, leads to a better value for the AARD of the dye solubility than Joback and Reids (1987) method. The latter is not surprising taking into consideration that the former gives an excellent approximation to the theoretically calculated Tc/Pc ratio for blue 14 (31.56), namely 32.11 versus 42.85 for the latter. It has been demonstrated that the sublimation pressure plays a dominant role in the correlation of solubility data and that, in many cases, the only way to obtain a reasonable calculation of these data is to consider the sublimation pressure as an adjustable parameter (Reverchon et al. 1995a, Neau et al. 1996). It has also been shown that, in the case of high molar mass compounds for which sublimation pressures cannot be measured, the safest way to estimate them is to correlate experimental vapour pressure data through an analytical relation and to use normal fusion properties in order to settle the sublimation pressure equation with respect to temperature (Neau et al. 1999). Thus, a possible route to estimate the sublimation pressure of a solid compound is to integrate the Clapeyron relation from the triple-point temperature Tt and pressure Pt, assuming a negligible dependence of the sublimation enthalpy with respect to temperature (Neau et al. 1999):
4.3.2. Melting properties
For most of the solutes extracted from vegetable material, the critical properties may not be experimentally accessible because of thermal cracking below their critical temperature. Hence, the values of the critical parameters and normal boiling temperatures should be considered as hypothetical quantities rather than properties with any physical meaning, which have to be estimated either by correlations or group contribution methods. A concise but critical analysis of the methods applied to estimate the critical parameters of solid solutes can be found in Fornari et al. (2010), and we will not further pursue this topic here. Still, it should be noted that usually there are no experimental data available with which to compare the estimated values. In view of this, it is recommendable to apply as an assessment tool of the reliability of the properties estimated the generalised semitheoretical expression advocated by Zbogar et al. (2006): Tc/Pc = 9.0673 + 0.43309 (Qw1.3+Qw1.95) (15)
P s H s 1 1 ln = R T Tt Pt
(17)
where H s is the sublimation enthalpy at the triple point of the pure component, which can be expressed with respect to the fusion and vapourisation enthalpies as H s = H fus + H vap (18)
where Tc is in Kelvin and Pc is in bar. The dimensionless parameter Qw is a measure of the van der Waals molecular surface area and is calculated as the sum of the group area parameters, Qk: Qw = kQk
k
(16)
where k is the number of times group k appears in the molecule. The group area parameters Qk are available in the UNIFAC tables. The inuence of the uncertainties in the values of the critical parameters is explored in detail by Gordillo et al. (2005b)
The practical interest of this method is thus to require, besides an EoS, fusion property data that can be either measured, found in the literature, or estimated (Garnier et al. 1999). In most cases the triple-point conditions (the temperature and pressure at the triple point) for the solute are unknown experimentally. However, for almost all heavy compounds, there is little difference between the triple-point temperature and the normal melting temperature. Indeed, this difference is usually <0.1 K, which is less than the scattering of experimental values of transition temperatures found in the literature. Furthermore, the difference in the heats of fusion at these two temperatures is also often negligible (Perry and Green 1999). Under this assumption, the enthalpy of fusion in Eq. (17) can be estimated with the fusion enthalpy measured at the normal melting temperature. Hence, if the melting temperature of the compound of interest is known it is possible to calculate Pt and H vap from an EoS.
Coniglio (1993), Trassy (1998), and more recently Neau et al. (1999) and Crampon et al. (2004) discuss in detail the reliable methods, among the numerous ones devoted to this subject. We would like, however, to mention also the contribution of Valderrama and Zavaleta (2005) who propose to calculate the sublimation pressures of pure solids from high-pressure solubility data using genetic algorithms. The sublimation pressure is considered as a parameter to be determined by regression analysis of experimental solubility data, and hence an optimisation problem, in which the difference between the correlated and experimental data of solubility is to be minimised, is solved using a method that applies biologically derived techniques such as inheritance, mutation, natural selection, and recombination to nd the optimum solution. In the case of compounds that may decompose before the melting point, all fusion properties have to be estimated. For example, Jain et al. (2004) advocate a combination of additive group contributions and non-additive molecular parameters to estimate the normal melting points of 1215 organic compounds. The melting points are calculated from the ratio of the total phase change enthalpy and entropy of melting. The total phase change enthalpy of melting is calculated from the enthalpic group contributions, whereas the total phase change entropy of melting is estimated using a semiempirical equation based on only two non-additive molecular parameters. If, however, the melting temperature is known, then it is possible to estimate H fus from the following empirical equation: H fus = 4.184kT fus (19)
with typical deviations from the experimental ones, where available, of about 10% to 25%. Taking into consideration the simplicity of the proposed method for such a difcult task, it appears sufcient for the needs for sublimation pressure predictions. The overall error for the families of organic compounds considered (hydrocarbons, halogenated aromatics, nitro-aromatics, alkanols, phenols, acids, ketones, and multifunctional ones) is in the range of 1040%, and the error for the total of about 2650 data points exceeds one order of magnitude in very few cases. Finally, if no experimental data for the solid molar volume is available, a value can be estimated according to the following extended relationship (Goodman et al. 2004), which allows including temperature dependence for solid density from Tt to substantially lower temperatures: T solid (T ) = 1.28-0.16 liquid (Tt ) Tt (21)
where k is an empirical parameter related to the properties of the solute, and for organic compounds it is usually in the range 1016 (Chen and Ma 2004). Yet another possibility is to estimate the sublimation enthalpy solely on the basis of the value for Hvap, taking into consideration that H fus is usually less than one quarter of the sum given by Eq. (16) (Prausnitz et al. 1999). Another route to pursue is presented by Coutsikos et al. (2003) who advocate a group contribution method for the prediction of the vapour pressures of organic solids, based on the concept of the hypothetical liquid: ln P S = ln P L + S Tm 1 R T
fus
where solid is the solid density and liquid (Tt) is the liquid density at the triple point, which is calculated from an EoS. Needless to say that the lack of reliable experimental data for most of the solutes extracted from vegetable matrices forces the application of correlations and estimation methods. The latter, of course, inevitably leads to uncertainties in the values obtained. The uncertainties in the values of the parameters of the pure components can seriously inuence the quality of SFE predictions. Sovova et al. (2001a) show on the example of the triolein+CO2 binary that the uncertainties in the values of the critical parameters might have a dramatic effect on the phase behaviour calculations and on the predicted extent of the VL region. Thus, applying some of the estimations of triolein critical parameters, the system was erroneously predicted to be homogeneous at very low values of the pressure. However, it should be underlined that to perform a detailed analysis of the inuence of the thermophysical properties uncertainties on the phase behaviour predictions and calculations of a solute+SC solvent binary is a very complex task and must be explored from many different angles.
4.4. Computational techniques to solve the equilibrium relations
(20)
The vapour pressure of the hypothetical liquid is obtained using the Abrams-Massaldi-Prausnitz equation developed for liquids (Abrams et al. 1974), and the entropy of fusion is estimated applying a group contribution method. Coutsikos et al. (2003) underline that experimental values for the entropy of fusion for most of the compounds are not available and reliable predictions of these values are extremely difcult and the few available correlations are cumbersome to use (e.g., Chickos et al. 1990, 1991, Dannenfelser and Yalkowsky 1996). Thus, the authors advocate a group contribution method to predict values for the entropy of fusion
The third vital element of a TMF comprises methods, algorithms, and numerical routines to model the complex phase behaviour of the solid+SCF (+entrainer) systems solve the equilibrium relations and calculate the solubility. Fornari et al. (2010) point out that correlating the solubility even for the simplest cases can be a very challenging task as the weakness of phase equilibrium predictions using an EoS are resulting not only from the weakness of the equation itself but also from the computational techniques applied. Xu et al. (2000) underline that when calculating the solubility of a solid at new conditions using a particular EoS model, there are two computational pitfalls that can be encountered in the calculation of solid-uid equilibrium:
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(i) Solid solubilities in SCFs are usually computed by locating a mole fraction, which satises the equi-fugacity equation relating the solute fugacity in the SCF, as predicted by the EoS, and the fugacity of the pure solid [see Eq. (5)]. However, at certain values of temperature, pressure, and kij, there can exist multiple solutions to the equi-fugacity condition. A common method for solving the equi-fugacity equation is successive substitution or some similar approach, using some small value of the solid solubility in the uid phase as the initial guess. In general, this strategy will only nd the smallest solubility root and may miss any larger values, if present, that satisfy the equi-fugacity equation. Thus, what is needed is a completely reliable method to determine all the roots to the equi-fugacity equation. (ii) Equi-fugacity is a necessary but not sufcient condition for stable solid-uid equilibrium. Solutions to the equi-fugacity equation must be tested for global thermodynamic phase stability. The problem can become even more complex, because a molecularly dissimilar system (different molecular size and force interactions) can exhibit very complex phase behaviour in the PT thermodynamic phase space. For example, the onset of liquid-liquid immiscibility can occur either as a break in the critical point locus or can outgrow from the solid-liquid-gas (SLG) locus. This outgrowth of the liquidliquid-gas (LLG) behaviour changes the nature of the SLG locus from a continuous one to one of two branches (with different composition of the liquid phases), and is accompanied by the formation of a quadruple point (solid-liquid-liquidgas, SLLG), from which four three phase loci originate. As molecular differences between the pure components become more pronounced, and the melting temperature of the heavier component is higher than the critical temperature of the solvent, the l = g critical point locus becomes discontinuous. Further molecular dissimilarities will cause the pure component phase equilibria in the PT space to draw further apart and the LLG will be replaced by two separate liquid-vapour regions, and the two disconnected SLG loci, terminating at an upper critical end point and at a lower critical end point, respectively, will have markedly different compositions. The PT diagram of the latter phase behaviour is usually referred to as typical for a solid+solute binary (Garcia and Luks 1999, Labadie et al. 2000). Moreover, in the presence of the solvent, the melting curve of the solute can be depressed, lowering its melting point. There are cases known of up to 70C depression of the melting point of a solute (Lemert and Johnston 1989). If this fact is not taken into consideration, and particularly when there is no optical view cell to observe the sample, then there is a strong possibility to mistakenly accept and report the experimental data as solid-uid equilibrium, while in reality it is vapour-liquid, and there is no solid present. Furthermore, for solid+SCF binaries, for which the difference between the melting temperature of the solute is not much higher than the critical temperature of the solvent CO2 (304.2 K), any of the PT diagrams discussed above is feasible
and the possibility to mistakenly interpret the solubility data measured is even stronger. For example, the solubility measurements for naphthalene (melting temperature 353.65 K) and biphenyl (melting temperature 344.15 K) in SC-CO2 were initially reported as representing solid-uid equilibrium because it was not realised that the experiments were carried out at temperatures in the vapour-liquid region (at temperatures above the upper critical end point). It was only later acknowledged that these measurements were actually representing the composition of a vapour phase in equilibrium with a liquid and that there was no solid present (McHugh and Paulaitis 1980, Xu et al. 2000). Thus, to have a viable and detailed description of the phase behaviour of a solid+SCF system in the thermodynamic phase space, and to correlate reliably the solid solubility, in addition to solute physical properties and a thermodynamic model, a variety of robust, effective, and efcient ash routines (SLG, LLG, LG, etc.), algorithms, and numerical procedures are required. When three phases, namely solid, liquid, and vapour, are in equilibrium, the following equations must be satised: T S= T L = T V PS = PL = PV f = f =f
S i L i V i
(22) (23) i = 1, 2 (24)
The liquid-vapour equilibrium conditions for the CO2+solid solute binary system, applying the above equations, are
L V 1 x1 = 1 y1 L V 2 x2 = 2 y2
(25) (26)
where the subscript 1 corresponds to SC-CO2 and subscript 2 to the solid solute. Furthermore, it is assumed that the solid phase is pure solute, and hence for the solid-liquid equilibrium the following holds:
L S = 2 x2 2
(27)
The following constraints also apply for the liquid and vapour phases:
x =1
i i =1
(28)
y =1
i i =1
(28a)
The fugacity coefcient of the solid solute is calculated according to (Prausnitz et al. 1999):
PSL ln S = ln 2 + 2
H TP 1 1 VTP - + (P -PTP ) R TTP T RT
(29)
Equation (29) relates the fugacity coefcient of the solid solute to the fugacity coefcient of the pure solute in the
PSL subcooled liquid phase at temperature T and pressure P ( 2 ), and it is assumed implicitly that there are no solid-solid phase transitions and that the solid phase is incompressible. The above system of equations is strongly non-linear and may have several solutions. The non-uniqueness is a particular problem and is a result of the mathematical presence of local minima and maxima in the Gibbs energy surface. This, in turn, relates to convergence to a local rather than global minimum, and to the impossibility to distinguish among thermodynamically stable and unstable equilibrium states. As pointed out previously, the equality of chemical potentials represents a necessary but not a sufcient condition for equilibrium, and hence a stability analysis routine and a phase identication procedure must be employed at each step to nd with guarantee the phase conguration with the minimum Gibbs energy, which is particularly important in regions of the thermodynamic phase space where the EoS has multiple roots as is the case around the SLG locus. Somewhat surprisingly, the practice of searching for all roots to the equi-fugacity condition and testing for phase stability appears not to be widespread among those who measure, model, and compute high-pressure solid-uid equilibria (Xu et al. 2000). Still, the need to test for stability and its inuence on phase diagrams has been an area of interest to some researchers. We will like to mention particularly the works of Xu et al. (2000) and Scurto et al. (2003) who described a new method for reliably computing solid-uid equilibrium without and with co-solvents at constant temperature and pressure based on interval analysis, in particular, an interval Newton/generalised bisection algorithm; Marcilla et al. (1997), who focused on low-pressure solid-liquid equilibrium and the need for stability analysis and were able to carefully map out the full phase diagrams for their selected systems, as well as the contributions by Corazza et al. (2004) and Sovova et al. (2007a). However, as pointed out by Fornari et al. (2010), it is only fair to say that some of the above-mentioned researchers applied local, initialisation-dependent solvers, which in general neither provide guarantee that all equi-fugacity roots are found nor that phase stability analysis is done correctly, while Xu et al. (2000) and Scurto et al. (2003) were the rst to present a technique that provides a mathematical and computational guarantee that all roots to the equi-fugacity equation are enclosed and that phase stability analysis is performed correctly and thus the stable solution to the solid-uid problem is determined with certainty.
5. Mathematical models for SFE kinetics

