ES2265714A1 - Production of anti oxidant extracts from grape bagasse comprises centrifugation of the liquid separated from the wine waste and mixed with wash water for extraction of apolar solvents - Google Patents

Abstract

The production of anti-oxidant extracts from grape bagasse has separation of the liquid from the wine-making solid waste by pressing, filtration or centrifugation. Filtration and centrifugation of the liquid mixed with water meanwhile used to wash the solid matter, is followed by extraction of the liquid by apolar solvents. EMBODIMENT - Distillation of the organic phase separated from the aqueous phase, and dehydration of the residue, complete the process.

Description

Procedure for obtaining extracts Antioxidants from fermented and distilled grape bagasse.

Procedure for obtaining extracts Antioxidants from fermented and distilled grape bagasse. He bagasse is from the alcohol industries, and the Extracts obtained as antioxidants are used in industries Food, cosmetic and pharmaceutical.

State of the art

Protection against oxidative deterioration of various products is a concern of various industries (food, pharmaceutical, cosmetic). As antioxidants, mainly synthetic compounds such as butylated hydroxytoluene (BHT), propyl gallate or butyrohydroxyanisole (BHA) are used. On the other hand, it has been found that components of phenolic nature present in vegetables have antioxidant activity comparable to synthetic antioxidants (Moure, A., Franco, D., Sineiro, J., Dominguez, H., Nuñez, MJ and JM Lema . (2000). Evaluation of extracts from Gevuina hazelnut hulls as antioxidants. Journal of Agricultural ad Food Chemistry, 48: 3890-3897; Heinonen, M., Lehtonen, PJ, & Hopia, AL (1998). Antioxidant activity of berry and fruit wines and liquors. Journal of Agricultural and Food Chemistry, 46, 25-31; Landbo, AK & Meyer, AS (2001). Ascorbic acid improves the antioxidant activity of European grape juices by improving the juices' ability to inhibit lipid peroxidation of human LDL in vitro, International Journal of Food Science and Technology, 36, 727-735).

Natural and synthetic antioxidants they have identical mechanisms of action, but there is interest in replace synthetic antioxidants with others of natural origin, due to factors such as: i) the health implications of consumers, for the biological actions they perform; ii) the solubility of natural antioxidants in water, oil and emulsions; iii) available data on toxicological studies of synthetic antioxidants, which recommend caution in the employment of these.

Most of the natural compounds with antioxidant activity is found in plants, and many of them They are polyphenolic in nature. In several studies carried out In recent years, the antioxidant potential of Vegetables, cereals, fruits, vegetables, seeds and waste Agricultural and industrial. They also have antioxidant activity some vegetable oils, refreshing and alcoholic drinks, having given special attention to the antioxidant capacity of the polyphenolic compounds present in alcoholic beverages such as Wine, whiskey, sake, sherry and cava. They are of particular interest, such as source of antioxidants, aromatic and medicinal plants and spices, while they have also been considered as sources potential antioxidant compounds certain roots, stems, barks and leaves of trees. Finally, it should be mentioned that it has Antioxidant activity detected in the fibrous part of bran of cereals, bean pods and peanut and hazelnut shells.

The raw materials of residual origin of agro-industrial processes that can serve as sources of antioxidants deserve particular attention. In this field, some materials have been considered as raw materials such as residues of potato skin, olive pomace, alpechines, grape seeds and wine bagasse and grape skins. Studies have been conducted that include the identification of active polyphenolic compounds in apple bagasse (Lu, Y. & Foo, LY (1997). Identification and quantitation of major polyphenols in apple pomace. Food Chemistry, 59, 187-194), seeds and citrus skins (Bocco, A., Cuvelier, ME, Richard, H., & Berset, C. (1998). Antioxidant activity and phenolic composition of citrus peel and seed extracts. Journal of Agricultural and Food Chemistry, 46, 2123 -2129), carrot pulp residues (Chen, BH, & Tang, YC (1998). Processing and stability of carotenoid powder from carrot pulp waste. Journal of Agricultural and Food Chemistry, 46, 2312-2318). Processing and stability of carotenoid powder from carrot pulp waste. Journal of Agricultural and Food Chemistry, 46, 2312-2318.). Processing and stability of carotenoid powder from carrot pulp waste. Journal of Agricultural and Food Chemistry, 46, 2312-2318), coconut by-products (Azizah, AH, Nik Ruslawati, NM, & Swee Tee, T. (1999). Extraction and characterization of antioxidant from cocoa by-products. Food Chemistry , 64, 199-202), non-volatile residues of orange essential oil (Vargas-Arispuro, I., Sanz, BI, Martínez-Téllez, MA, & Primo Yúfera, E. (1998). Antioxidant activity of compounds isolated from non-volatile residue of orange essential oil, Fats and Oils, 49, 159-164), and soy molasses (Hosny, M., & Rosazza, JPN (1999). Novel isoflavone, cinnamic acid, and triterpenoid glycosides in soybean molasses, Journal of Natural Products, 62, 853-858).

