METHOD OF IMPROVING FLAVOR STABILITY IN FERMENTED BEVERAGES

Abstract

Compositions and methods are disclosed for stabilizing the flavor of a fermented beverage, most particularly beer, by the addition of a composition comprising a tannin and a solid carrier prior to, or during early stages of, fermentation of the beverage. The invention is also directed to the fermented beverage prepared by such a method. The composition may include at least one polyphenol therein and may be in the form of a pellet.

Claims

1. A composition for improving a flavor stability of a fermented beverage produced from a fermentable medium, the composition comprising: a tannin; and a solid carrier, wherein the composition is in a form of a pellet.

2. The composition of claim 1, wherein the tannin is a hydrolyzable tannin.

3. The composition of claim 2, wherein the hydrolyzable tannin is a gallotannin.

4. The composition of claim 3, wherein the gallotannin is a gallic acid ester formed from glucose and gallic acid.

5. The composition of claim 1, wherein the solid carrier comprises at least one polyphenol.

6. The composition of claim 1, wherein the solid carrier comprises a solid hop residue obtained by extracting hops with carbon dioxide.

7. The composition of claim 6, wherein the solid carrier comprises a malt powder.

8. The composition of claim 1, wherein the tannin is in the composition in a range from about 3 weight % to about 20 weight % of the composition.

9. The composition of claim 1, wherein the solid carrier is in the composition in a range from about 80 weight % to about 97 weight % of the composition.

10. The composition of claim 1, wherein the composition further comprises water and has a moisture content ranging from about 1% to about 20%.

11. (canceled)

12. The composition of claim 1, wherein the composition further comprises at least one antioxidative ingredient selected from the group consisting of antiradical enzymes, antioxidative amino acids, chelating agents, malt polyphenol fractions, and mixtures thereof.

13. The composition of claim 1, wherein: the tannin is a gallotannin; the solid carrier comprises a solid hop residue obtained by extracting hops with carbon dioxide; the tannin is in the composition in a range from about 3 weight % to about 20 weight % of the composition; and the solid carrier is in the composition in a range from about 80 weight % to about 97 weight % of the composition.

14. A method for improving a flavor stability of a fermented beverage produced from a fermentable medium, the method comprising: adding a composition comprising a tannin and a solid carrier to a fermentable medium prior to fermentation in an amount effective to stabilize flavor; and thereafter fermenting the medium to prepare a fermented beverage having a stable flavor.

15. The method of claim 14, wherein the tannin is a gallotannin.

16. (canceled)

17. The method of claim 14, wherein the solid carrier comprises at least one of a solid hop residue and a malt.

18. The method of claim 17, wherein the solid hop residue is obtained by extracting hops with carbon dioxide.

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24. The method of claim 14, wherein the composition is added to the fermentable medium in an amount ranging from about 1 to 1500 ppm by weight.

25. A method for improving a flavor stability of a fermented beverage produced from a fermentable medium, the method comprising: adding a pelletized solid hop residue to a fermentable medium prior to boiling the fermentable medium in an amount effective to stabilize flavor; and thereafter fermenting the medium to prepare a fermented beverage having a stable flavor.

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34. A method for improving a flavor stability of a fermented beverage produced from a fermentable medium, the method comprising: adding a composition comprising a solid hop residue obtained by extracting hops with carbon dioxide to a fermentable medium prior to boiling the fermentable medium in an amount effective to stabilize flavor; and thereafter fermenting the medium to prepare a fermented beverage having a stable flavor.

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46. A method of producing a composition for improving a flavor stability of a fermented beverage produced from a fermentable medium, the method comprising: mixing a gallotannin powder and a solid carrier particles to create a mixture; and pelletizing the mixture to produce the composition.

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Description

BRIEF DESCRIPTION OF DRAWINGS

[0055] FIG. 1 is a graph showing the relationship between a stale papery note of a lager-style beer and a length of time for a trial composition comprising a tannin, and a control sample.

[0056] FIG. 2 is a graph showing the relationship between a papery note of a lager-style beer and a length of time, measured over a plurality of weeks, for multiple trials comprising a tannin, and a control sample.

[0057] FIG. 3 is a graph showing the relationship between the flavor stability of a lager-style beer and a length of time for a trial composition comprising a tannin, and a control sample, wherein MCTS represents a taste system.

[0058] FIG. 4 is a graph showing the relationship between the flavor stability of a lager-style beer and a length of time for a trial composition comprising a solid carrier, and a control sample, wherein MCTS represents a taste system.

[0059] FIG. 5 is a graph showing the relationship between a papery, stale, and oxidized note of a lager-style beer and a length of time for a trial composition comprising a tannin and a solid carrier, and a control sample.

[0060] FIG. 6 is a graph showing the relationship between a papery, stale, and oxidized note of a lager-style beer and a length of time for a trial composition comprising a tannin and a solid carrier, and a control sample.

[0061] FIG. 7 is a graph showing the relationship between the flavor stability of a lager-style beer and a length of time for a trial composition comprising a tannin and a solid carrier, and a control sample, wherein MCTS represents a taste system.

[0062] FIG. 8 is a graph showing the relationship between a papery, stale, and oxidized note of a lager-style beer and a length of time for a trial composition comprising a gallotannin and a solid hop carrier, and a control sample.

[0063] FIG. 9 is a graph showing the relationship between a H.sub.2S, mercaptan, sulphitic, and yeast roll up note of a lager-style beer and a length of time for a trial composition comprising a gallotannin and a solid hop carrier, and a control sample.

[0064] FIG. 10 is a graph showing the positive chelation of copper (Cu) and iron (Fe) when using a trial composition comprising a gallotannin and a solid hop carrier starting at the medium dosage rate and improving as the dosage is increased to a very high level.

