Obtaining a volatile fraction from juices or alcoholic beverages

Abstract

The present invention relates primarily to a method for obtaining a volatile fraction from a juice and/or an alcohol-containing beverage, comprising or consisting of the following steps: (a) distilling a mixture of substances from the juice and/or the alcohol-containing beverage, wherein the distillation is performed by a spinning cone column; (b) contacting the mixture of substances from step (a) with a sorbent to obtain a loaded sorbent; and (c) contacting the loaded sorbent from step (b) with a liquid desorbent to obtain the volatile fraction, wherein desired ingredients of the volatile fraction are concentrated as compared to the juice and/or alcohol-containing beverage such that an addition of 0.1% by mass or less of the volatile fraction to any food preparation produces a perceptible odor impression and/or taste impression in a test subject.

Claims

1. A method for obtaining a volatile fraction of concentrated aroma, flavor, and/or fragrance compounds from an ethanol-containing juice or beverage comprising ethanol and the aroma, flavor, and/or fragrance compounds, the method comprising: (a) obtaining a distillate from the ethanol-containing juice or beverage by subjecting the ethanol-containing juice or beverage to spinning cone column distillation, wherein the distillate comprises the aroma, flavor, and/or fragrance compounds; (b) contacting the distillate of (a) with a sorbent to obtain a loaded sorbent; and (c) recovering a volatile fraction containing the aroma, flavor, and/or fragrance compounds from the loaded sorbent of (b) by thermal desorption at a temperature of 90 to 200? C. using a desorbent of ethanol-free water vapor containing less than 5% by mass of organic compounds other than ethanol, wherein the aroma, flavor, and/or fragrance compounds in the volatile fraction of (c) are concentrated compared to the ethanol-containing juice or beverage such that a ratio of ethanol in the volatile fraction to a sum of aroma, flavor, and/or fragrance compounds in the volatile fraction (V(E/A)) is 0.1 to 20, and addition of 0.001 to 0.1% by mass of the volatile fraction to a food preparation produces a perceptible odor impression and/or taste impression.

2. The method according to claim 1, wherein the spinning cone column distillation is carried out in the form of a countercurrent distillation at a pressure of 1 to 500 mbar.

3. The method according to claim 2, wherein the countercurrent distillation is carried out with an inert gas.

4. The method according to claim 1, wherein the spinning cone column distillation is carried out using a strip ratio in the range of 1:1 to 10:1.

5. The method according to claim 1, wherein the ethanol-containing juice or beverage is maintained at a temperature of 28 to 70? C. for spinning cone column distillation.

6. The method according to claim 1, wherein the sorbent is a porous solid, which is surface-modified with organic residues.

7. The method according to claim 1, wherein the ethanol-containing juice or beverage is: a juice selected from fruit juice, berry juice, vegetable juice, or mixture thereof; or an alcoholic beverage selected from wine, wine-containing beverages, beer, beer-containing beverages, or mixtures thereof.

8. The method according to claim 3, wherein the inert gas is nitrogen.

9. The method according to claim 1, wherein the sorbent is a polystyrene.

10. The method according to claim 9, wherein the ethanol-containing juice or beverage is a fruit juice, a berry juice, a vegetable juice, or mixture thereof, selected from lemon juice, orange juice, tangerine juice, clementine juice, grapefruit juice, lime juice, kumquat juice, tangor juice, tangelo juice, melon juice, kiwi juice, papaya juice, avocado juice, acerola juice, bearberry juice, blackberry juice, blueberry juice, boysenberry juice, cherry juice, virgin grape cherry juice, cloudberry juice, red currant juice, black currant juice, date juice, scratch berry (Rubus caesius) juice, elderberry juice, grape juice, gooseberry juice, huckleberry juice, loganberry juice, olallieberry juice, mulberry juice, raisin juice, plains berry juice, prairie berry juice, cranberry juice, raspberry juice, pear juice, splendid raspberry (Rubus spectabilis) juice, sea buckthorn fruit juice, sloe fruit juice, strawberry juice, white cinnamon raspberry (Rubus parviflorus) juice, buckthorn fruit juice, grape berry juice, blueberry juice, apple juice, rhubarb juice, passion fruit juice, plum juice, apricot juice, nectarine juice, quince juice, kiwi juice, star fruit juice, lychee juice, pineapple juice, guava juice, papaya juice, passion fruit juice, mango juice, peach juice, carrot juice, tomato juice, cucumber juice, radish juice, beet juice, sauerkraut juice, celery juice, and spinach juice, or a mixture thereof.

