Product and method for stabilization / cold protection of fermentation broth

Abstract

A product and method for reducing cold turbidity in a fermentation broth is disclosed. The product may comprise green palygorskite, sepiolite, or a mixture thereof. The particle size distribution d50 of the product or the green palygorskite or the sepiolite can be 5-19 microns or 10-19 microns. The pore volume of the product or the green palygorskite or the sepiolite can be 0.5 to 1.9 mL / g or 0.7 to 1.5 mL / g; and / or the porosity is 30%-90% or 40%-80% or 45%-75%. The green palygorskite, sepiolite, or a mixture thereof may comprise particles having an intrinsic pore size in the range of 6-50 nm, or 10-50 nm, or 15-35 nm, or 20-30 nm. When 20-200g of the product is loaded on each HL of fermentation liquor, the stability of the product can be 40-100%.

Description

[0001] Cross Reference to Related Applications

[0002] This application claims priority to and the benefit of U.S. Patent Application Serial No. 17 / 984,051, filed November 9, 2022. TECHNICAL FIELD

[0003] The present disclosure relates generally to products comprising clay that are suitable for the stabilization or chill protection of fermented liquids such as beer, wine, cider, vinegar, and the like. BACKGROUND

[0004] For most fermented liquids (e.g., beer), chill haze is generally undesirable as consumers generally view haze as a defect and / or undesirable. When a fermented liquid is cooled below 0°C, chill haze can form whereby certain proteins react and clump together. If left untreated, a portion of the chill haze can develop into permanent haze present in the fermented liquid. This is particularly disadvantageous for beverages and consumable liquids.

[0005] Porous silica gels (hydrogels and xerogels) are commonly used in a two-step process to remove proteins that cause beer and other fermented liquids to haze. For example, these silica gels are added to un-stabilized beer to bind the proteins to the silica structure through a silica stabilization reaction. After the reaction is complete, the “spent” silicate gel particles must be removed through a filtration process. Silicate gel particle filtration kinetics are slow, reducing the efficiency of such products for stabilization and increasing the cost of producing beverages such as beer, wine, cider, and other fermented consumables such as vinegar.

[0006] U.S. Publication No. 2019 / 0270067 (the ‘067 Publication), published September 5, 2019, describes a composite filter aid comprising a structured composite material agglomerated from minerals with a protein adsorbing binder, wherein the structured composite material comprises particles of the protein adsorbing binder bound to a plurality of mineral particles (e.g., diatomite, natural glass such as perlite). While the disclosure of the ‘067 Publication can be beneficial, there remains a need for effective and less costly removal media capable of stabilizing and / or chill protecting liquids. SUMMARY

[0007] In one aspect of the present disclosure, a product for reducing chill haze in a fermented liquid is disclosed. The product can comprise a palygorskite or sepiolite. The product or palygorskite or sepiolite can have a particle size distribution d 50The pore size of the product or attapulgite or sepiolite product may be 5-19 microns or 10-19 microns. The pore volume of the product or attapulgite or sepiolite product may be 0.5-1.9 ml / g or 0.7-1.5 ml / g. The porosity of the product or attapulgite or sepiolite may be 30-90%, 40-80%, or 45-75%. The attapulgite may comprise particles having an intrinsic pore size in the range of 6-50 nm, 10-50 nm, 15-35 nm, or 20-30 nm, or the sepiolite may comprise particles having an intrinsic pore size in the range of 6-50 nm, 10-50 nm, 15-35 nm, or 20-30 nm. When the product is loaded at 20-200 g per HL of fermentation broth, the stability of the product can be 40-100%, when the product is loaded at 30-180 g per HL of fermentation broth, the stability of the product can be 50-100%, when the product is loaded at 35-100 g per HL of fermentation broth, the stability of the product can be 40-100%, or when the product is loaded at 75-100 g per HL of fermentation broth, the stability of the product can be 50-100%.

[0008] In one embodiment, the attapulgite or sepiolite may be treated with acetic acid, and the pH of the product may be 6-8, or 6.5-7.5, or 6.9-7.1, measured in a 2 wt% slurry in water.

[0009] In any of the above embodiments, the fermentation broth can be beer, and the beer soluble iron of the product does not exceed 1.5 parts per million (ppm) as measured by the improved ASBC method described herein, or the beer soluble iron of the product does not exceed 1.2 ppm, or the beer soluble iron of the product is 0.1-1.3 ppm.

[0010] In any of the above embodiments, the fermentation broth can be beer, and the beer stabilization capacity can be 40-100% when the product is loaded at 35-100 g per HL of beer, or 50-100% when the product is loaded at 75-100 g per HL of beer.

[0011] In any of the above embodiments, the specific surface area of ​​the product or attapulgite or sepiolite can be in the range of 90-130 m 2 / g or 90-150m 2 / g range.

[0012] In any of the above embodiments, the fermentation broth can be beer, wine, cider, or vinegar, wherein the product does not contain 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.

[0013] In any of the above embodiments, the fermentation broth can be a beer, wherein the beer is an IPA beer, a lager beer, or a pilsner beer.

[0014] In any of the above embodiments, the product can have an AI2O3 to Si ratio in the range of 0.17-0.22, a MgO to SiO2 ratio in the range of 0.12-0.16, and a MgO to AI2O3 ratio in the range of 0.75-0.85.

[0015] In another aspect of the disclosure, a method of producing a product for reducing chill haze in a fermentation broth is disclosed. The method can include heat treating palygorskite and / or sepiolite at a temperature of 200-600 °C or 250-600 °C to produce a heat treated material, wherein the product comprises the heat treated material. The product or heat treated palygorskite or heat treated sepiolite can have a particle size distribution d 50 may be 5-19 microns or 10-19 microns, the product or heat treated palygorskite or heat treated sepiolite can have a pore volume of 0.5-1.9 mL / g or 0.7-1.5 mL / g, and the product or heat treated palygorskite or heat treated sepiolite can have a porosity of 30-90% or 40-80% or 45-75%. The heat treated palygorskite can comprise particles having an intrinsic pore size in the range of 6-50 nm or 10-50 nm or 15-35 nm or 20-30 nm, or the heat treated sepiolite can comprise particles having an intrinsic pore size in the range of 6-50 nm or 10-50 nm or 15-35 nm or 20-30 nm. The product can have a stabilization capacity of 40-100% at a loading of 20-200 g of the product per HL of fermentation broth, 50-100% at a loading of 30-180 g of the product per HL of fermentation broth, 40-100% at a loading of 35-100 g of the product per HL of fermentation broth, or 50-100% at a loading of 75-100 g of the product per HL of fermentation broth.

[0016] In one embodiment, the method can further comprise fractionating the palygorskite and / or sepiolite to a particle size distribution d 50 of 5-19 microns, wherein the fractionating comprises agglomeration and / or air classification and / or sieving, and wherein the fermentation broth comprises beer, wine, cider, or vinegar.