DETAILED DESCRIPTION OF THE INVENTION

[0065] This invention provides novel compositions and methods for stabilizing the flavor of a fermented beverage made from a fermentable medium by adding a composition comprising a tannin and a solid carrier to the fermentable medium prior to fermentation.

[0066] The term about or approx., as used herein, refers to variation in the numerical quantity that may occur, for example, through typical measuring and liquid handling procedures used for making concentrates or solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients used to make the compositions or carry out the methods; and the like. The term about may also encompass amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. In one embodiment, the term about refers to a range of values +/5% of a specified value.

[0067] The term weight percent, wt. %, percent by weight, % by weight, and variations thereof, as used herein, refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100. It is understood that, as used here, percent, %, and the like may be synonymous with weight percent, wt. %, etc.

[0068] By antioxidant we mean a substance or nutrient capable of slowing or preventing the oxidation of other molecules. Oxidation is a chemical reaction that transfers electrons from a substance to an oxidizing agent. Oxidation reactions can produce free radicals, which start chain reactions that damage cells. When materials such as food or beverages are exposed to air, oxidative deterioration can occur. Oxidation can detrimentally affect the taste, color, and nutritional content of the food or beverage. To prevent this deterioration, compounds that prevent oxidation, antioxidants, are added to the food or beverage or are endogenous to the raw brewing ingredients. Antioxidants terminate these chain reactions by removing free radical intermediates, and inhibit other oxidation reactions by being oxidized themselves. Traditionally, the antioxidants are chemically synthesized. However, the possible toxicity of these compounds has stimulated the search for natural products like brewing ingredients with antioxidative properties. Similarly, a trend in the nutritional industry is to identify natural antioxidants.

[0069] In the methods of the present invention, the flavor of a fermented beverage is stabilized by adding a composition comprising a tannin and a solid carrier to a fermentable medium. By stabilize or stabilizing, we mean preserving the original, fresh flavor and character of the fermentable beverage during distribution and storage by reducing oxidation in the fermentable beverage.

[0070] By fermented beverage we mean any beverage produced by fermentation, including, but not limited to beer, wine, spirits, sake, cider, mead, kefir, yogurt and the like. By beer we mean any alcoholic beverage brewed from malt and hops, including but not limited to ales, stouts, lagers, porters, malt liquors, low-calorie, low-alcohol and light brews and the like.

[0071] By fermentable medium we mean any medium capable of being fermented to yield a fermented beverage. In one embodiment the fermentable medium is malt. By malt we mean any cereal grain, particularly barley, steeped in water until it is sprouted and used in brewing and distilling. However, in alternate embodiments, the fermentable medium is wort. By wort, we mean the liquor run-off after extracting a prepared solid material, such as a cereal grain or malt, with hot water.

[0072] The composition, as described herein, may be added to the fermentable medium at any time prior to fermentation. By fermentation we mean the conversion of carbohydrates to alcohols and carbon dioxide or organic acids using yeasts, bacteria, or a combination thereof, under anaerobic conditions. For instance, in one embodiment, the composition is added to the fermentable medium before fermentation or during mashing. By mashing we mean the brewing process where malt or grain is crushed and steeped in hot water to make wort. In alternate embodiments the composition is added to the fermentable medium before or during lautering. By lautering we mean the brewing process in which the mash is separated into the liquid wort and the solid residual grain. Lautering usually includes three steps: mashout, recirculation, and sparging. In another embodiment, the composition is added to the fermentable medium before or during sparging. By sparging we mean the brewing process where hot water is applied to the lautered grains to rinse out any remaining wort.

Tannins

[0073] In one embodiment, the composition comprises a tannin. Tannin, or alternatively a tannic acid, may generally be characterized as a polyphenolic biomolecule. Tannins, as used herein, may be classified as a condensed tannin, a hydrolyzable tannin, or a phlorotannin. Condensed tannins are polymers with a flavanol structured monomer. Alternatively, a hydrolyzable tannin may be defined as an aromatic compound, e.g., a gallic acid or an ellagic acid, and a sugar, e.g., glucose, that have formed an ester bond. Phlorotannin may be defined as a compound that is an oligomer of phlorglucinol. Generally, tannins are capable of binding to and precipitating proteins and various other organic compounds including amino acids and alkaloids.

[0074] In one specific embodiment, a tannin is provided as a hydrolyzable tannin and, in the preferred embodiment, a hydrolyzable tannin that is a gallic acid ester formed from glucose and gallic acid. In this particular embodiment, the tannin may be gallotannin.

[0075] Tannins are to be used as an antioxidant and/or chelating agent for the fermentable medium applied thereto. Further, in the preferred embodiment, the tannin is in a solid form. Preferably, the tannin is provided as a powder or a pellet.

[0076] In one embodiment, the tannin is in the composition in a range from about 3 weight % to about 20 weight %, based on a total weight of the composition and, in another embodiment, in a range from about 3 weight % to about 12 weight %. In a non-limiting example embodiment, the tannin is in the composition in an amount of about 10 weight %, compared to the total weight of the composition.

Solid Carrier

[0077] In one embodiment, the composition further comprises a solid carrier. A solid carrier, as used herein, may generally refer to solid material used in the composition. In a specific embodiment, the solid carrier comprises at least one of a hop residue and/or a solid hop residue. In the preferred embodiment, the solid carrier is a solid hop carrier obtained by extracting hops with carbon dioxide. In this specific embodiment, the hop residue may be a spent hop powder that may be a recycled product of a hop bitter resin and/or the result of a debittered hop powder. In another embodiment, the solid carrier comprises a malt, and in a particular embodiment, a malt powder.