11. The method of claim 1, wherein the ratio of the ethanol contained in the volatile fraction to the sum of the aroma, flavor, and/or fragrance compounds in the volatile fraction (V(E/A)) is 0.5 to 20.

12. The method of claim 1, wherein the ratio of the ethanol contained in the volatile fraction to the sum of the aroma, flavor, and/or fragrance compounds in the volatile fraction (V(E/A)) is 1 to 15.

13. A method for obtaining a volatile fraction of concentrated aroma, flavor, and/or fragrance compounds from an ethanol-containing juice or beverage comprising ethanol and the aroma, flavor, and/or fragrance compounds, the method comprising: (a) obtaining a distillate from the ethanol-containing juice or beverage by subjecting the ethanol-containing juice or beverage to spinning cone column distillation, wherein the distillate comprises the aroma, flavor, and/or fragrance compounds; (b) contacting the distillate of (a) with a sorbent to obtain a loaded sorbent; and (c) recovering a volatile fraction containing the aroma, flavor, and/or fragrance compounds from the loaded sorbent of (b) by thermal desorption at a temperature of 90 to 200? C. using an ethanol-free desorbent of water vapor containing less than 5% by mass of organic compounds other than ethanol, wherein the aroma, flavor, and/or fragrance compounds in the volatile fraction of (c) are concentrated compared to the ethanol-containing juice or beverage such that a ratio of ethanol in the volatile fraction to a sum of the aroma, flavor, and/or fragrance compounds in the volatile fraction (V(E/A)) is 0.5 to 20, and addition of 0.005 to 0.05% by mass of the volatile fraction to a food preparation produces a perceptible odor impression and/or taste impression.

14. The method according to claim 13, wherein the spinning cone column distillation is carried out in the form of a countercurrent distillation at a pressure of 1 to 500 mbar.

15. The method according to claim 13, wherein the countercurrent distillation is carried out with an inert gas.

16. The method according to claim 15, wherein the inert gas is nitrogen.

17. The method according to claim 13, wherein the spinning cone column distillation is carried out using a strip ratio in the range of 1:1 to 10:1.

18. The method according to claim 13, wherein the ethanol-containing juice or beverage is maintained at a temperature of 28 to 70? C. for spinning cone column distillation.

19. The method according to claim 13, wherein the sorbent is a porous solid, which is surface-modified with organic residues.

20. The method according to claim 13, wherein the ethanol-containing juice or beverage is: a juice selected from fruit juice, berry juice, and vegetable juice, or mixture thereof; or an alcoholic beverage selected from wine, wine-containing beverages, beer, beer-containing beverages, or mixtures thereof.

21. The method according to claim 20, wherein the ethanol-containing juice or beverage is a fruit juice, a berry juice, a vegetable juice, or mixture thereof, selected from lemon juice, orange juice, tangerine juice, clementine juice, grapefruit juice, lime juice, kumquat juice, tangor juice, tangelo juice, melon juice, kiwi juice, papaya juice, avocado juice, acerola juice, bearberry juice, blackberry juice, blueberry juice, boysenberry juice, cherry juice, virgin grape cherry juice, cloudberry juice, red currant juice, black currant juice, date juice, scratchberry (Rubus caesius) juice, elderberry juice, grape juice, gooseberry juice, huckleberry juice, loganberry juice, olallieberry juice, mulberry juice, raisin juice, plains berry juice, prairie berry juice, cranberry juice, raspberry juice, pear juice, splendid raspberry (Rubus spectabilis) juice, sea buckthorn fruit juice, sloe fruit juice, strawberry juice, white cinnamon raspberry (Rubus parviflorus) juice, buckthorn fruit juice, grape berry juice, blueberry juice, apple juice, rhubarb juice, passion fruit juice, plum juice, apricot juice, nectarine juice, quince juice, kiwi juice, star fruit juice, lychee juice, pineapple juice, guava juice, papaya juice, passion fruit juice, mango juice, peach juice, carrot juice, tomato juice, cucumber juice, radish juice, beet juice, sauerkraut juice, celery juice, spinach juice, or a mixture thereof.

