Products and methods for stabilizing / chill-proofing fermentation broths

Abstract

Disclosed are products and methods for reducing chill haze in fermentation broth. The products include attapulgite, sepiolite, or mixtures thereof. The products, or attapulgite or sepiolite, have a d of 5-19 microns or 10-19 microns. 50 The product or attapulgite or sepiolite may have a pore volume of 0.5-1.9 mL / g or 0.7-1.5 mL / g and / or a porosity of 30-90%, 40-80%, or 45-75%. The attapulgite or sepiolite or mixtures thereof may contain particles having a characteristic pore size in the range of 6-50 nm, 10-50 nm, 15-35 nm, or 20-30 nm. The product may have a stabilizing power of 40-100% at an addition of 20-200 g per 1 HL of fermentation broth.

Description

[Technical Field]

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS] This application claims priority to and the benefit of U.S. Patent Application No. 17 / 984,051, filed November 9, 2022.

[0002] The present disclosure relates generally to clay-containing products suitable for stabilizing or chill-proofing fermented liquids such as beer, wine, cider, or vinegar. [Background technology]

[0003] Chill haze is generally undesirable for most fermented liquids (e.g., beer) because consumers often perceive haze as a defect and / or objectionable. Chill haze forms when a fermented liquid is cooled below 0°C, resulting in the reaction and aggregation of certain proteins. If untreated, some of the chill haze can develop into a permanent haze present within the fermented liquid. This is particularly undesirable for beverages and consumable liquids.

[0004] Porous silica gels (hydrogels and xerogels) are commonly used in a two-step process to remove proteins that cause haze in beer or other fermentation liquids. For example, such silica gels are added to unstabilized beer, and the proteins are bound to the silica structure through a silica gel stabilization reaction. After the reaction is complete, the "spent" silica gel particles must be removed through a filtration process. Due to the slow filtration rate of silica gel particles, using such products for stabilization reduces efficiency and increases the cost of producing beverages such as beer, wine, and cider, as well as other fermentation consumables such as vinegar.

[0005] U.S. Publication No. 2019 / 0270067 ('067), published September 5, 2019, describes a composite filter aid comprising a structured composite formed by agglomerating a mineral with a protein-adsorbing binder, the structured composite comprising particles of the protein-adsorbing binder bound to a plurality of particles of a mineral (e.g., diatomaceous earth, natural glass such as perlite, etc.). While the disclosure of '067 is useful, an effective, inexpensive removal medium capable of stabilizing and / or chill-proofing liquids is desired. Summary of the Invention

[0006] In one aspect of the present disclosure, a product for reducing chill haze in a fermentation broth is disclosed. The product may include attapulgite or sepiolite. The product or attapulgite or sepiolite is d 50 The particle size distribution may be 5 to 19 microns or 10 to 19 microns. The product, attapulgite, or sepiolite may have a pore volume of 0.5 to 1.9 mL / g or 0.7 to 1.5 mL / g. The product, attapulgite, or sepiolite may have a porosity of 30 to 90%, 40 to 80%, or 45 to 75%. The attapulgite may contain particles having a characteristic pore size within the range of 6 to 50 nm, 10 to 50 nm, 15 to 35 nm, or 20 to 30 nm, and the sepiolite may contain particles having a characteristic pore size within the range of 6 to 50 nm, 10 to 50 nm, 15 to 35 nm, or 20 to 30 nm. This product may have a stabilizing power of 40-100% when added in an amount of 20-200g per 1HL of fermentation broth, or may have a stabilizing power of 50-100% when added in an amount of 30-180g per 1HL of fermentation broth, or may have a stabilizing power of 40-100% when added in an amount of 35-100g per 1HL of fermentation broth, or may have a stabilizing power of 50-100% when added in an amount of 75-100g per 1HL of fermentation broth.

[0007] In one embodiment, the attapulgite or sepiolite is treated with acetic acid and the product may have a pH of 6 to 8, or 6.5 to 7.5, or 6.9 to 7.1, measured as a 2 wt % slurry in water.

[0008] In any one of the above embodiments, the fermented liquid may be beer, and the product may have a beer-soluble iron content of 1.5 ppm or less, or may have a beer-soluble iron content of 1.2 ppm or less, or may have a beer-soluble iron content of 0.1 to 1.3 ppm, each measured by the modified ASBC method detailed herein.

[0009] In any one of the above embodiments, the fermented liquid may be beer, and the product may have a beer stabilizing power of 40-100% with the addition of 35-100g of product per HL of beer, or a beer stabilizing power of 50-100% with the addition of 75-100g of product per HL of beer.

[0010] In any one of the above embodiments, the product or attapulgite or sepiolite has a viscosity of 90 to 130 mPa as measured using the BET method. 2 / g or 90-150m 2 / g.

[0011] In any one of the above embodiments, the fermented liquid is beer, wine, cider, or vinegar and the product is free of a composite material comprising (a) attapulgite agglomerated with a first material that is not attapulgite or sepiolite, or (b) sepiolite agglomerated with a first material that is not attapulgite or sepiolite.

[0012] In any one of the above embodiments, the fermented liquid may be beer, and the beer may be an IPA, a lager, or a pilsner.

[0013] In any one of the above embodiments, the product may have a ratio of Al2O3 to SiO2 in the range of 0.17 to 0.22, a ratio of MgO to SiO2 in the range of 0.12 to 0.16, and a ratio of MgO to Al2O3 in the range of 0.75 to 0.85.

[0014] In another aspect of the present disclosure, a method for producing a product for reducing chill haze in a fermentation broth is disclosed. The method includes heat-treating attapulgite and / or sepiolite at a temperature of 200-600°C or 250-600°C to produce a heat-treated product, the product comprising the heat-treated product. The product or heat-treated attapulgite or heat-treated sepiolite has a d of 5-19 microns or 10-19 microns. 50 The product or heat-treated attapulgite or heat-treated sepiolite may have a pore volume of 0.5 to 1.9 mL / g or 0.7 to 1.5 mL / g, and the product or heat-treated attapulgite or heat-treated sepiolite may have a porosity of 30 to 90%, 40 to 80%, or 45 to 75%. The heat-treated attapulgite may contain particles having an intrinsic pore size within the ranges of 6 to 50 nm, 10 to 50 nm, 15 to 35 nm, or 20 to 30 nm, or the heat-treated sepiolite may contain particles having an intrinsic pore size within the ranges of 6 to 50 nm, 10 to 50 nm, 15 to 35 nm, or 20 to 30 nm. The product may have 40-100% stabilizing power with the addition of 20-200g of product per HL of fermentation broth, or 50-100% stabilizing power with the addition of 30-180g of product per HL of fermentation broth, or 40-100% stabilizing power with the addition of 35-100g of product per HL of fermentation broth, or 50-100% stabilizing power with the addition of 75-100g of product per HL of fermentation broth.

[0015] In one embodiment, the method further comprises: adding attapulgite and / or sepiolite to a solution of d 50 The fermented liquid may include sizing the fermented liquid to a particle size distribution of 5 to 19 microns, where sizing includes agglomeration and / or air classification and / or screening, and the fermented liquid may include beer, wine, cider, or vinegar.

[0016] In one embodiment, the method may further comprise mixing the attapulgite and / or sepiolite with acetic acid prior to the heat treatment, wherein the heat treatment is carried out at a temperature of 300-400°C, and the fermentation liquid includes beer, wine, cider, or vinegar.

[0017] In any one of the above embodiments, the product may have a pH of 6-8, 6.5-7.5, or 6.9-7.1 in a 2 wt% slurry.