Mathematical models that effectively describe the extraction kinetics of solid substrates in packed beds operating with SCFs are useful tools for the design and scale-up of SFE processes, with predictive models being of special interest to assess process feasibility preliminarily, and/or to validate experimental data for process scale-up (del Valle et al. 2006). Several aspects distinguish the SFE from plants from the extraction with conventional solvents. First, the external mass transfer
from plant surface to bulk uid is much faster due to the excellent transport properties of SCFs. Thus, as long as there is enough solute near the plant surface, the solution owing out of the extractor is saturated or near saturated. Second, a dry solvent such as pure carbon dioxide gradually removes from the plant the moisture remaining there after drying usually in the concentration of 810 wt.%. The permeability of an overdried plant tissue is extremely low, the diffusion of a solute through the plant surface is very slow, and thus it is easy to distinguish between the initial period of fast extraction of easily accessible solute and the nal period with much slower extraction. Brunner (1994) explains the sensitivity of cell walls to the moisture by the properties of an elementary membrane. The membrane consists, according to Danielli, of three bimolecular lipid layers with pores that can be passed by water and by lipids. If there is not enough water in the system, the pores are closed and the membrane becomes impermeable. Third, the low kinematic viscosity makes SCFs prone to natural convection induced by even small density gradients related to the differences in concentration (due to the extraction) or in temperature (due to the heat transfer through the wall of extractor). As a result, the ow pattern could differ signicantly from the plug ow, which ensures the best extractor performance. The most easily available experimental data on extraction kinetics are the extraction curves, the dependence of extraction yield on either extraction time, or the solvent-to-feed ratio, directly proportional to the time. These curves are compared with a mathematical model to adjust its parameters and to check whether it corresponds to the reality. To distinguish better between different models, del Valle et al. (2000b) recommend a multiobjective tting strategy when both experimental extraction curves and experimental residual concentration proles in solid phase should be tted by the models. A phenomenological model for SFE from plant materials is a mathematical description of extraction kinetics in the form of equation or a set of equations dening the solute concentrations in the extractor in dependence on extraction time and spatial coordinates. The extraction yield is then calculated from the outlet concentration. The models are usually not predictive; some of their parameters can be estimated according to literature correlations but at least one parameter is adjusted to t experimental data. The extraction process comprises phase equilibrium or adsorption/desorption kinetics, diffusion through the plant particles to their surface, external mass transfer from particle surface to the bulk uid, and displacement with the owing solvent. Different types of models are obtained combining different expressions for these steps. Probably the most thorough overview was published by del Valle and de la Fuente (2006), who focus on the extraction of vegetable oils but also mention the models for other types of solutes. The paper also contains a valuable survey of published correlations used to estimate some model parameters: binary diffusion coefcient of extracted substance in supercritical solvent, external mass transfer coefcient, coefcient of axial dispersion, effective internal diffusion coefcient, and also the relationships for
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the extract solubility in SCF and/or for its adsorption isotherm, when it is adsorbed on vegetable matrix. del Valle and de la Fuente (2006) started with a complex model and showed different possibilities for its simplication. Al-Jabari (2002) regarded the models as sets of blocks describing individual extraction steps; one or more blocks could be deleted when the corresponding step was marginal under given conditions. In the present paper, we follow the scenario advocated by Al-Jabari (2002) and judge on the importance of individual steps according to their characteristic times. Where possible, the relationships are presented in dimensionless form to facilitate comparison of the results from the papers using different notation.
5.1. Mass balance for solute
c + = c* cs+
( )
(34)
where cs is the local concentration within the particles and the superscript * denotes equilibrium. The solid phase concentration at particle surface, cs+ , is related through an internal mass transfer relationship to the average particle concentration. For example, the mass balance for a spherical particle of radius R and effective internal diffusion coefcient De is cs 3De cs = t R r =
r=R
J 1-
(35)
The basis for phenomenological SFE models is a differential mass balance equation for the solute in the packed bed (del Valle and de la Fuente 2006). On the assumption of plug ow, the mass balance equation for the uid phase is c c + u = J , c(h = 0) = 0, t h c(t = 0) = c0 (30)
where r is the radial co-ordinate (Esquvel et al. 1999, del Valle et al. 2000b). The initial concentrations at t = 0 when the outlet valve opens and the solution begins owing out of the extractor are related to the content of the solute in the plant put into the extractor, cu (kg m-3): cu -cs 0 = c0 . 1- (36)
where is the free void of extraction bed, c is the uid phase concentration (kg m-3), t is the extraction time, u is the interstitial velocity, h is the axial co-ordinate, J is the mass transfer rate per unit volume of bed, and the subscript 0 denotes the state at t = 0. The mass balance equation for the solute in the solid phase is
(1-)
cs = -J , cs (t = 0) = cs 0 t
(31)
where cs is the average solid phase concentration (kg m-3). Time-dependent concentration proles for uid and solid phase are obtained by integration of these equations. The extraction yield is calculated from the uid phase concentration at the extractor outlet: e= q c (h = H ) dt , f 0
t
e(t = 0) = 0
(32)
where e is the extraction yield in terms of mass of extract over the mass of plant inserted into extractor, q is the specic ow rate in terms of the solvent mass ow rate over the mass of plant, f is the solvent density, and H is the height of the packed bed. Eqs. (30) and (31) contain the mass transfer rate per unit volume of the extractor, J, which is given by the equation for external mass transfer: J = k f a (c+-c) (33)
They are usually chosen either on the assumption that no mass transfer has taken place until t = 0, it is c0 = 0 and cs0 = cu, or, on the opposite, on the assumption that phase equilibrium has been established during the static extraction before the solvent starts owing out of the extractor. The real initial concentrations may be between these limits and depend on the rate of mass transfer during the period of static extraction before t = 0. The models for the mass transfer during static extraction were published by Al-Jabari (2002) and Steffani et al. (2006). The content of solute in the plant loaded into the extractor is primarily expressed in mass fraction xu, (kg solute) (kg plant)-1, which can be converted to units (kg solute)(kg matrix)-1, where matrix is the insoluble part of the plant. Similarly, the contents of solute in both phases in the extractor are often expressed in mass ratio y (kg solute)(kg solvent)-1 and either mass fraction or mass ratio x, x expressed as (kg solute)(kg plant)-1 or (kg solute)(kg matrix)-1, respectively. The conversion between the volume-related and mass-related quantities is via densities f and s, where s is the density of plant particles calculated as either mass of plant or the mass of matrix over the volume of plant: c = f y, cs = s x, cs = s x . (37)
where the superscript+indicates the surface of a plant particle, kf is the uid phase (external) mass transfer coefcient, and a is the specic surface area. The concentrations at the particle surface are usually assumed to satisfy an equilibrium relationship:
(The solute, the volume of solid phase, and also the specic ow rate are related to the mass of matrix when the initial content of solute in the plant is high and thus the mass of the plant varies considerably during the extraction.) The alternative form of the model equations expressed in y and x is y y f + u = J , t h y(h = 0) = 0, y(t = 0) = y0 (30a)
110
(1-) s
t
x = -J , t
x ( t = 0 ) = x0
(31a)
e = q yout dt , e (t =0) = 0
0
(32a) (33a) (34a) (35a)
J = kf a f ( y+-y) y+ = y*(x+) x 3De x = t R r r = R xu -x0 = s (1-) f y0 = y0 .
(36a)
5.2. Extraction steps and their characteristic times
The value of Dax for SFE from plants is usually estimated from literature correlations for Peclet number, such as those developed by Tan and Liou (1989), Catchpole et al. (1996b), Funazukuri et al. (1998), or Yu et al. (1999). It seems, however, that these correlations based on the data measured without mass transfer may not be always valid in the situation of mass transfer in the extractor because the mass transfer causes concentration gradients leading to density gradients, which can invoke or suppress mixing, as mentioned below in Section 5.2.3. Reis-Vasco et al. (2000) extracted with CO2 the essential oil from leaves and observed that the axial dispersion coefcient was by one order of magnitude larger than according to the correlations and still the effect of axial dispersion on extraction kinetics was quite small. On the other hand, Zwiefelhofer and Brunner (1993), who extracted theobromine from cocoa shells, found a stronger dependence of the coefcient of axial dispersion on Reynolds number than according to the correlations. Another form of the uid phase mass balance frequently used for short (small) extractors is the lumped parameter model: dc c + = J , dt tr c(t = 0) = c0. (30c)
For any ow pattern, the characteristic time of washing out is equal to the mean residence time, tr = H/u. The course of washing out of a solute from the extractor is, however, not only a function of the dimensionless extraction time = t/tr but is also closely related to the ow pattern, as shown in Figure 3. Plug ow is an idealisation. In reality, axial dispersion is always present in the extractor, at least the dispersion by molecular diffusion and small-scale mixing due to the ow between the particles. The mass balance for the uid phase with the coefcient of axial dispersion Dax, combined with the Danckwerts boundary conditions, is
5.2.1. Washing out (uid displacement)
c c 2c + u -Dax 2 = J , h h t uc-Dax c =0 h for h = 0, (30b)
c = 0 for h = H. h
1.2 1.0 0.8
0.6 0.4 0.2 0 0 1 , 2 3
Figure 3 The effect of ow pattern on washing out of the solute from the extractor: () plug ow, ( + + ) ideal mixer.
Mathematically, this model is identical to the model for continuous stirred tank extractor (ideal mixer). The axial mixing can also be expressed by a series of n ideal mixers into which the extractor is divided along its height (Clavier et al. 1995, Reverchon 1996, Sovova 2005). The model is identical to the lumped parameter model for n = 1 and approaches the model with plug ow for a high number of mixers. Another ow pattern was used in a model for extractor divided on its cross section into zones with parallel plug ows of different rates. When the extractor is scaled-up, attention should be paid to ow patterns because the ow in the packed vessels of larger diameter becomes less homogeneous. Brunner (1994) showed that the local degree of extraction depends also on the radial coordinate of extractor. Particularly at small ow velocities, the local velocity and mass transfer are higher near the wall and thus the residual concentration in the particles is higher close to the axis of the extractor. Brunner (1994) suggests using the model with axial dispersion separately for the centre and the rim, with the amount of solvent for each section as an additional parameter, to simulate the radial distribution. A similar solution with the extractor divided into up to six parallel sections with plug ow of different ow rates was proposed by Sovova et al. (1994a) to t experimental extraction curves affected by natural convection in the extractor where the SC-CO2 dissolving vegetable oil owed from the bottom to the top. When del Valle et al. (2004a) extracted oil from milled seeds in a laboratory-scale extractor of 20 mm inner diameter and in a pilot extractor with a sample holder of 90 mm inner diameter, they found that the plug ow pattern was adequate for the smaller extractor (the axial dispersion was too low to affect the extraction rate), while the simulation of extraction rate in the larger extractor required dividing the extractor into inner and outer
e/x, g/g
111
zones of different ow rates. A review of the literature on the scale-up of pressurised uid extractors was recently published by Pronyk and Mazza (2009). Catchpole et al. (1996a) investigated the effect of extractor geometry on the extraction rate, comparing the extraction curves measured in the standard extractor with axial ow and in an extractor with radial horizontal ow through the bed of particles. When the extraction was controlled by external mass transfer, the extraction with the horizontal solvent ow was much slower than with the axial ow. The residual oil content in the particles was signicantly higher at the bottom than at the top of the bed, indicating that the bottom was bypassed.
