Beer with improved flavor stability

Abstract

The present invention relates to an alcohol-containing beer having an ABV ethanol content of at least 1% and containing 9(S),12(S),13(S)-trihydroxy-10(E)-octadecenoic acid (TOA) and free amino nitrogen (FAN) in a ratio of less than 0.035 mg of TOA per 1 mg of FAN. The inventors have discovered that selective removal of 9(S),12(S),13(S)-trihydroxy-10(E)-octadecenoic acid (TOA) from the malt before fermentation can slow down the aging of alcohol-containing beer during storage. Another aspect of the present invention is: • Steps to provide malt juice; • The step of bringing the malt juice into contact with ZSM-5 zeolite; The steps include: separating the treated malt juice from the ZSM-5 zeolite; The steps include: fermenting the treated malt with yeast to produce fermented malt with an alcohol content of at least 1% ABV; The step of separating yeast from the fermented malt juice. The present invention relates to a method for producing beer, which includes a series of steps.

Description

Technical Field

[0001] The present invention relates to an alcohol-containing beer with improved flavor stability, particularly a beer in which the formation of (E)-2-nonenal hardly occurs during storage. This beer is characterized by a low content of 9(S),12(S),13(S)-trihydroxy-10(E)-octadecenoic acid.

[0002] The present invention also relates to · a step of contacting wort with ZSM-5 zeolite; · a step of separating the treated wort from the ZSM-5 zeolite; · a step of fermenting the treated wort with yeast to produce a fermented wort having an ethanol content of at least 1% ABV; · a step of separating yeast from the fermented wort and relates to a method for producing an alcohol-containing beer.

[0003] The hydroxy fatty acid 9(S),12(S),13(S)-trihydroxy-10(E)-octadecenoic acid is selectively removed from wort by treatment with ZSM-5 zeolite.

Background Art

[0004] Beer undergoes various chemical reactions during storage, leading to inevitable flavor deterioration. Many of the resulting off-flavors are related to the presence of so-called aging aldehydes. Aging aldehydes may be generated, for example, by the oxidation of unsaturated fatty acids, the Strecker degradation of amino acids, and the Maillard reaction. Furthermore, aldehydes can also be released from non-volatile bound forms such as cysteine or bisulfite adducts.

Summary of the Invention

Problems to be Solved by the Invention

[0005] Beer contains trace amounts of lipids. The auto-oxidation of the fatty acid linoleic acid results in the formation of (E)-2-nonenal. This aldehyde gives old beer a cardboard-like flavor and has a very low flavor threshold of 0.03 μg / L.

[0006] ZSM-5 is an aluminosilicate zeolite belonging to the pentasil family of zeolites. Its chemical formula is Na n Al n Si 96-n O 192 ·16H2O (0 < n < 27). ZSM-5 is composed of multiple pentasil units linked by oxygen bridges to form pentasil chains. The pentasil unit is composed of eight 5-membered rings. In these rings, the vertices are Al or Si, and it is assumed that O is bonded between the vertices. The pentasil chains are interconnected by oxygen bridges to form a wavy sheet with 10-ring pores. Similar to the pentasil unit, each 10-ring pore has Al or Si as vertices, and it is assumed that O is bonded between each vertex. Each wavy sheet is connected by an oxygen bridge to form a structure consisting of a straight 10-ring channel running parallel to the wave and a sinusoidal 10-ring channel perpendicular to the sheet. The adjacent layers of the sheet are connected by an inversion point. The estimated pore diameter of the channel running parallel to the wave is 5.4 - 5.6 Å. The crystallographic unit cell of ZSM-5 has 96 tetrahedral positions (Si or Al), 192 octahedral positions, and compensating cations that vary in the range from 12 to infinity depending on the Si / Al ratio.

