Supercritical fluid extraction decaffeination

As one can see from Table 6.6-2 the decaffeination of coffee and tea is the largest application for supercritical fluid extraction, in terms of annual capacities and investment costs. Since the beginning of the 1970s, to the early 1990s, nearly 50% of the whole production capacity for decaffeination of coffee and tea changed to the supercritical extraction process. As the market for decaffeinated coffee is stable, no further plants have been installed within the past eight years. 

Caffeine is a naturally occurring substance found in the leaves, seeds, or fruits of more than 60 plants. These include coffee and cocoa beans, kola nuts, tea leaves, guarana (Paulinia cupana) and Paraguay tea. Thus it is present naturally in many beverages, such as coffee, tea, and cola drinks, or is added in small amounts (up to 200 ppm) in some soft drinks and in foods such as chocolate. Caffeine is obtained by solvent or supercritical fluid extraction from green coffee beans, mainly during the preparation of decaffeinated coffee. 

A significant development in supercritical fluid extraction was Zosel s patent for decaffeination between 1964 and 1981, which reported a procedure for the decaffeination of coffee beans with C02 [6-10]. Also, a number of patents of some food companies have been reported that concern the decaffeination of coffee [11]. The American Food Company, for example, has constructed an extraction vessel 7 ft in diameter and 70 ft tall for supercritical C02 decaffeination of coffee at the Houston, Texas plant. The current annual U.S. market for decaffeinated coffee is 2- 3 billion [4]. 

Extraction with supercritical CO2 is a technical process of increasing importance. It provides a mild and rapid technique for the extraction of low- or medium-polarity substances. Supercritical CO2 is used for supercritical fluid extraction (SFE) in important technical processes such as the decaffeination of coffee and the extraction of hops, as well as the extraction of naturally occurring compounds from biomaterials. As many applications are performed in the pharmaceutical, polymer, environmental and nutritional fields, direct on-line SFE-NMR would be an ideal tool to monitor the various extraction processes. 

FIGURE 17 Supercritical-fluid extraction in decaffeination process. 

Based on its ability to enhance solvating power by increasing fluid density, supercritical fluid extraction offers an attractive alternative for fractionation of fats and oils. It works by the phenomena of selective distillation and simultaneous extraction, as has been shown by many researchers [3-5]. While the use of supercritical fluids in the extraction of numerous biomaterials has been reported, its commercialization has been limited to the decaffeination of coffee and tea and to the extraction of flavors from hops and spices. The chemical complexity of most food ingredients and their tendency to react and degrade at elevated temperatures, emphasize the difficulties of supercritical solvent selection. Carbon dioxide is the preferred supercritical solvent (its properties have previously been cited [6]). 

Plants and plant extracts have been used as medicine, culinary spice, dye and general cosmetic since ancient times. Plant extracts are seen as a way of meeting the demanding requirements of the modem industry. In the past two decades, much attention has been directed to the use of near critical and supercritical carbon dioxide solvent, particularly in the food pharmaceutical and perfume industries. CO2 is an ideal solvent because it is non-toxic, non-explosive, readily available and easily removed from the extracted products. At present the major industrial-scale applications of supercritical fluid extraction (SFE) are hop extraction, decaffeination of coffee and tea, and isolation of flavours, fragrances and other components from spices, herbs and medicinal plants [1-4]. 

Fig. 3 Decaffeination of coffee beans using supercritical fluid extraction.

Supercritical fluid extraction offers several advantages over conventional extraction processes. The extraction is carried out at high pressures and then the extract is usually recovered by lowering the pressure, as the solubility is a strong function of fluid pressure. The compositions of the extracts are different from those from the liquid extraction. Supercritical fluid extraction has been well accepted for coffee decaffeination and is being applied in other food, cosmetics, and pharmaceutical applications. Supercritical carbon dioxide is an environmentally benign nonflammable fluid. 