[0078] The solid carrier may also preferably comprise at least one polyphenol. In some embodiments, the polyphenol is a flavonoid such as flavonol or quercetin. Further, the polyphenol may further be a dimer or a trimer polyphenol structure. In some embodiments, the dimer may be proanthocyanidin. In the preferred embodiment, the solid carrier may have antioxidative properties. For example, the solid carrier may be capable of being a chelating agent of divalent metal ions and/or capable of quenching reactive oxygen species and other free radicals through free radical hydrogen abstraction of the hydroxyl hydrogen.

[0079] In one embodiment, the solid carrier is in the composition in a range from about 80 weight % to about 97 weight % of the composition and, in another embodiment, in a range from about 88 weight % to about 97 weight %. In non-limiting example embodiments, the solid carrier is in the composition in an amount of about 90 weight %, or about 95 weight %, compared to the total weight of the composition.

Water

[0080] The composition may further include water or a moisture content. In some embodiments, the composition comprises water and has a moisture content ranging from about 1% to about 20%. In some embodiments, the composition has a moisture content from about 8% to about 12%. In a non-limiting example embodiment, the composition has a moisture content of about 10%.

Other Ingredients

[0081] The composition may also optionally include other ingredients and/or additives. For instance, in some embodiments, it may be desired to include antioxidative ingredients. Some preferred antioxidative ingredients may include antiradical enzymes like catalase and super oxide dismutase, antioxidative amino acids (e.g., tryptophan, leucine, alanine, glycine and cysteine), chelating agents, malt polyphenol fractions, and mixtures thereof.

[0082] The composition may be formed from a method comprising the steps of mixing a tannin powder and solid carrier particles to create a mixture and pelletizing the mixture to produce the composition. Before mixing, the tannin powder and/or the solid carrier may be dry, in a powder form, and have a moisture content ranging from about 0 to 15%. Preferably the moisture content is about 4%. In some embodiments, the solid carrier is first ground to a powder and the gallotannin is added and mixed in a predetermined amount. Then, water may be added to increase the moisture content to the desired level. If desired, the method may also include mixing at least one antioxidative ingredient with the gallotannin powder and the solid carrier particles. For example, antioxidative ingredients may include antiradical enzymes, antioxidative amino acids, chelating agents, malt polyphenol fractions, and mixtures thereof. After mixing, the hydrated powder may be pelletized into a pellet. The pellets may have a specific density, shape, size, texture, firmness, etc. After pelletizing, the pellets may then be weighted and vacuum packed into containers and stored until usage thereof.

[0083] During use, the containers, with the pellets therein, may be opened and the pellets poured into the desired container or a part of the process, such as a mash tun vessel at start of mash-in or later to the brew kettle.

[0084] In some embodiment, a mist of water is provided during the mixing of the tannin powder and the solid carrier particles. Further, pelletizing may be performed with a catalase and amino acids, such as non-Strecker amino acids. It may be desired to perform the aforementioned steps in order to prevent the formation of hydrogen peroxide or other undesired side products thereof during the production of the composition.

[0085] As previously discussed, in the preferred embodiments, the composition is in the form of a pellet. The pellets may be formed to be approximately 0.1 to 2 inches in length thereof. In a preferred embodiment, the pellets are approximately 1 inch in length. Further, the composition may be formulated so that the composition may be released in the fermentable medium at an effective rate of 8 minutes to 15 minutes.

[0086] The composition may be added to the fermentable medium in any amount effective to improve the flavor stability of the fermented beverage.

[0087] In one embodiment, a composition comprising a tannin and a solid carrier is added to the fermentable medium in an amount ranging from 1 to 1500 parts per million (ppm) by weight. In another embodiment, the composition is added to the fermentable medium in an amount ranging from 200 to 1200 ppm by weight. In another embodiment, the composition is added to the fermentable medium in an amount ranging from 200 to 600 ppm by weight. In non-limiting example embodiments, the composition is added to the fermentable medium in an amount of about 300 ppm by weight, or about 400 ppm by weight, or about 500 ppm by weight.

[0088] In one embodiment, a pelletized solid hop residue is added to a fermentable medium prior to boiling the fermentable medium in an amount effective to stabilize flavor. The pelletized solid hop residue may be added to the fermentable medium in an amount ranging from about 1 to 1000 ppm by weight. In another embodiment, the pelletized solid hop residue may be added to the fermentable medium in an amount ranging from in an amount ranging from 200 to 800 ppm by weight. In another embodiment, the pelletized solid hop residue may be added to the fermentable medium in an amount ranging from in an amount ranging from 400 to 600 ppm by weight.

[0089] In one embodiment, a composition comprising a solid hop residue obtained by extracting hops with carbon dioxide is added to a fermentable medium prior to boiling the fermentable medium in an amount effective to stabilize flavor. The solid hop residue can be added to the fermentable medium in an amount ranging from about 1 to 1000 ppm by weight. In another embodiment, the solid hop residue can be added to the fermentable medium in an amount ranging from in an amount ranging from 200 to 800 ppm by weight. In another embodiment, the solid hop residue can be added to the fermentable medium in an amount ranging from 400 to 600 ppm by weight.

[0090] The composition may be added to the fermentable medium at any time prior to, or during the early stages of, fermentation of the fermentable medium. In the preferred embodiments, the composition is added at the start of the malt mash-in process, before mashing of the malt, to the ground malt bill hopper, to the wort before lautering of the wort, before boiling of the wort and/or in the brew kettle during filling. The composition may be added to the fermentable medium prior to fermentation in an amount effective to stabilize the flavor.