[0017] In one embodiment, the method can further comprise mixing the palygorskite and / or sepiolite with acetic acid prior to the heat treating, wherein the heat treating is at a temperature of 300-400 °C, and wherein the fermentation broth comprises beer, wine, cider, or vinegar.

[0018] In any of the above embodiments, the product can have a pH in a 2 wt% water slurry of 6-8, 6.5-7.5, or 6.9-7.1.

[0019] In any of the above embodiments, the fermentation liquor can be beer, wherein the product can have a beer soluble iron of no more than 1.5 ppm, or a beer soluble iron of no more than 1.2 ppm, as measured by the modified ASBC method, and the product can have a beer stabilizing capacity of 40-100% when loaded at 35-100 g per HL of fermentation liquor, or a beer stabilizing capacity of 50-100% when loaded at 75-100 g per HL of fermentation liquor. In one refinement, the beer can be an IPA, a lager, or a pilsner.

[0020] In any of the above embodiments, the fermentation liquor can be beer, the product can have a permeability of 0.1-1 Darcy, and the product can have a beer stabilizing capacity of 40-100% when loaded at 35-100 g per HL of beer, or a beer stabilizing capacity of 50-100% when loaded at 75-100 g per HL of beer.

[0021] In any of the above embodiments, the fermentation liquor can include beer, wine, cider, or vinegar, and the product can be free of a composite material including: (a) attapulgite agglomerated with a first material that is not attapulgite or not sepiolite, or (b) sepiolite agglomerated with a first material that is not attapulgite or not sepiolite, and the product can have a ratio of AI2O3 to SiO2 in a range of 0.17-0.22, and the product can have a ratio of MgO to SiO2 in a range of 0.12-0.16, and the product can have a ratio of MgO to AI2O3 in a range of 0.75-0.85.

[0022] In yet another aspect of the present disclosure, a method for reducing cold haze in a fermentation broth is disclosed. The fermentation broth can include beer, wine, cider, or vinegar. The method can include: contacting or mixing the fermentation broth with a product comprising heat-treated palygorskite or heat-treated sepiolite; and recovering the product from the fermentation broth to obtain a resulting fermentation broth having a lower cold haze or a lower protein and / or polyphenol content compared to the fermentation broth before the contacting or mixing, wherein the product has a stabilization capacity of 40-100% at a loading of 20-200 g of the product per HL of the fermentation broth, or the product has a stabilization capacity of 50-100% at a loading of 30-180 g of the product per HL of the fermentation broth, or the product has a stabilization capacity of 40-100% at a loading of 35-100 g of the product per HL of the fermentation broth, or the product has a stabilization capacity of 50-100% at a loading of 75-100 g of the product per HL of the fermentation broth, wherein the heat-treated palygorskite can comprise particles having an intrinsic pore size in the range of 6-50 nm or 10-50 nm or 15-35 nm or 20-30 nm, or the heat-treated sepiolite can comprise particles having an intrinsic pore size in the range of 6-50 nm or 10-50 nm or 15-35 nm or 20-30 nm, wherein the product or the heat-treated palygorskite or the heat-treated sepiolite can have a particle size distribution d 50 may be 5-19 microns or 10-19 microns, wherein the product or the heat-treated palygorskite or the heat-treated sepiolite can have a pore volume of (a) 0.5-1.9 mL / g or 0.7-1.5 mL / g, wherein the product or the heat-treated palygorskite or the heat-treated sepiolite can have a porosity of 30-90% or 40-80% or 45-75%.

[0023] In one embodiment, the fermentation broth can be beer, where the beer can be an IPA, a lager, or a pilsner. The beer stabilizing capacity of the product can be 40-100% at 35-100 grams of the product per HL of beer load, or 50-100% at 75-100 grams of the product per HL of beer load. In one improvement, the product has a pH of 6-8, 6.5-7.5, or 6.9-7.1, as measured in a 2 wt% water slurry, where both are measured by the modified ASBC method, the product has a beer soluble iron of no more than 1.5 ppm, or the product has a beer soluble iron of no more than 1.2 ppm. In another improvement of this embodiment, the product has a permeability in water of 0.1-1 Darcy, the product can be 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 has a ratio of AI2O3 to SiO2 in the range of 0.17-0.22, and the product has a ratio of MgO to SiO2 in the range of 0.12-0.16, and the product has a ratio of MgO to AI2O3 in the range of 0.75-0.85.

[0024] BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 Scanning electron microscope (SEM) image of feed A (Acti-Gel 208) at low magnification (500x).

[0026] Figure 2 SEM image of feed B at high magnification (100,000x).

[0027] Figure 3 SEM image of feed B at low magnification (2000x).

[0028] Figure 4 Pore size distribution for Examples 1 and 2.

[0029] Figure 5 Pore size distribution for Examples 7 and 8. DETAILED DESCRIPTION

[0030] The present disclosure relates to a product for stabilizing / chilling a fermentation broth by adsorbing proteins from the fermentation broth. Such fermentation broths include, but are not limited to, beer, wine, cider, vinegar, and the like. Beer can include, but is not limited to, pilsner, lager (e.g., Helle, American lager, bock, March beer, black beer, and the like), ale (e.g., India Pale Ale (IP A), pale ale, bitter, saisson, three thread beer, gueuze, and the like), porter, stout, wheat beer, Belgian beer, sour beer, white beer, black beer, koelsch, lambic, steam beer, rye beer, Berliner Weisse, double bock, wheat bock, double beer, gueuze, malt liquor, old beer, and the like.

[0031] The product disclosed herein comprises or can be attapulgite or sepiolite or a mixture thereof. Attapulgite is sometimes referred to as palygorskite. To avoid confusion, the term "attapulgite" as used herein means attapulgite and / or palygorskite. As known in the art, both attapulgite and sepiolite are clay minerals of the chain lattice type, which have a structure different from other clays such as montmorillonite or bentonite. That is, the tetrahedral sheets of attapulgite or sepiolite are split into multiple ribbons by inversion because adjacent tetrahedral ribbons within one tetrahedral sheet point in opposite directions rather than one direction, thereby forming a ribbon structure of 2:1 layers connected at the edges, while the octahedral sheets are continuous only in two dimensions. The structural similarity between the two minerals is that the tetrahedra pointing in the same direction form 2:1 ribbons extending in the direction of the a axis, and the average b axis width in sepiolite is three connected tetrahedral chains and in attapulgite is two connected chains. Attapulgite and sepiolite are non-swelling clays, which are different from clays known to be swelling clays such as bentonite and montmorillonite. Swelling clays are clays that undergo a relatively large increase in volume in a water-based liquid (due to an increase in the interlamellar spacing of the clay particles).