5.2.2. Phase equilibrium With respect to the extraction from plants, it is necessary to mention that phase equilibrium, in addition to its dependence on pressure and temperature, is often affected also by the solute interaction with the plant matrix, particularly when the content of the solute in the plant is low a few weight per cent or less. The equilibrium uid phase concentration then decreases during the extraction, as sketched in Figure 4. The solubility, csat, as a characteristic of solute-solvent equilibrium can be applied particularly in the extraction of oils from seeds where the initial content of solute is expressed in tens of per cent. A widely accepted correlation for the solubility of common vegetable oils composed mostly of C18 fatty acids in dense CO2 was published by del Valle and Aguilera (1988):
et al. (1986) proved experimentally that the uid phase concentration of canola oil extracted from seed akes with SC-CO2 was constant and in agreement with Eq. (38) in the range of initial oil content, 0.20.7 g (g oil-free seed)-1. However, a decrease of equilibrium oil concentration was described in other works after the oil content in seeds decreased below approximately 25% (Bulley et al. 1984) or 15% (King et al. 1987), as depicted in the review of del Valle and de la Fuente (2006). This phenomenon was observed also by Perrut et al. (1997) who extracted sunower seed oil. They proposed a simple equilibrium relationship combining the oil solubility ysat for oil content in seed higher than a transition value xt and a linear equilibrium corresponding to oil-matrix interaction for lower oil content in seed, with a mass-related partition coefcient Km: y* = ysat for x* > xt, y* = Kmx for x xt, Kmxt < ysat (40)
Equation (40) can be readily converted to the relationship of volumetric concentrations c, cs. The more general Eq. (40) is reduced to Eq. (39) when the transition concentration xt is set to zero. The most frequently used relationship in the case of solutematrix interaction is a linear sorption isotherm with a constant partition coefcient K: c*= Kcs or y* = K m x, K m = K s f . (41)
csat =
10.742 f
18708 2186840 exp -26.810+ T T2
(38)
where T is the temperature in kelvins and both csat and f are in kg m-3. The equation is valid for pressures from 15.2 to 89.2 MPa, temperatures from 20C to 80C, and oil solubility below 100 kg m-3. If there is no solute-matrix interaction, the equilibrium uid phase concentration remains constant as long as there is still any solute in the solid phase: c* = csat for cs* > 0, y* = ysat for x* > 0, c* = 0 for cs* = 0, or y* = 0 for x* = 0. (39)
More complicated equilibrium relationships in the models for SFE are different adsorption isotherms such as Langmuir isotherm applied by Clavier et al. (1995) and Subra et al. (1998), Freundlich isotherm applied in the VTII model (Zwiefelhofer and Brunner 1993, Brunner 1994) and later, e.g., by Ghoreishi and Shari (2001), or the BET isotherm applied by Goto et al. (1998). Different equilibrium relationships were mutually compared (Salimi et al. 2008). Araus et al. (2009) propose that the sorption isotherms should be experimentally determined when modelling a given extraction process instead of selecting a certain equilibrium relationship in advance.
5.2.2.1. Equilibrium extraction The equilibrium extraction is an extraction with negligible mass transfer resistance. The characteristic time of equilibrium extraction is based on the assumption that the extraction rate is limited only by the initial uid phase equilibrium concentration established at t = 0 when c0 = c*(cs0). Thus, the characteristic time teq and the dimensionless time of equilibrium extraction eq are, respectively
Such discontinuous relationship could complicate numerical solution of differential equations of SFE models. Lee
c* csat c* csat
teq =
1- cs 0 tr , c0
eq =
teq tr
(42)
Particularly, for the two cases without solute-matrix interaction and with linear equilibrium:
cs ct cs
eq =
1- cu -1 csat 1- K
when c* = csat,
Figure 4 Equilibrium relationships: () no solute-matrix interaction, Eq. (10); (---) transition to linear equilibrium, Eq. (11); ( + + ) solute-matrix interaction with linear equilibrium, Eq. (12).
eq =
when c* = Kcs.
(43)
The expression eq for linear equilibrium is a reciprocal value of the dimensionless parameter introduced by Poletto and Reverchon (1996) in their parametric analysis of a model for the SFE with plug ow, internal or external mass transfer resistance, and linear equilibrium. The paper contains also the analytical solution of equilibrium extraction equations for plug ow, which is valid for both equilibrium relationships from Eq. (40). The concentration prole in the extractor is a discontinuous function of dimensionless axial co-ordinate z = h/H: c cs = = 1 for z and <1+ eq , 1+ eq c0 cs 0 c cs = = 0 else, c0 cs 0 and the extraction yield increases linearly until the extraction is complete: e = for <1+ eq , xu 1+ eq e = xu else. (45)
where is the characteristic dimension of a particle equal to its volume-to-surface ratio ( = R/3 for a spherical particle of radius R). The models for the extraction from particle surface (or from the particles with negligible internal mass transfer resistance) are obtained combining mass balance equations for both phases, Eq. (33) for the external mass transfer, and phase equilibrium relationship. As the internal mass transfer resistance is neglected, the concentration is assumed to be uniform across the particle and Eq. (34) is modied to the relationship c + = c*(cs ) . (34b)
(44)
5.2.3.1. Model for plug ow + no solute-matrix interaction Brunner (1984) introduced into the modelling of SFE
from plants a relationship valid for plug ow and no solutematrix interaction (when the equilibrium uid phase concentration equals the solubility of solute in the solvent, csat), which reads in the nomenclature of the present paper 1 z e c = 1- exp - . =1- exp - , f csat f xu 1+ eq (48)
On the other hand, the analytical solution of equilibrium extraction with linear equilibrium described by the lumped parameter model is e =1- exp xu 1+ eq (46)
(Goto et al. 1993, Al-Jabari 2002). Both extraction curves are compared in Figure 5. Evidently, the shape of the equilibrium extraction curve is determined by ow pattern in the same way as in the case of a simple washing out of a solute.
5.2.3. External mass transfer and extraction from particle surface It follows from Eqs. (30) and (33)
that the characteristic external mass transfer time and the dimensionless external resistance are, respectively: tf = = , k f a k f 1-
1.2 1.0 0.8
f =
tf tr
, k f atr
(47)
0.6 0.4 0.2 0 0 1+eq
Brunner (1984) used this relationship to describe the initial period of oil extraction from pre-pressed seed. According to Eq. (48), the extraction rate is constant and the corresponding section of extraction curve is a straight line. This equation is valid as long as all particles contain the solute. Lee et al. (1986) solved the mass balance equations numerically for both the initial period and the second extraction period, when the solute is exhausted rst at the extractor inlet and then the region free of solute extends until it reaches the extractor outlet. The model was tted to both experimental extraction curves and experimental solid phase concentration proles cs(h, t). The experiments with oil extracted from crushed seed with SC-CO2 were conducted in a wide range of ow rates and the evaluated external mass transfer coefcient was found to be directly proportional to u0.54. Although the extraction rate of oil from seed usually agrees with Eq. (48), S-shaped extraction curves were sometimes observed (Cocero and Garca 2001). This could be related to the mixing in the empty volume between the extractor and the separator. When a basket with the plant particles was placed into the extractor and a large empty space remained behind the basket in the ow direction, the outlet concentration was much lower than the oil solubility, although the residence time in the basket was sufcient to saturate the solution (Fiori 2007). This again could be explained by mixing of the saturated solution with pure solvent lling initially the empty place.
5.2.3.2. Model for plug ow + partial solute-matrix interaction Perrut et al. (1997) extracted sunower oil
e/x, g/g
, -
Figure 5 Equilibrium extraction with linear equilibrium: () plug ow, ( + + ) ideal mixer.
from seeds and observed that the slower extraction in the second period, following the rst constant rate period, was still controlled by phase equilibrium. They used therefore in the model for SFE the equilibrium relationship given by Eq. (40). The numerical solution of the model was compared
113
Table 2 CO2 extraction from plants: external mass transfer coefcients based on experimental data for different solutes, particle sizes, pressures and temperatures, and ow velocities. Solute/plant Fatty oil Fatty oil Fatty oil Fatty oil Fatty oil Fatty oil Fatty oil Essential oil Oleoresin Oleoresin Substrate Flaked canola seed Milled tomato seed Milled grape seed Milled sea buckthorn berries Milled sunower seed Milled wheat germ Crushed sunower seed Ground clove buds Milled black pepper berries Milled black pepper berries k f 105 m s-1 0.21.4 0.40.6 2.2 0.251.6 k f a 0 102 s-1 0.67 410 0.051 19 0.31 0.32 0.030.08 References Lee et al. 1986 Roy et al. 1994 Sovova et al. 1994a Stastova et al. 1996 Cocero and Garcia 2001 Lucas et al. 2007 Perrut et al. 1997 Reverchon and Marrone 1997 Sovova et al. 1995 Ferreira et al. 1999
with experimental curves, and the equilibrium parameters and kf were adjusted.
5.2.3.3. Model for plug ow + linear equilibrium Cocero and Garca (2001) adapted a model for desorption from particle surface to simulate the extraction of oil from seed with SC-CO2 modied with alcohols. The mass balance equations were integrated numerically. The analytical solution of the model equations, which evaluation however requires numerical methods, was published by Lucas et al. (2007). 5.2.3.4. Model for mixer + linear equilibrium Neglecting the accumulation term in Eq. (30c) and using the equilibrium relationship according to Eq. (41), Papamichail et al. (2000) obtained analytical solution of the ordinary differential equations (in the present nomenclature):
cout =
e Kcu exp , =1- exp 1+ f eq 1+ f xu eq 1+ f
(49)
5.2.3.5. Model for mixer + partial solute-matrix interaction Moreover, Papamichail et al. (2000) solved the SFE
model for the conditions of negligible internal mass resistance, lumped parameters, and the equilibrium relationship given by Eq. (40). The accumulation term in mass balance for the uid phase, Eq. (30c), was again neglected to obtain the approximate analytical solution: yout e y 1 , = sat for t = 1+ f ( xu -xt ) ( ysat ), = ysat 1+ f xu xu 1+ f
extraction curves measured once at a given ow rate and once at a very low ow rate, when the solution at the extractor outlet is saturated. Several results of kf evaluation from experimental extraction curves are shown in Table 2. The kf values are usually of the order of magnitude 10-6 m s-1, the volumetric mass transfer coefcient is not far from 1 min-1, and the characteristic time of external mass transfer in SC-CO2, tf , is usually close to 1 min or even less. It is a common practice to use Eq. (48) to evaluate kf via f . Nevertheless, it is evident from Eqs. (48)(50) that the effect of external mass transfer resistance on the outlet concentration depends on the ow pattern, as illustrated also in Figure 6 and discussed in the literature (Sovova 2005). Thus, Eq. (48) should be used to evaluate kf only when the ow pattern is close to plug ow. The lower values of kf a obtained by Ferreira et al. (1999) are based on experiments in a horizontal extractor where the ow pattern was most probably different, as indicated by the results on SFE in a horizontal extractor published by Catchpole et al. (1996a). Channelling is an exception from the rule that the characteristic time of external mass transfer in the SFE from plants is only a few minutes or even tenths of minutes. When the particles forming the extraction bed stick closely together, the solvent breaks several channels in the bed and passes through them with a high velocity. As the specic interfacial
1.2
1.0 0.8 cout/cO, 0.6 0.4 0.2 0 0 1 f, 2 3
K ( - t ) xK yout = t m exp - m , 1+ f 1+ f K ( - t ) x e =1- t exp - m for > t . xu xu 1+ f
(50)
where is the solvent-to-matrix mass ratio in the extraction bed, = f /[(1-)s]. The models for SFE from particle surface enable, among others, calculation of kf from experimental extraction curves. The initial y(h = H)/ysat or c(h = H)/csat ratio can be determined experimentally from initial slopes of
Figure 6 Extraction from particle surface: the dependence of outlet concentration on dimensionless external mass transfer resistance: () plug ow, ( + + ) ideal mixer.
114