EXAMPLES

[0091] The following Examples are presented for purposes of illustration and not of limitation. Unless otherwise stated, all percentages recited in these examples are weight percentages based on the total specified composition weight. Further, as previously noted, the compositions, as disclosed herein, help improve the flavor stability and shelf life of the fermented beverage added thereto. As such, the following examples, and the experiments disclosed therein, provide comparative results showing such.

Example 1. Tannin Properties

[0092] As discussed herein, tannins and, more preferably gallotannins and/or gallic acids, are chelating agents of divalent metals and work quickly in aqueous solutions. Analytical results of gallotannins or tannic acids, i.e., Tan'activ GTH or Brewtan B, are shown in Table 1.

TABLE-US-00001 TABLE 1 Values Characteristics Unit Tan'activ GTH Brewtan B Method Appearance light hazelnut powder light hazelnut powder Tannins % 95.4 94.7 ISO 14088: 2012* Tannins (dry) % 99.8 99.5 ISO 14088: 2012* Non Tannins % 0.2 0.5 ISO 14088: 2012* Insolubles % 0.0 0.0 ISO 14088: 2012* Water % 4.4 4.8 ISO 14088: 2012* T/nT Ratio 477.00 189.40 ISO 14088: 2012* pH (1%) 3.3 3.5 TAN/04 Ashes (dry) 550 C. % 0.05 0.09 TAN/06 Ethyl alcohol Solubility Pass Test Pass Test TAN/10 Water Solubility Pass Test Pass Test TAN/10 Gums & Dextrins Pass Test Pass Test TAN/13 Resinous substances Pass Test Pass Test TAN/14 Free Gallic Acid 0.41 <0.04 HPLC/GA2

Example 2. Tannin Test

[0093] Methods and Materials. A gallotannin composition, i.e., Brewtan B as shown in Table 1, was added to the wort stream of a lager-style beer at mash-in at 26 ppm. A directional difference was determined if a measured p-value was 0.05 or less. Further, a significant difference was determined if a measured p-value was 0.06 to 0.15. Overall, a flavor stability test was determined as successful or non-successful. A sensory trial at 75 F. was performed, and a stale note was taken.

[0094] Results. Table 2 shows the flavor stability results of using a composition comprising a gallotannin. Significant flavor stability success was observed with the composition usage at mash-in for eight out of ten trials. The non-significant difference, i.e., NSD, in flavor stability trials only showed a directional improvement in less oxidized flavor of a p-value of 0.110 with high-sulfur or SO.sub.2 contents. Further, Trial 11 showed a disappearance of upstream wort success that was due to high Fe diatomaceous earth (DE) filter material used for filtration. Even though the beer was metallic, the oxidized note was still a directional improvement with a p-value of greater than 0.050 even after nine months under heat treatment at 68 F. Trials 1 and 6 showed an ANOVA significant sensory flavor stability improvement and success in the reduction of the off-note papery after 16 weeks at 75 F., i.e., p-value=0.00. As seen in Trials 12a and 12b, an NSD at 8 weeks at 75 F. was observed, but a significant difference success was observed in the reduction of the sulphidic off-note, with a subsequent increase in Malty/Grainy in Trial 12b.

[0095] With reference to FIG. 1, the trans 2-nonenal (t2N) derived papery oxidized note was lower than a control in Trial 6. Similarly, in reference to FIG. 2, the t2N derived papery oxidized note, was tracked mostly at lower levels than a control in Trial 12a and 112b. Overall, the lager beer treated with the gallotannin composition showed significant improvements in flavor stability in ten out of twelve production trials with the reduction of stale, papery, oxidized, and sulphidic off-notes, especially in longer periods of forced aging treatments.

TABLE-US-00002 TABLE 2 Flavor Directional Significant Stability Sensory Stale Note Trial Difference Difference Success Trial Improvement p-value 1 N/A Yes Yes 8 weeks Papery 0.024 (8 weeks) 2 N/A Yes Yes 18 months Stale 0.053 (8 weeks) Production 3 N/A Yes Yes 18 months Stale 0.003 (8 weeks) Production 4 N/A Yes Yes 18 months Stale 0.001 (8 weeks) Production 5 N/A Yes Yes 18 months Stale 0.001 (8 weeks) Production 6 Yes Yes Yes ANOVA Papery 0.000 (2 months) (0-16 Session weeks) 7 Yes Yes Yes 0, 3, 7 Oxidized 0.030 (6 months) (16 weeks, 3, weeks) 4, 5, 6 months 8 Yes Yes Yes 1, 2, 3, 4, Oxidized 0.040:0.040 (6 months) (8 and 20 5, and 6 weeks) months 9 Yes NSD No 8, 12, 16, Oxidized 0.110 (2 and 4 Difference and 20 months) weeks 10 Yes (4 Yes Yes 8, 12, 16, Oxidized 0.020 months) (20 20 and 24 weeks) weeks 11 No NSD No 9 months Oxidized >0.050 Difference 12a No NSD No 8 weeks No Difference NSD Difference 12b Yes Yes TBD 17 weeks Sulphidic, 0.013; (4 and 8 Malty/Grny 0.020 weeks)

[0096] Electron paramagnetic resonance (EPR), trans 2-nonenal (t2N), and thiobarbituric index (TBI) analytical results were determined for Trials 6, 11, 12a, and 12b. The results are shown in Table 3. Trial 6 showed beneficial reductions in EPR T150, i.e., the quantity of free-radicals metric, through the brewing process and in the packaged beer. Further, in this trial, lower EPR T150, longer lag time, i.e., quantity of antioxidants metric, lower Fe levels and lower total and free t2N, showed percent improvements of 40.2, 6.2, 38.5, 1.5, and 10.5, respectively.