[0018] In any one of the above embodiments, the fermented liquid may be beer, wherein the product may have 1.5 ppm or less of beer-soluble iron as measured by the modified ASBC method, or 1.2 ppm or less of beer-soluble iron, and the product may have 40-100% beer stabilizing power at a dosage of 35-100 g per 1 HL of fermented liquid, or 50-100% beer stabilizing power at a dosage of 75-100 g per 1 HL of fermented liquid. The refined beer may be an IPA, lager, or pilsner.

[0019] In any one of the above embodiments, the fermented liquid may be beer, the product may have a permeability of 0.1 to 1 Darcy, and the product may have a beer stabilizing power of 40 to 100% with the addition of 35 to 100 g of product per HL of beer, or a beer stabilizing power of 50 to 100% with the addition of 75 to 100 g of product per HL of beer.

[0020] In any one of the above embodiments, the fermented liquid is beer, wine, cider, or vinegar, and the product is free of a composite material comprising (a) attapulgite agglomerated with a first material that is not attapulgite or sepiolite, or (b) sepiolite agglomerated with a first material that is not attapulgite or sepiolite, and the product may have a ratio of Al2O3 to SiO2 in the range of 0.17 to 0.22, a ratio of MgO to SiO2 in the range of 0.12 to 0.16, and a ratio of MgO to Al2O3 in the range of 0.75 to 0.85.

[0021] In yet another aspect of the present disclosure, a method for reducing chill haze in a fermentation liquor is disclosed. The fermentation liquor can include beer, wine, cider, or vinegar. The method can include contacting or mixing the fermentation liquor with a product comprising heat-treated attapulgite or heat-treated sepiolite, and recovering the fermentation liquor from the product to obtain a resultant fermentation liquor having lower chill haze or lower amounts of proteins and / or polyphenols than the fermentation liquor had prior to the contacting or mixing step, wherein the product has a stabilizing power of 40-100% at a dosage of 20-200 g per 1 HL of fermentation liquor, or a stabilizing power of 50-100% at a dosage of 30-180 g per 1 HL of fermentation liquor, or a stabilizing power of 100-200 g per 1 HL of fermentation liquor. The heat-treated attapulgite can have a stabilizing power of 40 to 100% when added in an amount of 35 to 100 g per 1 HL of fermentation broth, or a stabilizing power of 50 to 100% when added in an amount of 75 to 100 g per 1 HL of fermentation broth, and the heat-treated attapulgite can contain particles having an intrinsic pore size within the range of 6 to 50 nm, 10 to 50 nm, 15 to 35 nm, or 20 to 30 nm, or the heat-treated sepiolite can contain particles having an intrinsic pore size within the range of 6 to 50 nm, 10 to 50 nm, 15 to 35 nm, or 20 to 30 nm, and the product or the heat-treated attapulgite or the heat-treated sepiolite can have a stabilizing power of 40 to 100% when added in an amount of 35 to 100 g per 1 HL of fermentation broth, or a stabilizing power of 50 to 100% when added in an amount of 75 to 100 g per 1 HL of fermentation broth, and the heat-treated attapulgite or the heat-treated sepiolite can have ... 50 may have a particle size distribution of 5 to 19 microns or 10 to 19 microns, and the product or heat-treated attapulgite or heat-treated sepiolite may have a porosity of (a) 0.5 to 1.9 mL / g or 0.7 to 1.5 mL / g, wherein the product or heat-treated attapulgite or heat-treated sepiolite may have a porosity of 30 to 90%, 40 to 80%, or 45 to 75%.

[0022] In embodiments, the fermented liquid may be beer, and the beer may be an IPA, lager, or pilsner. The product may have a beer stabilizing power of 40-100% when 35-100g of product is added per 1HL of beer, or a beer stabilizing power of 50-100% when 75-100g of product is added per 1HL of beer. The refined product has a pH of 6-8, or 6.5-7.5, or 6.9-7.1, as measured in a 2% by weight water slurry, and the product has a beer-soluble iron content of 1.5 ppm or less, or a beer-soluble iron content of 1.2 ppm or less, as measured by the modified ASBC method. In another refinement of the embodiment, the product may have a permeability in water of about 0.1 to 1 darcy, the product is free of composites comprising (a) attapulgite agglomerated with a first material that is not attapulgite or sepiolite, or (b) sepiolite agglomerated with a first material that is not attapulgite or sepiolite, and the product may have an Al2O3 to SiO2 ratio in the range of 0.17 to 0.22, the product may have an MgO to SiO2 ratio in the range of 0.12 to 0.16, and the product may have an MgO to Al2O3 ratio in the range of 0.75 to 0.85. [Brief explanation of the drawings]

[0023] [Figure 1] 1 is a scanning electron microscope (SEM) image of Feed Material A (Actigel 208) at low magnification (500x). [Figure 2] 1 is an SEM image of Feedstock B at high magnification (100,000x). [Figure 3] 1 is an SEM image of Feedstock B at low magnification (2000x). [Figure 4] 1 shows the pore size distributions of Examples 1 and 2. [Figure 5] 1 is a pore size distribution of Examples 7 and 8. DETAILED DESCRIPTION OF THE INVENTION

[0024] The present disclosure relates to a product for stabilizing / chill-proofing fermented liquors by adsorbing proteins from the fermented liquor. Such fermented liquors include, but are not limited to, beer, wine, cider, vinegar, etc. Beer may include pilsner, lager (e.g., Hell, American Lager, Bock, Maruzen, Schwarzbier, etc.), ale (e.g., India Pale Ale (IPA), pale ale, bitter, saison, malt beer, tripel, bier de garde, etc.), porter, stout, wheat beer, Belgian beer, sour beer, witbier, dunkel, kolsch, lambic, steam beer, rye beer, Berliner Weiss, doppelbock, weizenbock, dubel, gueuze, malt liquor, altbier, etc.

[0025] The products disclosed herein may comprise or be attapulgite, sepiolite, or a mixture thereof. Attapulgite is sometimes referred to as palygorskite. To avoid confusion, as used herein, the term "attapulgite" refers to attapulgite and / or palygorskite. As known in the art, attapulgite and sepiolite are each chain-type clay minerals and are structurally distinct from other clays such as montmorillonite or bentonite. That is, the tetrahedral sheets of attapulgite or sepiolite are split into ribbons by inversion, as adjacent tetrahedral bands within a tetrahedral sheet face in opposite directions rather than in one direction, creating a ribbon structure with 2:1 layers joined at the edges, while the octahedral sheets are continuous in only two dimensions. The structures of both minerals are similar in that the tetrahedra are oriented in the same direction, forming ribbons with a 2:1 ratio, extending along the a-axis, with an average width along the b-axis of three tetrahedral chains in sepiolite and two in attapulgite. Unlike clays known as swelling clays, such as bentonite or montmorillonite, attapulgite and sepiolite are non-swelling clays. Swelling clays are clays that undergo a relatively large increase in volume (due to an increase in the interlayer spacing of the clay particles) in aqueous liquids.

[0026] Although natural attapulgite or sepiolite can each have chill-proofing effects, attapulgite-sepiolite or sepiolite cannot be used directly to chill-proof fermented liquids. For example, adding natural attapulgite to fermented liquids (e.g., beer) can result in a very strong earthy or "cardboard"-like odor and / or flavor in the fermented liquid, which is unacceptable to breweries and other producers of fermented liquids used in beverages. In addition, natural attapulgite undesirably reduces the acidic / sour notes of beer because contact with natural attapulgite increases the pH of the beer. Natural sepiolite also has similar drawbacks.