Coffee decaffeination with carbon dioxide has been the object of a large amount of effort in research and development at the Max Planck Institute for Coal Research in Germany and at other academic and industrial laboratories in Europe and the United States. An indication of the intensity of effort applied to this process comes from a review article that lists the United States patents on decaffeination granted up to the end of 1981 (Paulaitis et al., 1983a). Several earlier patents were inadvertently omitted from that list a corrected version is given in table 10.1. Research activity on supercritical fluid extraction of stimulants from coffee, tea, and cocoa has continued, indicated by the number of United States patents granted since that review article was published some of them are listed in table 10.2. 

COMMERCIAL PROCESS. A practical example of a supercritical fluid extraction process is the decaffeination of coffee. Coffee beans are first soaked in water to make the extraction more selective and then are loaded into an extraction vessel through which supercritical CO2 is circulated to dissolve the caffeine. In a separate scrubbing vessel the caffeine is transferred from the CO2 to water, also at high pressure. Extraction is continued until the caffeine content of the beans, originally... 

The application of supercritical fluids, for example SCCO2, as an environmentally acceptable replacement for conventional solvents, is well documented in the industry. Based on the work of Zosel, the decaffeination of coffee and tea using SCCO2 was the first industrial use of this technology [1]. The advantages of supercritical fluids are not only useful in separation techniques, for example supercritical fluid extraction (SFE) or supercritical chromatography (SFC), their application as process solvents is well recognized [2, 3]. 

Not every pharmaceutical will eventually be comminuted by supercritical fluid nucleation, not every polymer processed for molecular weight control by supercritical fluid extraction, not every flavor concentrated by supercritical fluid extraction but some will be. Two applications listed in the table are already in commercial production, and several are in advanced pilot plant development and test market evaltiation. Hops extraction is being carried out by Pfizer, Inc. in its plant in Sydney, NE (33), and General Foods Corporation has constructed a coffee decaffeination... 

Extraction vessel used in the Maxwell House Coffee Company supercritical CO2 decaffeination plant in Houston, Texas. (From McHugh, M. and Krukonis, V. Supercritical Fluid Extraction, 2nd ed., Butterworth-Heinemann, Boston, 1994. With permission.)... 

Illustration 8.4 Coffee Decaffeination by Countercurrent Supercritical Fluid Extraction... 

Indeed, the most novel approach to decaffeinate green coffee beans, which has attained industrial application, is supercritical fluid extraction (SFE) using carbon dioxide CO Supercritical CO2 is selective for the extraction of caffeine, there is no associated waste treatment of a toxic solvent and extraction times are moderate. Moreover, supercritical CO2 coupled with ethanol or water was investigated to extract caffeine Ifom green tea leaves. 

Supercritical fluid extraction (SFE), a newly developed technique, is used for laboratorial and industrial purposes because it presents a series of advantages compared to the conventional extraction processes, especially for the extraction of thermolabile components [21,22]. It was first presented as a patent for decaffeination of coffee [23]. Since then, SFE has been used for many years as an alternative extraction method, which causes less pollution to the environment. The concept of the critical point was defined in 1822 as the highest pressure and temperature at which a pure substance could exist in vapor-liquid equilibrium. Above this point, supercritical fluid (SCF) is formed. These qualities make SCFs have higher diffiisivities and less degradation of solutes than ordinary solvents to extract active components. 

A recent development in liquid-liquid extraction has been the use of supercritical fluids as the extraction-solvent. Carbon dioxide at high pressure is the most commonly used fluid. It is used in processes for the decaffeination of coffee and tea. The solvent can be recovered from the extract solution as a gas, by reducing the pressure. Super critical extraction processes are discussed by Humphrey and Keller (1997). 

Extraction with supercritical fluids (e.g., C02) 80-300 decaffeinated coffee (tea) spices, hops colours drugs oils, lecithine and fats tobacco (nicotine) perfumes... 

Supercritical fluids (scf) are highly compressed liquids or gases. The latter already have an established role in "clean extraction (substitution of chlorinated/organic solvents) on an industrial scale (e. g. decaffeination of coffee and tea, extraction of hops, spices, etc.). The specific physical and chemical properties of scf make them particularly suitable for a variety of other applications, e. g. reactions, powder technology and impregnation. 

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