[0097] Trial 11 showed beneficial wort flavor stability percentage improvements in the EPR Area, i.e., free radical metric, Fe reduction, and TBI reduction, i.e., lipid peroxidation metric. As previously mentioned, Trial 11 used a high Fe diatomaceous earth (DE) filter material, followed by a control which negated the upstream improvements and probably adversely affected the NSD, nine month flavor stability testing.

[0098] Trial 12 showed mixed results with a similar Fe increase after primary filtration with DE that remained higher than a control in aging and packaged beer. The increase in Fe seemed to affect the NSD, 8 weeks at 75 F. testing shown in Table 2, but not the significant reduction in sulphidic and an increase in grainy/sweet seen at 17 weeks at 75 F. However, the packaged beer trials did show improvements in EPR T150, total and free t2N, showing percent reductions of 8.8, 12.7, and 7.3, respectively. Without intending to be bound by theory, these results help support the theory that reactive oxygen species (ROS) and t2N free and bound papery notes arise at the start of malt mash-in from Fe catalyzed free radical lipid peroxidation.

TABLE-US-00003 TABLE 3 Total Free % T/C Total Free Trial 6 EPR T150 Lagtime Fe T2N T2N TBI EPR T150 Lagtime Fe T2N T2N TBI 1stWort Control 4355 1stWort Trial 3984 12.5 KETTLE Full Control 19716 KETTLE Full Trial 13670 30.7 Kettle KO Control 21215 Kettle KO Trial 16772 20.9 Cool Wort Control 26470 Cool Wort Trial 23260 12.1 EOF Control 25369 EOF Trial 20606 18.8 Pkg Control 31326 86.9 26 0.714 0.124 Pkg Trial 18773 92.3 16 0.703 0.111 40.1 6.2 38.5 1.5 10.5 Trial 11 Area 10.sup.5 Lagtime Fe T2N T2N TBI Area 10.sup.5 Lagtime Fe T2N T2N TBI 1stWort Control 4 146 8.3 1stWort Trial 4 63 5.6 0.0 56.7 32.5 KETTLE Full Control 29 71 12.3 KETTLE Full Trial 19 50 10.0 34.6 30.0 18.7 Kettle KO Control 18 53 16.3 Kettle KO Trial 15 23 10.6 16.5 57.4 35.0 Cool Wort Control 31 64 20.9 Cool Wort Trial 22 31 10.9 27.3 51.4 47.8 Pkg Control 53 Pkg Trial 73 37.9 Trial 12 EPR T150 Lagtime Fe T2N T2N TBI EPR T150 Lagtime Fe T2N T2N TBI Cool Wort Control 93833 211 0.409 0.165 Cool Wort Trial 69672 188 0.433 0.179 25.7 11.1 5.7 8.2 EOF Control 29742 180.0 121 0.226 0.052 EOF Trial 33780 114.0 97 0.225 0.048 13.6 36.7 19.7 0.4 7.7 Aging Control 60836 101.0 26 0.234 0.061 Aging Test 76812 98.0 31 0.224 0.072 26.3 3.0 17.7 4.3 18.0 Pkg Control 62661 89 11 0.646 0.124 Pkg Trial 57159 79 18 0.564 0.115 8.8 11.2 63.6 12.7 7.3

[0099] Analytical data was taken and is shown in Table 4 and FIG. 3 for Trials 6, 12a, and 12b. Stale aldehydes, i.e., heptanal, hexanal, and octanal, were reduced in the trials, compared to the control, by 3.8, 6.6, and 13.3 percent, respectively. There were reduced Off-Taste/Aroma (OTA) complaints. The fresh flavored alcohols and fruity esters increased in the trials, showing a more fresh tasting beer after warm storage for 17 weeks at 75 F. Overall, the packaged Fe was lowered by 7.1 percent in the trials. Further, lower Fe will help mitigate Fenton catalytic reactive oxygen reactions and the decrease in Fe in the packaged beer supports and shows the chelation ability of gallotannins.

[0100] The use of gallotannin also showed an ability of gallotannin to reduce haze-active proteins in mashing and brewing without adversely affecting the foam-enhancing proteins in the beer. As such, this should reduce the need for polyvinyl polypyrrolidone, i.e., PVPP, in beer production filtration costs.

TABLE-US-00004 TABLE 4 6 12 Control Test Trial Pkg Control Pkg Trial Pkg Control Pkg Trial Avg Avg % T/C Heptanal ppb 0.22 0.21 0.04 0.04 0.130 0.125 3.8 Hexanal ppb 1.39 1.27 0.27 0.28 0.830 0.775 6.6 Octanal ppb 0.39 0.33 0.06 0.06 0.225 0.195 13.3 Polyphenols mg/L 93.5 95.9 70.5 75.4 82 86 4.5 Nibem 30 sec. 166 159 142 154 154 157 1.6 Total Esters mg/L 29.5 31.9 20.7 21.4 25 27 6.2 Total Vol mg/L 110.4 114.9 86.5 90 98 102 4.1 Amyl alcohol mg/L 12.6 12.9 11.5 11.8 12.05 12.35 2.5 Isoamyl alcohol mg/L 40.8 41.7 32.1 33.7 36.45 37.70 3.4 Isobutyl alcohol mg/L 11.1 11.4 7.9 8 9.50 9.70 2.1 Propanol mg/L 7.7 8.6 6.5 6.7 7.10 7.65 7.7 Ethyl acetate mg/L 27.1 29.4 18.7 19.3 22.90 24.35 6.3 Isoamyl acetate mg/L 2.1 2.2 1.8 1.8 1.95 2.00 2.6 Ethyl butyrate mg/L 11.1 11.4 0.1 0.1 5.60 5.75 2.7 Ethyl propanoate mg/L 7.7 8.6 0 0.1 3.85 4.35 13.0 Isopropyl acetate mg/L 27.1 29.4 0 0 13.55 14.70 8.5 Fe ppb 25.6 16 11 18 18.3 17.0 7.1 Total Forced EBC 0.23 0.13 0.51 0.42 0.370 0.275 25.7 Total Forced FTU 16 9 35 29 26 19 25.5