[0027] Disclosed herein are novel products that may contain or be attapulgite, sepiolite, or mixtures thereof, as well as methods for making and using such products. For example, test results indicate that such novel products significantly reduce chill haze in a wide range of fermented beverages. Furthermore, because conventional chill-proofing agents have very low permeability, the use of the more highly permeable products disclosed herein during filtration of fermented liquids (e.g., beer) in filter paper / media, as a body feed, or mixed with a filter aid as a body feed, even at low concentrations, significantly reduces the filtration time of such fermented liquids (e.g., beer), providing brewers and others with significant efficiency gains due to the reduced stabilization / chill-proofing process time. For example, the use of the novel more permeable products disclosed herein can improve the process efficiency of stabilization and chill-proofing by simplifying the traditional two-step process of (1) silica gel stabilization reaction and (2) subsequent filtration to remove "used" silica gel particles in the treatment of fermentation broth into a single simultaneous stabilization and filtration process in which the fermentation broth is filtered and chill-proofed (e.g., passed through filter paper or media impregnated with the novel more permeable products disclosed herein, or when such novel more permeable products are used as body feed or mixed with a filter aid used as body feed). This simplified process reduces cost and complexity. Filtration time as an adsorbent is significantly reduced compared to conventional silica gel or diatomaceous earth composite products, further reducing costs and increasing production throughput. In other embodiments, the novel products disclosed herein can be used in similar processes as current, more expensive, conventional chill-proofing agents (e.g., silica gel), achieving the desired chill-proofing at a lower cost. For example, in one embodiment, the new products disclosed herein are added to the maturation tanks utilized in the fermentation process and then filtered.

[0028] Such novel products for stabilizing / chill-proofing fermentation broths may comprise or be attapulgite, sepiolite, or mixtures thereof. The products or attapulgite or sepiolite may be 5-19 microns or 10-19 microns d 50 The product, attapulgite, or sepiolite may further have a pore volume of 0.5 to 1.9 mL / g or 0.7 to 1.5 mL / g. The product, attapulgite, or sepiolite may have a porosity within the range of 30 to 90%, 40 to 80%, 49 to 72%, or 45 to 75%. The attapulgite may comprise particles having a characteristic pore size within the range of 6 to 50 nm, 10 to 50 nm, 15 to 35 nm, or 20 to 30 nm, or the sepiolite may comprise particles having a characteristic pore size within the range of 6 to 50 nm, 10 to 50 nm, 15 to 35 nm, or 20 to 30 nm. The product may have 40-100% stabilizing power with the addition of 20-200g of product per HL of fermentation broth, 50-100% stabilizing power with the addition of 30-180g of product per HL of fermentation broth, 40-100% stabilizing power with the addition of 35-100g of product per HL of fermentation broth, and 50-100% stabilizing power with the addition of 75-100g of product per HL of fermentation broth.

[0029] In any one of the above embodiments, the attapulgite or sepiolite may have a pore spacing of about 2 microns to about 50 microns with a peak position of about 15 microns to about 30 microns, or may have a pore spacing of about 2 microns to about 20 microns with a peak position of about 3 microns to about 17 microns.

[0030] In any one of the above embodiments, the attapulgite or sepiolite is treated with acetic acid and the product may have a pH in water measured as a 2 wt % slurry of 6 to 8, or 6.5 to 7.5, or 6.9 to 7.1.

[0031] In any one of the above embodiments, the fermented liquid may be beer, and the product may have a beer-soluble iron content of 1.5 ppm or less, or 1.2 ppm or less, or 0.1 to 1.3 ppm, as measured by the modified ASBC method.

[0032] In any one of the above embodiments, the fermented liquid may be beer, and the product may have a beer stabilizing power of 40-100% with the addition of 35-100g of product per HL of beer, or a beer stabilizing power of 50-100% with the addition of 75-100g of product per HL of beer.

[0033] In any one of the above embodiments, the product or attapulgite or sepiolite has a viscosity of 90 to 130 mPa₂, respectively, measured using the BET method. 2 / g or 90-150m 2 / g.

[0034] In any one of the above embodiments, the product or attapulgite or sepiolite may further comprise a d in the range of 2 to 8 microns or 4 to 7 microns. 10 and / or a particle size distribution having a d in the range of 10 to 70 microns or 20 to 42 microns 90 The particle size distribution may have the following structure:

[0035] In any one of the above embodiments, the fermented liquid may be beer, wine, cider, or vinegar. The product does not include a composite material or is free of a composite material comprising (a) attapulgite agglomerated with a first material that is not attapulgite or sepiolite, or (b) sepiolite agglomerated with a first material that is not attapulgite or sepiolite.

[0036] In any one of the above embodiments, the fermented liquid may be beer, wherein the beer is an IPA, a lager, or a pilsner.

[0037] In any one of the above embodiments, the product may have a ratio of Al2O3 to SiO2 in the range of 0.17 to 0.22, a ratio of MgO to SiO2 in the range of 0.12 to 0.16, and a ratio of MgO to Al2O3 in the range of 0.75 to 0.85.

[0038] In some embodiments, the product produced may be in granular or powder form, or may be in a non-extruded (non-extrusion) form. In one or more embodiments, the product may be free of composite materials. In one or more embodiments, the product may be free of composite materials containing (1) attapulgite or sepiolite and (2) other materials agglomerated with the attapulgite or sepiolite. In one or more embodiments, the product may be free of synthetic alkaline earth metal silica and / or polyvinyl resin and / or diatomaceous earth and / or natural glass and / or swelling clay. Synthetic alkaline earth metal silica may include, but is not limited to, synthetic magnesium silicate and synthetic calcium silicate. Natural glasses include, but are not limited to, perlite, volcanic ash, pumice, pumisite, ash, obsidian, pitchstone, rice husk ash, and mixtures thereof. Swelling clays include, but are not limited to, montmorillonite, bentonite, and the like.

[0039] In any one of the above embodiments, the fermented liquid may be beer, wine, cider, or vinegar.

[0040] In any one of the above embodiments, the attapulgite or sepiolite may be heat treated.

[0041] [Product Preparation] The method of manufacturing the above-mentioned product may include the step of selecting natural attapulgite or natural sepiolite or a mixture thereof for processing. Attapulgite / palygorskite has the chemical formula (Mg,Al)SiO 10 Sepiolite is a magnesium aluminum phyllosilicate with the formula (OH)4H2O. 15 It is a fibrous hydrated magnesium silicate with the formula (OH)26H2O. The proportions of various elements vary depending on the deposit from which attapulgite or sepiolite is found. Both minerals have a similar crystal structure: sepiolite has chains of three tetrahedrons, while attapulgite has chains of two.

[0042] The bulk chemistry of the attapulgite or sepiolite used in the feedstock influences the extractable metals profile of the resulting product, as such impurities may form extractable metals when the product is contacted with the fermentation broth. Therefore, the attapulgite or sepiolite may undergo a purification process to reduce impurities prior to further processing as disclosed herein. Such purification processes are known in the art.

[0043] This process may include sizing the selected material (attapulgite or sepiolite, or a mixture thereof). Such sizing of the selected material may include agglomeration, air classification, and / or screening of the selected material (attapulgite or sepiolite, or a mixture thereof). In one embodiment, agglomeration may be performed using a mechanical process (e.g., spray drying, high-shear mixing, etc.) with or without a binder. Spray drying techniques for agglomeration are known to those skilled in the clay industry. One exemplary known method is to prepare a slurry of the material (e.g., attapulgite, sepiolite, or a mixture thereof) and water and utilize a spray dryer to disperse the slurry into droplets using high-pressure nozzles, disks, etc. The inlet and outlet air temperatures of the spray dryer vary depending on the dryer used. The droplets then generally form rounded agglomerates of particles, which are collected downstream in a drying chamber. Alternatively, other suitable methods known in the art may be used to spray the dry or agglomerated clay, such as the use of high shear mixers, such as turbulizers and pin mixers, or agglomerators, such as rotary drum agglomerators, with or without a binder.

