WO2010040114A1

WO2010040114A1 - Process for extending beverage stability

Info

Publication number: WO2010040114A1
Application number: PCT/US2009/059459
Authority: WO
Inventors: Christopher D. Timmons; Drew Johansson; Kathrine A. Hall
Original assignee: Asemblon, Inc.
Priority date: 2008-10-02
Filing date: 2009-10-02
Publication date: 2010-04-08

Abstract

There is disclosed a method for removing metal ions from a beverage by exposing the beverage to a porous silica gel functionalized with a metal chelating agent and then later removing the porous silica gel from the beverage. There is further disclosed various materials that can be used, during processing, to improve the shelf life of beverage, such as beer, wine and other alcoholic beverages. More specifically, there is disclosed an anti-oxidation process comprising the chelating of transition and alkaline earth metal ions, such as Fe, Cu, Mn and Mg, via a cross- linked chelation moiety in an extremely thin or monolayer coating that is bound to a porous solid phase through surface hydroxyl groups and a silane moiety. There is disclosed a beer beverage that is characterized by having an iron and copper content lower than any content previously achieved due to the inherent introduction of iron and copper ions from the source hops or other component materials.

Description

Process for Extending Beverage Stability Technical Field

The present disclosure provides a method for removing metal ions from a beverage by exposing the beverage to a porous silica gel functionalized with a metal chelating agent and then later removing the porous silica gel from the beverage. This disclosure also provides various materials that can be used, during beverage processing, to improve the shelf life of beverage. Beverages that are candidates for the disclosed process include, for example, beer, wine and other alcoholic beverages. More specifically, the present disclosure provides an anti-oxidation process comprising chelating transition and alkaline earth metal ions, such as Fe, Cu, Mn, and Mg with a cross-linked chelation moiety in an extremely thin or monolayer coating that is bound to a porous solid phase through surface hydroxyl groups and a silane moiety. The present disclosure further provides a beer beverage that is characterized by having a reduced iron and copper content in beer whereby the inherent introduction of iron and copper ions is from beer sources such as hops, brewing water, barley (malted), stainless steel vessels, and filtration aids. Background

Several beverages, including fruit juices, wine, sake and beer are colloidally unstable. Beer, in particular, forms a haze that can be seen as visible light passes through it. This haze is known to brewers as NMPs (non-microbiological particles). Throughout the brewing process, steps are taken to minimize NMP formation and development to provide more colloidal stability to the resulting beer product. NMPs are generated by agglomeration of proteins (17-45%) and polyphenolic compounds (-17%). NMPs form beginning with polymerization of polyphenolic compounds by an oxidation reaction catalyzed by any free radical oxygen present. The less soluble polyphenolic polymers form aggregates with proteins wherein the aggregates formed can range in size from 1-30 micrometers (average diameter). The beer brewing process seeks to remove NMPs wherever possible so that the resulting product will not contain the visible haze. The brewing process for NMP removal is generally through a filtration. However, as packaged beer ages, further oxidation of the beer will result in more haze formation. Thus, brewers have been using filter aids (such as amorphous silica and polyvinylpolypyrolidone (PVPP)) that are mixed with pre-filtered beer to adsorb non-aggregated (soluble) polyphenols and proteins to remove them so past-packaging oxidation will not generate haze. However, filter aides while effective in removing much of the soluble polyphenols and proteins, do not address the problem of beverage oxidation. Oxidation continues to generate free radical oxygen species that, in turn, generate off-flavors of the beverage product. Therefore, there is a need in the field of beverage manufacture to improve shelf life of beverage products that get "spoiled" due to oxidation of the beverage product. The present disclosure provides a process for producing beverages with enhanced shelf life due to removal of those elements that catalyze the oxidation of such beverages, particularly beer.

In filtering beverages, such as beer, filtration steps often pass the beverage through filter media. Filter media, often includes beds of loose diatomaceous earth. Filter sheets incorporating diatomaceous earth with fibers such as cellulose are also used. Such sheets of filter media often contain small amounts of various minerals, including iron compounds. A certain portion of the iron content is soluble in the beverages which are treated and called "beverage soluble iron" or "BSI." The presence of high levels of BSI is detrimental to taste and stability of the beverages. Therefore, while it is certainly desirable to have filter media with low soluble iron content, it is also desirable to selectively remove iron from the beverage.

U.S. Patent 4,134,857 addresses this problem by removing iron from the filter media and providing low iron content for use in filtering beverages. However, this does not address other sources of iron in the beverage.

Other methods for treating diatomaceous earth used as filter aids in beverages are described in U.S. Patents 4,187,174; 2,701,240; and 1,992,647. Therefore, the processes that have been available for many decades have focused on treating the filter aids and not the actual beverage to remove soluble iron.

For wines, a "blue fining" process involves treating the wine beverage with potassium hexacyanoferrate (II) along with precipitation with sparingly soluble Prussian blue. Other metal ions, including Cu, Zn, Mn and Cd are co-precipitated. While the blue fining process is established, there are disadvantages in terms of toxicology and in terms of titrating correctly the amount of potassium hexacyanoferrate (II) or else too high a dose will form hydrocyanic acid and too low a dose will result in cloudy wine.

In many products in the food and beverage industry spoilage and/or shelf-life is largely affected by oxidation in a negative way. For example, in beer, metal ions Fe(II), Fe(III), Cu(I), and Cu(II) react with various oxygen-containing chemicals to produce free radical oxygen species, that are responsible for degrading the flavor and shortening the beer shelf life. Therefore, there is a need in the art to significantly reduce iron and other metal soluble ion contents in beverages.

The present disclosure was made to address this issue.

Summary

The present disclosure provides a process for making beverages more stable to oxidation, comprising:

(a) adding a chelating compound, linked to a porous solid phase, comprising a covalent or semi-covalently bound anchor moiety, a linker moiety and a chelating moiety to the beverage to chelate free metal ions in the beverage; and

(b) removing the solid supported chelating compound and the solid support from the beverage prior to packaging.

Preferably, the chelating compound is silane linked to a hydroxylated surface such as silicon dioxide, and has a triaminetetraacetate (TTA) chelating moiety. Preferably, the silane anchor moiety of the chelating compound is a polymerized mixture of a SiO₂ (formula (I) of a composition having a structure: Silane Moiety - C2-20 alkane - chelating moiety (I) wherein the chelating moiety is triaminetetraacetate (TTA) in either the acidic, basic (tetrasodium salt), or neutral (disodium salt) form, or a mixture thereof. Preferably, the composition is selected from the group consisting of: N-(trimethoxysilylpropyl) diethylenetriaminetetraacetic acid, sodium salt Si-TTA-COONa; N-(trimethoxysilylpropyl) diethylenetriaminetetraacetic acid (Si-TTA- COOH); N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Si-Triamine); N-(2-aminoethyl)-3- aminopropylmethyldimethoxysilane; (3-trimethoxysilylpropyl) diethylenetriamine; N- (trimethoxysilylpropyl) ethylenetriamine, triacetic acid, sodium salt; 2-(trimethoxysilylpropanol)- 1,3-diamino~N,N,N',N'-tetraacetic acid; mixture of N-(2-aminoethyl)-3- aminopropylmethyldimethoxysilane and tetra(ethylene glycol) trimethoxysilane; mixture of 3- (trimethoxysilylpropyl) diethylenetriamine and tetra(ethylene glycol) trimethoxysilane; mixture of N-(trimethoxysilylpropyl) ethylenediamine, tridactic acid, sodium salt, and tetra(ethyleneglycol) trimethoxysilane; mixture of 2-(trimethoxysilylpropanol)- 1 ,3-diamino— N,N,N',N'-tetraacetic Acid and tetra(ethylene glycol) trimethoxysilane; vinylmethoxysilane, vinyltrimethoxysilane, vinylethoxy silane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- glycidoxypropyltrimethoxysilane, 3 -methacryloxypropyltrimethoxy silane, 3- mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine, N,N'-bis [3 -(trimethoxysilyl)propyl] ethylenediamine, N-(beta-aminoethyl)-gamma- aminopropylmethyldimethoxysilane, N-(beta-aminoethyl)-gamma-aminopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma- glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma- glycidoxypropylmethyldimethoxysilane, 2-(3 ,4-epoxycyclohexyl)ethyltrimethoxysilane, gamma- methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma- mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, N- [2- (vinylbenzylamino)ethyl]-3- aminopropyltrimethoxysilane, and combinations thereof. Preferably, the silane moiety is on a porous substrate selected from the group consisting of silica gel, CPG (controlled pore glass), synthetic or natural polymer, and combinations thereof. The present disclosure further provides a beer product made by a brewing process further comprising:

(a) adding a chelating compound, linked to a porous solid phase, comprising a covalent or semi-covalently bound anchor moiety, a linker moiety and a chelating moiety to the beverage to chelate free metal ions in the beverage; and (b) removing the solid supported chelating compound and the solid support from the beverage prior to packaging.

Preferably, the chelating compound is silane linked to a hydroxylated surface such as silicon dioxide, and has a triaminetetraacetate (TTA) chelating moiety. Preferably, the silane anchor moiety of the chelating compound is a polymerized mixture of a SiO₂ (formula (I) of a composition having a structure:

Silane Moiety - C2-20 alkane - chelating moiety (I) wherein the chelating moiety is triaminetetraacetate (TTA) in either the acidic, basic (tetrasodium salt), or neutral (disodium salt) form, or a mixture thereof. Preferably, the composition is selected from the group consisting of: N-(trimethoxysilylpropyl) diethylenetriaminetetraacetic acid, sodium salt Si-TTA-COONa; N-(trimethoxysilylpropyl) diethylenetriaminetetraacetic acid (Si-TTA- COOH); N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Si-Triamine); N-(2-aminoethyl)-3- aminopropylmethyldimethoxysilane; (3-trimethoxysilylpropyl) diethylenetriamine; N- (trimethoxysilylpropyl) ethylenetriamine, triacetic acid, sodium salt; 2-(trimethoxysilylpropanol)- 1,3-diamino~N,N,N',N'-tetraacetic acid; mixture of N-(2-aminoethyl)-3- aminopropylmethyldimethoxysilane and tetra(ethylene glycol) trimethoxysilane; mixture of 3-

(trimethoxysilylpropyl) diethylenetriamine and tetra(ethylene glycol) trimethoxysilane; mixture of N-(trimethoxysilylpropyl) ethylenediamine, tridactic acid, sodium salt, and tetra(ethyleneglycol) trimethoxysilane; mixture of 2-(trimethoxysilylpropanol)- 1 ,3-diamino~N,N,N',N'-tetraacetic Acid and tetra(ethylene glycol) trimethoxysilane; vinylmethoxysilane, vinyltrimethoxysilane, vinylethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- glycidoxypropyltrimethoxysilane, 3 -methacryloxypropyltrimethoxy silane, 3 - mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N-(beta-aminoethyl)-gamma- aminopropylmethyldimethoxysilane, N-(beta-aminoethyl)-gamma-aminopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma- glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma- glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, gamma- methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma- mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, N- [2- (vinylbenzylamino)ethyl]-3- aminopropyltrimethoxysilane, and combinations thereof. Preferably, the silane moiety is on a porous substrate selected from the group consisting of silica gel, CPG (controlled pore glass), synthetic or natural polymer, and combinations thereof.

The present disclosure further comprises a beer product having a reduced concentration of iron, wherein the iron concentration of a malt beer, light lager or ale is less than 0.05 mg/L, of a dark lager or ale is less than 0.10 mg/L and of a Porter or stout beer is less than 0.25 mg/L.

The present disclosure further provides a beer product having a reduced concentration of iron, wherein the iron concentration of a malt beer, light lager or ale is less than 0.05 mg/L, of a dark lager or ale is less than 0.10 mg/L and of a Porter or stout beer is less than 0.25 mg/L, produced by a process comprising:

Preferably, the chelating compound is silane linked to a hydroxylated surface such as silicon dioxide, and has a triaminetetraacetate (TTA) chelating moiety. Preferably, the silane anchor moiety of the chelating compound is a polymerized mixture of a SiO₂ (formula (I) of a composition having a structure: Silane Moiety - C2-20 alkane - chelating moiety (I) wherein the chelating moiety is triaminetetraacetate (TTA) in either the acidic, basic (tetrasodium salt), or neutral (disodium salt) form, or a mixture thereof. Preferably, the composition is selected from the group consisting of: N-(trimethoxysilylpropyl) diethylenetriaminetetraacetic acid, sodium salt Si-TTA-COONa; N-(trimethoxysilylpropyl) diethylenetriaminetetraacetic acid (Si-TTA- COOH); N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Si-Triamine); N-(2-aminoethyl)-3- aminopropylmethyldimethoxysilane; (3-trimethoxysilylpropyl) diethylenetriamine; N- (trimethoxysilylpropyl) ethylenetriamine, triacetic acid, sodium salt; 2-(trimethoxysilylpropanol)- 1,3-diamino~N,N,N',N'-tetraacetic acid; mixture of N-(2-aminoethyl)-3- aminopropylmethyldimethoxysilane and tetra(ethylene glycol) trimethoxysilane; mixture of 3- (trimethoxysilylpropyl) diethylenetriamine and tetra(ethylene glycol) trimethoxysilane; mixture of N-(trimethoxysilylpropyl) ethylenediamine, tridactic acid, sodium salt, and tetra(ethyleneglycol) trimethoxysilane; mixture of 2-(trimethoxysilylpropanol)- 1 ,3-diamino~N,N,N',N'-tetraacetic Acid and tetra(ethylene glycol) trimethoxysilane; vinylmethoxysilane, vinyltrimethoxysilane, vinylethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine, N,N'-bis [3 -(trimethoxysilyl)propyl] ethylenediamine, N-(beta-aminoethyl)-gamma- aminopropylmethyldimethoxysilane, N-(beta-aminoethyl)-gamma-aminopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma- glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma- glycidoxypropylmethyldimethoxysilane, 2-(3 ,4-epoxycyclohexyl)ethyltrimethoxysilane, gamma- methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma- mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, N- [2- (vinylbenzylamino)ethyl]-3- aminopropyltrimethoxysilane, and combinations thereof. Preferably, the silane moiety is on a porous substrate selected from the group consisting of silica gel, CPG (controlled pore glass), synthetic or natural polymer, 2-[2-(bis(carboxymethyl)amino)ethyl-(2- methylamino-2-oxoethyl)amino] acetic acid,and combinations thereof. Brief Description of the Figures

Figure 1 shows a molecular structure of a TTA monolayer on a silicon dioxide surface. Figure 2 shows an EPR oxidation profile of New Belgium Fat Tire (beer). The data set

TTA-Si is an average of 5 experiments exposing TTA-Si (166 g/hL) to Fat Tire beer for 30 min, followed by removal of the TTA-Si via centrifugation and forced aging of the beer supernatant for 48 hrs at 32 ºC. The data set labeled "Control" represents an average of 5 samples of non-treated Fat Tire Beer exposed to identical aging parameters.