[0007] Hamberg (Trihydroxyoctadecenoic Acids in Beer: Qualitative and Quantitative Analysis, J.Agric.Food Chem. (1991), 39, 1568-1572) reported that 9,10,13- and 9,12,13-trihydroxyoctadecenoic acid are present in beer and originate from linoleic acid. All 16 isomers were detected in beer, but approximately 60% of the total amount of 9,10,13- and 9,12,13-trihydroxyoctadecenoic acid was accounted for by a single isomer, namely 9(S),12(S),13(S)-trihydroxy-10(E)-octadecenoic acid.

[0008] Japanese Patent Publication No. 2010124748 describes a method for producing a fermented malt beverage, which includes treating malt juice with activated carbon to remove trans-2-nonenal.

[0009] International publication no. 206 / 065557 is, a. The step of bringing a beverage into contact with a silica filter medium in which one or more silanes have reacted with surface active groups, b. The step of binding one or more odor components to a silica filter medium, c. A step of separating the beverage from the silica filter medium. This document describes methods for preventing or reducing off-flavors in beverages, including [specific methods mentioned].

[0010] International Publication No. 2007 / 061602 describes a method for removing 2,4,6-trichloroanisole from a beverage, comprising the step of contacting the beverage with a molecular sieve which is zeolite Y (forjasite) having a Si / Al ratio of at least 5.

[0011] International Publication No. 2018 / 213154 describes a method for modifying the flavor profile of a food, comprising the step of processing the food in the presence of one or more molecular sieves that remove all or part of one or more flavor compounds and one or more toxic compounds.

[0012] International Publication No. 2020 / 055233 describes a method for producing alcohol-free beer, in which alcohol-free beer is brought into contact with a hydrophobic silicate molecular sieve containing SiO2 and Al2O3 in a molar ratio of at least 15.

[0013] De Rouck et al. (The impact of wort production on the flavor quality and stability of pale lager beer, BrewingScience January / February 2013 (Voi.66) 1-11) describes a study comparing coarse-ground lautertan operation with fine-ground thin-bed mash filtration operation. The study describes beers with an ethanol content of 5.49% (v / v) and a FAN content of 78.31 mg / L, as well as beers with an ethanol content of 5.3% (v / v) and a FAN content of 91.38 mg / L. Table 2 shows that the trihydroxy fatty acid content of the two types of malt used in the production of the aforementioned two beers was 3.17 mg / L and 3.07 mg / L, respectively.

[0014] Esterbauer et al. (Isomere Trihydroxy-octadecensauren in Bier: Beweise fur ihr Vorkommen und ihre quantitative Bestimmung, Z. Lebensm. Unters.-Forsch. 164, 255-259 (1977)) describe a study that analyzed commercially available beers from the United States and Austria and measured the amount of the isomer trihydroxyoctadecenoic acid present in them. Table 2 reports the concentration levels of 9(S),12(S),13(S)-trihydroxy-10(E)-octadecenoic acid (G1), which are 468 μg / 100 mL and 760 μg / 100 mL, corresponding to 4.68 mg / L and 7.60 mg / L, respectively. [Means for solving the problem]

[0015] The inventors have discovered that by selectively removing 9(S),12(S),13(S)-trihydroxy-10(E)-octadecenoic acid (TOA) from wort before fermentation, the aging of alcoholic beer during storage can be retarded.

[0016] Thus, one aspect of the present invention relates to an alcoholic beer having a reduced TOA content, more specifically, an alcoholic beer having an ethanol content of at least 1% ABV and containing TOA and free amino nitrogen (FAN) in a ratio of less than 0.035 mg of TOA per 1 mg of FAN.

[0017] TOA is thought to be formed from linoleic acid during the malting and saccharification processes of barley and other grains. Although the inventors do not wish to be bound by theory, it is thought that during the storage of beer, TOA is readily oxidized to form (E)-2-nonenal, which thereby contributes to the flavor of the beer.

[0018] Free amino nitrogen (Fan) is a measure of the concentration of individual amino acids and small peptides (1-3 units). FAN is a breakdown product of proteins in raw materials such as malted barley and unmalted grains.