area is extremely small, the external volumetric mass transfer coefcient kf a decreases and tf increases by several orders of magnitude against usual values. So it was for example in the extraction of essential oil from sticky particles in a large-scale extractor (Berna et al. 2000). The external mass transfer coefcient in packed beds was correlated with the physical properties of solute and solvent, ow velocity, and particle size d in terms of Sherwood, Reynolds, and Schmidt numbers. The most frequently used correlations to estimate kf in SFE models are listed in Table 3 together with references to some of their applications; more extensive reviews of kf correlations together with ranges of their validity are offered by del Valle and de la Fuente (2006) and particularly by Puiggene et al. (1997). The last lines of Table 3 indicate the correlations that include also the Grashoff number, Gr, which is proportional to the density differences in the uid phase which induce natural convection. The natural (free) convection can enter the models for SFE either by changing ow pattern, as mentioned above in Section 5.2.1, or by changing kf as proposed in a series of papers by Stuber et al. (1996), Puigenne et al. (1997), and Germain et al. (2005). In the calculation of Sherwood number, the term containing Gr is either added to the term for the forced convection in the case of gravity assisted mass transfer (usually solvent downow) or subtracted from it in the case of gravity opposed mass transfer (usually solvent up-ow). The numbers Sh and Sc include the binary diffusion coefcient of a solute in supercritical solvent, D. Although D depends on pressure, temperature, and chemical composition, its value does not vary substantially under the conditions of SFE. Its order of magnitude is usually 10-9 m2 s-1 or close to this value. For example, D of essential oils in CO2 under pressure of 910 MPa and at temperature 40C was found in the range 110-8210-8 m2 s-1, and D of fatty oils in CO2 at 2830 MPa and 40C was 310-9 m2 s-1 (Germain et al. 2005). Typical kf values under the conditions of SFE from plants, calculated from the correlations, are then of the order of magnitude 10-6 or 10-5 m s-1.
5.2.4. Internal and overall mass transfer
5.2.4.1. Effective diffusivity According to Ficks second law, the equation for symmetrical diffusion in a spherical particle of radius R is
c cs De 2 cs cs = 0 for r = 0, J = -De a s = r , r t r 2 r r r
(51)
r =R
Bartle et al. (1990) simulated the SFE controlled by internal diffusion using this equation with initial and boundary conditions cs = cu for t = 0, cs = 0 for r = R. The solution was taken from an analogical case of heat transfer from a sphere: e xu =1- x xu =1- cs cu , D t e 6 1 =1- 2 2 exp -n2 2 e2 xu n =1 n R (52)
The model is therefore called the hot ball model. The higher terms of the innite series become negligible after a short time and the extraction curve is then D t e 6 =1- 2 exp - 2 e2 . xu R (53a)
The internal mass transfer is characterised in the models by either effective diffusion coefcient, De, or solid phase (internal) mass transfer coefcient, ks, the later one in analogy to the external mass transfer coefcient.
Table 3
Thus, the effective diffusivity can be estimated from the slope of a plot of ln(1-e/xu) against the extraction time at sufciently high extraction times. The solution of a model for mass transfer from a slab-like particle (Bartle et al. 1991b) is of a similar form as Eq. (52). The next step was made by Reverchon et al. (1993, 1994b) who adapted for the SFE of essential oils a mathematical description of heat transfer from a sphere that takes into account also the external mass transfer. No interface was assumed at particle surface as the internal diffusion was assumed to take place in the pores of a porous particle that are lled with solvent. The solution of model equations shows that the external mass transfer resistance is important only in the very beginning of the extraction and later it does not affect the extraction kinetics because it is negligible in comparison with increasing internal mass transfer resistance. In their third paper on the hot ball model, Bartle et al. (1992b) extended Eq. (52) by an expression including the solubility of solute in the solvent, respecting the fact that the uid phase concentration is limited by the solubility. It is evident, however, that the models where mass transfer and
Correlations for the external mass transfer coefcient (Sh = kf d/D, Re = udf /(), Sc = /f D). Published by Wakao and Funazkri 1978, Wakao and Kaguei 1982 Tan et al. 1988 Catchpole 1991 (PhD thesis), cited in Brunner 1994, p. 160 Puiggen et al. 1997 Lim et al. 1990 Puiggen et al. 1997 Applied by Brunner 1984, Recasens et al. 1989, Peker et al. 1992, Goto et al. 1993, 1996, Ghoreishi and Shari 2001, Skerget and Knez 2001, Vedaraman et al. 2005 Reverchon et al. 1993, 1994a, Reverchon and Sesti Osseo 1994a, Goodarznia and Eikani 1998, del Valle et al. 2004a, Perakis et al. 2005 Gaspar et al. 2003, Lu et al. 2007 del Valle et al. 2006, Araus et al. 2009 Roethe et al. 1992 Germain et al. 2005
Correlation Sh=2+1.1 Re0.6Sc1/3 Sh=0.38 Re0.83 Sc1/3 Sh=0.839 Re0.667 Sc1/3 Sh=0.206 Re0.8Sc1/3 Sh=Sh(Re, Sc, Gr) Sh=Sh(Re, Sc, Gr)
115
phase equilibrium are expressed independently, such as those discussed below in Sections 5.35.6, correspond better to the situation where both steps control the extraction kinetics.
5.2.4.2. Mass transfer coefcient The internal mass transfer rate is often approximated by a function of the average solid phase concentration:
5.2.4.4. Overall mass transfer resistance and linear driving force When linear equilibrium and parabolic con-
J = ks a s x -x + = ks a cs -cs+ .
(53)
centration proles in particles are assumed, the two driving forces represented by the concentration differences between the average solid phase concentration and the solid phase concentration at particle surface, Eq. (53), and between the uid phase concentrations at particle surface and in bulk uid, Eq. (33), are combined into a linear driving force and multiplied by the combined mass transfer coefcient, kcomb, to calculate the mass transfer rate: J = kcomb a (Kcs -c), kcomb = kcomb = kf 1+ KBi 5 kf 1+ KBi 3 1 kcomb = 1 K + , k f ks (57)
The solution of Eq. (53) together with Eq. (31) and with initial and boundary conditions cs = cu for t = 0, cs+ = 0 is t t e =1- exp - , ti = , i = i xu ks tr ti (54)
for a sphere, for a slab
where ti is the characteristic time of internal mass transfer. The dimensionless internal mass transfer resistance i was used, e.g., by Poletto and Reverchon (1996) in the analysis of extraction kinetics. It can be shown that a formally identical result is obtained when a parabolic concentration prole is assumed in the particles. After the parabolic concentration prole substitution into Eq. (51) for spherical particle, into analogous equations for diffusion in a long cylindrical particle, and in a slab-like particle, and after integration of these equations with the above-mentioned initial and boundary conditions one obtains t e 2 =1- exp - , ti = xu De ti (54a)
(Recasens et al. 1989, Goto et al. 1990, Peker et al. 1992). A combined mass transfer resistance in terms of characteristic times can be introduced as tcomb = t f + K t = t + t , comb = f + s eq . 1- s f s eq (58)
where is equal to 3/5 for a sphere, 1/2 for a cylinder, and 1/3 for a slab (Catchpole et al. 1996a, Reverchon 1996). Thus, a conversion between the estimates of De and ks is possible: De ; k = 5De/R for a sphere, s ks = 3De/R for a slab of thickness 2R. ks = (55)
The internal-to-external mass transfer resistance ratio is often expressed in terms of Biot number Bi = kf R/De: Bi = 5kf /ks for a sphere, Bi = 3kf /ks for a slab of thickness 2R. (56)
It is evident from Eq. (58) that when the partition coefcient K is low, the external mass transfer resistance may affect the overall mass transfer rate more than the internal mass transfer resistance, although tf is much smaller than ts, or in other words, although the external mass transfer coefcient is considerably bigger than the internal mass transfer coefcient (Peker et al. 1992). The dependence of extraction rate on both mass transfer resistances was evident also in the extraction of theobromine from cocoa shells, where the equilibrium is described by Freundlich isotherm (Zwiefelhofer and Brunner 1993, Brunner 1994). A good approximation of extraction curves calculated with linear driving force and lumped parameter model offers Eq. (49) when comb is substituted for f: e =1- exp . eq 1+ f + s xu
(49a)
5.2.4.3. Applications The internal mass transfer was a controlling step in the extraction of caffeine with nitrous oxide from water-soaked coffee beans, where De in the pores lled with water was as high as 110-10 m2 s-1 (Brunner 1984). When essential oil is extracted with CO2 from dry plants, the mass transfer resistance is by orders of magnitude higher. Thus, the effective diffusivity of vanilla essential oil extracted from chopped beans was estimated to 310-13 m2 s-1 (Nguyen et al. 1991), essential oils from basil, marjoram, and rosemary leaves were extracted with De 1.210-132.810-13 m2 s-1 (Reverchon et al. 1993, 1994a), and De of essential oils from sage and celery aerial parts and from coriander seed was 1.410-125.110-12 m2 s-1 (Catchpole et al. 1996a).
5.3. One-stage models 5.3.1. Diffusion model 5.3.1.1. Model equations The model includes the internal diffusion in a homogeneous and usually non-porous solid, phase equilibrium at particle surface characterised by a partition coefcient, external mass transfer to bulk uid, and ow with the uid to the extractor outlet. Goodarznia and Eikani (1998) solved model equations for linear equilibrium and ow with axial dispersion, using the method of nite differences for the three independent variables: time, axial coordinate of the extractor, and radial
coordinate of spherical particles. del Valle et al. (2000b) assumed a plug ow pattern in the extractor, divided the extraction bed and the substrate particles into several discand spherical-shell-shaped volume elements, respectively, and integrated the obtained ordinary differential equations in time using a fourth-order Runge-Kutta method. This numerical solution technique was used also by Araus et al. (2009) to integrate model equations for the ow with axial dispersion.
5.3.1.2. Simplied forms The diffusion model equations are simplied using the assumption of parabolic concentration prole in the particles, enabling further combining the internal and external mass transfer resistances using the linear driving force. The concentration in the solid phase is then characterised by the average solid phase concentration and the number of independent variables is reduced to two, the time and the axial coordinate. Brunner (1994) presented the VTII model with linear driving force, Freundlich isotherm, and ow with axial dispersion. Catchpole et al. (1996a) published analytical solution of equations of the diffusion model with linear driving force and plug ow. The dimensionless uid phase concentration prole is a function of two dimensionless variables, z/comb and (t/tr-z)/(eqcomb). Its approximations are presented, too, and it is shown that the extraction curve is reduced to Eq. (54a) when the extraction is controlled solely by the internal mass transfer and thus the ow pattern does not affect the extraction rate. The model with plug ow, linear equilibrium, and neglected external mass transfer resistance was derived by Reverchon (1996) to simulate the extraction of sage; the model equations were solved using the method of characteristics or, alternatively, dividing the extractor axially into a series of mixed extractors and integrating the set of ordinary differential equations by a fourth-order Runge-Kutta method. This model with linear equilibrium, neglected external mass transfer resistance, and plug ow pattern was analysed by Poletto and Reverchon (1996) who evaluated the concentration proles and extraction curves for different values of two dimensionless parameters = 1/eq and s. They concluded that the mass transfer resistance can be neglected and equilibrium model can be used when s/eq 0.02. When s/eq 2, the mass transfer resistance prevails, the concentration proles in the extractor are at, and therefore the ow pattern has little effect on the overall extraction rate; the mathematically simpler lumped parameter model is then recommended. When s / eq is between 0.02 and 2, both equilibrium and mass transfer resistance must be taken into account. These results are easily generalised to overall mass transfer resistance when s is substituted by eqcomb. The lumped parameter model has analytical solution dependent on initial conditions. The extraction curve for zero uid phase concentration at t = 0 is
The dimensionless parameter used in the paper of Peker et al. (1992) where this analytical solution was published is equal to 1/[comb(1-)] in the present notation.
5.3.1.3. Model parameters
The adjustable model parameter is the effective internal diffusivity De, which is evaluated by tting the calculated extraction curves to experimental data. The other model parameters are usually estimated from correlations (the external mass transfer coefcient and the axial dispersion coefcient) or from an experimental extraction curve, where the initial equilibrium uid phase concentration is read from its initial slope and the content of extractable solute from its horizontal asymptote; these two values are used to estimate the partition coefcient. Alternatively, the partition coefcient is taken from the literature (Reverchon 1996, Goodarznia and Eikani 1998).