Example 3. Solid Carrier Test

[0101] Methods and Materials. Cone hops were ground into a fine powder to increase the efficiency of hop alpha, beta acids, hop oils, and total resin extraction by a liquid to super-critical CO.sub.2 phase solvent. Once the hop bitter resins were removed, the resulting debittered hop powder was removed and collected. The debittered powder was repelletized into a hop pellet. Table A below (from Sharp, D.C., Vollmer, D. M., YangPing Qian, and Shellhammer, T. H., J. Am. Soc. Brew. Chem. 75(2):101-108, 2917) shows typical alpha acid and beta acid levels in spent hops after super-critical CO.sub.2 extraction.

TABLE-US-00005 TABLE A Spent Hop Bittering Acid Specifications.sup.a UV/visible HPLC Variety Alpha % Beta % Alpha % Beta % Simcoe (2011)* 0.2 0.4 0.2 0.7 Cascade 0.3 0.4 0.2 0.0 Summit 0.8 0.3 0.1 0.0 Columbus (2011)* 0.6 0.6 0.4 0.0 Cluster 0.8 0.4 0.4 0.2 Horizon 0.1 0.1 0.0 0.0 Magnum 1.2 0.4 1.0 0.2 Nugget 0.6 0.4 0.5 0.1 Northern Brewer 0.2 0.1 0.1 0.0 Styrian Aurora 0.1 0.2 0.1 0.0 Nelson Sauvin 0.0 0.3 0.1 0.0 Hallertau Mittelfrh 0.2 0.2 0.1 0.0 Willamette 0.3 0.3 0.2 0.1 Centennial (2011)* 0.4 0.3 0.2 0.0 German Spalt 0.3 0.2 0.1 0.0 Tettnanger 0.3 0.1 0.1 0.0 Hersbrucker 0.2 0.1 0.0 0.0 Perle 1.0 0.2 0.6 0.2 .sup.aAsterick (*) indicates industrial-scale supercritical fluid CO.sub.2 extraction.

[0102] The hop pellet composition comprising a spent by-product of natural hop pellets and hop extract was added at 511 ppm to the malt mash-in vessel of a lager-style beer at the start of malt mash-in and at the same time as was done with the compositions in Example 2.

[0103] Results. With reference to Table 5, the trials that included the solid carrier were added to the malt mash-in and the brew kettle. The trials showed a significant improvement in the flavor stability and, in particular, in reducing the papery stale off flavor thereof.

TABLE-US-00006 TABLE 5 MVB MVB MVB MVB Brewery: Test 1 Test 2 Test 3 Control Sample ID: CDHMASHING CDHKETTLE CO2MASHING Control Package Code: 8 WK ANOVA Point Point Point Point Target LTL UTL Weighting F-value p-value Average Loss Average Loss Average Loss Average Loss Estery 3 2.9 3.1 0.65 1.2 1.11 1.3 1.04 1.2 1.11 1.2 1.11 Hoppy 2 1.9 2.1 1.00 1.8 0.10 1.8 0.10 1.9 1.7 0.20 Stale 0.0 0.3 1.80 2.5 3.96 2.3 3.60 3.1 5.04 2.8 4.50 Yeast Sulphurs 0.0 0.1 1.65 0.1 0.0 0.1 0.3 0.33 Non-Yeast Sulphurs 0.0 0.1 1.65 0.0 0.0 0.0 0.0 Isoamyl Acetate 2 1.9 2.1 0.35 1.23 0.32 0.6 0.46 0.8 0.39 0.6 0.46 0.6 0.46 (Estery) Ethyl Hexanoate 0.0 0.0 0.00 0.40 0.75 0.2 0.1 0.2 0.2 (Estery) Ethyl Acetate 0.0 0.0 0.00 0.00 1.00 0.4 0.4 0.4 0.4 (Estery) Kettle Hop 0.0 0.0 0.00 1.0 0.41 1.7 1.7 1.7 1.6 (Hoppy) Hop Oil 0.0 0.0 0.00 1.00 0.41 0.1 0.1 0.2 0.1 (Hoppy) Malty 2 1.9 2.1 1.00 0.64 0.59 2.0 1.9 1.9 2.0 Sour 1 0.9 1.1 1.00 1.00 0.41 1.1 1.0 1.2 0.10 1.3 0.20 Sweet 2 1.9 2.1 1.00 1.33 0.29 2.0 1.8 0.10 2.1 1.8 0.10 Bitter 2 1.9 2.1 1.00 1.25 0.31 1.9 2.1 1.9 2.0 Astringent 1 0.9 1.1 1.00 1.80 0.17 1.4 0.30 1.7 0.60 1.5 0.40 1.3 0.20 Body 2 1.9 2.1 1.00 0.00 1.00 2.0 2.0 2.0 2.0 Diacetyl 0.0 0.3 1.50 1.07 0.38 0.3 0.1 0.1 0.0 H2S (Yeast 0.0 0.0 0.00 1.00 0.41 0.0 0.0 0.1 0.2 Sulphurs) Mercaptan 0.0 0.0 0.00 1.00 0.41 0.0 0.0 0.0 0.1 (Yeast Sulphurs) Autolysed 0.0 0.0 0.00 1.00 0.41 0.1 0.0 0.0 0.0 (Yeast Sulphurs) Oxidized (Stale) 0.0 0.0 0.00 0.50 0.68 1.6 1.4 1.6 1.3 Papery (Stale) 0.0 0.0 0.00 2.97 0.05 0.9 0.9 1.5 1.5 Metallic 0.0 0.5 1.30 1.98 0.14 0.3 0.0 0.0 0.0 MCTS Score: 4.07 4.17 2.89 2.90 Total Point 5.9 5.8 7.1 7.1 Loss:

TABLE-US-00007 TABLE 6 % 32-wks T-FSP vs. % 56-wks T-FSP vs. Active Active State Compound At 75 F. CR.sup.2 At 75 F. CR.sup.2 Early Late Free Stale Aldehydes FREE 2-Furfural 13.72% .sup.I 0.9938 .sup.I 15.93% .sup.I 0.9866 .sup.I *** .sup.I ** .sup.I FREE Methional 3.49% .sup.I 0.9996 .sup.I 0.91% 0.8583 *** .sup.I NS FREE 5-Methyl furfural 7.75% .sup.I 0.9971 .sup.I 0.02% 0.6833 *** .sup.I NS FREE Phenylacetaldehyde 9.56% .sup.I 0.9961 .sup.I 8.07% .sup.I 0.9598 .sup.I *** .sup.I ** .sup.I FREE Pentanal 1.24% .sup.I 0.9952 .sup.I 3.94% .sup.I 0.9157 .sup.I *** .sup.I * .sup.I FREE Octanal 4.38% .sup.I 0.9788 .sup.I 4.31% .sup.I 0.9747 .sup.I ** .sup.I ** .sup.I FREE 3-Methyl butanal 3.36% .sup.I 0.9651 .sup.I 2.64% .sup.I 0.9616 .sup.I ** .sup.I ** .sup.I FREE Heptanal 6.18% .sup.I 0.9448 .sup.I 5.59% .sup.I 0.9010 .sup.I * .sup.I * .sup.I FREE E-2-Octenal 10.36% 0.8894 1.62% .sup.I 0.9161 .sup.I NS * .sup.I Avg 6.21% .sup.I 0.9838 .sup.I 5.21% .sup.I 0.9140 .sup.I ** .sup.I * .sup.I % Free Stale Aldehydes 36.1% 43.9% *** >99% C.L. % Bound Stale Aldehydes 63.9% 56.1% ** >95% C.L. Green = Improvement (.sup.I) * >90% C.L. NS Not Significant Total (Free & Bound) Stale Aldehydes TOTAL Heptanal 7.90% .sup.I 1.0000 .sup.I 9.43% .sup.I 0.9678 .sup.I *** .sup.I ** .sup.I TOTAL Phenylacetaldehyde 8.76% .sup.I 0.9960 .sup.I 7.72% 0.7327 *** .sup.I NS TOTAL Benzaldehyde 10.88% .sup.I 0.9936 .sup.I 11.66% .sup.I 0.9817 .sup.I *** .sup.I ** .sup.I TOTAL E-2-Octenal 8.40% .sup.I 0.9908 .sup.I 88.88% 0.8483 *** .sup.I NS TOTAL Pentanal 8.40% .sup.I 0.9908 .sup.I 10.96% 0.8228 *** .sup.I NS TOTAL Octanal 5.02% .sup.I 0.9837 .sup.I 6.34% 0.8927 ** .sup.I NS TOTAL 5-Methyl furfural 6.52% .sup.I 0.9683 .sup.I 6.44% .sup.I 0.9716 .sup.I ** .sup.I ** .sup.I TOTAL Hexanal 10.41% .sup.I 0.9605 .sup.I 11.69% .sup.I 0.9029 .sup.I ** .sup.I * .sup.I TOTAL 2-Furfural 16.62% .sup.I 0.9548 .sup.I 15.93% .sup.I 0.9479 .sup.I ** .sup.I * .sup.I TOTAL E,Z-2,6-Nonadienal 24.88% .sup.I 0.9493 .sup.I 23.21% .sup.I 0.9571 .sup.I * .sup.I ** .sup.I TOTAL 2-Methyl butanal 4.12% .sup.I 0.9362 .sup.I 4.70% .sup.I 0.9334 .sup.I * .sup.I * .sup.I Avg 17.22% .sup.I 0.9749 .sup.I 11.87% .sup.I 0.9518 .sup.I ** .sup.I ** .sup.I % Free Stale Aldehydes 36.1% 43.9% *** >99% C.L. % Bound Stale Aldehydes 63.9% 56.1% ** >95% C.L. Green = Improvement (.sup.I) * >90% C.L. NS Not Significant

[0104] Overall, as shown in FIG. 4, the estimated improvement of the solid carrier added to the lager beer trials at the start of malt mash-in was 2.3 weeks of increased flavor stability, i.e., about 20.4%, over the control beer. There were reduced Off-Taste/Aroma (OTA) complaints.

Example 4. Solid Hop Carrier Test 1

[0105] Methods and Materials. Testing was performed on ten brews of a lager-style beer. A solid hop carrier was added to the malt mash-in vessel in a dry pellet form at the start of malt mash-in, as the liquefied malt tangentially entered the malt mash-in vessel. The tests were compared to a control sample after a total of 26 weeks and at roughly 75 F. The comparative results were measured every two weeks. Further, a mean of the results for the ten brews was calculated.

[0106] Results. As shown in FIG. 5, the lager-style beer test trials showed significant improvement in flavor stability by generally reducing the papery, oxidized, and stale off-notes in the test trials over the 26 week period.