[0019] Since both TOA and FAN are derived from barley and / or other grains, a low TOA / FAN ratio indicates a decrease in TOA.

[0020] Another aspect of the present invention relates to a method for producing beer, comprising the following successive steps. · providing wort having a specific gravity of 4.5-20ρ; · contacting the wort with ZSM-5 zeolite having a molar ratio of SiO2 / Al2O3 of at least 1,000 for at least 15 minutes; · separating the treated wort from the ZSM-5 zeolite; ·Fermenting the treated wort with yeast to produce a fermented wort having an alcohol content of at least 1% ABV; ·Separating the yeast from the fermented wort.

[0021] When the wort is treated with ZSM-5 zeolite, the TOA content of the wort and the beer produced therefrom is significantly reduced. The formation of (E)-2-nonenal that occurs during storage of the zeolite-treated beer is also reduced.

Mode for Carrying Out the Invention

[0022] A first aspect of the present invention relates to a beer having an ethanol content of at least 1% ABV and containing 9(S),12(S),13(S)-trihydroxy-10(E)-octadecenoic acid and free amino nitrogen (FAN) in a ratio of less than 0.035 mg of TOA per 1 mg of FAN.

[0023] As used herein, the term "beer" refers to a yeast-fermented malt beverage optionally hopped. Beer typically ·Mashing a mixture containing barley malt, optionally adjunct grains, and water to produce a mash; ·Separating the mash into wort and spent grains; ·Boiling the wort to produce a boiled wort; ·Fermenting the boiled wort with live yeast to produce a fermented wort; ·Subjecting the fermented wort to one or more additional process steps (e.g., aging and filtration) to produce beer; ·Packing the beer into a sealed container such as a bottle, can, or keg and is produced by a process consisting of these basic steps.

[0024] As used herein, the term "lager beer" refers to a beer brewed and conditioned at a temperature of 15°C or less. The yeast used in the production of lager beer gathers at the bottom of the beer during fermentation and is therefore referred to as bottom-fermenting yeast.

[0025] In a particularly preferred embodiment, the beer of the present invention is a lager beer.

[0026] The free amino nitrogen (FAN) content of beer can be appropriately measured by the European Brewing Association (EBC) Analytica - Method 9.10.2 (Measurement of free amino nitrogen in beer by individual analyzer (NOPA method) - 2017).

[0027] The beer of the present invention preferably contains TOA and FAN in a ratio of 0.005 to 0.033 mg of TOA per 1 mg of FAN, and more preferably in a ratio of 0.010 to 0.030 mg of TOA per 1 mg of FAN.

[0028] The FAN content is preferably in the range of 40 to 200 mg / L, more preferably 50 to 180 mg / L, and most preferably 60 to 140 mg / L.

[0029] Preferably, the TOA content of the beer is less than 5 mg / L, more preferably 0.5 to 4 mg / L, even more preferably 1.0 to 3.6 mg / L, and most preferably 2.0 to 3.3 mg / L.

[0030] The beer preferably contains 0 to 0.05 μg / L of (E)-2-nonenal, more preferably 0.005 to 0.03 μg / L of (E)-2-nonenal, and most preferably 0.008 to 0.02 μg / L of (E)-2-nonenal.

[0031] The beer preferably contains (E)-2-nonenal and FAN in a ratio of 0.1 to 1 μg of (E)-2-nonenal per 1 mg of FAN, more preferably 0.02 to 5 μg of (E)-2-nonenal per 1 mg of FAN, and most preferably 0.03 to 0.1 μg of (E)-2-nonenal per 1 mg of FAN.

[0032] The advantages of the present invention are particularly evident in beer that has been stored for a long period of time. During storage of beer, the furfural content in the beer gradually increases. According to a preferred embodiment, the (stored) beer of the present invention contains 50 to 600 μg / L of furfural, more preferably 70 to 500 μg / L of furfural μg / L, and most preferably 100 to 400 μg / L of furfural.