p exp ( p2 ) -p2 exp ( p1 ) e where =1- 1 xu p1 -p2 1 p1 = -b + b2 -4 B , 2 b =1+ 1 comb + B, B = 1 p2 = -b- b2 -4 B , 2 1 combeq . (59)
5.3.1.4. Applications del Valle et al. (2000b) examined two modications of the model neglecting either the external mass transfer resistance or the internal mass transfer resistance (for the extraction from particle surface). The sensitivity analysis of the effect of f and s resulted in nding that the extraction curves are almost identical for different internal and external mass transfer characteristic times as long as the combined characteristic time is constant, but the solid phase concentration prole in the axial direction is atter when the contribution of external resistance increases. Thus, a multiobjective t to both experimental extraction curves and experimental solid phase concentration proles was recommended to identify the major mass transfer resistance. The results of application of the model on the extraction of different essential oils are listed in Table 4. It is interesting to compare the different De values obtained from the same slightly scattered experimental data, in one instance assuming slab-like particles and in another spherical particles (see the rst two lines of the table). Evidently, the assumption of spherical particles is not correct when pieces of leaves or owers of size larger than about 0.5 mm are extracted. When the result calculated for inadequate particle shape is skipped, the values of De are in the range 210-13710-13 m2 s-1. The diffusion model was successfully applied also to the extraction of theobromine from cocoa seed shells (Brunner 1994) or the extraction of caffeine from water-soaked coffee beans (Peker et al. 1992). To sum up, the diffusion model is appropriate when the mass transfer resistance is mainly inside the plant particles and the equilibrium is characterised by partition coefcient. The model, however, does not t the broken extraction curves of the SFE of fatty oils (triglycerides) from seeds where the equilibrium uid phase concentration is equal to the oil solubility in the solvent, at least in the rst extraction period, while the diffusion model is based on the proportionality between the equilibrium solid and uid phase concentrations. 5.3.2. Desorption model 5.3.2.1. Model equations
The desorption model, also called DDD (desorption-dissolution-diffusion) model, is a model for porous particles with pores lled with the solvent.
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Table 4 Effective diffusion coefcients of volatile oils extracted with SC-CO2, evaluated from experimental extraction curves using the diffusion model. Herb Particle size (mm) Pressure/temperature (MPa/C) De 1012 (m2 s-1) References Source of data Reverchon 1996 Reverchon 1996 Reis-Vasco et al. 2000 Reverchon et al. 1993 Reverchon et al. 1993 Sovova et al. 1994b
Sage leaves 0.253.1 9/50 0.6a Reverchon 1996 Sage leaves 0.253.1 9/50 8.5 Araus et al. 2009 Pennyroyal leaves 0.30.7 10/50 58.2 Araus et al. 2009 Basil leaves 0.17 10/40 0.2 del Valle et al. 2000a Basil and marjoram leaves 0.17 10/40 0.2 Goodarznia and Eikani 1998 Caraway seed 0.5 910/40 0.50.7 Goodarznia and Eikani 1998 a Slab-like particles were assumed, in contrast to spherical particles in other calculations.
It consists of solute desorption on the pore walls, its internal diffusion to particle surface, external mass transfer, and displacement with bulk uid. With respect to the solute transport, there is no interface at particle surface, and therefore K = 1 is substituted into the formula for linear driving force, Eq. (57). Two mass balance equations are written for the particles, one for the pores and one for the solid matrix. Recasens et al. (1989) formulated a general model for SCF regeneration of a porous adsorbent in a packed bed of spherical particles where the solvent ows with axial dispersion. A nonlinear Langmuir-type kinetics of adsorbate desorption from the pore walls was assumed. [The Langmuir-type kinetics on particle surface was later considered by Al-Jabari (2003) in a model for SFE.] Recasens et al. (1989) derived also two simplied versions of the general model, based on linear driving force and plug ow: the model with instantaneously established equilibrium and the model with irreversible desorption, and derived their analytical solutions. These models have only two parameters, the overall mass transfer coefcient and either partition coefcient or desorption rate constant. The linear equilibrium between the solid phase and the uid lling the pores enables a reduction of two mass balances for particles to one equation. Srinivasan et al. (1990) proved that a rst-order, reversible adsorption model (containing both equilibrium constant and desorption rate constant) successfully ts the detailed experimental data on desorption of ethyl acetate from activated carbon with SC-CO2. Numerical solution of model equations is described in more details in several papers. For the ow with axial dispersion, Ghoreishi and Shari (2001) assumed the Freundlich adsorption isotherm and used the technique of orthogonal collocation on nite elements, and Meireles et al. (2009) assumed the linear equilibrium and applied the nite difference method. The lumped parameter model is usually combined with linear driving force, which leads to an analytical solution formally identical with the solution for the diffusion model, Eq. (59), where comb is given by Eq. (58) and eq by Eq. (43); however, the partition coefcient K in Eq. (43) that was written for the interface at particle surface must be substituted by Kpp for a porous particle: K pp = K 1- + K (60)
where K is the partition coefcient on the pore walls (inversed adsorption equilibrium constant) and is the porosity of the particle (Peker et al. 1992, Goto et al. 1994). When a more complex phase equilibrium relationship such as the BET isotherm applied by Goto et al. (1998) is used, the ordinary differential equations of the lumped parameter model are solved numerically.
5.3.2.2. Model parameters
The axial dispersion coefcient is calculated from literature correlations. The effective internal diffusivity De in the particles of porosity and tortuosity ltor is estimated as De = D ltor (61)
(del Valle et al. 2006). The estimation of De is even simpler when the tortuosity is assumed to be equal to 1/: De = 2D (61a)
(Goto et al. 1993, Skerget and Knez 2001, Meireles et al. 2009). The resulting internal mass transfer resistance is even smaller than the external resistance based on the external mass transfer coefcient kf calculated from literature correlations. Thus, the overall mass transfer resistance is low and the extraction kinetics is close to that of equilibrium extraction. The most important model parameter, the partition coefcient, is determined by tting the experimental extraction curves.
5.3.2.3. Applications to SFE
The model with irreversible desorption rate was tested in the study on SFE of -carotene from carrots published by Subra et al. (1998) with the conclusion that the model based on adsorption equilibrium would be more adequate. The model with adsorption equilibrium corresponds better to experimental data measured for different ow rates, is applied most frequently, and only this model will be discussed below. Goto et al. (1993) simulated the extraction of peppermint volatile oil with SC-CO2. The peppermint leaves were regarded as slabs. The process could be simulated as equilibrium extraction due to the negligible effect of mass transfer resistance. The only model parameter, the equilibrium constant of the linear equilibrium relationship, was evaluated in dependence on extraction pressure and temperature. A more general equilibrium relationship, the BET isotherm, was introduced into the model by Goto et al. (1998)
and applied on the same set of experimental data. Adjusting the equilibrium parameters, the volatile oil extraction could be simulated as desorption while only a weak solute-matrix interaction was assumed for the initial period of the extraction of cuticular wax. Meireles et al. (2009) used the desorption model with linear equilibrium and axial dispersion to simulate the extraction of vetiver oil from particles as small as 0.18 mm. The effect of mass transfer resistance was almost negligible according to the model. The experimental data, however, showed a decrease in the extraction rate after about 80% of solute had been extracted. The model ability to predict the effects of scale-up was proved by tting the partition coefcient to experimental data from a smaller extractor, prediction of extraction kinetics in a larger equipment, and comparison of the results with experimental extraction curves in this equipment. Skerget and Knez (2001) applied the desorption model to evaluate extraction curves measured for different plants: cocoa, paprika, pepper, and Silybum mariannum; the solvents used were CO2 and propane. The effect of pressure and temperature on the extraction kinetics was investigated. More details on the extraction of S. mariannum and its model can be found in the paper published by Hadolin et al. (2001). Again, the controlling factor in the model was the equilibrium. The model simulates tightly the initial sections of extraction curves but the agreement is not as good in the following section of some of the curves. Mongkholkhajornsilp et al. (2005) matched the model to experimental extraction curves of nimbin extracted from neem seeds with CO2. The seed was ground to different particle sizes ranging from 0.575 to 1.85 mm. The extraction rate decreased with increasing particle size but the model could not simulate this behaviour as long as the mass transfer resistance [based on the correlations of Wakao and Funazkri (1978) and Tan et al. (1988), and on De according to Eq. (61a)] was negligible. Instead of considering a larger internal mass transfer resistance, the authors decided to decrease the external mass transfer coefcient and developed a new correlation for kf .
5.3.2.4. Comment The porous and tortuous structure of different pre-pressed vegetable substrates was evidenced by del Valle et al. (2006). Generally, however, natural materials have cellular structure and thus diffusion across the cell walls may be slower than through the pores of a porous substrate (Roy et al. 1996a). Roethe et al. (1992) proposed a detailed model for parallel mass transfer through the pores and through the cells, each of them characterised by its own effective diffusivity. On the basis of a comparison between scanning electron microscope (SEM) images of the substrate structure and the results of Hg-porosity measurement, they drew a conclusion about the volumetric fraction of pores open for mass transfer in green coffee beans. 5.3.3. Shrinking core model 5.3.3.1. Model equations The shrinking core model assumes a sharp boundary within a porous spherical particle between extracted part and inner non-extracted part, the core. The pores in the core are lled with condensed solute up to
the boundary, where the solute dissolves in the solvent and diffuses then through the external shell to the particle surface. The core initially lls the whole particle; as the extraction proceeds, the core boundary moves to the centre. Equilibrium is assumed at the core boundary; the uid phase concentration is equal to csat. The internal mass transfer resistance is located in the shell surrounding the core and increases as the core shrinks. The complete model consists of the description of internal diffusion, external mass transfer, mass balance for uid, and mass balance for the particles, which is limited on the core. Zero concentration in the uid phase outside particles is assumed at t = 0. The model was formulated for the ow with axial dispersion and the partial differential equations were solved numerically by Crank Nicholsons method (Goto et al. 1996, Roy et al. 1996a). The equations of the model for plug ow were integrated in time using a modied Rosembrock formula after the spatial derivatives had been substituted by nite differences (Germain et al. 2005, del Valle et al. 2006).
5.3.3.2. Simplied form When some slow changes of the core radius are neglected in the equations of the model for plug ow, a quasi-steady-state analytical solution is obtained as a dependence of the core radius rc on extraction time and axial coordinate (King and Catchpole 1993, p. 184, Goto et al. 1996):
3 = c
z 1 x -z r where c = c , =1exp com 1+ eq xu R comb 1 cs 0 1- , comb = f + 5 s -1 . 1- c csat (62)
eq =
5.3.3.3. Model parameters Goto et al. (1996) analysed the effects of internal and external mass transfer resistance and of axial dispersion on extraction kinetics. As expected, the extraction is slower and occurs similarly in the whole extractor when s is large. The effect of axial dispersion is therefore observed only when the mass transfer resistance is low, as shown for s = 0.67 (parameter a in the paper equals to 15s) and for Peclet number <100. The extraction rate according to the quasi-steady state solution is higher than the rate calculated with the complete model; the agreement of both models increases with decreasing Bi. For large Bi, the sudden initial change of the concentration at the particle surface contradicts to the assumption for quasi-steady solution. The model parameters are usually obtained from the literature except for the effective internal diffusivity De, which is determined by tting the calculated extraction curves to experimental data (Goto et al. 1996). 5.3.3.4. Applications Goto et al. (1996) simulated with the model the literature data published by Brunner (1984) on the SFE of rapeseed oil from pre-pressed seeds. The values of model parameters were taken from the paper together with the data, except for Dax, which was estimated according to other literature sources and the only adjusted model parameter, De, which was found to be 0.7510-101.510-10 m2 s-1. The complete model equations were solved numerically because the