[0032] While both natural attapulgite or sepiolite have chilling efficacy, attapulgite or sepiolite cannot be used directly for chilling of fermentation broths. For example, when natural attapulgite is added to a fermentation broth, such as beer, it produces a very strong earthy or "cardboard" odor and / or taste in the fermentation broth. This is unacceptable to breweries and other producers of fermentation broths for beverages. In addition, natural attapulgite also undesirably reduces the acidity / sourness in beer due to the increase in pH of the beer resulting from the contact of the beer with the natural attapulgite. Similar drawbacks exist for natural sepiolite.

[0033] Disclosed herein are new products that can comprise or can be attapulgite or sepiolite or mixtures thereof, as well as methods of making and using such products. Due to the unique porous structure, pore size, and high surface area of the new products disclosed herein, such products can be used to effectively stabilize fermentation broth by adsorbing proteins and the like that cause the appearance of haze and / or chill haze in beverages (e.g., beer, wine, cider, etc.) and other consumable liquids (vinegar, etc.). For example, test results indicate that such new products significantly reduce chill haze in various fermented beverages. Moreover, due to the very low permeability of traditional chill proofing agents, the use of the products disclosed herein (which have higher permeability when used in filter paper / filter media or as a bulk feed or mixed with filter aids as a bulk feed during filtration of fermentation broth (e.g., beer), even at lower concentrations, significantly shortens the filtration time of such fermentation broth (e.g., beer), which provides a significant efficiency gain for brewers and the like (due to the reduction in stabilization / chill proofing process time). For example, the use of the new products disclosed herein, which have higher permeability, enables the simplification of the traditional two-step fermentation broth treatment process (i.e., (1) a silica gel stabilization reaction and (2) a subsequent filtration to remove "spent" silica gel particles) into a single process step in which the stabilization and filtration of the fermentation broth are performed simultaneously (e.g., when filter paper or filter media is impregnated with the new products disclosed herein, which have higher permeability, or when such new products are used as a bulk feed or mixed with filter aids as a bulk feed). This simplification of the stabilization and chill proofing process increases the efficiency of the stabilization and chill proofing process. The simplified process reduces costs and complexity. The filtration time using such products as adsorbents is significantly reduced compared to traditional silica gel and diatomaceous earth composite products. This further reduces costs and increases production capacity. In other embodiments, the new products disclosed herein can be used in a similar process to the currently more expensive traditional chill proofing agents (e.g., silica gel) and achieve the desired chill proofing effect at a significantly lower cost. For example, in one embodiment, the new products disclosed herein can be added to the aging tanks used in the fermentation process and then filtered out.

[0034] Such new products for stabilizing / chill proofing fermentation broth can comprise attapulgite or sepiolite or mixtures thereof. The product or attapulgite or sepiolite can have a particle size distribution d 50The product or the palygorskite or the sepiolite can have a pore volume of 0.5-1.9 mL / g or 0.7-1.5 mL / g. The product or the palygorskite or the sepiolite can have a porosity in the range of 30-90% or 40-80% or 49-72% or 45-75%. The palygorskite can comprise particles having an intrinsic pore size in the range of 6-50 nm or 10-50 nm or 15-35 nm or 20-30 nm, or the sepiolite can comprise particles having an intrinsic pore size in the range of 6-50 nm, 10-50 nm, 15-35 nm or 20-30 nm. The product can have a stabilization capacity of 40-100% at a load of 20-200 g of the product per HL of fermentation broth, or the product can have a stabilization capacity of 50-100% at a load of 30-180 g of the product per HL of fermentation broth, or the product can have a stabilization capacity of 40-100% at a load of 35-100 g of the product per HL of fermentation broth, or the product can have a stabilization capacity of 50-100% at a load of 75-100 g of the product per HL of fermentation broth.

[0035] In any of the above embodiments, the palygorskite or the sepiolite can have an interporosity size of about 2 microns to about 50 microns, peaking at about 15 microns to about 30 microns; or an interporosity size of about 2 microns to about 20 microns, peaking at about 3 microns to about 17 microns.

[0036] In any of the above embodiments, the palygorskite or the sepiolite can be treated with acetic acid, and the product can have a pH in water of 6-8 or 6.5-7.5 or 6.9-7.1, measured in a 2 wt% slurry.

[0037] In any of the above embodiments, the fermentation broth can be beer, and the product can have a beer-soluble iron content of no more than 1.5 ppm, or a beer-soluble iron content of no more than 1.2 ppm, or a beer-soluble iron content of 0.1-1.3 ppm, each measured by the modified ASBC method.

[0038] In any of the above embodiments, the fermentation broth can be beer, and the product can have a beer stabilization capacity of 40-100% at a load of 35-100 g of the product per HL of beer, or the product can have a beer stabilization capacity of 50-100% at a load of 75-100 g of the product per HL of beer.

[0039] In any of the above embodiments, the product or the palygorskite or the sepiolite can have a specific surface area in the range of 90-130 m 2 / g or 90-150 m 2 / g, each measured by the BET method.

[0040] In any of the above embodiments, the product or the green palygorskite or the sepiolite can have a particle size distribution d 10 It can also be in the range of 2-8 microns or 4-7 microns; and / or a particle size distribution d 90 It can be in the range of 10-70 microns or 20-42 microns.

[0041] In any of the above embodiments, the fermented liquid can be beer, wine, cider, or vinegar. In some embodiments, the product can be free of composites, or free of composites comprising: (a) green palygorskite agglomerated with a first material that is not green palygorskite or sepiolite; or (b) sepiolite agglomerated with a first material that is not green palygorskite or sepiolite.

[0042] In any of the above embodiments, the fermented liquid can be beer, wherein the beer is an IPA, a lager, or a pilsner.

[0043] In any of the above embodiments, the product can have an Al203to Si02ratio in the range of 0.17-0.22, a MgO to Si02ratio in the range of 0.12-0.16, and a MgO to Al203ratio in the range of 0.75-0.85.

[0044] In some embodiments, the product produced can be in the form of a granule or a powder, or can be in a non-extruded (non-extruded) form. In one or more embodiments, the product can be free of composites. In one or more embodiments, the product can be free of composites comprising: (1) green palygorskite or sepiolite, and (2) other materials, wherein the other materials are agglomerated with the green palygorskite or sepiolite to form the composite. In one or more embodiments, the product can be free of synthetic alkaline earth metal silicas and / or polyethylene resins and / or diatomaceous earth and / or natural glass and / or expanded clay. Synthetic alkaline earth metal silicas can include, but are not limited to, synthetic magnesium silicate and synthetic calcium silicate. Natural glass can include, but is not limited to, perlite, volcanic ash, pumice, floatstone, white sand, obsidian, pine tar stone, rice hull ash, and mixtures thereof. Expanded clay can include, but is not limited to, montmorillonite and bentonite.

[0045] In any of the above embodiments, the fermented liquid can be beer, wine, cider, or vinegar.