Figure 3 shows an EPR oxidation profile of New Belgium Fat Tire and triamine-Si. The data set Triamine-Si is an average of 2 experiments exposing Triamine-Si (166 g/hL) to Fat Tire beer for 30 min, followed by removal of the Triamine-Si via centrifugation and forced aging of the beer supernatant for 48 hrs at 32 ºC. The data set labeled "Control" represents an average of 2 samples of non-treated Fat Tire Beer exposed to identical aging parameters.

Figure 4 shows an EPR oxidation profile of Sierra Nevada Pale Ale with TTA-Si. The data set TTA-Si is an average of 4 experiments exposing TTA-Si (166 g/hL) to Sierra Nevada beer for 30 min, followed by removal of the TTA-Si via centrifugation and forced aging of the beer supernatant for 48 hrs at 32 ºC. The data set labeled "Control" represents an average of 4 samples of non-treated Sierra Nevada Beer exposed to identical aging parameters.

Figure 5 shows an EPR oxidation profile of Sierra Nevada Pale Ale with triamine antioxidant. The data set Triamine is an average of 2 experiments exposing Triamine-Si (166 g/hL) to Sierra Nevada beer for 30 min, followed by removal of the Triamine-Si via centrifugation and forced aging of the beer supernatant for 48 hrs at 32 ºC. The data set labeled "Control" represents an average of 2 samples of non-treated Sierra Nevada Beer exposed to identical aging parameters.

Figure 6 shows an EPR oxidation profile of Sam Adams Boston Lager with Triamine-Si Antioxidant. The data set Triamine is an average of 2 experiments exposing Triamine-Si (166 g/hL) to Sam Adams beer for 30 min, followed by removal of the Triamine-Si via centrifugation and forced aging of the beer supernatant for 48 hrs at 32 ºC. The data set labeled "Control" represents an average of 2 samples of non-treated Sam Adams Beer exposed to identical aging parameters. Figure 7 shows an EPR oxidation profile of Corona Lager with Triamine-Si antioxidant.

The data set Triamine is an average of 2 experiments exposing Triamine-Si (166 g/hL) to Corona beer for 30 min, followed by removal of the Triamine-Si via centrifugation and forced aging of the beer supernatant for 48 hrs at 32 ºC. The data set labeled "Control" represents an average of 2 samples of non-treated Corona Beer exposed to identical aging parameters. Figure 8 shows an EPR oxidation profile of Woodridge Cabernet Sauvignon with TTA-Si.

The data set TTA-Si is an average of 2 experiments exposing TTA-Si (166 g/hL) to Cabernet Sauvignon for 30 min, followed by removal of the TTA-Si via centrifugation and forced aging of the wine supernatant for 48 hrs at 32 ºC. The data set labeled "Control" represents an average of 2 samples of non-treated Cabernet Sauvignon exposed to identical aging parameters.

Figure 9 depicts the proton NMR spectra for the TTA-Si stability study described in Example 2. It indicates that nothing from the coating leached off into the model beer. The NMR spectra shown in Figure 10 depict the control sample from the experiment shown in Figure 9 and described in Example 2. Detailed Description Process for Functionalizing Silica

Silica is functionalized by using the silane derivative of the tetrasodium salt of TTA (ethylenediaminetriaceticacid acetamide). The silane coating is stable to about pH 2.0 at about 250 ºC and will not leach off the solid phase into a beverage. Thus, the functionalized silica and adsorbed metal ions (chelated) are insoluble and can be removed from the beverage product through filtration or even centrifugation. In beer, for example, from about 10 to about 200 g/hL of the disclosed functionalized silica (considered the disclosed "filter aide) is added either alone or with other commonly used filter aides for beer production (i.e., brewing). Contact times or the time from addition of the product to the beverage to its removal can range from minutes to hours depending on the desired result. Alternatively, the filter aide can be used as a fining agent for clarifying cask-brewed beer. The filter aide is added to a brite tank or the fermenter, alone or with other fining agents, and allowed to settle over time. The materials to be mixed with the beverage are applied to porous silica materials with a hydroxylated surface. The coatings are applied using roughly 0.03-0.06 mmol of the coating molecule per gram of silica gel by a soak method. Specifically, a 2-4% solution of silane (one of each of (1) N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, (2) (3-trimethoxysilylpropyl) diethylenetriamine, triacetic acid sodium salt, (3) N-trimethoxysilypropyl) ethylenediamine, triacetic acid sodium salt, (4) 2-(trimethoxysilylpropanol)-1,3-diamino~N,N,N',N'-tetraacetic acid, (5) mixture of N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane and tetra(ethylene glycol) trimethoxysilane, (6) mixture of 3-trimethoxysilypropyl) diethylenetriamine and tetra(ethylene glycol) trimethoxysilane, (7) mixture of N-( trimethoxysilylpropyl) ehtylenediamine, triacetic acid sodium salt and tetra(ethyleneglycol) trimethoxysilane, and (8) mixture of 2- (trimethoxysilylpropanol)-l ,3-diamino~N,N,N',N'-tetraacetic Acid and tetra(ethylene glycol) trimethoxysilane) in ethanol was prepared. A slurry of silica gel (get silica specs) was suspended in the2-4% solution for 30 min. Silica gel was removed via filtration on a buchner funnel and rinsed with ethanol (30 mL), distilled water (30 mL), and ethanol (30 mL). The silica gel was placed in a vacuum oven for 10 min at 110 ºC and 450 mTorr.

Chemical characterization of the coatings was achieved via x-ray photoelectron spectroscopy (XPS). Table 1 below provides the XPS data for the TTA-Si (tetrasodium salt) and Triamine-Si coatings on silica gel, as well as non-coated silica gel which represents a reference blank.

In beer, the anti-oxidation effect of the coatings was assessed using electron paramagnetic resonance (EPR) spectroscopy. As beer ages, EPR lag time for beer exposed to both TTA-Si and Triamine-Si, increases when compared to a control. The increase in lag time correlated to a lower concentration of free radical oxygen species, which, when reduced, correlates to a longer shelf life. For beers that do not have an EPR lag time, exposure to TTA-Si and Triamine-Si slows the rate of free radical production during forced aging, indicating an increase in beer stability.