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corresponding s in the range 0.330.47 was too small for the simplied analytical solution. The shrinking core model was found suitable to describe the extraction of lipids from pre-pressed or aked seeds also by del Valle et al. (2006). The solubility of vegetable oils in CO2 at given pressure and temperature, csat or ysat, which can be obtained from a literature correlation, really ts the experimental extraction curves and gives evidence that the equilibrium is, at least in the initial extraction period, independent of the substrate. The model was used to predict De from the particle microstructure and binary diffusion coefcient D according to Eq. (60) for both new experimental data and data from the literature. The extraction kinetics was not far from the equilibrium extraction because of high values of De between 1.810-11 and 8.610-10 m2 s-1. The amount of extractable oil varied according to the technique of seed pretreatment. The agreement of predicted extraction curves with experimental ones was very good. Germain et al. (2005) simulated the extraction of oil from pre-pressed rapeseeds with the shrinking core model to examine the effect of solvent ow direction in the extractor on the extraction kinetics. The topic is related to natural convection occurring at low uid velocities, when the mass transfer could be either assisted by gravity (under solvent down-ow for solutions denser than pure solvent) or opposed by gravity (usually under solvent up-ow). They tted the model for plug ow to experimental extraction curves and evaluated the decrease in the external mass transfer coefcient when the solvent ow direction was changed to the up-ow. The decrease was from 7.410-6 to 210-6 m s-1 for the supercial velocity as small as 0.17 mm s-1 but no change was observed at the velocity 1.5 mm s-1 when kf was 1.910-5 m s-1 for both ow directions. The model was applied also to other vegetable substrates and solutes, mostly volatile oils. Roy et al. (1996a) simulated the SFE of volatile oil from freeze-dried ginger root with CO2 at 24.5 MPa and 40C. The particles of ginger were sieved into size fractions from 0.35 to 2.56 mm; the initial content of oil in the root was 3.8 wt.% and the porosity of the particles was 0.81. The parameters determined by tting the model to experimental extraction curves were De = 2.510-10 m2 s-1 and csat = 1.23 kg m-3 (ysat = 1.38 g kg-1). The authors observed that the experimental data for smaller particle size could not be simulated with this model as the nal part of extraction was much slower than predicted. Akgun et al. (2000) integrated the equations of the model for plug ow numerically to simulate the extraction of volatile oil from lavender owers frozen in liquid nitrogen before being crushed. The agreement of experimental extraction curves and the curves calculated with adjusted model parameter De = 1.210-11 m s-2 was satisfactory. Spricigo et al. (2001) used the shrinking core model to represent the nutmeg essential oil extraction with liquid CO2. The adjusted effective diffusion coefcient varied from 1.510-12 to 2.510-11 m2 s-1. An unusual form of the shrinking core model where the solute is initially present in both pores and solid part of a particle was described by Doker et al. (2004) and applied later by Salgin et al. (2006). Some model equations were probably distorted by typographical errors. The adjusted De was of the
order 10-11 to 10-10 m2 s-1 in the rst paper and 10-10 m2 s-1 or even 10-9 m2 s-1 in the second study, and thus the internal diffusion had little effect on the extraction kinetics. Steffani et al. (2006) simulated the extraction of volatile oil from the leaves of ho-sho, a tree native in East Asia, using two models: the shrinking core model and a model of porous particles where the rate of diffusion from the pore wall into the bulk pore is proportional to a kinetic parameter and no volatile oil-matrix interaction is assumed. To sum up, the shrinking core model appropriately simulates the extraction from porous substrates rich in solute, such as vegetable oils from pre-pressed seeds or essential oils lling glandular ducts of leaves or owers. The effective diffusivity is usually of the order of 10-11 to 10-10 m2 s-1 and thus ts < teq and the extraction is governed by equilibrium, except for extremely large particles where the effect of internal mass transfer prevails. Although the equilibrium in the shrinking core model is characterised by solubility, the model is applied also to the extraction of essential oils where it is known that solute-matrix interaction exists.
5.4. Models based on complex structure of plant particles 5.4.1. Broken and intact cell models Vegetable oil is extracted from seed particles obtained by milling. The SEM images of a surface of particles after the extraction shows a layer of broken cells, the cavities from where the oil was removed (Marrone et al. 1998, Reverchon and Marrone 2001). The SFE begins as the extraction from particle surface (see Section 5.2.3), it means from the mechanically damaged cells with broken walls, which may be in several layers below particle surface, and then it continues from intact cells in the particle core where the oil diffuses through low permeable cell walls and the extraction is therefore slower. The broken and intact cell (BIC) models describe this process. An important parameter of BIC models is the initial fraction of easily accessible solute, G, which is equal to the solute in broken cells over the solute in broken and intact cells and which value is therefore between 0 and 1. The observed extraction periods correspond to characteristic times of extraction steps. As the relation of characteristic times is usually tf < tr < teq and teq < ti , the extraction in the rst period of extraction from broken cells is governed by equilibrium and the controlling step in the second period is the internal mass transfer. (An exception is the extraction from extremely small particles or from the particles with low mass transfer resistance; in such case, teq > ti , the effect of internal diffusion is marginal, and a simple one-stage model should be applied.) When this mass transfer mechanism is built into a SFE model for plug ow, the extraction curves calculated using the model consist of three parts, denoted by Povh et al. (2001) as the constant extraction rate period, when all particles in the extractor contain easily accessible solute, the falling extraction rate period, when the particles near to the solvent inlet are already free of easily accessible solute which is still present near the solvent outlet, and the diffusion controlled extraction period, where the mass transfer is governed solely by internal diffusion.
The BIC models were developed gradually. Semi-empirical models (Goodrum et al. 1996, Hong et al. 1990, Yoo and Hong 1996) described extraction curves composed of two sections, the rst one given by Eq. (48) for the extraction from particle surface and the second section by Eq. (54) or (54a) for internal diffusion. Alternatively, Cygnarowicz-Provost (1996) introduced into the model an empirical mass transfer coefcient, the initial value of which is equal to kf and, in dependence on the solute content in particles, was monotonously decreasing. Lack (1985) under supervision of Prof. Marr utilised the analogy of SFE with a drying process and modied the relevant equations for drying. In the SFE model written for plug ow, J according to Eq. (33) is multiplied by a function of average solute concentration in the particles, x, which is equal to unity until the easily accessible solute is depleted and then it monotonously decreases with decreasing x. The shape of the function can be adjusted to t different experimental extraction curves; when J in the second period is directly proportional to x and when the accumulation term in the mass balance for the uid phase with plug ow pattern is neglected, the model has analytical solution. Sovova (1994) modied the term J so that it after the depletion of free oil describes the internal mass transfer, on the condition that ti >> tf and therefore cs+ can be set equal to zero, and used this analytical solution. This approximate model for SFE, more consistently described later (Stastova et al. 1996), is frequently used to evaluate model parameters from experimental extraction curves. It yields good results when applied to the SFE of vegetable oil from seeds; however, with respect to the conditions used in its derivation, it should not be applied when the solubility of the solute is high or when a solute-matrix interaction exists. Gaspar et al. (2003) derived a simple and efcient version of the BIC model for the SFE of essential oil from oregano bracts, where the easily accessible solute from disrupted glands dissolves completely before t = 0 and then the solute from intact cells diffuses to the interface with a rate derived by Bartle et al. (1991b) in the version of hot ball model for slabs. No equilibrium relationship is necessary in this model as the rst period is a simple washing out and the second part is controlled by internal diffusion. The fraction of free solute was G = 0.51, the effective diffusivity was De = 210-14 410-14 m2 s-1. Reis-Vasco et al. (2000) applied the BIC model to the extraction of essential oil from pennyroyal leaves where two kinds of trichomes contain the essential oil: peltate trichomes that are on the surface, assumed to be broken, and capitate trichomes protected by cell wall and cuticle, representing the intact cells. Extraction curves e(q) measured at different ow rates overlapped until 70% essential oil were extracted; moreover, the curves measured for different particle sizes overlapped up to this point. Thus it was assumed that the extraction of 70% of essential oil was the equilibrium extraction. The model was written for the ow with axial dispersion and for the linear equilibrium. When the easily accessible essential oil was depleted, the extraction from the capitate trichomes was controlled by internal mass transfer resistance. The only adjusted model parameter, ks, was 1.410-7 m s-1 for
average particle diameters 0.3, 0.5, and 0.7 mm. The De range, estimated from these values, is 410-12810-12 m2 s-1. In their versatile software for numerical simulation of SFE, most probably of the BIC type, Clavier et al. (1995) used the linear driving force. The equilibrium was represented by either solubility (no solute-matrix interaction) or Langmuirtype adsorption isotherm, and the uid ow was simulated by a series of mixers, allowing taking into account the length of the bed (for an extremely short laboratory extractor the number of mixers is reduced to one). To describe the mass transfer inside the particles in more detail, three mass balance equations are integrated: for the uid phase, for the region of broken cells, and for the region of intact cells. The solute from intact cells diffuses to the region of broken cells, and from broken cells to bulk uid (Sovova et al. 1994b). The mass transfer resistance in the region of broken cells can be neglected and equilibrium is established between the concentration in broken cells and the uid phase concentration at particle surface. When essential oil is extracted from seed, it is partitioned between the liquid vegetable oil in seed and the supercritical solvent (Sovova et al. 2001b). Perrut et al. (1997) observed a solute-matrix interaction in the second period of SFE of vegetable oil from seed with SC-CO2. The slope of the extraction curves was rst determined by oil solubility in CO2, and when the free oil was depleted, it decreased to a value corresponding to the equilibrium uid phase concentration of oil adsorbed on matrix. The solution owing out of the extractor was saturated in both extraction periods, as indicated by the extraction experiments, when the extraction curves e(q) measured under the conditions of different residence times of the solvent in the extractor overlapped in both periods. It seems probable that the solute-matrix interaction exists also in the SFE of vegetable oils, such as in the extraction of other solutes, at least for a part of oil initially present in the seed. A versatile BIC model could therefore incorporate the equilibrium relationship given by Eq. (40), which allows simulating the transition from the extraction of free solute to the extraction of bound solute, and includes the simpler case when the bound solute is extracted from the very beginning. Such BIC model was derived for different ow patterns, analysed, and simplied relationships for calculation of approximate extraction curves were derived (Sovova 2005). The analysis of the model for plug ow shows that the existing solute-matrix interaction practically is not visible on the shape of extraction curve when the characteristic time of its equilibrium extraction is smaller than the characteristic time of equilibrium extraction calculated on the basis of solubility. According to Eq. (43), the condition is Kcs0 > csat. Marrone et al. (1998) modied the BIC model with three mass balance equations assuming that the oil inside the intact cells is adsorbed on the matrix (with linear equilibrium), in contrast to the free oil in broken cells, and diffuses directly to the SCF. The number of adjustable parameters was reduced estimating G from SEM images of extracted particles. The free easily accessible oil was assumed to ll the surface layer of broken cells which depth was determined from the shape