[0033] (Storage) beer preferably contains furfural and FAN in a ratio of 0.5 to 8 μg of furfural per 1 mg of FAN, more preferably 1 to 6 μg of furfural per 1 mg of FAN, and most preferably 1.2 to 4 μg of furfural per 1 mg of FAN.

[0034] The beer of the present invention differs from ordinary beer in that the (E)-2-nonenal content increases during storage at a relatively lower rate compared to the rate of increase of the furfural content. Therefore, in a preferred embodiment, the (stored) beer contains (E)-2-nonenal and furfural in a weight ratio of less than 1:6,000, more preferably 1:100,000 to 1:10,000, and most preferably 1:60,000 to 1:12,000.

[0035] The ethanol content of the beer is preferably in the range of 2-8% ABV, more preferably in the range of 4-7% ABV, and most preferably in the range of 4.5-6.5% ABV.

[0036] The beer preferably has a specific gravity in the range of 4.5 to 20, more preferably 8 to 19, and most preferably 14 to 18 at 20°C.

[0037] The beer of the present invention preferably contains no adjuncts, i.e., is 100% grain beer. More preferably, the beer is 100% malt beer. Most preferably, the beer is 100% barley malt beer.

[0038] Another aspect of the present invention relates to a method for producing beer, comprising the following sequence of steps. • A step of providing malt juice with a specific gravity of 4.5-20ρ; The steps include: bringing malt juice into contact with ZSM-5 zeolite having SiO2 / Al2O3 in a molar ratio of at least 1,000 for at least 15 minutes; • The step of separating the treated malt juice from the ZSM-5 zeolite; The steps include: fermenting the processed malt with yeast to produce fermented malt with an alcohol content of at least 1% ABV; • The step of separating yeast from fermented malt.

[0039] In a particularly preferred embodiment, the method of the present invention yields the beer described herein.

[0040] In this method, the malt juice that is brought into contact with the ZSM-5 zeolite preferably has a specific gravity of 10 to 18ρ, more preferably 10 to 15ρ.

[0041] Preferably, the malt juice is brought into contact with the ZSM-5 zeolite by combining 1000 parts by weight of malt juice with at least 1 part by weight of ZSM-5 zeolite. More preferably, the malt juice is brought into contact with the ZSM-5 zeolite by combining 1000 parts by weight of malt juice with 2 to 10 parts by weight of ZSM-5 zeolite.

[0042] The malt juice is preferably in contact with ZSM-5 zeolite for 30 to 300 minutes, more preferably for 40 to 240 minutes.

[0043] When the malt juice is brought into contact with the zeolite, it is preferable that it has a temperature in the range of 0 to 95°C, more preferably in the range of 2 to 50°C.

[0044] The ZSM-5 zeolite used in this method preferably has a molar ratio of SiO2 / Al2O3 greater than 2,000.

[0045] The surface area of ​​ZSM-5 zeolite is preferably at least 100 m². 2 / g, more preferably 150~2,000m 2 / g, most preferably 200-1,000m 2 The value is / g. The surface area of ​​the hydrophobic molecular sieve can be determined by the BET method.

[0046] The malt may be brought into contact with the zeolite by mixing the malt with the zeolite. Alternatively, the malt may be brought into contact with the zeolite by passing it through a column packed with zeolite.

[0047] When malt is brought into contact with zeolite by mixing it with zeolite, the treated malt may be separated from the zeolite by, for example, decantation, filtration, or centrifugation. Preferably, the malt treated with zeolite is separated from the zeolite before fermentation.

[0048] The processed malt is preferably fermented with bottom-fermenting yeast.

[0049] Preferably, the treated malt is fermented at a temperature of 0-15°C, more preferably 4-14°C, and most preferably 7-12°C.

[0050] In this method, the processed malt is preferably fermented with yeast to produce fermented malt having an alcohol content in the range of 2-12% ABV, more preferably 4-10% ABV, and most preferably 4.5-7.5% ABV.