[0046] In any of the above embodiments, the green palygorskite or sepiolite can be heat treated.

[0047] Preparation of Product

[0048] Methods of making the above products can include selecting natural palygorskite or natural sepiolite or mixtures thereof for processing. Palygorskite / sepiolite is a magnesium-aluminum phyllosilicate with the chemical formula (Mg, Al)2Si4O 10 (OH)4H2O. Sepiolite is a fibrous hydrous magnesium silicate with the chemical formula Mg4SiO 15 (OH)2-6H2O. The percentage of various elements can vary depending on the source deposit of the palygorskite or sepiolite. Both minerals have similar crystal structures, with sepiolite having three connected tetrahedral chains and palygorskite having two connected chains.

[0049] The bulk chemistry of the palygorskite or sepiolite used in the feed can affect the extractable metal properties of the final product, as these impurities can form extractable metals when the product is contacted with a fermentation broth. Thus, the palygorskite or sepiolite can be subjected to a purification process to reduce impurities prior to the further processing disclosed herein. Such purification processes are known in the art.

[0050] The method can include sizing the selected material (palygorskite, sepiolite, or mixtures thereof). Sizing the selected material can include agglomeration, air classification, and / or screening of the selected material (palygorskite, sepiolite, or mixtures thereof). In one embodiment, agglomeration can be performed by mechanical processes (e.g., spray drying, high shear mixing, etc.) with or without the use of a binder. Spray drying techniques for agglomeration are known to those of ordinary skill in the clay industry. One exemplary known method is to prepare a slurry of the material (e.g., palygorskite, sepiolite, or mixtures thereof) and water, and then disperse the slurry into droplets using a spray dryer through a high pressure nozzle, disk, etc. The inlet and outlet air temperatures of the spray dryer depend on the dryer used. The droplets then become roughly spherical particle agglomerates and are collected downstream of the drying chamber.

[0051] Alternatively, other suitable methods known in the art can be used to spray dry the clay or agglomerate the clay, such as using high shear mixers (e.g., turbulent mixers and pin mixers) or agglomerators (e.g., rotary drum agglomerators), etc. These methods can be used with or without a binder.

[0052] Air classification can be performed using methods known in the art. For example, the palygorskite in certain embodiments discussed herein was classified using an Alpine TM 200 ATP air classifier (Hosokawa Micron Powder Systems, Summit, NJ) to produce a coarse fraction. The Alpine TMThe 200 ATP classifier utilizes the following parameters: classifier wheel speed of 5000 rpm, total gas flow of 500 SCFM (standard cubic feet per minute), and a feed rate of 390 pounds per hour (176.9 kg / hr). The yield of the coarse fraction is 82%. Other suitable wheel speeds, gas flows, and feed rates can also be used to produce a suitable coarse fraction.

[0053] Similarly, screening can be performed by methods known in the art. For example, a Ro-Tap sieve shaker with a screen can be used to obtain a fraction that is greater than or less than a desired size. For example, a Ro-Tap sieve shaker with a screen can be used to obtain a fraction that is greater than 400 mesh (also referred to as +400) or 500 mesh (+500) or other desired mesh. A vibrating screen can also be used for particle separation.

[0054] Optionally, the method can also include mixing the material (natural and / or fractionated and / or purified sepiolite / attapulgite / mixtures thereof) with an acetic acid solution until well mixed to adjust the pH of the selected material. The present inventors have found that the addition of natural sepiolite at a high pH can reduce the sourness of beer and affect beer flavor, as the typical pH of a barley-based beer is generally around 4.1 to 4.5, while the pH of a wheat-based beer is slightly lower. In one embodiment, the mixing of the material with the acetic acid solution adjusts the pH of the selected material as measured in water to a pH in the range of 6-8. In another embodiment, the mixing of the material with the acetic acid solution adjusts the pH of the selected material as measured in water to a pH in the range of 6.5-7.5. In another embodiment, the mixing of the material with the acetic acid solution adjusts the pH of the selected material as measured in water to a pH in the range of 6.9-7.1 or a pH of about 7. In one embodiment, the concentration of the acetic acid solution can be in the range of 5% to 15% acetic acid. In each of the embodiments discussed herein, the natural sepiolite is mixed with a 10% acetic acid solution in a KitchenAid 5 quart food blender at low speed until well mixed (e.g., for about 30 minutes). Using a 10% concentration of the acetic acid solution, the weight percent of liquid (acetic acid solution) to solid (sepiolite, attapulgite, or mixtures thereof) can be about 5 to about 10 weight percent liquid (acetic acid solution) and about 95 to 90 weight percent solid (sepiolite, attapulgite, or mixtures thereof). For example, in each of the embodiments herein, 200 g of the selected natural sepiolite is mixed with 20 g of a 10% acetic acid solution until well mixed to adjust the pH of the natural sepiolite. The weight percent of liquid to solid can vary for other concentrations of acetic acid solution in the range of 5-15%. In other embodiments, the mixing time can vary. For example, the liquid and solid material can also be mixed for 10-60 minutes or other appropriate time period to mix well. Other food grade acids, such as citric acid, can also be used to adjust the pH of the sepiolite or attapulgite.

[0055] The method also includes heat treating the material (attapulgite, sepiolite, or a mixture thereof). In embodiments where the method includes mixing the material (attapulgite, sepiolite, or a mixture thereof) with an acetic acid solution, the resulting mixture can be placed in a ceramic boat or other suitable container and then heat treated at about 200 to about 600 °C, about 250 to about 600 °C, about 250 to about 500 °C, or about 300 to 400 °C. In one embodiment, the heat treatment can be for about 10 to about 60 minutes. For example, in one embodiment, the heat treatment can be for about 30 minutes at about 250 °C to about 500 °C. The above method can remove the earthy smell in a fermented liquid (e.g., beer) resulting from contact with natural attapulgite or natural sepiolite. In embodiments where the natural material (attapulgite, sepiolite, mixture thereof) is not treated with an acetic acid solution, the material (attapulgite, sepiolite, or a mixture thereof) can be placed in a ceramic boat or other suitable container and heated in a muffle furnace to about 200 to about 600 °C, or about 250 to about 600 °C, or about 250 to about 500 °C, or about 300 to 400 °C to remove the earthy smell in a beer resulting from contact with natural attapulgite or natural sepiolite. In one embodiment, the heat treatment can be for about 10 to about 60 minutes. For example, in one embodiment, the heat treatment can be for about 30 minutes at about 250 °C to about 500 °C.