Figure 2 shows an EPR oxidation profile of New Belgium Fat Tire after treatment with TTA-Si sodium salt. The data set TTA-Si is an average of 5 experiments where triaminetettracetate tetra sodium salt (triaminetetraacetate supported silica, Aldrich), silica supported (TTA-Si, 166 g/hL) was mixed with 30 mL of degassed bottled beer (1.5 min of sonication at room temperature) in a 50 mL conical centrifuge vial - and stirred for 30 min. TTA- Si was then removed from the beer via centrifugation (5 min at 1000 rpm). After centrifugation, 20 mL of the beer were removed from the conical vial (leaving 10 mL of beer and the pellet of spent TTA-Si in the centrifugation vial) and placed in a 20 mL clear glass scintillation vial and sealed under nitrogen gas. The 20 ml samples were then stored in the dark in a water bath at 32 ºC for 48 hours. The samples were frozen solid in a lab freezer, packaged on dry ice, and sent to Bruker Biospin for EPR analysis. The data set labeled "Control" in Figure 2 represents an average of 5 samples of non-treated Fat Tire Beer. Since centrifugation was used to remove the silica gel from the TTA-Si samples, the Control samples were also subjected to the exact same centrifugation method to eliminate variables. Degassed bottled beer (1.5 min of sonication at room temperature) (30 mL) was placed in a 50 mL conical centrifugation vial and stirred for 30 min. The beer was then centrifuged (5 min at 1000 rpm) and 20 mL were removed from the centrifuge vial using a pipetmen and placed in a 20 mL clear glass scintillation vial. The samples were sealed under nitrogen, frozen solid, and sent away for EPR analysis. The 20 ml samples were then stored in the dark in a water bath at 32 ºC for 48 hours. The samples were frozen solid in a lab freezer, packaged on dry ice, and sent to Bruker Biospin for EPR analysis. Analysis at Bruker Biospin was conducted their beer analysis method that is certified by the American Society of Brewing Chemists (ASBC).

The procedure for the ASBC EPR method is as follows. The samples were degassed and added to 15 mL septum capped vials. Next, the spin trap reagent N-t-butyl-phenylnitrone (PBN) was dispensed into the liquid, mixed thoroughly and the vial thus prepared was placed in a heating block at 60 ºC. The Bruker e-scan epr spectrometer was used to record EPR measurements every ~20 minutes for approximately 3 hr, the samples remained in the heating block at 60 ºC for the entire experiment. The reference reagent used in the experiment was 2,2,6,6- tetramethylpiperidine-N-oxyl (TEMPO) and was analyzed every ~20 min during the experiment at 60 ºC. The error bars show the standard deviations for each measurement.

Table 2 below shows the average EPR intensity readings at 150 minutes during a 3 hr long EPR experiment for both the control and TTA-Si sample sets with New Belgium Fate Tire Ale. The intensity at 150 min of aging at 60 ºC is commonly called the T- 150 value. In a large production brewery, it is inefficient to display full oxidation profiles, such as Figure 2, for beer coming off the assembly line. Brewers have decided that the T-150 value is a good measure for quality offered by a single data point. Table 2 also displays the average EPR Lag Time for both the control and TTA-Si sample sets with New Belgium Fat Tire Ale. As beer and other beverages are oxidized the natural antioxidants present will impede oxidation for a certain time until they are all used up. The time it takes for those natural antioxidants to be spent is called the lag time. Brewers use this value to estimate the quantity and quality of the natural antioxidants in their beer. A longer lag time signifies a more stable beverage. Many beverages do not have a lag time, even beer. In such cases the T-150 value is the only parameter used.

Table 3 below shows the T- 150 data for an EPR experiment using varying amounts of TTA-Si sodium salt in Fat Tire. Aside from varying quantities, the experimental procedure was the same as or similar to that described for the data in Figure 2. The purpose of the experiment was to determine the TTA-Si functional range, or the range of TTA-Si (g) to volume of beer ratio that imparts a consistent, positive, and substantial effect as an antioxidant. Amounts of TTA-Si, ranging between 50-166 g/hL, were used. A total of 8 (20 mL) EPR samples were produced using the same procedure described for the experiment in Figure 2. Masses of TTA-Si used in each of the 8 samples were as follows; 0.05g (166 g/hL), 0.045 g (150g/hL), 0.04Og (133 g/hL), 0.035g/hL (116 g/hL), 0.03g (100 g/hL), 0.025g (83 g/hL), 0.02Og (66 g/hL), 0.015 g (50 g/hL). These data indicate that in Fat Tire, the TTA-Si functional range is between 133 g/hL and 116 g/hL. Increasing the quantity above 133 g/hL did not improve the function of the resulting beer product and did not improve or lengthen self life.

Figure 3 shows an EPR oxidation profile of New Belgium Fat Tire after treatment with triamine-Si. The data set Triamine-Si was an average of 2 experiments where diethylenetriamine silica supported chelator (triamine-Si, 166 g/hL) was mixed with 30 mL of degassed bottled beer (1.5 min of sonication at room temperature) in a 50 mL conical centrifuge vial for 30 min. The Triamine-Si was then removed from the beer via centrifugation (5 min at 1000 rpm). After centrifugation, 20 mL of the beer were removed from the conical vial (leaving 10 mL of beer and the pellet of spent triamine-Si in the centrifugation vial) and placed in a 20 mL clear glass scintillation vial and sealed under nitrogen gas. The 20 ml samples were then stored in the dark in a water bath at 32 ºC for 48 hours. The samples were frozen solid in a lab freezer, packaged on dry ice, and sent to Bruker Biospin for EPR analysis. The data set labeled "Control" represents an average of 2 samples of non-treated Fat Tire Beer. Since centrifugation was used to remove the silica gel from the Triamine-Si samples, the Control samples were also subjected to the same centrifugation method to eliminate variables. Degassed bottled beer (1.5 min of sonication at room temperature) (30 mL) was placed in a 50 mL conical centrifugation vial and stirred for 30 min. The beer was then centrifuged (5 min at 1000 rpm) and 20 mL were removed from the centrifuge vial using a pipetteman and placed in a 20 mL clear glass scintillation vial. The samples were sealed under nitrogen, frozen solid, and sent away for EPR analysis. The 20 ml samples were then stored in the dark in a water bath at 32 ºC for 48 hours. The samples were frozen solid in a lab freezer, packaged on dry ice, and sent to Bruker Biospin for EPR analysis. Analysis at Bruker Biospin was conducted their beer analysis method that is certified by the

American Society of Brewing Chemists (ASBC). The procedure for the ASBC EPR method is as follows. The samples were degassed and added to 15 mL septum capped vials. Next, the spin trap reagent N-t-butyl-phenylnitrone (PBN) was dispensed into the liquid, mixed thoroughly and the vial thus prepared was placed in a heating block at 60 ºC. The Bruker e-scan epr spectrometer was used to record EPR measurements every ~20 minutes for approximately 3 hr, the samples remained in the heating block at 60 ºC for the entire experiment. The reference reagent used in the experiment was 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and was analyzed every ~20 min during the experiment at 60 ºC. The error bars show the standard deviations for each measurement. The average T- 150 values and EPR lag times for this experiment are listed in Table 4.