[0044] Air classification can be carried out using processes known in the art. For example, the attapulgite of the specific examples discussed herein is manufactured by Alpine TMThe coarse fraction was produced by classification using a 200 ATP air classifier (Hosokawa Micron Powder Systems, Summit, NJ). TM The following parameters were used for the 200 ATP classifier: classifier wheel speed of 5000 rpm, total air flow of 500 SCFM (Standard Cubic Feet per Minute), and feed rate of 390 lbs / hr (176.9 kg / hr). The coarse fraction yield was 82%. Other suitable wheel speeds, air flow rates, and feed rates may be utilized to produce a suitable coarse fraction.

[0045] Similarly, screening can be performed by processes known in the art. For example, a low-tap sieve shaker equipped with a mesh screen can be used to obtain fractions above or below a desired size. For example, a low-tap sieve shaker equipped with a mesh screen can be used to obtain fractions above 400 mesh (also called +400) or 500 mesh (+500) or other desired mesh sizes. Vibrating screens can also be used for particle separation.

[0046] Optionally, the method may further include a step of mixing the selected material (natural and / or sized and / or purified attapulgite / sepiolite / mixtures thereof) with an acetic acid solution until well mixed to adjust the pH of the selected material. The inventors discovered that because the typical pH value of barley-based beer is usually around 4.1 to 4.5, and the pH value of wheat-based beer is slightly lower, adding natural attapulgite with a higher pH reduces the sourness nuance of the beer and affects the flavor of the beer. In one embodiment, the pH of the selected material measured in water is adjusted to a pH within the range of 6 to 8 by mixing the material with the acetic acid solution. In another embodiment, the pH of the selected material measured in water is adjusted to a pH within the range of 6.5 to 7.5 by mixing the material with the acetic acid solution. In another embodiment, the pH of the selected material measured in water is adjusted to a pH within the range of 6.9 to 7.1 or about 7 by mixing the material with the acetic acid solution. In one embodiment, the acetic acid solution may have an acetic acid concentration within the range of 5 to 15%. In various embodiments discussed herein, natural attapulgite was mixed with a 10% acetic acid solution in a KitchenAid 5-quart food mixer at low speed until well mixed (e.g., about 30 minutes). Using a 10% acetic acid solution, the weight percent of the liquid (acetic acid solution) mixed with the solid (attapulgite, sepiolite, or a mixture thereof) can be about 5 to about 10% by weight of the liquid (acetic acid solution) and about 95 to about 90% by weight of the solid (attapulgite, sepiolite, or a mixture thereof). The weight percent of the liquid to solid can be varied with other concentrations of acetic acid solution within the 5 to 15% range. In other embodiments, the mixing time can vary. For example, the liquid and solid materials can be mixed for 10 to 60 minutes or other suitable time periods to ensure a good mixture. Other food-grade acids, such as citric acid, can also be used to adjust the pH of the attapulgite or sepiolite.

[0047] The method may further include a step of heat-treating the material (attapulgite, sepiolite, or a mixture thereof). In an embodiment in which the method includes a step of mixing the material (attapulgite, sepiolite, or a mixture thereof) with an acetic acid solution, the resulting mixture may be placed in a ceramic boat or other suitable container and then heat-treated at about 200 to about 600°C, or about 250 to about 600°C, or about 250 to about 500°C, or about 300 to about 400°C. In one embodiment, the heat treatment may be for about 10 minutes to about 60 minutes. For example, in one embodiment, the heat treatment may be at about 250°C to about 500°C for about 30 minutes. This removes the earthy flavor in the fermentation liquid (e.g., beer) resulting from contact with the natural attapulgite or natural sepiolite. In embodiments in which the natural material (attapulgite, sepiolite, or mixture thereof) has not been treated with an acetic acid solution, such material (attapulgite, sepiolite, or mixture thereof) may be placed in a ceramic boat or other suitable container and heated in a muffle furnace at about 200 to about 600°C, or about 250 to about 600°C, or about 250 to about 500°C, or about 300 to about 400°C to remove earthy notes in the beer due to contact with the natural attapulgite or natural sepiolite. In one embodiment, the heat treatment may be for about 10 minutes to about 60 minutes. For example, in one embodiment, the heat treatment may be at about 250°C to about 500°C for about 30 minutes.

[0048] In one or more embodiments, the product produced may be in particulate or powder form, or may be in a non-extruded (non-extrusion) form. In one or more embodiments, the product may be free of composite materials. In one or more embodiments, the product may be free of composite materials comprising (1) attapulgite or sepiolite and (2) other materials that aggregate with the attapulgite or sepiolite to form a composite. In one or more embodiments, the product may have an Al2O3 to SiO2 ratio in the range of 0.17 to 0.22, the product may have an MgO to SiO2 ratio in the range of 0.12 to 0.16, and the product may have an MgO to Al2O3 ratio in the range of 0.75 to 0.85. In one or more embodiments, the product may be free of synthetic alkaline earth metal silica and / or polyvinyl resin and / or diatomaceous earth and / or natural glass and / or swelling clay. Synthetic alkaline earth metal silica may include, but is not limited to, synthetic magnesium silicate and synthetic calcium silicate. Natural glasses include, but are not limited to, perlite, volcanic ash, pumice, pumice, shirass, obsidian, pitchstone, rice husk ash, and mixtures thereof. Swelling clays include, but are not limited to, montmorillonite and bentonite.

[0049] [Adsorption process] Each of the products disclosed herein can be used to adsorb proteins that cause chill haze in fermentation liquors. Fermentation liquors include, but are not limited to, beer, wine, cider, vinegar, and the like. A method for reducing chill haze in a fermentation liquor can include contacting (or mixing) the fermentation liquor with any one of the products disclosed herein, which contains or is attapulgite or sepiolite, or a mixture thereof, for a contact time. For example, in one embodiment, the fermentation liquor can flow through a filter paper / media impregnated with the new product. In another embodiment, the new product can be used as a body feed or mixed with a filter aid used as a body feed. In yet another embodiment, the new product can be added to an aging tank used in a fermentation process. In one embodiment, the contact time can vary depending on the application. For example, when the new product is used in an application where it is impregnated into filter paper or media, in some embodiments, the contact time can be from about 25 seconds to about 60 minutes. In other similar embodiments, the contact time can vary. On the other hand, if added to an aging tank, the contact time may be longer (e.g., in one embodiment, from one hour to several days) depending on the aging process the producer uses for the fermentation broth. Contact times may also vary when used as a body feed or mixed with a filter aid used as a body feed.

[0050] The dosage is a quantity of product sufficient to reduce chill haze in a fermentation broth for a given contact time, achieving a stabilizing power of at least 40-100%, 50-100%, 60-100%, 70-100%, 80-100%, or about 50-80%. As used herein, the term "Stabilizing Power of a dosage of adsorbent in a given fermentation broth" refers to the percentage reduction in chill haze in the fermentation broth for a given contact time with the adsorbent compared to the same dosage of silica hydrogel (SH) in the same fermentation broth under the same conditions. This calculation is described later in this specification. For example, in embodiments, the product may have a % stabilizing power of at least 40-100%, or 50-100%, or 60-100%, or 70-100%, or 80-100% at a loading of 20-200 grams (g) of product per hectoliter (HL) of fermentation liquor, or at a loading of 25-125 g of product per HL of fermentation liquor, or at a loading of 35-100 g of product per HL of fermentation liquor, or at a loading of 75-100 g of product per HL of fermentation liquor, respectively.