[0056] In one or more embodiments, the product produced can be in the form of a granule or a powder, or in a non-extruded (non-extruded) form. In one or more embodiments, the product can be free of a composite material. In one or more embodiments, the product can be free of a composite material comprising: (1) attapulgite or sepiolite, and (2) another material, wherein the other material is agglomerated with the attapulgite or sepiolite to form the composite material. In one or more embodiments, the product can have an Al2O3to SiO2ratio in the range of 0.17 to 0.22, a MgO to SiO2ratio in the range of 0.12 to 0.16, and a MgO to Al2O3ratio in the range of 0.75 to 0.85. In one or more embodiments, the product can be free of synthetic alkaline earth silicas and / or polyethylene resins and / or diatomaceous earth and / or natural glass and / or expanded clay. Synthetic alkaline earth silicas can include, but are not limited to, synthetic magnesium silicate and synthetic calcium silicate. Natural glass can include, but is not limited to, perlite, volcanic ash, pumice, volcanic pumice, white sand, obsidian, pine tar stone, rice hull ash, and mixtures thereof. Expanded clay can include, but is not limited to, montmorillonite and bentonite.

[0057] Adsorption Process

[0058] The products disclosed herein can be used to adsorb proteins and the like that cause cold haze in fermentation broth. Fermentation broth can include, but is not limited to, beer, wine, cider, vinegar, and the like. Methods of reducing cold haze in fermentation broth can include contacting (or mixing) the fermentation broth with any of the products disclosed herein for a period of time, the products comprising or can be attapulgite or sepiolite or mixtures thereof. For example, in one embodiment, the fermentation broth can be flowed through filter paper / filter media that can be impregnated with the new product. In another embodiment, the new product can be used as the primary feed or mixed with a filter aid used as the primary feed. In another embodiment, the new product can be added to the aging tank used in the fermentation process. In one embodiment, the contact time can vary depending on the application. For example, when the new product is used in applications where it is impregnated in filter paper or filter 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. When added to the aging tank, the contact time can be longer (e.g., in one embodiment, from one hour to several days), depending on the aging process employed by the producer of the fermentation broth. The contact time when used as the primary feed or mixed with a filter aid used as the primary feed can also vary.

[0059] at an amount sufficient to reduce the amount of cold haze in the fermentation broth at a given contact time such that the % stabilization capacity is at least 40-100%, 50-100%, 60-100%, or 70-100%, or 80-100%, or about 50-80%. As used herein, the term "stabilization capacity" of a dose of adsorbent in a given fermentation broth refers to the percentage reduction in the amount of cold haze in the fermentation broth at a given contact time as compared to a silica hydrogel (SH) in the same fermentation broth under the same conditions. The method of calculation will be described later. For example, in one embodiment, the % stabilization capacity of the product can be at least 40-100% or 50-100% or 60-100% or 70-100% or 80-100% when loaded at 20-200 grams (g) of the product per hundred liters (HL) of fermentation broth, or 25-125 g of the product per HL of fermentation broth, or 35-100 g of the product per HL of fermentation broth, or 75-100 g of the product per HL of fermentation broth.

[0060] For example, in one embodiment, the product can have a % stability in beer (beer stability %) of at least 40-100% at a load of 20-200 g / HL of beer or a load of 25-125 g / HL of beer; in another improvement, the product can have a beer stability % of at least 50-100% at a load of 20-200 g / HL of beer or a load of 25-125 g / HL of beer; in another improvement, the product can have a beer stability % of at least 60-100% at a load of 20-200 g / HL of beer or a load of 25-125 g / HL of beer; in another improvement, the product can have a beer stability % of at least 70-100% at a load of 20-200 g / HL of beer or a load of 25-125 g / HL of beer; in another improvement, the product can have a beer stability % of at least 80-100% at a load of 20-200 g / HL of beer or a load of 25-125 g / HL of beer, or in another improvement, the product can have a beer stability % of at least 50-80% at a load of 20-200 g / HL of beer or a load of 25-125 g / HL of beer.

[0061] The method further comprises recovering the product from the fermentation broth to obtain a resulting fermentation broth having a lower cold haze or a lower content of proteins and / or polyphenols that cause cold haze than the fermentation broth prior to the contacting or mixing. The resulting fermentation broth can be recovered by collecting / capturing the final fermentation broth after the cold protection (e.g., by a filter paper or filtration medium impregnated with the product, or by a pre-coat layer containing the product, etc.), or by filtering or separating the product from the fermentation broth (e.g., from a slurry or a maturation tank, etc.), or by any other suitable method known to one skilled in the art to obtain the resulting fermentation broth or to separate the resulting fermentation broth from the product used for the cold protection.

[0062] Other adsorption methods can be used and the contact time can be adjusted as desired.

[0063] Test Method Descriptions

[0064] Surface Area, Pore Volume, Pore Size Distribution, Porosity

[0065] Surface area was measured by nitrogen adsorption by the BET (Brunauer-Emmett-Teller) method. Pore volume and pore size distribution of a material sample were determined by mercury porosimetry. Mercury porosimetry uses mercury as the invading fluid to measure the pore volume of a (weighed) material sample enclosed within the sample cell of a porosimeter. The sample cell is evacuated to remove air from the pores of the sample. The sample cell and porosimeter are filled with mercury. Since mercury does not wet the material surface, it must be forced into the pores by an external pressure. A gradually increasing pressure is applied to allow the mercury to enter the pores. The equilibrium pressure required is inversely proportional to the size of the pores, requiring only a slight pressure to force the mercury into large pores, while a greater external pressure is required to force the mercury into small pores. The porosimeter reads the volume of mercury forced in, and uses the force-in data to calculate the pore size distribution, porosity, average pore size, and total pore volume. A Micromeritics AutoPore IV 9500 was used herein to analyze the samples.

[0066] Assuming cylindrical pores, the surface distribution can be derived from the pore volume distribution used in the calculation. An estimate of the total surface area of a material sample can be made from the pressure / volume curve (Rootare, 1967) without using a pore model as follows:

[0067]

[0068] where A = total surface area,

[0069] γ = surface tension of mercury,

[0070] θ = contact angle of mercury with the material pore wall,

[0071] p = externally applied pressure,

[0072] V = pore volume,

[0073] From the function V = V(p), the integral can be calculated by numerical methods.

[0074] From the pressure versus mercury intrusion data, the instrument generates the volume and size distribution of the pores according to the Washburn equation (Washburn, 1921) as follows:

[0075]

[0076] where d i = pore diameter at the equilibrium external pressure

[0077] γ = surface tension of mercury

[0078] θ = contact angle of mercury with the material pore wall

[0079] P i = externally applied pressure

[0080] The average pore diameter is determined from the cumulative intrusion volume and the total surface area of the material sample as:

[0081]

[0082] where D = average pore diameter

[0083] V = total intrusion volume of mercury

[0084] S = total surface area

[0085] Porosity is the fraction of the total material volume occupied by pore space. Porosity is calculated from the mercury intrusion data. United States American Society of Brewing Chemists (ASBC) Beer 27 Test Method

[0086] Total beer chill haze is measured using a haze meter. The haze meter cuvette is cooled in a small ice water bath containing a wetting agent (only the outside is in contact). The beer container is removed from the constant temperature bath at 0°C, the cuvette is rinsed and then filled with the chilled beer sample without stirring any sediment. The cuvette is placed in the small ice water bath and then agitated with a thermometer to degas the beer. When the beer in the cuvette is at 0°C, the cuvette is placed in the sample chamber of the haze meter and a reading is taken by the haze meter. This reading is in units of haze units (NTU). The "chill haze [ML刘1] " measured herein is the total chill haze after cooling the fermentation broth (e.g., beer) at 0°C.