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and size of oil-bearing cells, which was typically 2030 m according to the species. This approach was applied by Reverchon and Marrone (2001) to evaluate the internal mass transfer resistance from experimental data measured in their laboratory and also different sets of extraction curves available in the literature. The resulting De values were relatively high. The reason could be that when G is xed at a lower value than the real fraction of free oil is, the effective diffusivity is automatically adjusted to a value ensuring that the extraction will not be slowed down after depletion of free solute (in terms of characteristic times, tf << teq and ti << teq) and the extraction is controlled by equilibrium in both periods. This BIC model was further applied and analysed by Fiori and colleagues (Fiori 2007, Fiori et al. 2007) who found that the depth of the region with easily accessible oil is approximately two layers of cells. They also improved the accuracy of modelling, simulating simultaneous extraction from the particles of a wide size distribution (Fiori et al. 2008). Finally they developed and further applied a new model for SFE of oil from seed where, after the oil from broken cells is removed, the oil from the rst layer of intact cells diffusing through one cell wall is extracted. After its depletion, the oil from the second intact layer diffusing through two cell walls is extracted, etc. Thus the model combines the feature of BIC model and shrinking core model (Fiori et al. 2009, Fiori 2010).
5.4.2. Models for SFE of essential oils tailored to plant microstructure iovi and co-workers linked the models
for SFE of essential oils with the shape, structure, and location of secretory structures from where they are extracted and with behaviour of these structures during the extraction, studied on SEM images. Thus, a model including the mechanism of breakage of peltate glandular trichomes on the surface of leaves of Lamiaceae family plants was derived and adjusted to experimental data (iovic et al. 2005). The next extracted plants were those from Asteraceae family where the essential oil is extracted from secretory ducts and the mass transfer resistance is relatively low (iovic et al. 2007) and, in contrast, the valerian root where the secretory cells have a thick cuticularised lining and the extraction rate depends on its breakage (iovic et al. 2007a). The results for different types of secretory structures are summarised and the models are further developed in the last paper (Stamenic et al. 2008).
5.5. Models for SFE of mixtures
All extracts from plants are mixtures of many substances. When mixture components are similar, such as triglycerides in vegetable oils, the mixture can be regarded as a pseudocomponent and the above-described models can be applied directly. When, however, the major components of extract are of very different solubilities, the overall extraction curve will be composed of several extraction curves of different shapes and the rst decrease in extraction rate may correspond to the point when the more soluble component was depleted but the extraction of easily accessible less soluble components continues. Moreover, the extracted components can affect each
other, for example, when the more soluble component acts as entrainer for the less soluble component. The gradual changes in extract composition are denoted as fractionation in time. The fractionation in time was observed for example during CO2 extraction of sage essential oil consisting of monoterpenes, oxygenated monoterpenes, sesquiterpenes, and oxygenated sesquiterpenes (Reverchon et al. 1995b), while the extraction of three oxygenated monoterpenes, the major components of peppermint oil, was simultaneous (Goto et al. 1993). Also the extraction of savory oleoresin with subcritical water showed a strong fractionation in time among individual components of essential oil (Kubatova et al. 2001). One group of models for multicomponent SFE from plants includes the models that describe the extraction of each selected component or each group of components as not affected by co-extracted substances. The BIC model was applied to simulate CO2 extraction of essential oil, piperine, and lipids from black pepper seed, each component with its own model parameters (Sovova et al. 1995). Franca and Meireles (2000) used an empirical expression with different parameters for extraction curves of free fatty acids, triglycerides, and -carotene to simulate time fractionation of vegetable oil extracted from pressed palm oil bres. This approach was applied also by Martinez et al. (2003) to simulate the extraction of oleoresin from ginger rhizome, composed of monoterpenes, sesquiterpenes, and other hydrocarbons. Goto et al. (1994) proposed a modication of the lumped parameter desorption model with linear driving force, where a continuous mixture is extracted instead of one extracted substance. The concept of the continuous mixture simulates a mixture of groups of a large number of components as continuous functions of some mixture property, in this case as the Gaussian function of molecular mass. The partition coefcient dened in the paper as K = cs/c was assumed to be directly proportional to the molecular mass and the kinetics of the extraction of two groups of components was predicted. In the second group of models, the equilibrium of a mixture of extracted substances with the solvent is taken into account. The initial extraction of easily accessible extract is simulated as the equilibrium extraction based on separation factors known from the models for SFE of liquids in countercurrent columns. Shen et al. (1997), who extracted oil from rice bran with SC-CO2, recognised that the rate of extraction of minor oil components was related to the rate of extraction of major component and evaluated their separation factors towards triglycerides from the ratio of initial slopes of extraction curves. Gaspar (2002) studied the CO2 extraction of volatile oil from oregano bracts under different extraction conditions and evaluated the selectivity of individual essential oil components. Sovova et al. (2010) implemented the separation factor of -sitosterol to triglycerides into a model for the extraction of sea buckthorn oil from particle surface. Another possibility is to link the different rates of extraction of different extract components with their diffusion coefcients. Machmudah et al. (2006) applied the shrinking core model to the CO2 extraction of nutmeg oil, distinguishing between components with lower molecular weight (terpene
hydrocarbons) and components with higher molecular weight (oxygenated terpenes and myristicin), the effective diffusivity of which was adjusted to approximately 2.5 lower value than the diffusivity of the hydrocarbons, to t experimental data on overall extraction yield and on the changes in extract composition. The ability of the shrinking core model to simulate the fractionation in time was studied in detail by Tezel et al. (2000) who assumed that the components differ in both solubility and effective diffusivity. They also took into account that due to the different rates of extraction of two components, there are two shrinking cores in the spherical particles the inner core containing both condensed components and the outer core where only the slower extracted component is condensed. The faster extracted component must diffuse through the outer core before it is dissolved in the solvent lling the pores outside the outer core. Moreover, Tezel et al. (2000) adapted for the extraction of mixtures the desorption model with a Langmuir-like adsorption isotherm where several extract components compete for active sites; the components differ in both adsorption isotherm constants and effective diffusivities.
6. Conclusions
Large-scale SFE from plant materials is considered nowadays a standard process. It has extended from the rst applications extraction of avour and aroma from hops, extraction of caffeine from raw coffee beans, and the extraction of spices to other branches as, for example, the extraction of biologically active substances from medical plants and the extraction of herbicides from rice. More and more plant materials are tested for extraction with SC-CO2 in laboratories around the world. SFE with SC-CO2 modied with entrainers is nding application as a fast and easy to be automated technique for the extraction of analytes from plant matrix prior to their chromatographic analysis. As the SFE from plants is more and more widely applied in practice, its theory is often regarded as more or less complete, and its further research superuous (redundant) and marginal. The contemporary research is nding new and fascinating applications of supercritical solvents in formation of micro- and nanoparticles, in chemical and enzymatic reactions as reaction medium, in the production and treatment of polymers, and others. Nevertheless, new tasks arise with practical applications of SFE from plants, as the optimisation of operating conditions and of plant pre-treatment with the aim to increase the extraction yield, reduce the extraction time or the solvent consumption, and/or to increase the concentration of efcient substances in the extract or maintain their level constant extract despite of changing quality of the extracted plant material. While in other chemical engineering branches with longer history, the engineers and technicians can solve such tasks using a set of equations and formulae that are based on a comprehensive theory, supercritical extraction from plants still lacks such widely accepted theory and recommended mathematical relationships. Moreover, there is a lack of such theory in the extraction of valuable substances from plant
materials generally, even for the extraction with liquid solvents at atmospheric pressure despite of its long tradition. As shown in the present review, extensive experimental and theoretical research has been carried out by tremendous number of researchers and a large amount of knowledge on supercritical extraction from plants has been collected. It is, thus, probably time to synthesise the knowledge and formulate practically applicable mathematical relationships describing the process generally. Phase equilibrium has been measured for many substances and can be understood with the help of thermodynamic modelling. There are correlations enabling estimation of the mass transfer resistance in SCF, and the internal mass transfer resistance has been evaluated from the course of extraction. Attention is being paid also to the effect of ow pattern on the extraction rate, which is important especially in the scale-up process. However, the most intriguing features concerning the extract composition, such as mutual interactions of the components of extracted mixtures or solute-to-matrix interaction in dependence on extraction conditions, have not yet been studied sufciently to be included into the theory to make it complete. Although the representation of botanical materials by mathematical relationships applicable in engineering practice requires severe simplications, the authors believe that the chemical engineering approach to the extraction of plants will enable its rational optimisation and development of new efcient procedures and new products of high quality.
Acknowledgements
Financial support by the Ministry of Education, Youth and Sports of the Czech Republic (projects 2B06024 and 2B06049) is gratefully acknowledged.
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Helena Sovov is a scientist in the eld of supercritical uid extraction at the Institute of Chemical Process Fundamentals (ICPF) in Prague, CR. Her primary research interest is in the modelling and simulation of kinetics of extractions. She studied at the Institute of Chemical Technology in Prague where she received a Masters degree in 1970, and at the ICPF where she received a CSc (PhD) degree in chemical engineering in 1975. She is a member of the working party of High Pressure Technology of the European Federation of Chemical Engineering.
Roumiana P. Stateva is a professor at the Institute of Chemical Engineering, Bulgarian Academy of Sciences. She has an MSc in chemical cybernetics and a PhD in chemical engineering from the Mendeleev University of Chemical Technology, Moscow, Russia. Her research is devoted to the modelling and efcient calculation of phase equilibria of complex systems, and to the development of original methods for the prediction of properties from the chemical structure of pure substances.