[0051] For example, in one embodiment, the product may have a % stabilizing power in beer (% Beer Stabilizing Power) of at least 40-100% with the addition of 20-200g / HL of beer or with the addition of 25-125g / HL of beer, and in another refinement, the product may have a % Beer Stabilizing Power of at least 50-100% with the addition of 20-200g / HL of beer or with the addition of 25-125g / HL of beer, and in another refinement, the product may have a % Beer Stabilizing Power of at least 60-100% with the addition of 20-200g / HL of beer or with the addition of 25-125g / HL of beer. in another refinement, the product may have at least 70-100% beer stabilizing power with the addition of 20-200g / HL of beer or 25-125g / HL of beer, in another refinement, the product may have at least 80-100% beer stabilizing power with the addition of 20-200g / HL of beer or 25-125g / HL of beer, or in another refinement, the product may have at least 50-80% beer stabilizing power with the addition of 20-200g / HL of beer or 25-125g / HL of beer.

[0052] The method further includes recovering the product from the fermentation liquor to obtain a resultant fermentation liquor that has lower chill haze or reduced amounts of proteins and / or polyphenols that cause chill haze than the fermentation liquor had prior to the contacting or mixing step. The resultant fermentation liquor may be recovered by recovering / capturing the resultant fermentation liquor after chill proofing, by filtering or separating the product from the fermentation liquor, or by other suitable methods known to those skilled in the art for obtaining the resultant fermentation liquor or for separating the resultant fermentation liquor from the product used for chill proofing.

[0053] Other adsorption methods may be used and contact times may be adjusted accordingly.

[0054] [Test method explanation] <Surface area, pore volume, pore size distribution, porosity> Surface area was measured using the nitrogen adsorption method of the Brunauer-Emmett-Teller (BET) method. The pore volume and pore size distribution of the samples were measured using mercury porosimetry. Mercury porosimetry uses mercury as the invading fluid to measure the pore volume of a weighed sample material enclosed within the sample chamber of a penetrometer. The sample chamber is evacuated to remove air from the sample's pores. The sample chamber and penetrometer are filled with mercury. Because mercury does not wet the sample surface, it must be forced into the pores by external pressure. To force the mercury into the pores, gradually increasing pressures are applied. The required equilibrium pressure is inversely proportional to the pore size; only small pressures are needed to force mercury into macropores, while much larger external pressures are needed to force mercury into small pores. The penetrometer reads the volume of invaded mercury, and the invading data are used to calculate pore size distribution, porosity, average pore size, and total pore volume. A Micromeritics AutoPore IV 9500 was used for the sample analysis herein.

[0055] Assuming cylindrical pores, the surface distribution can be derived from the pore volume distribution and used in the calculation. Without using a pore model, the total surface area of ​​a material sample can be estimated from the pressure / volume curve (Rootare, 1967) as follows:

number

[0056] From the pressure versus mercury intrusion data, the instrument generates the pore volume and size distribution according to the Washburn equation (Washburn, 1921):

number

[0057] The average pore diameter is calculated from the cumulative penetration volume and total surface area of ​​the material sample using the following formula:

number

[0058] Porosity is the percentage of voids in a material's total volume. Porosity was calculated from mercury intrusion data.

[0059] [27 Beer Test Methods of the American Society of Brewing Chemists (ASBC)] The (total) chill haze of beer was measured using a haze meter. The nephelometer cuvette was chilled (external contact only) in a small ice-water bath containing a humectant. The beer container was removed from the 0°C bath, and the cuvette was rinsed and filled with the chilled beer sample without disturbing the sediment. The cuvette was placed in a small ice-water bath and the beer was degassed while stirring with a thermometer. Once the temperature of the beer in the cuvette reached 0°C, the cuvette was placed in the nephelometer sample chamber and read by the nephelometer. The measurement is in nephelometric turbidity units (NTU). The "chill haze" measured herein is the total chill haze of the fermentation liquid (e.g., beer) after it has been chilled to 0°C.

[0060] [pH test of adsorbent in water] The pH of the adsorbent in water was measured for an exemplary embodiment of the novel product disclosed herein. 196.0 g of distilled water was placed in a multi-mixer cup. 4.0 g of the test product was added to the distilled water to create a 2 wt. % slurry. The mixing cup was placed in the multi-mixer and mixed for 5 minutes. A magnetic stir bar was placed in a 100-250 milliliter (mL) beaker and placed on an electric stirrer. The distilled water and product slurry was removed from the mixer and poured into the beaker. The stirrer speed was adjusted to achieve a steady, gentle circulation. The pH was determined by submerging a pH electrode in the slurry to obtain a pH measurement.

[0061] [pH test of adsorbent in water] The pH of the adsorbent in beer was measured for an exemplary embodiment of the novel product disclosed herein. 150.0 g of beer was placed in a multi-mixer cup. 2.0 g of the test product was added to distilled water to create a 1.3 wt.% slurry. The mixing cup was placed in the multi-mixer and mixed for 5 minutes. A magnetic stir bar was placed in a 100-250 milliliter (mL) beaker and placed on an electric stirrer. The beer and product slurry was removed from the mixer and poured into the beaker. The stirrer speed was adjusted to achieve a steady, gentle circulation. The pH was determined by submerging a pH electrode in the slurry to obtain a pH measurement.

[0062] [Beer soluble iron test] The amount of beer-soluble iron was measured for exemplary embodiments of the novel products disclosed herein using the following modified American Society of Brewing Chemists (ASBC) test: A 500 milliliter (mL) flask containing 200 g of Budweiser beer was degassed. A 5 g sample of a representative absorbent was added to the degassed beer. The mixture was stirred at 1 minute intervals for a total of 6 minutes. The mixture was then filtered through a 19-26 micron filter paper, and the iron concentration in the beer was measured by inductively coupled plasma (ICP) spectrometry. [Example]

[0063] The products of Examples 1-8 each contain attapulgite and were prepared from different attapulgite feedstocks as shown in Table 1.

[0064] [Table 1]

[0065] Feedstock A was prepared using Acti-Gel 208® (Active Minerals International, LLC), a commercially available attapulgite product. Acti-Gel 208 is a natural attapulgite purified and agglomerated by spray drying. Figure 1 shows an SEM image of Feedstock A (Acti-Gel 208) at low magnification (500x).

[0066] The major elemental composition of Feedstock A, as determined by wavelength-dispersive X-ray fluorescence (XRF) analysis of Acti-Gel 208, is shown in Table 2.

[0067] [Table 2]

[0068] Feed Material B was prepared using a commercially available attapulgite product, Min-U-Gel 400® (Active Minerals International, LLC). The Min-U-Gel 400 product is an air-classified, unrefined natural attapulgite. Figure 2 shows an SEM image of Feed Material B at high magnification (100,000x). Figure 3 shows an SEM image of Feed Material B at low magnification (2000x). The major element composition of Min-U-Gel 400, as determined by wavelength-dispersive X-ray fluorescence (XRF) analysis, is shown in Table 3.

[0069] [Table 3]

[0070] Feedstock C was prepared using a commercially available attapulgite product, Min-U-Gel 200® (Active Minerals International, LLC). The Min-U-Gel 200 product is an air-classified, unpurified natural attapulgite. The major element composition of Min-U-Gel 200, as determined by wavelength-dispersive X-ray fluorescence (XRF) analysis, is shown in Table 4.

[0071] [Table 4]

[0072] Feedstock D was prepared from natural attapulgite feedstock mined near Climax, Georgia by Active Minerals International, LLC. The major element composition of this feedstock, as determined by wavelength-dispersive XRF, is shown in Table 5.

[0073] [Table 5]

[0074] The nitrogen adsorption method based on the Brunauer-Emmett-Teller (BET) theory measured feedstocks A to D at 88 to 142 m 2 The particle size (d 50 ) is approximately 8 to 19 microns.

[0075] Feedstocks A-D also contain approximately 9-14% moisture by weight (at 104°C (220°F)).