[0087] Adsorbent pH in Water Test

[0088] For the exemplary embodiments of the new products disclosed herein, the pH of the adsorbent in water is measured. 196.0 g of distilled water is placed in a multi-functional beaker. Four (4.0) g of the product to be tested is added to the distilled water to create a 2 wt% slurry. The beaker is placed on a multi-functional stirrer and stirred for five (5) minutes. A magnetic stir bar is placed in a 100-250 milliliter (mL) beaker and placed on an electric stirrer. The slurry of distilled water and product is removed from the stirrer and poured into the beaker. The speed of the stirrer is adjusted to create a steady, gentle circulation. The pH is determined by immersing a pH electrode into the slurry and obtaining a pH measurement.

[0089] Adsorbent pH in Beer Test

[0090] For exemplary embodiments of the novel products disclosed herein, the pH of the adsorbent in beer was measured. 150.0 g of beer was placed in a multifunctional stirring cup. Two (2.0) g of the product to be tested was added to the beer to produce a slurry of approximately 1.3 wt %. The stirring cup was placed on a multifunctional stirrer and stirred for five (5) minutes. A magnetic stirring bar was placed in a 100-250 milliliter (mL) beaker and placed on an electric stirrer. The slurry of beer and product was removed from the stirrer and poured into the beaker. The speed of the stirrer was adjusted to produce a stable, gentle circulation. The pH was determined by immersing a pH electrode in the slurry and obtaining a pH measurement.

[0091] Beer Soluble Iron Test

[0092] In the following modified American Society of Brewing Chemists (ASBC) test, the soluble iron content of beer was measured for exemplary embodiments of the novel products disclosed herein. A 500 milliliter (mL) flask containing 200 g of Budweiser beer was degassed. Five (5) g of a representative adsorbent sample was added to the degassed beer. The mixture was spun once every minute for a total of six (6) minutes. The mixture was then filtered using 19-26 micron filter paper, and the iron concentration in the beer was measured using inductively coupled plasma (ICP) spectroscopy.

[0093] Example

[0094] The products of Examples 1-8 all contain attapulgite. The products of Examples 1-8 were prepared from the different attapulgite feeds listed in Table 1.

[0095] Table 1. Feed

[0096]

[0097] Use commercially available Acti-Gel (Active Minerals International, LLC), an attapulgite product, was used as feed to prepare feed A. Acti-Gel 208 product is natural attapulgite that has been purified and agglomerated by spray drying. Figure 1 SEM image of feed A (Acti-Gel 208) at low magnification (x500).

[0098] The major elemental composition of Feed A, as determined by wavelength dispersive X-ray fluorescence (XRF) analysis for Acti-Gel 208, is shown in Table 2.

[0099] Table 2. Major oxide composition (on ignition basis) of the purified natural attapulgite product Acti-Gel 208 used as feed.

[0100]

[0101]

[0102] 1 Although these elements are reported as oxides, they are actually present in complex aluminosilicate forms

[0103]

[0104] Min-U-Gel 400 product is a non-purified natural palygorskite that has been air classified. SEM image of feed B at high magnification (100,000x). Figure 2 SEM image of feed B at low magnification (2000x). The major elemental composition of Min-U-Gel 400 as determined by wavelength dispersive X-ray fluorescence (XRF) analysis is shown in Table 3. Figure 3 Table 3. Major oxide composition (loss on ignition basis) of air classified natural palygorskite Min-U-Gel 400 used as feed.

[0105]

[0106]

[0107] 1 Although these elements are reported as oxides, they are actually present in complex aluminosilicate forms

[0108] Min-U-Gel 200 product is a non-purified natural palygorskite that has been air classified. (Minerals International, LLC) as feed to make feed C. Min-U-Gel The major elemental composition of Min-U-Gel 200 as determined by wavelength dispersive X-ray fluorescence (XRF) analysis is shown in Table 4.

[0109] Table 4. Major oxide composition (loss on ignition basis) of air classified natural palygorskite Min-U-Gel 200 used as feed.

[0110]

[0111] 2 Although these elements are reported as oxides, they are actually present in complex aluminosilicate forms

[0112] ​​Feed D was prepared using natural attapulgite mined by Active Minerals International LLC near Climax, Georgia as the feed. The major elemental composition of the feed, as determined by wavelength dispersive X-ray fluorescence (XRF) analysis, is shown in Table 5.

[0113] Table 5. Major oxide compositions (on ignition basis) of natural attapulgite materials used as feed.

[0114]

[0115]

[0116] 1 Although these elements are reported as oxides, they actually exist as complex aluminosilicates.

[0117] Feed AD had a nitrogen adsorption capacity of 88 m 2 / g to 142m 2 The particle size of these feeds (d 50 ) is about 8-19 microns.

[0118] Feeds AD also contained approximately 9-14 wt% moisture at 104°C (220°F).

[0119] Example 1-2

[0120] By mixing 200 grams (g) of feed A with 20 g of 10% acetic acid solution in Example 1 was prepared from Charge A by mixing at low speed in a 5 quart food blender for 30 minutes. The resulting mixture was then placed in a ceramic boat and heat treated at 250°C for 30 minutes. Similarly, 200 grams (g) of Charge A was mixed with 20 g of a 10% acetic acid solution in a Example 2 was prepared from Charge A by mixing in a 5 quart food blender at low speed for 30 minutes. The resulting mixture was then heated at 300°C for 30 minutes.

[0121] Examples 3-6

[0122] For each of Examples 3-6, 100 g of Charge B was placed in a ceramic boat and heated in a muffle furnace for 30 minutes. Example 3 was heated in a muffle furnace at 300° C., Example 4 was heated in a muffle furnace at 400° C., Example 5 was heated in a muffle furnace at 500° C., and Example 6 was heated in a muffle furnace at 600° C.

[0123] Example 7

[0124] Example 7 was prepared by using an Alpine TM Example 7 was prepared by using an Alpine TM The 200 ATP classifier utilized the following parameters: wheel speed of the classifier was 5000 rpm, total air flow was 500 SCFM (standard cubic feet per minute), and the feed rate was 390 pounds per hour (176.9 kg / hr). The particle size distribution of a representative sample of the coarse fraction obtained is shown in Table 6.