Finally, it is known that in grape pulp and must (Landbo, AK & Meyer, AS (2001). Ascorbic acid improves the antioxidant activity of European grape juices by improving the juices' ability to inhibit lipid peroxidation of human LDL in vitro . International Journal of Food Science and Technology, 36, 727-735), grape seeds (Koga, T., Moro, K., Nakamori, K., Yamakoshi, J., Hosoyama, H., Kataoka, S., & Ariga, T. (1999). Increase of antioxidative potential of rat plasma by oral administration of proanthocyanidin-rich extract from grape seeds. Journal of Agricultural and Food Chemistry, 47, 1892-1897), wine (Frankel, EN, Waterhouse , AL & Teissedre, PL (1995). Principal phenolic phytochemicals in selected California wines and their antioxidant activity in inhibiting oxidation of human low-density lipoproteins. Journal of Agricultural and Food Chemistry, 43, 890-894), and waste products of winemaking (Heinonen, M., Lehtonen, PJ, & Hopia, AL (1998). Antioxidan t activity of berry and fruit wines and liquors. Journal of Agricultural and Food Chemistry, 46, 25-31; Spanos, GA, & Wrolstad, RE (1990). Influence of processing and storage on the phenolic composition of Thompson seedless grape juice. Journal of Agricultural and Food Chemistry, 38, 1565-1571; Lu, Y., & Foo, LY (1999). The polyphenol constituents of grape pomace. Food Chemistry, 65, 1-8) compounds with antioxidant power and other related biological properties are present. There are patents that claim the use of grape seeds (Nkiliza and Marzelle EP0692480; Enrong et al ., WO0211744), grape pulp (Pointer, WO0209722), and grape bagasse (Saura Calixto and García Larrauri, ES2130092) as sources of antioxidants and / or dietary fiber.

Antioxidants can act in various ways during oxidation (for example, by sequestering metal ions, capturing free radicals, acting as reducing agents, breaking down peroxides, etc.). In food systems oxidation involves the oxidation of lipids, while in in vivo systems free radicals can also damage proteins, DNA and other molecules (Moure, A., Cruz, J. Franco, D., Dominguez, JM, Sineiro , J. Domínguez, H., Núñez, MJ and Parajó, JJ (2001). Natural antioxidants from residual sources. Food Chemistry, 72: 145-171).

The object of the present invention is to: a) a procedure for obtaining fractions with power antioxidant made from fermented and distilled grape bagasse (a solid residue of the alcohol industry without any value for companies), and b) the use as an antioxidant of the fractions obtained according to said process.

Embodiment

The embodiment of the present invention is carried carried out according to the following stages:

Stage a) Grape bagasse from the alcohol industry is subjected to a separation stage solid-liquid by pressing through filtration of a mesh between 1 and 20 mm, centrifuged at speeds between 300 rpm and 10,000 rpm, or pressed at pressures between 10 and 50 bar, for separate part of the liquid that soaks the bagasse, obtaining a solid material, and a liquid in amounts between 0.2 g / kg and 4 g / kg of bagasse.

Stage b). The solid resulting from the stage previous is subjected to a water wash with water with relationships greater than 0.1 g of water per kg of solid and less than 50 g of water per kg of solid. Then this mass is subjected to filtration, centrifugation or pressing under the conditions indicated in step a), obtaining an aqueous suspension that is mixed with the liquid obtained in the previous stage.

Stage c). The liquids of stages a) and b) are mix and this mixture is allowed to settle, filtered or centrifuged to separate suspended solids, obtaining a liquid that is subjected to a solvent extraction stage. These solvents they will be apolar solvents partially miscible with water and authorized for food use, such as ethyl acetate, ether ethyl or acetone. As a result of this operation you get two phases: an aqueous phase and an organic phase.

Stage d). The aqueous phase of step c) is discards and the organic phase undergoes an operation of distillation, recovering as solvent the distillate, which reuse and leaving as a residue a suspension containing the non-volatile antioxidant substances

Stage e). The residue indicated in step d) is subjected to low temperature dehydration by lyophilization, vacuum evaporation or drying, not exceeding a temperature of 45 ° C, finally obtaining an extract in the form of solid or concentrated aqueous solution with water content less than 10%.