Description

EXAMPLES

(1) 1. Distillation of Fruits by a Spinning Cone Column

(2) The distillative production/distillation of an aromatic, aqueous or aqueous-alcoholic solution of fruits in water is carried out as described in DE 36 86 492 T2. The spinning cone column is run in countercurrent at a vacuum of 80 to 100 mbar. During this process, the aqueous solution is heated to 50-60? C. and the temperature is maintained. The stripping ratio is about 5-6 with respect to return flow to clearance. The evaporation rate is increased by increasing the temperature and decreasing the stripping ratio to such an extent that there is no reduction in sensory quality. Nitrogen is used as an inert gas to protect the volatile fraction from undesirable oxidation reactions. The distillate yield is between 1/100 and 1/200 of the liquid raw material used.

(3) TABLE-US-00001 TABLE 1 Obtaining distillates from fruits by spinning cone column distillation Amount of value-adding flavor compounds Sensory at 0.9% Aqueous Amount Concentrate in the by mass dosing phase (AP) [kg] [kg] AP [mg/kg] of AP Williams 100 1 470 estrous, pear, pear puree sweet, ripe, juicy White 200 1 170 green, estrous, peach peachy, fruity, puree juicy Orange 200 1 83 floral, orange, juice fresh pungent, juicy Apple 100 1 570 green, aldehydic, puree fruity, stale, juicy

(4) Table 1 shows that by using a spinning cone column, distillates identical in sensory terms to the starting raw material are obtained. The water phase is diluted back to the initial concentration for tasting, i.e. a dosage of 0.9% by mass corresponds to a concentration by a factor of 110. In general, the distillate amounts to 0.5% or 1% by mass of the starting raw material, which means that the flavor compounds have already been enriched.

(5) However, the concentration of the flavoring substances is too low and the dosage of, for example, 0.9% by mass in the foodstuff is too high for these distillates to be incorporated into flavoring mixtures. Another limiting factor is the amount of main fermentation products, which, expressed in terms of ethanol, is between 0.1 and 10% by volume in the distillate according to Table 2 when concentrated by a factor of 100.

(6) TABLE-US-00002 TABLE 2 Ethanol contents of purees and juices from various fruits after fresh processing and processing of the fruits after one day of storage Value- EtOH adding Ratio content flavor Ethanol/ calculated EtOH compounds Sum at EtOH content content flavor 100-fold content after 1 after com- concen- Fruit juices, directly after day 1 day pounds tration each freshly production storage storage V(E/A) of stored pressed [mg/kg] [mg/kg] [mg/kg] [ ] product Orange juice 468 486 8.83 55 4.86 Tangerine 229 246 6.16 40 2.46 juice type Clemenules Strawberry <10 24 4.93 5 0.24 juice White peach 151 907 3.92 231 9.07 juice Calanda 119 135 4.64 29 1.35 peach juice

(7) The storage tests with the freshly squeezed fruit juices in Table 3 show that significant amounts of ethanol are present after just one day storage of a fruit, which far exceed the sum of the value-giving flavor compounds in their quantity. Thus, the ratio of ethanol to the sum of value-giving flavor compounds is >1 (Table 2). The amount of the ratio depends essentially on the stability of the fruit and the type of fruit. In practice, fruits are often stored for 24 hours after mechanical harvesting until processing, since the harvest itself, transport and the many processing stages on an industrial scale require this time, which is why the formation of main fermentation products is unavoidable.