[0125] Table 6. Particle size distribution of the coarse fraction of feed D and classified material D.

[0126] Materials d10 (μm) d50 (μm) d90 (μm) Feed D 3.89 13.49 33.93 Coarse Fraction 4.26 14.13 30.67

[0127] The coarse fraction of the air classified feed D was then mixed with 20 g of a 10% acetic acid solution in a KitchenAid 5 quart food blender for 30 minutes at low speed. The resulting mixture was then placed in a ceramic boat and heat treated at 400 °C for 30 minutes.

[0128] Example 8

[0129] Example 8 was prepared by sieving feed C using a rotary sieve shaker with a 500 mesh screen. The feed C was vibrated on the 500 mesh screen for about 10 minutes. The 200 g of the portion of the feed C that did not pass through the 500 mesh screen (the +500 mesh portion of the feed C) was mixed with 20 g of a 10% acetic acid solution in a KitchenAid 5 quart food blender for 30 minutes at low speed. The resulting mixture was then placed in a ceramic boat and heat treated at 400 °C for 30 minutes.

[0130] Example 9

[0131] Example 7 was prepared by using an Alpine TM Example 9 was prepared by using an Alpine TM The 200 ATP classifier utilized the following parameters: wheel speed of the classifier was 5000 rpm, total air flow was 500 SCFM (standard cubic feet per minute), and the feed rate was 390 pounds per hour (176.9 kg / hr). The particle size distribution of a representative sample of the coarse fraction obtained is shown in Table 6.

[0132] The coarse fraction was then vibrated on a 400 mesh sieve on a rotary sieve shaker for about 10 minutes. The 200 g coarse fraction of feed D that did not pass through the 400 mesh sieve (the +400 mesh portion of feed D) was then mixed with 20 g of a 10% acetic acid solution in a KitchenAid 5 quart food blender for 30 minutes at low speed. The resulting mixture was then placed in a ceramic boat and heat treated at 400°C for 30 minutes.

[0133] Example 10

[0134] Example 10 was prepared from feed A by placing 100 g of feed A in a ceramic boat and heating in a muffle furnace at 400°C for 30 minutes.

[0135] Cold Haze Test

[0136] Each of the products disclosed herein can be used to stabilize beer by adsorbing the proteins that cause cold haze. Adsorbents 1-10 herein were each tested according to the ASBC Beer Method 27 to determine (total) cold beer haze (as described herein, supra).

[0137] For the cold haze testing of each adsorbent in Examples 1-9, a representative sample of the respective adsorbent was added to 200 mL of isopropyl alcohol (IPA) or lager beer at a dosage of 40 g / hundred liters (HL) to about 100 g / HL. For comparative purposes, a representative sample of feed A was added to 200 mL of Pilsner beer. Similarly, a representative sample of silica hydrogel (Sil-Aide® A100, Gusmer Enterprises, Inc.) was added to 200 mL of Pilsner beer, IPA, and lager beer at a dosage of 40 g / HL to about 100 g / HL. A100, Gusmer Enterprises company) was added to 200 mL of Pilsner beer, IPA, and lager beer at a dosage of 40 g / HL to about 100 g / HL.

[0138] The fermentation broth containing the respective adsorbent was placed on a shaker and shaken for 30 minutes, and then filtered using 19-26 micron filter paper to remove the adsorbent. Each filtered fermentation broth (beer) was then placed in a constant temperature (0°C + / - 0.2°C) ice bath for about 24 hours. For each cooled filtered beer, a sample of the cooled filtered beer was loaded into a cuvette, cooled in an 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 according to the ASBC Beer Method 27 using a haze meter. The results of the cold haze testing are shown in Table 7. Cold haze is expressed in nephelometric turbidity units (NTU), which is a unit used to measure the turbidity of a fluid or the presence of suspended particles in a fluid.

[0139] Table 7. Results of cold haze testing of adsorbents.

[0140]

[0141]

[0142] Adsorbent Stability Test

[0143] Cold haze removal by the adsorbent is the difference between the cold haze of a given amount of a blank (untreated) fermentation broth and the cold haze of the same amount of the fermentation broth after treatment with the adsorbent. For example, in Table 7, the cold haze of a blank (untreated) IPA beer was measured to be 24.65 NTU, while the cold haze of the same IPA beer after treatment with 100 g / mL of Example 4 was measured to be 11.95 NTU. Thus, the cold haze removal by the adsorbent of Example 4 was the difference between 24.65 NTU and 11.95 NTU, or 12.7 NTU.

[0144] The stabilization ability (%) of the novel adsorbent products disclosed herein can be 40-100%. The stabilization ability of a given dose of adsorbent in a given fermentation broth compared to the same dose of silica hydrogel (SH) can be determined as a percentage of the ratio of the cold haze removed by a given dose of adsorbent to the cold haze removed by the same dose of silica hydrogel, as shown in the following calculation for stabilization ability (%).

[0145]

[0146] Adsorbent Beer Stability Test

[0147] The beer stabilization ability of a given dose of adsorbent in a given beer compared to the same dose of silica hydrogel (SH) in the same beer can be determined as a percentage of the ratio of the (total) cold haze removed from the beer by a given dose of adsorbent to the (total) cold haze removed from the beer by the same dose of silica hydrogel, as shown in the following calculation for beer stabilization ability (%).

[0148]

[0149] For example, as discussed above, the cold haze removed from the IPA tested with a 100 g / mL dose of Example 4 was calculated to be 12.7 NTU (24.65-11.95 NTU). The cold haze removed from the IPA with a 100 g / mL dose of silica hydrogel was calculated to be 24.65-9.15 NTU, or 15.5 NTU. Thus, the beer stabilization ability (%) of the adsorbent of Example 4 for the IPA tested was 12.7 / 15.5, or about 82%. The beer stabilization ability (%) of the novel adsorbent products disclosed herein can be 40-100%. Table 8 shows the beer stabilization ability (%) of the exemplary adsorbents in Table 7.

[0150] Table 8. Beer stabilization ability.

[0151]

[0152]

[0153] The permeability of various exemplary adsorbent products disclosed herein can range from less than 0.01 to about 0.6 Darcy. For example, Table 9 shows the permeability of the products of Examples 1-2, 4, and 7-8 in water as compared to Feed A.

[0154] Table 9. Permeability of selected exemplary adsorbents.

[0155] Adsorbent Permeability (Darcy) Feed A <0.01 Example 1 0.05 Example 2 0.40 Example 4 <0.01 Example 7 0.1 Example 8 0.05

[0156] The pH of the disclosed exemplary novel adsorbents in water can range from 6 to about 8. For example, Table 10 shows the pH of the adsorbent products of Examples 1-2 and 7-8 in water. For comparison, the pH of Feeds A and B in water were also measured.

[0157] Table 10. pH in water.