[0076] [Example 1-2] Example 1 was prepared from Feed Material A by mixing 200 g of Feed Material A with 20 g of 10% aqueous acetic acid in a KitchenAid® 5-quart food mixer on low speed for 30 minutes. The resulting mixture was placed in a ceramic boat and heat-treated at 250°C for 30 minutes. Similarly, Example 2 was prepared from Feed Material A by mixing 200 g of Feed Material A with 20 g of 10% aqueous acetic acid in a KitchenAid® 5-quart food mixer on low speed for 30 minutes. The resulting mixture was then heat-treated at 300°C for 30 minutes.

[0077] [Examples 3-6] For each of Examples 3 to 6, 100 g of Feed Material B was placed in a ceramic boat and heated in a muffle furnace for 30 minutes, with Example 3 heated to 300°C in the muffle furnace, Example 4 heated to 400°C in the muffle furnace, Example 5 heated to 500°C in the muffle furnace, and Example 6 heated to 600°C in the muffle furnace.

[0078] [Example 7] Example 7 was prepared from Feedstock D by air classifying Feedstock D using an Alpine 200 ATP™ air classifier (Hosokawa Micron Powder Systems, Summit, NJ) to produce a coarse fraction. The following parameters were used for the Alpine 200 ATP™ air classifier: classifier wheel speed 5000 rpm, total air volume 500 SCFM (standard cubic feet per minute), and feed rate 390 lb / hr (176.9 kg / hr). The yield of the coarse fraction was 82%. The particle size distribution (psd) of a representative sample of the resulting coarse fraction is shown in Table 6.

[0079] [Table 6]

[0080] The air-classified coarse fraction of Feed D was then mixed with 20 g of 10% aqueous acetic acid in a KitchenAid 5-quart food mixer at low speed for 30 minutes, and the resulting mixture was then placed in a ceramic boat and heat-treated at 400°C for 30 minutes.

[0081] [Example 8] Example 8 was prepared by sieving Feed C using a Rotap sieve shaker equipped with a 500-mesh screen. Feed C was shaken on the 500-mesh screen for approximately 10 minutes. The portion of Feed C that did not pass through the 500-mesh screen (the +500 mesh portion of Feed C) was then mixed with 20 g of 10% aqueous acetic acid in a 5-quart KitchenAid food mixer on low speed for 30 minutes. The resulting mixture was placed in a ceramic boat and heat-treated at 400°C for 30 minutes.

[0082] [Example 9] Example 9 was prepared from Feedstock D by air classifying Feedstock D using an Alpine 200 ATP™ air classifier (Hosokawa Micron Powder Systems, Summit, NJ) to produce a coarse fraction. The following parameters were used for the Alpine 200 ATP™ air classifier: classifier wheel speed: 5000 rpm, total air volume: 500 SCFM (standard cubic feet per minute), and feed rate: 390 lb / hr (176.9 kg / hr). The yield of the coarse fraction was 82%. The particle size distribution of a representative sample of the resulting coarse fraction is shown in Table 6.

[0083] This coarse fraction was then shaken on a 400-mesh screen in a Rotap sieve shaker for approximately 10 minutes. 200 g of the portion of the air-classified Feed D coarse fraction that did not pass through the 400-mesh screen (the +400 mesh portion of Feed D) was mixed with 20 g of 10% aqueous acetic acid in a KitchenAid 5-quart food mixer at low speed for 30 minutes. The resulting mixture was placed in a ceramic boat and heat-treated at 400°C for 30 minutes.

[0084] [Example 10] Example 10 was prepared from Feed Material A by placing 100 g of Feed Material A in a ceramic boat and heating in a muffle furnace at 400° C. for 30 minutes.

[0085] [Chill Haze Test] Each of the products disclosed herein can be used to stabilize beer by adsorbing proteins that cause chill haze. Each of the adsorbents 1-10 herein was tested according to the ASBC Beer 27 test method for measuring (total) chill haze in beer (as previously described herein).

[0086] For chill haze testing of each adsorbent in Examples 1-9, a representative sample of each adsorbent was added to 200 mL of IPA or lager at doses ranging from 40 g / hectoliter (HL) to approximately 100 g / HL. For comparison, a representative sample of Feed A was added to 200 mL of pilsner beer. Similarly, a representative sample of silica hydrogel (Britesorb Al00®, Gusmer Enterprises, Inc.) was added to 200 mL of pilsner beer, IPA, and lager at doses ranging from 40 g / HL to approximately 100 g / HL.

[0087] The fermentation broth containing each adsorbent was placed on a shaker and shaken for 30 minutes, then filtered through 19-26 micron filter paper to remove the adsorbent. The filtered fermentation broth (beer) was placed in a constant-temperature ice bath (0°C ± 0.2°C) for approximately 24 hours. For each chilled filtered beer, a sample of the chilled filtered beer was placed in a cuvette, chilled in the ice bath, and degassed (by stirring). When the beer in the cuvette was at 0°C, the cuvette was placed in the sample chamber and analyzed with a haze meter according to ASBC Beer Test Method 27. The chill haze test results are shown in Table 7. Chill haze is expressed in nephelometric turbidity units (NTU), a unit used to measure the turbidity of a liquid, or the presence of suspended particles in a liquid.

[0088] [Table 7-1] [Table 7-2]

[0089] [Adsorbent stabilization test] The chill haze removed by an adsorbent is the difference between the chill haze of a given amount of blank (untreated) fermentation broth and the chill haze of the same amount of fermentation broth after treatment with the adsorbent. For example, in Table 7, the chill haze of a blank (untreated) IPA beer was measured to be 24.65 NTU, and the chill haze of the same IPA beer after treatment with 100 g / mL of Example 4 was measured to be 11.95 NTU. Therefore, the chill haze removed by the adsorbent of Example 4 was the difference between 24.65 NTU and 11.95 NTU, or 12.7 NTU.

[0090] The stabilization power (%) of the novel adsorbents disclosed herein for fermentation broth is between 40% and 100%. The stabilization power of a given dose of adsorbent in a given fermentation broth compared to the same dose of silica hydrogel (SH) in the same fermentation broth can be determined as the percentage of the chill haze removed by the dose of adsorbent compared to the chill haze removed by the same dose of silica hydrogel, as shown in the following calculation for stabilization power (%):

number

[0091] [Beer stabilization test of adsorbent] The beer stabilizing power of a dosage of adsorbent in a given beer compared to the same dosage of silica hydrogel (SH) in the same beer can be determined as the percentage ratio of the (total) chill haze removed from the beer by the dosage of adsorbent to the (total) chill haze removed from the beer by the same dosage of silica hydrogel, as shown in the following calculation for Beer Stabilizing Power (%):

number

[0092] For example, as noted above, the chill haze removed by treating the tested IPA with a 100 g / mL dosage of Example 4 is calculated to be 12.7 NTU (24.65-11.95 NTU). The chill haze removed by IPA with a 100 g / mL amount of silica hydrogel is calculated to be 24.65-9.15 NTU, or 15.5 NTU. Therefore, the beer stabilization capacity (%) of the adsorbent of Example 4 for the tested IPA is 12.7 / 15.5, or approximately 82%. The beer stabilization capacity (%) of the novel adsorbent products disclosed herein can be between 40% and 100%. Table 8 shows the beer stabilization capacity (%) of the exemplary adsorbents of Table 7.

[0093] [Table 8]

[0094] The permeabilities of various exemplary adsorbent products disclosed herein range from 0.01 to less than about 0.6 darcy. For example, Table 9 shows the permeability in water of the products of Examples 1-2, 4, and 7-8 compared to Feed A.

[0095] [Table 9]

[0096] The disclosed exemplary new adsorbents can have an aqueous pH ranging from 6 to about 8. For example, the aqueous pH of adsorbent product Examples 1-2 and 7-8 is shown in Table 10. For comparison, the aqueous pH was also measured for each of Feed Materials A and B.