(8) To determine the amount of flavor compounds, an alcoholic extract is diluted with solvent, e.g. pentane, and transferred directly to a gas chromatograph (GC) by liquid injection into a cold feed system (CIS 4, Gerstel). The sample is transferred from the cold feed system to the separation column at 40? C. with a heating rate of 12? C./s to 180? C. (5 min isothermal).

(9) If an aqueous solution, such as a puree, is present, 100 mg of the sample is stirred with a polydimethylsiloxane (PDMS) coated magnetic stir bar (10 mm long, 1 mm layer thickness) for 1 h. The magnetic stir bar is then removed. The magnetic stir bar is then removed and subsequently baked at 150? C. degrees using a thermal desorption unit on the GC. The volatile compounds are thereby applied to the chromatographic system (GC 7890B, Agilent) (capillary column with WAX coating 30 m?0.25 mm?0.25 ?m), separated in the process (temperature program from 40? C. at 3? C./min to 230? C., helium flow of 2 ml/min) and analyzed by mass spectrometry (MSD 5977B, Agilent). The MS transfer line was heated to 280? C., the ion source to 230? C., and the quadrupole to 150? C. Mass spectrometric detection was performed in positive EI mode at 70 eV in full-scan mode (m/z 25-350). Data acquisition was performed using GC-MS Mass Hunter software (Agilent 807.05.2479) and data analysis was performed using AMDIS (V 3.2.13.03.08).

(10) The peak areas are then set in relation to 2-nonanol, as a known standard/comparison, and are output as content data, taking response factors into account.

(11) To determine the alcohol content, 100 ?l of the sample to be analyzed is placed in a 100 ml volumetric flask and diluted to the intended level (100 ml at room temperature or standard conditions) by adding water. The solution is analyzed by high-performance liquid chromatography (HPLC, Agilent 1100). Separation is performed on a LiChrospher 100 RP-8, 5 ?m (250 mm?4 mm) column at a flow rate of 0.9 ml/min, isocratically with water as the mobile phase. A refractive index detector is used for detection and ethanol is quantified via external calibration.

(12) Distillation with the spinning cone column raises the concentration of value-giving flavor compounds from single-digit mg/kg values to triple-digit mg/kg values and enriches value-giving flavor compounds. Thus, the SCC distillate of white peach shows a concentration of value-giving flavor compounds of 170 mg/kg and an ethanol content of 0.4% by mass, and thus an improvement, i.e., in terms of the present invention, a decrease in the ratio of ethanol (in mg) to total flavor compounds (V(E/A) ratio) (in mg) from 24 to 22.

(13) 2. Adsorption/Desorption Process

(14) The distillate is then further concentrated by an adsorption/desorption process, preferably without the use of organic solvents. In the adsorptive concentration of aqueous solutions, as described in EP 2 075 320 A1, the aqueous solution is passed through a bed of a porous sorbent surface-modified with organic residues. The bulk is subsequently eluted with a small amount of an organic solvent, preferably ethanol, compared to the aqueous solution.

(15) TABLE-US-00003 TABLE 3 Analysis of flavor concentrates by sorptive concentration of spinning cone column distillates of white peach (A) and orange juice (B). A Distillate Concentrate Name [mg/kg] [mg/kg] Hexanol 81.0 17828 2-E-hexenol 44.6 7421 2-E-hexenal 20.0 5648 3-Z-hexenol 7.8 970 Hexanal 5.1 1001 3-E-hexenol 1.3 319 Linalool 1.2 223 1,3-pentenol 1.2 23 Isoamylalcohol 0.6 33 2-Z-pentenol 0.5 5 gamma-decalacton 0.5 260 2-Z-hexenol 0.4 139 3-Z-hexenylacetate 0.4 91 Isobutanol 0.3 2 Benzylalkohol 0.3 46 2-E-hexenylacetate 0.2 63 (B) Distillate Concentrate Name [mg/kg] [mg/kg] Linalool 29.2 8544 Octanol 8.2 2012 Isoamylalcohol 5.2 317 Ethylbutyrate 4.9 1225 4-Terpinenol 4.9 1198 alpha-Terpineol 4.0 1027 2-E-Hexenal 2.6 674 Octanal 2.5 725 3-Hydroxy-ethylhexanoate 2.5 535 2-Methylbutanol 2.4 90 Hexanol 2.4 396 Ethylacetate 2.1 91 Hexanal 1.7 576 3-Z-Hexenol 1.2 156 Isobutanol 0.9 17 Citronellol 0.8 218 Neral 0.7 333 Nerol 0.7 178 Geranial 0.7 389 Geraniol 0.6 145