Example 5Solid Hop Carrier Test 2

[0107] Methods and Materials. Testing was performed on six brews of a lager-style beer. A composition comprising a solid hop carrier was added to the malt mash-in vessel in a dry pellet form at the start of malt mash-in, as the liquefied malt tangentially entered the malt mash-in vessel. The tests were compared to a control sample after a total of four weeks and at roughly 75 F. A sensory evaluation was performed on the fresh brew and then subsequently every two weeks for a total of four weeks. The tests were carried out until the control and test trials diverged therefrom. Further, a mean of the results for the six brews was calculated.

[0108] Results. As shown in FIGS. 6 and 7, the lager-style beer test trials showed significant improvement in flavor stability by reducing the papery and stale-roll up off-note in the beer, along with and improved the flavor stability of the fermented beverage by an increased 1.4 weeks. The trial, labeled as SHN CDH Chinook in FIG. 6 used Chinook hops in which the hop bitter resins were removed, and the resulting debittered hop powder was repelletized into a Choice Debittered Hops (CDH) pellet. In this trial, there were reduced Off-Taste/Aroma (OTA) complaints. See FIG. 7.

Example 6Gallotannin and Solid Hop Carrier Test

[0109] Methods and Materials. Testing was performed on 176 brews of a lager-style beer. A composition comprising gallotannin powder and a solid hop powder carrier in which the hop bitter resins were removed using super-critical CO.sub.2 extraction was added at 537 ppm to the malt mash-in vessel in a dry pellet form at the start of malt mash-in, as the liquefied malt tangentially entered the malt mash-in vessel. The weight ratio of gallotannin powder to solid hop powder was 1:9. The tests were compared to a control sample after a total of 18 weeks and at roughly 75 F. The comparative results were measured every two weeks. Further, the composition outperformed the control beer showing reduced stale and sulphitic staling notes. Off Taste/Aroma (OTA) complaints were non-existent during this period.

[0110] Results. As shown in FIGS. 8 and 9 (in which the trial is labeled as GOL CRLT FSP), the lager-style beer test trials showed significant improvement in flavor stability.

[0111] Results. As shown in Table 6, the usage of the flavor stability pellet comprising gallotannin powder and a solid hop powder carrier in which the hop bitter resins were removed using super-critical CO.sub.2 extraction in mashing had a significant, positive impact in reducing the development of several off-taste stale aldehydes in the aged beer, both in the free-state and total (free+bound) state. In the trials of Table 6 and FIG. 10, the flavor stability pellet (FSP) had a weight ratio of gallotannin powder to solid hop powder of 1:20. The shift in the 32-weeks versus 56-weeks free:bound aldehyde ratio (36.1:63.9 versus 43.1:56.1, respectively) indicated that the bound stale aldehydes are still being released into a free state in packaged beer and the FSP test beer is still effective in showing improved reduction in staling at 56-weeks.

[0112] As shown in FIG. 10, lab-scale tests where FSP was dosed at various levels from: zero addition (control) to low (269 ppm FSP based on mash), medium (537 ppm FSP based on mash), high (805 ppm FSP based on mash), and very (v.) high levels (1073 ppm FSP based on mash) at the start of mashing. Samples were taken at the end of mashing and analyzed for Cu and Fe metals using an ICP metals method. The graph clearly shows the positive chelation of Cu and Fe levels starting at the medium dosage rate of FSP and improving as the dosage is increased to a very high level. With mitigation though chelation of divalent transition metals like copper and especially iron, the catalysis for reactive oxygen species (ROS) radical generation is also mitigated, which results in less aldehyde production and a more flavor stable beer.

Summary of Examples 1-6

[0113] The CDH hop polyphenols appeared to retard the ROS staling reactions in the malt mash by both antioxidative hydrogen abstraction and transition metal chelation. Since a connection between sensory papery off-notes and the compound t-2-nonenal (t2N) in stale beer has been established, the antiradical activity of CDH is focused on the inactivation and retardation of lipoxygenase A and B (LOX). LOX levels in malt are known to promote stale precursor compounds through enzymatic and free radical oxidation of the unsaturated fatty acids (UFA) and the fact that the LOX enzyme needs Fe to function. The strong stale compound, t2N is a product of UFA oxidation. Thus, the extremely low papery levels in 26-week old beer stored at 75 F. strongly indicates that the antiradical activity of CDH hop polyphenols is due to a strong chelating capability to remove divalent metal catalysts, such as iron, copper and manganese, preventing t2N production from free radical oxidation of UFA.

[0114] The production of t2N and the precursors of other stale compounds are mitigated and the harmful LOX activity is denatured by these hop polyphenols. Its use in malt mashing, improves the known staling LOX effect by giving normal malt a low LOX activity quality.

[0115] The hop polyphenols and the gallotannin powders act as antioxidant utilizing both metal chelation and ROS quenching by hydrogen abstraction. When formed in a pellet using the appropriate amount of water to bind the pellet together, the pellet provides a slow release of the gallotannins and hop polyphenols by controlling the moisture %, pellet tightness and dispersion rate (e.g., 4-10% moisture, medium-crumbly tightness, dispersion rate in 65 C. H.sub.2O of 8-15 minutes).

[0116] Thus, the invention provides compositions and methods for flavor stabilizing the flavor of a fermented beverage (e.g., beer) by the addition prior to, or during an early stage of, fermentation of a composition comprising a tannin and a solid carrier therein.

[0117] Although the invention has been described in considerable detail with reference to certain embodiments, one skilled in the art will appreciate that the present invention can be practiced by other than the described embodiments, which have been presented for purposes of illustration and not of limitation. Therefore, the scope of the appended claims should not be limited to the description of the embodiments contained herein.