Example

It starts from 100 kg of ink grape bagasse fermented and distilled from the manufacturing process of brandy, containing between 0.5 and 1.5 g of leachable liquid per 100 g dry inert solid. This material is subjected to a process that includes the following stages:

to)

Pressing the solid residue in a hydraulic press at a pressure of 30 atmospheres, and collection of drained liquid.

b)

Washing with water of the residual solid in the previous stage collecting an aqueous suspension and discarding the solid phase

C)

Mixture of liquids resulting from stages a) and b) and making a fine solid separation by filtration

d)

Extraction with ethyl acetate of the liquid phase of the previous stage, obtaining an aqueous phase that is discarded and an organic phase that is subjected to distillation to recover the solvent.

and)

Vacuum evaporation of the liquid residual distillation carried out in step d), at a temperature below 45 ° C, until 95% of water is removed Present.

F)

Drying in a vacuum oven at 45 ° C for 48 hours, and at a pressure of 0.01 atm.

The dry solid was determined the content of phenolic compounds as equivalent in gallic acid by the Folin-Denis method, obtaining between 0.166 and 0.173 kg. The antioxidant activity was also determined by the DFPH radical uptake method (α radical, α-diphenyl-? -pyril hydrile) (von Gadow, A., Joubert, E., Hansmann, CF (1997). Comparison of the antioxidant activity of aspalathin with that of other plant phenols of rooibos tea ( Aspalathus linearis ), α-tocopherol, BHT and BHA. J. Agric. Food Chem. 45: 632-638) with 50% inhibition of the DFPH radical being observed with concentrations between 0.4 and 0.791 g / L.

To predict or simulate the activity antioxidant extract in emulsion systems, the Antioxidant Activity Coefficient (CAA) for the kinetics of discoloration of β-carotene in an emulsion with linoleic acid (Miller, H. E. A. (1971). Simplified method for the evaluation of antioxidants. Journal of the American Oil Chemist's Society, 45, 91). The CAA for a concentration of 0.5 g / L is 436.24, while BHA and BHT for concentrations of 0.5 g / L have a CAA of 875.8 and 853.8 respectively.

The advantages as an antioxidant of the fractions that are obtained from the process include: stability to storage, high content of phenolic compounds (between 0.166 and 0.173 g of equivalent gallic acid / 100 g dry solid), high antioxidant power (EC50 = 0.40-0.719g / L). As a comparative fact, It should be mentioned that the antioxidant activity is slightly lower than commercial synthetic antioxidants such as BHA (EC50 = 0.241 g / L), but have an activity of up to 8 times higher than that of the BHT (EC50 = 2,794 g / L).

Claims (2)

1. Procedure for obtaining extracts antioxidants from fermented and distilled grape bagasse, which It comprises the following stages:

to)

He bagasse is subjected to a filtration operation through a mesh between 1 and 20 mm, centrifuged at speeds between 300 rpm and 10,000 rpm, or pressed at pressures between 10 and 50 bar to separate part of the liquid that soaks the bagasse, obtaining a material solid, and a liquid in amounts between 0.2 g / kg and 4 g / kg of bagasse; This liquid contains polyphenols, among others components.

b)

He solid resulting from step a) is washed with water with ratios greater than 0.1 g of water per kg of solid and less than 50 g of water per kg of solid; subsequently undergoes filtration, centrifugation or pressing under the conditions indicated in step a), obtaining a residual solid that is discarded, and a liquid containing polyphenols, among other components.

C)

The liquids obtained in stages a) and b) are subjected to a solid-liquid separation operation as filtration, centrifugation or sedimentation, to remove solids in suspension.

d)

He liquid obtained in step c) is processed by extraction with non-polar solvents, such as ethyl acetate, suitable for food use, in order to separate the sugar fraction and that of antioxidant compounds. The resulting aqueous phase is discards and the organic phase is subjected to distillation to recover the solvent and obtain a solvent-free residue, which contains non-volatile substances with activity antioxidant

and)

To the residue resulting from step d) at least 90% of the water present, using dehydration techniques such as evaporation and / or drying and / or atomization and / or lyophilization, or other that are applied for the same purpose, not exceeding a temperature of 45 ° C and the nonvolatile solutes being contained in an extract, which can be presented as a solid or as an aqueous suspension containing a maximum of 10% water.

2. The use of the extract with properties antioxidants, obtained according to claim 1, in the industry Food, cosmetic and pharmaceutical.