Figure 4 shows an EPR oxidation profile of Sierra Nevada Pale Ale after treatment withTTA-Si sodium salt. The data set TTA-Si is an average of 4 experiments where triaminetettracetate tetra sodium salt, silica support. The average T-150 values and EPR lag times for this experiment are listed in Table 4. TTA-Si (166 g/hL) was mixed with 30 mL of degassed bottled beer (1.5 min of sonication at room temperature) in a 50 mL conical centrifuge vial for 30 min. The TTA-Si was then removed from the beer via centrifugation (5 min at 1000 rpm). After centrifugation, 20 mL of the beer were removed from the conical vial (leaving 10 mL of beer and the pellet of spent TTA-Si in the centrifugation vial) and placed in a 20 mL clear glass scintillation vial and sealed under nitrogen gas. The 20 ml samples were then stored in the dark in a water bath at 32 ºC for 48 hours. The samples were frozen solid in a lab freezer, packaged on dry ice, and sent to Bruker Biospin for EPR analysis. The data set labeled "Control" represents an average of 4 samples of non-treated Sierra Nevada Beer. Since centrifugation was used to remove the silica gel from the TTA-Si samples, the Control samples were also subjected to the same centrifugation method to eliminate variables. Degassed bottled beer (1.5 min of sonication at room temperature) (30 mL) was placed in a 50 mL conical centrifugation vial and stirred for 30 min. The beer was then centrifuged (5 min at 1000 rpm) and 20 mL were removed from the centrifuge vial using a pipetteman and placed in a 20 mL clear glass scintillation vial. The samples were sealed under nitrogen, frozen solid, and sent away for EPR analysis. The 20 ml samples were then stored in the dark in a water bath at 32 ºC for 48 hours. The samples were frozen solid in a lab freezer, packaged on dry ice, and sent to Bruker Biospin for EPR analysis. Analysis at Bruker Biospin was conducted their beer analysis method that is certified by the American Society of Brewing Chemists (ASBC). The procedure for the ASBC EPR method is as follows. The samples were degassed and added to 15 mL septum capped vials. Next, the spin trap reagent N-t-butyl- phenylnitrone (PBN) was dispensed into the liquid, mixed thoroughly and the vial thus prepared was placed in a heating block at 60 ºC. The Bruker e-scan epr spectrometer was used to record EPR measurements every ~20 minutes for approximately 3 hr, the samples remained in the heating block at 60 ºC for the entire experiment. The reference reagent used in the experiment was 2,2,6, 6-tetramethylpiperidine-N-oxyl (TEMPO) and was analyzed every ~20 min during the experiment at 60 ºC. The error bars show the standard deviations for each measurement. The average T- 150 values and EPR lag times for this experiment are listed in Table 5.

Figure 5 shows an EPR oxidation profile of Sierra Nevada Pale Ale after treatment with triamine-Si antioxidant. The data set Triamine is an average of 2 experiments where diethylenetriamine silica supported chelator (triamine-Si, 166 g/hL) was mixed with 30 mL of degassed bottled beer (1.5 min of sonication at room temperature) in a 50 mL conical centrifuge vial for 30 min. The Triamine-Si was then removed from the beer via centrifugation (5 min at 1000 rpm). After centrifugation, 20 mL of the beer were removed from the conical vial (leaving 10 mL of beer and the pellet of spent triamine-Si in the centrifugation vial) and placed in a 20 mL clear glass scintillation vial and sealed under nitrogen gas. The 20 ml samples were then stored in the dark in a water bath at 32 ºC for 48 hours. The samples were frozen solid in a lab freezer, packaged on dry ice, and sent to Bruker Biospin for EPR analysis. The data set labeled "Control" represents an average of 2 samples of non-treated Fat Tire Beer. Since centrifugation was used to remove the silica gel from the Triamine-Si samples, the Control samples were also subjected to the exact same centrifugation method to eliminate variables. Degassed bottled beer (1.5 min of sonication at room temperature) (30 mL) was placed in a 50 mL conical centrifugation vial and stirred for 30 min. The beer was then centrifuged (5 min at 1000 rpm) and 20 mL were removed from the centrifuge vial using a pipetteman and placed in a 20 mL clear glass scintillation vial. The samples were sealed under nitrogen, frozen solid, and sent away for EPR analysis. The 20 ml samples were then stored in the dark in a water bath at 32 ºC for 48 hours. The samples were frozen solid in a lab freezer, packaged on dry ice, and sent to Bruker Biospin for EPR analysis. Analysis at Bruker Biospin was conducted their beer analysis method that is certified by the

American Society of Brewing Chemists (ASBC). The procedure for the ASBC EPR method is as follows. The samples were degassed and added to 15 mL septum capped vials. Next, the spin trap reagent N-t-butyl-phenylnitrone (PBN) was dispensed into the liquid, mixed thoroughly and the vial thus prepared was placed in a heating block at 60 ºC. The Bruker e-scan epr spectrometer was used to record EPR measurements every ~20 minutes for approximately 3 hr, the samples remained in the heating block at 60 ºC for the entire experiment. The reference reagent used in the experiment was 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and was analyzed every ~20 min during the experiment at 60 ºC. The error bars show the standard deviations for each measurement. The average T- 150 values and EPR lag times for this experiment are listed in Table 6.

Figure 6 shows an EPR oxidation profile of Sam Adams Boston Lager after treatment with Triamine-Si Antioxidant. The data set Triamine is an average of 2 experiments where diethylenetriamine silica supported chelator (triamine-Si, 166 g/hL) was mixed with 30 mL of degassed bottled beer (1.5 min of sonication at room temperature) in a 50 mL conical centrifuge vial for 30 min. The Triamine-Si was then removed from the beer via centrifugation (5 min at 1000 rpm). After centrifugation, 20 mL of the beer were removed from the conical vial (leaving 10 mL of beer and the pellet of spent triamine-Si in the centrifugation vial) and placed in a 20 mL clear glass scintillation vial and sealed under nitrogen gas. The 20 ml samples were then stored in the dark in a water bath at 32 ºC for 48 hours. The samples were frozen solid in a lab freezer, packaged on dry ice, and sent to Bruker Biospin for EPR analysis. The data set labeled "Control," represents an average of 2 samples of non-treated Sam Adams Beer. Since centrifugation was used to remove the silica gel from the Triamine-Si samples, the Control samples were also subjected to the exact same centrifugation method to eliminate variables. Degassed bottled beer (1.5 min of sonication at room temperature) (30 mL) was placed in a 50 mL conical centrifugation vial and stirred for 30 min. The beer was then centrifuged (5 min at 1000 rpm) and 20 mL were removed from the centrifuge vial using a pipetman and placed in a 20 mL clear glass scintillation vial. The samples were sealed under nitrogen, frozen solid, and sent away for EPR analysis. The 20 ml samples were then stored in the dark in a water bath at 32 ºC for 48 hours. The samples were frozen solid in a lab freezer, packaged on dry ice, and sent to Bruker Biospin for EPR analysis. Analysis at Bruker Biospin was conducted their beer analysis method that is certified by the American Society of Brewing Chemists (ASBC). The procedure for the ASBC EPR method is as follows. The samples were degassed and added to 15 mL septum capped vials. Next, the spin trap reagent N-t-butyl-phenylnitrone (PBN) was dispensed into the liquid, mixed thoroughly and the vial thus prepared was placed in a heating block at 60 ºC. The Bruker e-scan epr spectrometer was used to record EPR measurements every ~20 minutes for approximately 3 hr, the samples remained in the heating block at 60 ºC for the entire experiment. The reference reagent used in the experiment was 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and was analyzed every ~20 min during the experiment at 60 ºC. The error bars show the standard deviations for each measurement. The average T- 150 values and EPR lag times for this experiment are listed in Table 7.