(16) Table 3 shows the GC-MS/FID analysis of white peach puree (A) and orange juice (B). At a concentration factor of 200, 3.4% sum of all value-giving flavor compounds is to be expected. 3.6% were actually measured in the concentrate from the white peach.

(17) In the case of orange juice, 1.8% would be expected at complete recovery, and 2.2% was actually determined. This deviation is due to the better detectability of trace components in the concentrate. The analytical values, as well as the sensory properties of the rediluted concentrates, show that the combination of spinning cone column distillation and sorptive concentration is suitable for converting the authentic-smelling distillate into a concentrate without any reduction in the odor quality and without any noticeable change in the profile of the value-giving flavor compounds.

(18) It was found that the contents of alcohols, in particular butanol, isobutanol, 2-methylbutanol, isoamyl alcohol and 1,3-pentenol (Table 3) are depleted in the concentrate without being sensory perceptible. For example, the recovery of isobutanol is 3.5%, isoamyl alcohol is 26% and 1,3-pentenol is 10% (Table 3 A), and the recovery of isobutanol is 9%, 2-methylbutanol is 19% and isoamyl alcohol is 31% in the concentrate on the orange juice (Table 3 B).

(19) When the adsorbent material was thermodesorbed with steam and the oil phase was obtained from the apple, the fruit's own ethanol was largely reduced (Table 4).

(20) TABLE-US-00004 TABLE 4 Gas chromatographic analysis of an apple water phase and its concentrates obtained therefrom using various adsorbent materials as well as eluents. Ad-/ Ad/ Ad-/ desorption desorption desorption with with Output with polystyrene activated apple polystyrene and water carbon and water and ethanol vapor water vapor phase as as as distillate eluent (A) eluent (B) eluent (C) Name [mg/kg] [mg/kg]. [mg/kg]. [mg/kg]. 2-E-Hexenal 24.63 1601.32 29807.59 4.90 Hexanal 8.45 202.10 13430.34 2.09 Hexanol 36.16 7104.88 234557.04 22.71 2-E-Hexenol 4.94 1736.44 40814.51 3.58 2-Methylbutanol 3.07 2465.38 36193.31 3.19 Butylalcohol 1.52 2595.18 10555.63 2.32 Isoamylalcohol 0.52 752.96 11309.28 0.30 Butylacetate 10.68 399.12 9585.36 2.88 2-Methylbutylacetate 7.35 217.81 6408.29 1.05 Hexylacetate 4.13 120.80 5081.51 0.53 2-E-Hexenylacetate 2.88 74.37 2933.37 0.48 Ethylbutyrate 2.01 85.00 1751.00 0.63

(21) To carry out the solvent-free desorption, a common activated carbon (70 g CarboTech CGF4/90), as well as a special crosslinked macroporous polystyrene (147 g Lewatit? VP OC 1064) were first loaded with the water phase at 5.5 and 7 kg each. After loading, the column filling was dried with inert gas (nitrogen) and then eluted with water vapor (Table 5 B and C). The elution of the polystyrene material with ethanol served as a comparison (Table 5 A). The columns here each have an inner diameter of 3.7 cm and a height of 25 cm. The desorption of the columns filled with activated carbon or the crosslinked macroporous polystyrene as adsorbent material was carried out in each case with steam at 5 mL/min and 2 bar and was stopped after condensation of five times the column volume.