[0097] [Table 10]

[0098] The pH of the beer was measured before and after treatment with various exemplary embodiments, and the results are shown in Table 11. As can be seen in Table 11, the pH of the beer was only slightly increased by stabilization with the novel adsorbents disclosed herein.

[0099] [Table 11]

[0100] The novel sorbent products disclosed herein can have (a) beer soluble iron of 1.5 ppm or less as measured by the modified ASBC method discussed herein, or 0 to about 1.5 ppm as measured by the modified ASBC. For example, the concentrations of iron in beer are shown in Table 12 for various exemplary embodiments.

[0101] [Table 12]

[0102] The novel adsorbent products disclosed herein have d in the range of 2-8 microns or 4-7 microns. 10 , d in the range of 5 to 19 microns or 10 to 19 microns 50 , and d in the range of 10 to 70 microns or 20 to 42 microns 90 For example, Table 13 shows particle size distributions for various exemplary embodiments as measured by a laser particle size analyzer. The novel adsorbent products disclosed herein may have pore volumes ranging from 0.5 to 1.9 mL / g or 0.7 to 1.5 mL / g, and porosities ranging from 30 to 90%, 40 to 80%, 49 to 72%, or 45 to 75%. For example, Table 13 shows pore volumes and porosities measured by mercury intrusion for various exemplary embodiments.

[0103] [Table 13]

[0104] FIG. 4 shows the pore size distributions (measured by mercury intrusion) for Examples 1 and 2, and FIG. 5 shows the pore size distributions (measured by mercury intrusion) for Examples 7 and 8. As used herein, "intrinsic pores" refer to (a) pores located on the surface of attapulgite or sepiolite particles, or (b) pores located within the structure of attapulgite or sepiolite particles. As used herein, "inter pores" refer to (a) interstices located between attapulgite or sepiolite particles, or (b) pores located between aggregated particles of attapulgite or sepiolite. The distributions in FIG. 4 show small intrinsic pores of about 20 nanometers (nm) to about 30 nm and large pore spacings of about 3 microns to about 19 microns with a peak at about 19 microns for the products of Examples 1 and 2. The distribution in Figure 5 shows that the products of Examples 7-8 have small intrinsic pores of about 20 nm to about 30 nanometers (nm) and large pore spacing of about 3 microns to about 15 microns, with a peak at about 3 microns to about 15 microns. Additionally, Examples 1-2 have a porosity of about 72% and a total intrusion volume of about 1.3 mL / g to about 1.4 mL / g, indicating that Examples 1-2 are quite porous. Examples 7-8 have a porosity of about 49% to about 58% and a total intrusion volume of about 0.7 mL / g to about 0.86 mL / g, indicating that Examples 7-8 are still quite porous. The high surface area and unique porous structure of these products make them effective adsorbents for a variety of applications, including protein adsorption. [Industrial Applicability]

[0105] In general, the foregoing disclosure finds utility in removing proteins that cause chill haze from fermented liquids (e.g., beer). As explained above, chill haze is generally undesirable for fermented liquids, particularly most beers (e.g., lagers or pilsners), as consumers often perceive the haze as a defect and / or undesirable. Chill haze forms when beer, wine, etc., is chilled below 0°C, resulting in the reaction and aggregation of certain proteins. Without treatment, some of the chill haze can become permanent haze.

[0106] Clays such as montmorillonite or bentonite are generally unsuitable for chill-proofing processes because their swelling properties cause excessive entrapment of the fermentation liquor, resulting in volume loss of the desired fermentation liquor and increased disposal costs associated with the clay swelling with the liquid. Treatments used to reduce the swelling of these clays can be unacceptable to end users.

[0107] Porous silica gels (hydrogel and xerogel) are commonly used in a two-step process to remove proteins that cause haze in beer. These silica gels are added to unstabilized beer, and the proteins bind to the highly porous silica structure through a silica gel stabilization reaction. After the reaction is complete, the silica gel particles are removed through a filtration process. Historically, the slow kinetics of conventional silica gel products, including hydrogel and xerogel, have made the stabilization and chill haze removal processes for fermentation liquids (e.g., beer) inefficient, making the cost of such products quite high. The manufacturing process of synthetic silica gels can also have a high carbon footprint.

[0108] The novel products disclosed herein can be used as adsorbents to reduce proteins that cause chill haze in fermentation liquids (e.g., beer, wine, cider, vinegar). Such products have high removal efficiency.

[0109] The use of more permeable embodiments of the novel products disclosed herein, including attapulgite or sepiolite, or mixtures thereof, can improve the efficiency of chill-proofing processes by simplifying the traditional two-step process of silica gel stabilization and filtration to remove silica gel particles into a single process: simultaneous stabilization and filtration. For example, using such more permeable embodiments, even at low concentrations, during filtration of fermented liquids (e.g., beer) in filter paper / media, as body feed, or mixed with a filter aid as body feed, can significantly reduce the processing time of such fermented liquids (e.g., beer), providing brewers and others with significant efficiency gains due to the reduced stabilization / chill-proofing process time. This simplified process reduces costs and complexity. Furthermore, filtration times are significantly reduced when such more permeable embodiments are used as adsorbents compared to conventional silica gel and diatomaceous earth composite products. This further reduces costs and increases production throughput.

[0110] In other embodiments, the new products disclosed herein can be used in the same processes as current, more expensive, conventional chill-proofing agents (e.g., silica gel) to achieve the desired chill-proofing at a lower cost. For example, in one embodiment, the new products disclosed herein can be added to maturation tanks utilized in a fermentation process and then filtered.

[0111] Furthermore, the products disclosed herein are non-swelling and do not undesirably trap fermentation liquor. Additionally, the inventors have discovered that heat treatment of attapulgite or sepiolite, or a mixture thereof, between 200 and 600°C prevents the release or persistence of "earthy" odors in fermentation liquor treated with the novel products described herein, reducing and stabilizing chill haze. After pH adjustment, the inventors have discovered that the novel products do not affect the sourness of beer. Additionally, embodiments of the novel products disclosed herein are processed natural minerals that provide the desired chill-proofing, resulting in a more economical end product compared to traditional chill-proofing products made from synthetic silica gel.

[0112] From the foregoing, it will be appreciated that, while only certain embodiments have been set forth for purposes of illustration, alternatives and modifications will be apparent to those skilled in the art in light of the foregoing description. These and other alternatives are considered equivalents and within the spirit and scope of this disclosure and the appended claims.

Claims

1. 1. A product for reducing chill haze in a fermentation broth, the product comprising attapulgite or sepiolite; The product or the attapulgite or the sepiolite has a d of 5 to 19 microns or 10 to 19 microns. ５０ and having a particle size distribution having the product or the attapulgite or the sepiolite has a pore volume of 0.5 to 1.9 mL / g or 0.7 to 1.5 mL / g; the product or the attapulgite or the sepiolite has a porosity of 30-90%, or 40-80%, or 45-75%, the attapulgite comprises particles having a characteristic pore size in the range of 6 to 50 nm, or 10 to 50 nm, or 15 to 35 nm, or 20 to 30 nm, or the sepiolite comprises particles having a characteristic pore size in the range of 6 to 50 nm, or 10 to 50 nm, or 15 to 35 nm, or 20 to 30 nm; The product has a stabilizing power of 40-100% when added in an amount of 20-200 g per HL of fermentation liquid, or a stabilizing power of 50-100% when added in an amount of 30-180 g per HL of fermentation liquid, or a stabilizing power of 50-100% when added in an amount of 75-100 g per HL of fermentation liquid. product.

2. 10. The product of claim 1, wherein the attapulgite or sepiolite is treated with acetic acid, and the product has a pH measured in a 2 wt. % slurry in water of 6 to 8, or 6.5 to 7.5, or 6.9 to 7.