Figure 7 shows an EPR oxidation profile of Corona Lager after treatment with Triamine-Si antioxidant. The data set Triamine is an average of 2 experiments where diethylenetriamine silica supported chelator (triamine-Si, 166 g/hL) was mixed with 30 mL of degassed bottled beer (1.5 min of sonication at room temperature) in a 50 mL conical centrifuge vial for 30 min. The Triamine-Si was then removed from the beer via centrifugation (5 min at 1000 rpm). After centrifugation, 20 mL of the beer were removed from the conical vial (leaving 10 mL of beer and the pellet of spent triamine-Si in the centrifugation vial) and placed in a 20 mL clear glass scintillation vial and sealed under nitrogen gas. The 20 ml samples were then stored in the dark in a water bath at 32 ºC for 48 hours. The samples were frozen solid in a lab freezer, packaged on dry ice, and sent to Bruker Biospin for EPR analysis. The data set labeled "Control," represents an average of 2 samples of non-treated Fat Tire Beer. Since centrifugation was used to remove the silica gel from the Triamine-Si samples, the Control samples were also subjected to the exact same centrifugation method to eliminate variables. Degassed bottled beer (1.5 min of sonication at room temperature) (30 mL) was placed in a 50 mL conical centrifugation vial and stirred for 30 min. The beer was then centrifuged (5 min at 1000 rpm) and 20 mL were removed from the centrifuge vial using a pipetman and placed in a 20 mL clear glass scintillation vial. The samples were sealed under nitrogen, frozen solid, and sent away for EPR analysis. The 20 ml samples were then stored in the dark in a water bath at 32 ºC for 48 hours. The samples were frozen solid in a lab freezer, packaged on dry ice, and sent to Bruker Biospin for EPR analysis. Analysis at Bruker Biospin was conducted their beer analysis method that is certified by the American Society of Brewing Chemists (ASBC). The procedure for the ASBC EPR method is as follows. The samples were degassed and added to 15 mL septum capped vials. Next, the spin trap reagent N-t- butyl-phenylnitrone (PBN) was dispensed into the liquid, mixed thoroughly and the vial thus prepared was placed in a heating block at 60 ºC. The Bruker e-scan epr spectrometer was used to record EPR measurements every ~20 minutes for approximately 3 hr, the samples remained in the heating block at 60 ºC for the entire experiment. The reference reagent used in the experiment was 2,2,6, 6-tetramethylpiperidine-N-oxyl (TEMPO) and was analyzed every ~20 min during the experiment at 60 ºC. The error bars show the standard deviations for each measurement. The average T- 150 values and EPR lag times for this experiment are listed in Table 8.

Figure 8 shows an EPR oxidation profile of Woodridge Cabernet Sauvignon after treatment with TTA-Si. The data set TTA-Si is an average of 2 experiments where diethylenetriamine silica supported chelator (triamine-Si, 166 g/hL) was mixed with 30 mL of wine in a 50 mL conical centrifuge vial for 30 min. The Triamine-Si was then removed from the wine via centrifugation (5 min at 1000 rpm). After centrifugation, 20 mL of the wine was removed from the conical vial (leaving 10 mL of wine and the pellet of spent triamine-Si in the centrifugation vial) and placed in a 20 mL clear glass scintillation vial and sealed under nitrogen gas. The 20 ml samples were then stored in the dark in a water bath at 32 ºC for 48 hours. The samples were frozen solid in a lab freezer, packaged on dry ice, and sent to Bruker Biospin for EPR analysis. The data set labeled "Control," represents an average of 2 samples of non-treated wine. Since centrifugation was used to remove the silica gel from the Triamine-Si samples, the Control samples were also subjected to the exact same centrifugation method to eliminate variables. Wine (30 mL) was placed in a 50 mL conical centrifugation vial and stirred for 30 min. The wine was then centrifuged (5 min at 1000 rpm) and 20 mL were removed from the centrifuge vial using a pipetman and placed in a 20 mL clear glass scintillation vial. The samples were sealed under nitrogen, frozen solid, and sent away for EPR analysis. The 20 ml samples were then stored in the dark in a water bath at 32 ºC for 48 hours. The samples were frozen solid in a lab freezer, packaged on dry ice, and sent to Bruker Biospin for EPR analysis. Analysis at Bruker Biospin was conducted their beer and wine analysis method that is certified by the American Society of Brewing Chemists (ASBC). The procedure for the ASBC EPR method is as follows. The samples were degassed and added to 15 mL septum capped vials. Next, the spin trap reagent N-t-butyl-phenylnitrone (PBN) was dispensed into the liquid, mixed thoroughly and the vial thus prepared was placed in a heating block at 60 ºC. The Bruker e-scan epr spectrometer was used to record EPR measurements every ~20 minutes for approximately 3 hr, the samples remained in the heating block at 60 ºC for the entire experiment. The reference reagent used in the experiment was 2,2,6, 6-tetramethylpiperidine-N-oxyl (TEMPO) and was analyzed every ~20 min during the experiment at 60 ºC. The error bars show the standard deviations for each measurement. The average T- 150 values and EPR lag times for this experiment are listed in Table 9.

Example 1

This example provides a TTA-Si Beer adsorption study. Use of the solid phase antioxidant TTA-Si in the brewery is analogous to the use of filter aides herein. In both cases of TTA-Si and filter aides, a solid material is added to the beer and later filtered out. TTA-Si is meant to function as an antioxidant by removing metal ions, whereas filter aides impart beer stability by removing haze forming polyphenols and proteins. In order to keep TTA-Si from interfering with the function of any filter aides a brewery may use, it is important to know if anything other than metal ions are adsorbing onto the surface.

An adsorption study was conducted using TTA-Si in New Belgium Fat Tire beer. Prior to analysis with XPS, TTA-Si was added to the beer at a ratio of 166 g/hL for 30 min to form a TTA- Si/beer slurry. The slurry was then separated on a centrifuge (5 min 1000 rpm) and a beer supernatant and pellet (composed primarily of TTA-Si) formed. The beer supernatant was poured off and the TTA-Si pellet was washed with water (20 mL) and acetone (20 mL), dried under vacuum, and placed in an oven for 10 min at 110 ºC. The same procedure was conducted using regular (non-functionalized) silica gel as a control. XPS analysis was also conducted on clean (no beer added) TTA-Si and regular silica gel. To eliminate variables, both of the clean samples were washed with water (20 mL) and acetone (20 mL), dried under vacuum, and placed in an oven for 10 min at 110 ºC prior to XPS analysis. The results are depicted below (Table 10). There was little adsorption on the TTA-Si samples, whereas the regular silica gel had an adsorption layer present. A reduction in Si, and an increase in C and N indicates protein adsorption. Without being bound by theory, the apparent non- fouling character of the TTA-Si is likely due to the ionic interactions of the tetraacetate sodium salt on TTA-Si.

Example 2 The use of the TTA-Si sodium salt has shown to increase the pH of the treated beverage.

In beer, the use of TTA-Si sodium salt at 166g/hL results in an average increase of 0.15 pH units, tested with several beers. In many cases, a small increase in beer pH is a desired effect. It has been shown that beers with higher pH are generally more stable. However, it may be undesirable to alter the pH of the beverage, thus two formulations exist to keep the pH neutral while using TTA-Si sodium salt:

1. A mixture of acidic TTA-Si (the protonated carboxylic acid) and the TTA-Si sodium salt at a ratio of 7:3 respectively, in both beer and wine, keeps the pH constant.

2. A slurry of TTA-Si sodium salt is generated in a minimal amount of acidic water (HCl titrated to obtain a neutral pH when mixed with TTA-Si sodium salt), the neutral slurry is then dosed into the beverage without altering the beverage pH. This method is feasible in a brewery since most solid adsorbents are added in a slurry.