Supercritical Fluid Extraction From Vegetable Materials - Sovova

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Rev Chem Eng 27 (2011): 79156 2011 by Walter de Gruyter Berlin Boston. DOI 10.1515/REVCE.2011.

Supercritical uid extraction from vegetable materials

Helena Sovov1,* and Roumiana P. Stateva2

H. Sovov and R.P. Stateva: SFE from vegetable materials

(sc) Pressure (l) C (s) T Temperature (g)

2. SFE from plants

Figure 2 Simplied scheme of the extraction equipment with CO2 recycle.

H. Sovov and R.P. Stateva: SFE from vegetable materials

H. Sovov and R.P. Stateva: SFE from vegetable materials

H. Sovov and R.P. Stateva: SFE from vegetable materials

3. Plants and extracts

4. Thermodynamic modelling of systems vegetable solute + SC-CO2 + entrainer

Plants extracted with pure or modied carbon dioxide.

H. Sovov and R.P. Stateva: SFE from vegetable materials

Birch (Betula pendula) leaves Black caraway (Bunium persicum) fruit

Blessed thistle (Cnicus benedictus) leaves, owering tops

Cardamom (Elettaria cardamomum) seed

H. Sovov and R.P. Stateva: SFE from vegetable materials

Cereals Chamomile (Matricaria chamomilla syn. Chamomilla recutita) owers

Cherry (Prunus avium) seed, pomace

H. Sovov and R.P. Stateva: SFE from vegetable materials

Taiwan tangerine (Citrus depressa) peel

Coconut palm (Cocos nucifera) copra, meal

Coffee (Coffea) beans

Cordia verbenacea leaves Coriander (Coriandrum sativum) fruit, seed

Cork oak (Quercus suber) bark

Cratoxylum prunifolium leaves Crocus, autumn (Colchicum autumnale) seed

H. Sovov and R.P. Stateva: SFE from vegetable materials

Douglas-r (Pseudotsuga menziesii) bark Dragonhead (Dracocephalum moldavica) herb

McDonald et al. 1983 Hawthorne et al. 1993, Kakasy et al. 2006

Espinheira santa (Maytenus aquifolium, M. ilicifolia) leaves

H. Sovov and R.P. Stateva: SFE from vegetable materials

Frankincense (Boswellia thurifera, B. carterii) resin

Ginkgo, maidenhair tree (Ginkgo biloba) leaves

Ginseng (Panax ginseng) root hair, leaves, seed

Terpene trilactones ginkgolides, bilobalide; avonoids Oil, ginsenosides; saponins

Grape (Vitis vinifera) seed, pulp, skin

Oleoresin Resveratrol, piceid, emodin, physcion Volatile oil, antioxidants

H. Sovov and R.P. Stateva: SFE from vegetable materials

Kava (Piper methysticum) herb, stems, root

Lavender (Lavandula intermedia, L. stoechas, L. augustifolia) owers

H. Sovov and R.P. Stateva: SFE from vegetable materials

Maize (corn) (Zea mays) bran, germ

Marjoram (Majorana hortensis syn. Origanum majorana L.) leaves

Moso-bamboo (Phyllostachys heterocycla)

Mushrooms and fungi

Nitraria tangutorum seed Nutmeg (Myristica fragrans) nutmeg, mace

H. Sovov and R.P. Stateva: SFE from vegetable materials

Onion (Allium cepa) bulb, skin

Oleoresin, avour, sulphur, quercetin Volatile oil

Orange jasmine (Murraya paniculata) owers

Oregano, wild marjoram (Origanum vulgare, O. virens) leaves, bracts

Osage orange tree (Maclura pomifera) root bark, fruit

H. Sovov and R.P. Stateva: SFE from vegetable materials

Physic nut (Jatropha curcas) seed Pepper tree (Schinus molle)

Ragwort (Senecio inaequidens, S. cordatus)

Rain daisy (Dimorphotheca pluvialis) seed

Rape, canola (Brasica napus, B. campestris) seed

Rose of Jericho (Anastatica hierochuntica) aerial part

H. Sovov and R.P. Stateva: SFE from vegetable materials

Rosemary (Rosmarinus ofcinalis) leaves

Alkaloids Volatile oil

H. Sovov and R.P. Stateva: SFE from vegetable materials