[0051] The present invention is further illustrated by the following non-limiting embodiments. [Examples]

[0052] Example 1 A lager beer with an ethanol content of 5% ABV (for reference) was manufactured as follows: • Sediment was removed from boiled hop-added malt (specific gravity 16°) in a whirlpool bath; The clarified malt was cooled and fermented at 8°C for 15 days; The fermented beer was filtered, adjusted, and then bottled.

[0053] Example 2 Lager beer (Beer 1) was produced in the same manner as the beer in Example 1, with the only difference being that the clarified malt was brought into contact with ZSM-5 zeolite before fermentation, as follows: The clarified malt juice was cooled to 8.5°C; Zeolite was added at a concentration of 10 g / L; The malt and zeolite mixture was kept at 8.5°C while being stirred, and maintained for 5 hours. Zeolite was removed from the malt by filtration.

[0054] The ZSM zeolite powder used had the following properties: - MFI Zeolite -SiO2 / Al2O3 molar ratio is 1,000 or higher -BET surface area: approx. 350m 2 / g -Pore diameter: 5.6 Å (linear), 5.3 Å (sinusoidal)

[0055] Example 3 The lager beers from Examples 1 and 2 were stored at 30°C for 3 months.

[0056] The beer was analyzed at the start of the storage period and after storage. The analysis results are summarized in Table 1.

[0057] [Table 1]

[0058] Example 4 Several types of commercially available lager beer were stored at 30°C for three months. The beer was analyzed at the beginning and end of the storage period. The analysis results are summarized in Tables 2 and 3.

[0059] [Table 2]

[0060] Table 3

Claims

1. An alcohol-containing beer having an ABV ethanol content of at least 1.0%, and containing 9(S),12(S),13(S)-trihydroxy-10(E)-octadecenoic acid (TOA) and free amino nitrogen (FAN) in a ratio of less than 0.035 mg of TOA per 1 mg of FAN.

2. The beer according to claim 1, wherein the beer has a FAN content of 40 to 200 mg / L.

3. The beer according to claim 1 or 2, wherein the beer has a TOA content of less than 5 mg / L.

4. The beer according to any one of claims 1 to 3, wherein the beer contains 0 to 0.05 μg / L of (E)-2-nonenal.

5. The beer according to any one of claims 1 to 4, wherein the beer contains 50 to 600 μg / L of furfural.

6. The beer according to any one of claims 1 to 5, wherein the beer contains (E)-2-nonenal and furfural in a weight ratio of less than 1:6,000.

7. The beer according to any one of claims 1 to 6, wherein the beer has an ethanol content of 3 to 6% ABV.

8. A beer according to any one of claims 1 to 7, having a specific gravity in the range of 4 to 20ρ at 20℃.

9. The beer according to any one of claims 1 to 8, wherein the beer is 100% grain beer.

10. - A step of providing malt juice with a specific gravity of 4.5 to 20ρ; - The malt juice and SiO ２ / Al ２ O ３ The steps include: bringing a ZSM-5 zeolite having at least 1,000 molar ratios into contact with the substance for at least 15 minutes; - The step of separating the treated malt juice from the ZSM-5 zeolite; - A step of fermenting the processed malt with yeast to produce fermented malt with an alcohol content of at least 1% ABV; - The step of separating yeast from the fermented malt juice and A method for producing alcohol-containing beer, including [the specified ingredient].

11. The method according to claim 10, wherein the method yields the beer according to any one of claims 1 to 9.

12. The method according to claim 10 or 11, wherein 100 parts by weight of malt juice is brought into contact with the ZSM-5 zeolite by combining the malt juice with at least 1 part by weight of ZSM-5 zeolite.

13. The method according to any one of claims 10 to 12, wherein the treated malt is fermented with bottom-fermenting yeast.

14. The method according to any one of claims 10 to 13, wherein the temperature at the time of contact between the malt juice and the zeolite is in the range of 2 to 50°C.

15. The ZSM-5 zeolite is at least 100 m ２ The method according to any one of claims 10 to 14, having a surface area of ​​ / g.

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