(22) The eluate of the activated carbon shows a loading of 40 mg/kg and thus no concentration compared to the initial water phase. Surprisingly, it was found that in comparison, the flavor compounds could be quantitatively eluted from the polystyrene material with water vapor, resulting in the turbidity of the eluate followed by the formation of an oil phase. The recovery of water vapor desorption is comparable to ethanolic desorption, except for ethanol and the fusel alcohols (Table 5). The content of ethanol in the oil was <1%. The adsorption and desorption processes thus resulted in further concentration of the flavor compounds and depletion of ethanol and fuselic alcohols, so that the ratio of ethanol to total flavor compounds is clearly <1.

(23) Tasting of the water phase at 0.1%, compared to the ethanolic concentrate at 30 mg/kg dosage, (Table 4 A) and the solvent-free aroma oil at 10 mg/kg dosage (Table 4 B) on water, showed strongly pronounced green, fruity-estrusy, apple-like notes that are authentic and comparable to the initial water phase. Thus, it was demonstrated that the combination of special distillation and adsorption/desorption described here yields a highly concentrated flavor concentrate with V(E/A) <1, which at low dosage to the food (e.g., <0.1%) imparts to it an intense flavor corresponding to the starting material.

(24) The gradual concentration of value-adding flavor compounds and depletion of main fermentation products by combining spinning cone column distillation and adsorption/desorption makes it possible to obtain a particularly intensive and authentic concentrate during the dealcoholization of beer (Table 5).

(25) TABLE-US-00005 TABLE 5 Gas chromatographic analysis of a distillate and concentrate obtained from Pilsner beer Pilsner beer Beer flavor SCC distillate concentrate Name [mg/kg] [mg/kg] 2-Methylbutanol 246.10 1493.7 Isoamylalkohol 230.94 5464.9 Isobutanol 103.92 263.3 2-Phenylethylalkohol 19.18 1116.7 Isoamylacetate 5.83 335.6 Octanoic acid 5.63 283.7 2-Phenylethylacetat 2.55 189.0 Ethylcapronate 2.18 48.9 Butanol 1.57 3.4 Ethylcaprylate 0.33 20.3 Isobutylacetate 0.03 20.0

(26) The spinning cone column distillate with an ethanol content of 45% by volume from a beer Pilsner type with 5% by volume was concentrated 250-fold. Adsorption was performed with a 300 L capacity stainless steel column filled with polystyrene material and desorbed with 100 kg of beer alcohol. Rearomatization of the dealcoholized base was performed with 0.3 g/L of the concentrate, giving it back its typical floral, terpenic, malty notes without exceeding the residual alcohol content of 0.05% by volume. The V(E/A) ratio improved from 2500 for the beer used at 5% by volume to 690 for the distillate at 45% by volume and to 94 for the beer concentrate after elution with beer alcohol and <1 for desorption with water vapor, respectively.

(27) TABLE-US-00006 TABLE 6 Gas chromatographic analysis of a distillate and concentrate obtained therefrom from wine Wine SCC Wine flavor distillate concentrate Name [mg/kg] [mg/kg] Isoamylalcohol 1278.89 1742.3 Isobutanol 162.25 30.5 Ethylcapronate 118.46 3620.6 Isoamylacetate 109.26 7335.6 Ethylcaprylate 85.30 3415.1 Ethylbutyrate 57.42 427.5 Ethylcaprinate 35.94 1449.7 Hexanol 23.05 230.8 Hexylacetate 19.86 891.3 Butanol 5.17 2.3 2-Phenylethylalcohol 2.79 20.9 3-Z-Hexenol 1.47 3.1 Linalool 1.39 24.2

(28) The distillate according to Table 6 contains 60% alcohol by volume and is diluted with water in a ratio of 1/10 for adsorption. By adsorption of 8000 kg of diluted red wine with a 20 L column filled with the polystyrene adsorbent material and desorption with 16 kg of a strongly alcoholic wine fraction, a wine flavor concentrate is obtained, which at a dosage of 0.035% to the dealcoholized wine gives it back its typical red-fruity, flowery and spicy character. With an alcohol content of 0.015% by volume of the dealcoholized wine, the total alcohol content after rearomatization is 0.05% by volume, at which a 0.0% by volume claim can be made.