1.

3. 2. The product of claim 1, wherein the fermented liquid is beer, and the product has a beer-soluble iron content of 1.5 ppm or less, or 1.2 ppm or less, or 0.1 to 1.3 ppm, as measured by the modified ASBC method, respectively.

4. 2. The product according to claim 1, wherein the fermented liquid is beer, and the product has a beer stabilizing power of 40 to 100% when added in an amount of 35 to 100 g per 1 HL of beer, or a beer stabilizing power of 50 to 100% when added in an amount of 75 to 100 g per 1 HL of beer.

5. In the product according to claim 4, the product or the attapulgite or the sepiolite, when measured using the BET method, has a surface area in the range of 90 to 130 m ２ / g or 90 to 150 m ２ / g, the product.

6. 10. The product of claim 1, wherein the fermented liquid is beer, wine, or vinegar; The product is free of a composite material comprising (a) attapulgite agglomerated with a first material that is not attapulgite or sepiolite, or (b) sepiolite agglomerated with the first material that is not attapulgite or sepiolite.

7. 10. The product of claim 1, wherein the fermented liquid is beer, and the beer is an IPA, a lager, or a pilsner.

8. 10. The article of claim 1, wherein the article is made of SiO ２ Al to ２ O ３ The ratio is in the range of 0.17 to 0.22, The product is SiO ２ The ratio of MgO to MgO is in the range of 0.12 to 0.16, The product is Al ２ O ３ The ratio of MgO to ZnO is in the range of 0.75 to 0.

85.

9. 1. A method for producing a product for reducing chill haze in a fermentation broth, comprising: heat treating the attapulgite and / or sepiolite at a temperature of 200 to 600°C or 250 to 600°C to produce a heat-treated material; the article of manufacture comprises the heat-treated material; The product or heat-treated attapulgite or heat-treated sepiolite has a d of 5 to 19 microns or 10 to 19 microns. ５０ and having a particle size distribution having the product or heat-treated attapulgite or heat-treated sepiolite has a pore volume of 0.5 to 1.9 mL / g or 0.7 to 1.5 mL / g; the product or heat-treated attapulgite or heat-treated sepiolite has a porosity of 30-90%, or 40-80%, or 45-75%; the heat-treated attapulgite comprises particles having a characteristic pore size in the range of 6 to 50 nm, or 10 to 50 nm, or 15 to 35 nm, or 20 to 30 nm, or the heat-treated sepiolite comprises particles having a characteristic pore size in the range of 6 to 50 nm, or 10 to 50 nm, or 15 to 35 nm, or 20 to 30 nm; The product has a stabilizing power of 40-100% when added in an amount of 20-200 g per HL of fermentation liquid, or a stabilizing power of 50-100% when added in an amount of 30-180 g per HL of fermentation liquid, or a stabilizing power of 50-100% when added in an amount of 75-100 g per HL of fermentation liquid. method.

10. 10. The method of claim 9, further comprising: dissolving the attapulgite and / or sepiolite in a granular form having a d of 5 to 19 microns. ５０ wherein the sizing step comprises agglomeration and / or air classification and / or screening, and wherein the fermented liquid includes beer, wine, cider, or vinegar.

11. 10. The method of claim 9, further comprising the step of mixing the attapulgite and / or sepiolite with acetic acid prior to the heat treating step, The heat treatment step is performed at 300 to 400°C, The fermented liquid may include beer, wine, cider, or vinegar.

12. 10. The method of claim 9, wherein the product has a pH of 6 to 8, or 6.5 to 7.5, or 6.9 to 7.1 in a 2 wt% water slurry.

13. 13. The method of claim 12, wherein the fermented liquor is beer, and the product has 1.5 ppm or less of beer-soluble iron, or 1.2 ppm or less of beer-soluble iron, respectively, as measured by the modified ASBC method; The method wherein the product has a beer stabilizing power of 40-100% at an addition of 35-100 g per HL of beer, or a beer stabilizing power of 50-100% at an addition of 75-100 g per HL of beer.

14. 14. The method of claim 13, wherein the beer is an IPA, a lager, or a pilsner.

15. 10. The method of claim 9, wherein the fermented liquid is beer; said product having a permeability of 0.1 to 1 darcy; The method wherein the product has a beer stabilizing power of 40-100% at an addition of 35-100 g per HL of beer, or a beer stabilizing power of 50-100% at an addition of 75-100 g per HL of beer.

16. 10. The method of claim 9, wherein the fermented liquid is beer, wine, or vinegar; the product is free of (a) attapulgite agglomerated with a first material that is not attapulgite or sepiolite, or (b) a composite material comprising sepiolite agglomerated with the first material that is not attapulgite or sepiolite; The product is SiO ２ Al to ２ O ３ The ratio is in the range of 0.17 to 0.22, The product is SiO ２ The ratio of MgO to MgO is in the range of 0.12 to 0.16, The product is Al ２ O ３ The ratio of MgO to SiO2 is in the range of 0.75 to 0.

85.

17. 1. A method for reducing chill haze in a fermentation liquid, the fermentation liquid including beer, wine, cider, or vinegar, the method comprising: contacting or mixing the fermentation liquor with heat-treated attapulgite or heat-treated sepiolite; and recovering said product from said fermentation liquor to obtain a resultant fermentation liquor having less chill haze or having lower protein and / or polyphenol content than said fermentation liquor had before said contacting or mixing step, the product has a stabilizing power of 40-100% when added in an amount of 20-200 g per HL of fermentation liquid, or a stabilizing power of 50-100% when added in an amount of 30-180 g per HL of fermentation liquid, or a stabilizing power of 50-100% when added in an amount of 75-100 g per HL of fermentation liquid, the heat-treated attapulgite comprises particles having a characteristic pore size in the range of 6 to 50 nm, or 10 to 50 nm, or 15 to 35 nm, or 20 to 30 nm, or the heat-treated sepiolite comprises particles having a characteristic pore size in the range of 6 to 50 nm, or 10 to 50 nm, or 15 to 35 nm, or 20 to 30 nm; The product or the heat-treated attapulgite or the heat-treated sepiolite has a d of 5 to 19 microns or 10 to 19 microns. ５０ and having a particle size distribution having The product or the heat-treated attapulgite or the heat-treated sepiolite (a) has a pore volume of 0.5 to 1.9 mL / g or 0.7 to 1.5 mL / g; The method wherein the product or the heat treated attapulgite or heat treated sepiolite has a porosity of 30-90%, or 40-80%, or 45-75%.

18. 18. The method of claim 17, wherein the fermented liquid is beer, and the beer is an IPA, a lager, or a pilsner; The method of claim 1, wherein the product has a stabilizing power of 40-100% at an addition of 35-100 g of the product per HL of beer, or a stabilizing power of 50-100% at an addition of 75-100 g of the product per HL of beer.

19. 19. The method of claim 18, wherein the product has a pH of 6-8, or 6.5-7.5, or 6.9-7.1, as measured in a 2 wt. % water slurry, and the product has 1.5 ppm or less beer-soluble iron, or 1.2 ppm or less beer-soluble iron, as measured by the modified ASBC method, respectively.

20. 20. The method of claim 18, wherein the product has a permeability in water of 0.1 to 1 darcy, the product is free of (a) attapulgite agglomerated with a first material that is not attapulgite or sepiolite, or (b) a composite material comprising sepiolite agglomerated with the first material that is not attapulgite or sepiolite; The product is SiO ２ Al to ２ O ３ The ratio is in the range of 0.17 to 0.22, The product is SiO ２ The ratio of MgO to MgO is in the range of 0.12 to 0.16, The product is Al ２ O ３ The ratio of MgO to SiO2 is in the range of 0.75 to 0.85.

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