3. A mixture of TTA-Si (the protonated carboxylic acid) and Triamine-Si at a ratio of 7:3 respectively, in both beer and wine, keeps the pH constant. 4. A slurry of TTA-Si (the protonated carboxylic acid) is generated in a minimal amount of basic water (NaOH titrated to obtain a neutral pH when mixed with TTA-Si), the neutral slurry is then dosed into the beverage without altering the beverage pH. This method is feasible in a brewery since most solid adsorbents are added, in a slurry, and sodium hydroxide is commonly used in breweries. Example 3

Triaminetetraacetate coatings on TTA-Si (in both acid and sodium salt) are stable in aqueous and organic solutions to a pH of ~2.0 (Sigma-Aldrich). In beer, the pH rarely or perhaps never falls below 3.0. Thus, the coating will be stable in all types of beer. However, throughout the brewing process, the temperature of the beer varies considerably. The application of TTA-Si in the brewery will occur when the beer is cold (~13 ºC), though in some stages of brewing the beer temperature can reach 60 ºC. Thus, it was decided to analyze the thermal stability of TTA-Si in a model beer solution at 60 ºC.

A solution of 5% deuterated ethanol in deuterated water was prepared (3.0 mL), and TTA- Si sodium salt was added to it at a 166 g/hL mass to volume ratio. The slurry was heated for 30 min at 60 ºC in the dark using a hot water bath. The TTA-Si slurry was then removed from the heat and separated on a centrifuge (5 min, 1000 rpm). The supernatant was transferred to an NMR tube and analyzed with a 500 MHz proton NMR with 16 scans. A control was prepared using the exact same model beer with out exposure to TTA-Si. The control sample was also heated at 60 ºC for 30 min and placed on the centrifuge (5 min, 1000 rpm). Figure 9 depicts the proton NMR spectra for the TTA-Si stability study. It indicates that nothing from the coating leached off into the model beer. The NMR spectra in Figure 10 depicts the control sample from this experiment.

Example 4

This example provides testing of five formulations of beer filter material. The materials used in these formulations are labeled A-F and are shown below.



Materials A through F can be used along or in one of several preferred embodiments described herein. A preferred formulation is a mixture of materials A and C at a ratio of 7:3 respectively.

The dry powders of materials A and C are mixed together in a shaker and are stored cold and dry for use as a filter aid in beer. In beer, the filter aide is added into a buffering tank containing mixing beer prior to filtration or centrifugation and is dosed at 10-200 g/hL of processed beer depending on the desired result. This filter aide is compatible with all other types of filter aides and can be removed by any standard brewery centrifugation or filtration procedure. The adsorbed compound on the filter aide does not leach off the silica gel into the beer. Upon analysis, the silica gel or any component so added is present in the final packaged product. The chelating moieties bonded to the filter aide function to remove metal ions such as Fe(II), Fe(III), Cu(I), and Cu(II) from the beer, thus stabilizing it from oxidation. A preferred formulation is a mixture of materials A and F at a ratio of 7:3 respectively.

The dry powders of materials A and F are mixed together in a shaker and are stored cold and dry for use. In beer, the filter aide is added into a buffering tank containing mixing beer prior to filtration or centrifugation and is dosed at 10-200 g/hL of processed beer depending on the desired result. This filter aide is compatible with all other types of filter aides and can be removed by any standard brewery centrifugation or filtration procedure. The adsorbed compound on the filter aide does not leach off the silica gel into the beer. Upon analysis, the silica gel or any component so added is present in the final packaged product. The chelating moieties bonded to the filter aide function to remove metal ions such as Fe(II), Fe(III), Cu(I), and Cu(II) from the beer, thus stabilizing it from oxidation. A preferred formulation is a mixture of materials B and G at a ratio of 7:3 respectively.

The dry powders of materials B and G are mixed together in a shaker and are stored cold and dry for use. In beer, the filter aide is added into a buffering tank containing mixing beer prior to filtration or centrifugation and is dosed at 10-200 g/hL of processed beer depending on the desired result. This filter aide is compatible with all other types of filter aides and can be removed by any standard brewery centrifugation or filtration procedure. The adsorbed compound on the filter aide does not leach off the silica gel into the beer. Upon analysis, the silica gel or any component so added is present in the final packaged product. The chelating moieties bonded to the filter aide function to remove metal ions such as Fe(II), Fe(III), Cu(I), and Cu(II) from the beer, thus stabilizing it from oxidation.

A preferred formulation is produced using the method for producing material D. In beer, the filter aide is added into a buffering tank containing mixing beer prior to filtration or centrifugation and is dosed at 10-200 g/hL of processed beer depending on the desired result. This filter aide is compatible with all other types of filter aides and can be removed by any standard brewery centrifugation or filtration procedure. The adsorbed compound on the filter aide does not leach off the silica gel into the beer. Upon analysis, the silica gel or any component so added is present in the final packaged product. The chelating moieties bonded to the filter aide function to remove metal ions such as Fe(II), Fe(III), Cu(I), and Cu(II) from the beer, thus stabilizing it from oxidation.

A preferred formulation is produced using the method for producing material E above. In beer, the filter aide is added into a buffering tank containing mixing beer prior to filtration or centrifugation and is dosed at 10-200 g/hL of processed beer depending on the desired result. This filter aide is compatible with all other types of filter aides and can be removed by any standard brewery centrifugation or filtration procedure. The adsorbed compound on the filter aide does not leach off the silica gel into the beer. Upon analysis, the silica gel or any component so added is present in the final packaged product. The chelating moieties bonded to the filter aide function to remove metal ions such as Fe(II), Fe(III), Cu(I), and Cu(II) from the beer, thus stabilizing it from oxidation.

Claims

We claim:

1. A process for making beverages more stable to oxidation, comprising:

2. The process for making beverages more stable to oxidation of claim 1, wherein the chelating compound is silane linked to a hydroxylated surface such as silicon dioxide, and has a triaminetetraacetate (TTA) chelating moiety.

3. The process for making beverages more stable to oxidation of claim 1, wherein the silane anchor moiety of the chelating compound is a polymerized mixture of a SiO₂ (formula (I) of a composition having a structure:

Silane Moiety - C2-20 alkane - chelating moiety (I) wherein the chelating moiety is triaminetetraacetate (TTA) in either the acidic, basic (tetrasodium salt), or neutral (disodium salt) form, or a mixture thereof.

4. The process for making beverages more stable to oxidation of claim 1, wherein the composition is selected from the group consisting of: N-(trimethoxysilylpropyl) diethylenetriaminetetraacetic acid, sodium salt Si-TTA-COONa; N-(trimethoxysilylpropyl) diethylenetriaminetetraacetic acid (Si-TTA-COOH); N-(2-aminoethyl)-3- aminopropyltrimethoxysilane (Si-Triamine); N-(2-aminoethyl)-3- aminopropylmethyldimethoxysilane; (3-trimethoxysilylpropyl) diethylenetriamine; N- (trimethoxysilylpropyl) ethylenetriamine, triacetic acid, sodium salt; 2-(trimethoxysilylpropanol)- 1,3-diamino~N,N,N',N'-tetraacetic acid; mixture of N-(2-aminoethyl)-3- aminopropylmethyldimethoxysilane and tetra(ethylene glycol) trimethoxysilane; mixture of 3-

(trimethoxysilylpropyl) diethylenetriamine and tetra(ethylene glycol) trimethoxysilane; mixture of N-(trimethoxysilylpropyl) ethylenediamine, tridactic acid, sodium salt, and tetra(ethyleneglycol) trimethoxysilane; mixture of 2-(trimethoxysilylpropanol)- 1 ,3-diamino— N,N,N',N'-tetraacetic Acid and tetra(ethylene glycol) trimethoxysilane; vinylmethoxysilane, vinyltrimethoxysilane, vinylethoxy silane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- glycidoxypropyltrimethoxysilane, 3 -methacryloxypropyltrimethoxy silane, 3 - mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N-(beta-aminoethyl)-gamma- aminopropylmethyldimethoxysilane, N-(beta-aminoethyl)-gamma-aminopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma- glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma- glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, gamma- methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma- mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, N- [2- (vinylbenzylamino)ethyl]-3- aminopropyltrimethoxysilane, and combinations thereof.

5. The process for making beverages more stable to oxidation of claim 1, wherein the silane moiety is on a porous substrate selected from the group consisting of silica gel, CPG

(controlled pore glass), synthetic or natural polymer, and combinations thereof.

6. A beer product made by a brewing process further comprising:

7. The beer product made by a brewing process of claim 6, wherein the chelating compound is silane linked to a hydroxylated surface such as silicon dioxide, and has a triaminetetraacetate (TTA) chelating moiety.

8. The beer product made by a brewing process of claim 6, wherein the silane anchor moiety of the chelating compound is a polymerized mixture of a SiO₂ (formula (I) of a composition having a structure:

9. The beer product made by a brewing process of claim 6, wherein the composition is selected from the group consisting of: N-(trimethoxysilylpropyl) diethylenetriaminetetraacetic acid, sodium salt Si-TTA-COONa; N-(trimethoxysilylpropyl) diethylenetriaminetetraacetic acid (Si-TTA-COOH); N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Si-Triamine); N-(2- aminoethyl)-3-aminopropylmethyldimethoxysilane; (3-trimethoxysilylpropyl) diethylenetriamine; N-(trimethoxysilylpropyl) ethylenetriamine, triacetic acid, sodium salt; 2- (trimethoxysilylpropanol)-1,3-diamino~N,N,N',N'-tetraacetic acid; mixture ofN-(2-aminoethyl)- 3-aminopropylmethyldimethoxysilane and tetra(ethylene glycol) trimethoxysilane; mixture of 3- (trimethoxysilylpropyl) diethylenetriamine and tetra(ethylene glycol) trimethoxysilane; mixture of N-(trimethoxysilylpropyl) ethylenediamine, tridactic acid, sodium salt, and tetra(ethyleneglycol) trimethoxysilane; mixture of 2-(trimethoxysilylpropanol)- 1 ,3-diamino— N,N,N',N'-tetraacetic Acid and tetra(ethylene glycol) trimethoxysilane; vinylmethoxysilane, vinyltrimethoxysilane, vinylethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- glycidoxypropyltrimethoxysilane, 3 -methacryloxypropyltrimethoxy silane, 3 - mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine, N,N'-bis [3 -(trimethoxysilyl)propyl] ethylenediamine, N-(beta-aminoethyl)-gamma- aminopropylmethyldimethoxysilane, N-(beta-aminoethyl)-gamma-aminopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma- glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma- glycidoxypropylmethyldimethoxysilane, 2-(3 ,4-epoxycyclohexyl)ethyltrimethoxysilane, gamma- methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma- mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, N- [2- (vinylbenzylamino)ethyl]-3- aminopropyltrimethoxysilane, and combinations thereof.

10. The beer product made by a brewing process of claim 6, wherein the silane moiety is on a porous substrate selected from the group consisting of silica gel, CPG (controlled pore glass), synthetic or natural polymer, and combinations thereof.

11. A beer product having a reduced concentration of iron, wherein the iron concentration of a malt beer, light lager or ale is less than 0.05 mg/L, of a dark lager or ale is less than 0.10 mg/L and of a Porter or stout beer is less than 0.25 mg/L.

12. A beer product having a reduced concentration of iron, wherein the iron concentration of a malt beer, light lager or ale is less than 0.05 mg/L, of a dark lager or ale is less than 0.10 mg/L and of a Porter or stout beer is less than 0.25 mg/L, produced by a process comprising:

13. The beer product having a reduced concentration of iron, wherein the iron concentration of a malt beer, light lager or ale is less than 0.05 mg/L, of a dark lager or ale is less than 0.10 mg/L and of a Porter or stout beer is less than 0.25 mg/L of claim 12, wherein the chelating compound is silane linked to a hydroxylated surface such as silicon dioxide, and has a triaminetetraacetate (TTA) chelating moiety.

14. The beer product having a reduced concentration of iron, wherein the iron concentration of a malt beer, light lager or ale is less than 0.05 mg/L, of a dark lager or ale is less than 0.10 mg/L and of a Porter or stout beer is less than 0.25 mg/L of claim 12, wherein the silane anchor moiety of the chelating compound is a polymerized mixture of a SiO₂ (formula (I) of a composition having a structure:

15. The beer product having a reduced concentration of iron, wherein the iron concentration of a malt beer, light lager or ale is less than 0.05 mg/L, of a dark lager or ale is less than 0.10 mg/L and of a Porter or stout beer is less than 0.25 mg/L claim 12, wherein the composition is selected from the group consisting of: N-(trimethoxysilylpropyl) diethylenetriaminetetraacetic acid, sodium salt Si-TTA-COONa; N-(trimethoxysilylpropyl) diethylenetriaminetetraacetic acid (Si-TTA-COOH); N-(2-aminoethyl)-3- aminopropyltrimethoxysilane (Si-Triamine); N-(2-aminoethyl)-3- aminopropylmethyldimethoxysilane; (3-trimethoxysilylpropyl) diethylenetriamine; N- (trimethoxysilylpropyl) ethylenetriamine, triacetic acid, sodium salt; 2-(trimethoxysilylpropanol)- 1,3-diamino~N,N,N',N'-tetraacetic acid; mixture of N-(2-aminoethyl)-3- aminopropylmethyldimethoxysilane and tetra(ethylene glycol) trimethoxysilane; mixture of 3- (trimethoxysilylpropyl) diethylenetriamine and tetra(ethylene glycol) trimethoxysilane; mixture of N-(trimethoxysilylpropyl) ethylenediamine, tridactic acid, sodium salt, and tetra(ethyleneglycol) trimethoxysilane; mixture of 2-(trimethoxysilylpropanol)- 1 ,3-diamino— N,N,N',N'-tetraacetic Acid and tetra(ethylene glycol) trimethoxysilane; vinylmethoxysilane, vinyltrimethoxysilane, vinylethoxy silane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- glycidoxypropyltrimethoxysilane, 3 -methacryloxypropyltrimethoxy silane, 3- mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine, N,N'-bis [3 -(trimethoxysilyl)propyl] ethylenediamine, N-(beta-aminoethyl)-gamma- aminopropylmethyldimethoxysilane, N-(beta-aminoethyl)-gamma-aminopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma- glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma- glycidoxypropylmethyldimethoxysilane, 2-(3 ,4-epoxycyclohexyl)ethyltrimethoxysilane, gamma- methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma- mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, N- [2- (vinylbenzylamino)ethyl]-3- aminopropyltrimethoxysilane, and combinations thereof.

16. The beer product having a reduced concentration of iron, wherein the iron concentration of a malt beer, light lager or ale is less than 0.05 mg/L, of a dark lager or ale is less than 0.10 mg/L and of a Porter or stout beer is less than 0.25 mg/L of claim 12, wherein the silane moiety is on a porous substrate selected from the group consisting of silica gel, CPG (controlled pore glass), synthetic or natural polymer, and combinations thereof.