[0158] Adsorbent pH in Water Feed A 8.5 Feed B 9.7 Example 1 7.7 Example 2 7.5 Example 7 6.5 Example 8 6.6

[0159] The pH of beer was measured before and after treatment with various exemplary embodiments. The results can be seen in Table 11. As can be seen from Table 11, the pH of the beer only slightly increased after stabilization using the novel adsorbents disclosed herein.

[0160] Table 11. pH in beer.

[0161] pH in Beer Blank Beer 4.1 Example 1 4.3 Example 2 4.2 Blank Beer 3.8 Example 7 4.0 Example 8 4.0

[0162] The novel adsorbent products disclosed herein can have: (a) beer soluble iron of no more than 1.5 ppm as measured by the modified ASBC method discussed herein, or beer soluble iron of 0 to about 1.5 ppm as measured by the modified ASBC. For example, Table 12 shows the concentration of iron in beer in various exemplary embodiments.

[0163] Table 12. Concentration of beer soluble iron.

[0164] Beer Soluble Iron (ppm) Example 10 1.30 Example 7 1.15 Example 8 0.94

[0165] The novel adsorbent products disclosed herein can have: d 10 in the range of 2-8 microns or 4-7 microns;d 50 in the range of 5-19 microns or 10-19 microns; andd 90in the range of 10-70 microns or 20-42 microns. For example, Table 13 shows the particle size distribution of various exemplary embodiments measured by a laser particle size analyzer. The novel adsorbent products disclosed herein can have: a pore volume in the range of 0.5-1.9 mL / g or 0.7-1.5 mL / g, and a porosity in the range of 30-90% or 40-80% or 49-72% or 45-75%. For example, Table 13 shows the pore volume and porosity of various exemplary embodiments measured by mercury intrusion.

[0166] Table 13. Particle size distribution.

[0167]

[0168] Figure 4 The pore size distribution of Examples 1-2 (measured by mercury intrusion) is shown in FIG. 1, and Figure 5 The pore size distribution of Examples 7-8 (measured by mercury intrusion) is shown in FIG. 2. As used herein, “inherent porosity” is: (a) a pore disposed on the surface of a palygorskite or sepiolite particle; or (b) a pore disposed in the structure of a palygorskite or sepiolite particle. As used herein, “interstitial porosity” is: (a) a pore disposed between particles of palygorskite or sepiolite; or (b) a pore disposed between agglomerated particles of palygorskite or sepiolite. Figure 4 The distribution shown in FIG. 1 shows that for the products of Examples 1-2, the small inherent pores are about 20 nanometers (nm) to about 30 nm, and the large interstitial pores are about 3 microns to about 19 microns, with a peak at about 19 microns. Figure 5 The distribution shown in FIG. 2 shows that for the products of Examples 7-8, the small inherent pores are about 20 nanometers (nm) to about 30 nm, and the large interstitial pores are about 3 microns to about 15 microns, with a peak at about 3 microns to about 15 microns. In addition, the porosity of Examples 1-2 is about 72%, and the total intrusion volume is about 1.3 mL / g to about 1.4 mL / g, which indicates that Examples 1-2 have a fairly high porosity. The porosity of Examples 7-8 is about 49% to about 58%, and the total intrusion volume is about 0.7 mL / g to about 0.86 mL / g, which indicates that Examples 7-8 still have a fairly high porosity. The high surface area and unique porous structure of these products make them effective adsorbents for a variety of applications, including protein adsorption.

[0169] Industrial Applicability

[0170] In general, the foregoing disclosure can be used to remove the proteins responsible for chill haze from a fermented liquid, such as from beer. As previously explained, chill haze is generally undesirable for fermented liquids, especially for most beer (e.g., lager and pilsner), as consumers generally view haze as a defect and / or undesirable. When beer or wine and the like is cooled below 0°C, chill haze can form, and as a result, certain proteins can react and clump together. Without treatment, some of the chill haze can develop into permanent haze.

[0171] Clays such as montmorillonite and bentonite are generally not suitable for chill prevention processes because they can trap too much of the fermented liquid due to their swelling properties. This can result in a loss of volume of the desired fermented liquid and increased disposal costs associated with the swelling of the clay with liquid. Treatment methods to reduce the swelling of these clays can not be acceptable to end users.

[0172] Porous silica gels (hydrogels and xerogels) are generally used in a two-step process to remove the proteins responsible for beer haze. These silica gels are added to the un-stabilized beer, and the proteins are bound to the highly porous silica structure through a silica gel stabilization reaction. After the reaction is complete, the silicate gel particles are removed through a filtration process. Conventionally, traditional silica gel products, including hydrogels and xerogels, have slow kinetics, making the stabilization and chill haze removal process for fermented liquids (e.g., beer) less efficient, and such traditional products are quite expensive. The production process for synthetic silica gels can also result in a higher carbon footprint.

[0173] The new products disclosed herein can be used as adsorbents for reducing the proteins responsible for chill haze in fermented liquids (e.g., beer, wine, cider, vinegar), and the like. Such products have higher removal efficiency.

[0174] Using the more permeable embodiments of the new products disclosed herein comprising attapulgite or sepiolite or mixtures thereof, the traditional two-step process of silica gel stabilization reaction and filtration to remove the silica gel particles can be simplified into a single step (i.e., stabilization and filtration are performed simultaneously), thereby improving the efficiency of the chill prevention process. For example, during the filtration of a fermented liquid (e.g., beer), even at low concentrations, using such more permeable embodiments in the filter paper / filter media, or using them as the bulk feed, or mixing them with filter aids as the bulk feed, results in a significant reduction in the processing time for such fermented liquids (e.g., beer), which provides a significant efficiency gain for brewers and the like, as the stabilization / chill prevention process time is reduced. The simplified process reduces costs and complexity. Furthermore, the filtration time is significantly reduced using such more permeable embodiments as adsorbents compared to traditional silica gel and diatomaceous earth composite products. This further reduces costs and increases production capacity.

[0175] In other embodiments, the new product disclosed herein can be used in a similar process to the currently more expensive traditional chill proofing agents (e.g., silica gel) and achieve the desired chill proofing effect at a significantly lower cost. For example, in one embodiment, the new product disclosed herein can be added to the aging tank used in the fermentation process and then filtered out.

[0176] Further, the product disclosed herein is non-swelling and does not adversely trap the fermentation broth. Further, the inventors have found that heat treating the attapulgite, sepiolite, or mixture thereof between 200 to 600 °C prevents the release and residual of "earthy taste" in the fermentation broth treated with the new product described herein, thereby reducing and stabilizing chill haze. After pH adjustment, the inventors have found that the new product does not affect the sour taste of the beer. Further, the embodiments of the new product disclosed herein that provide the desired chill proofing performance are based on a naturally occurring mineral that is processed and manipulated, which makes the end product more economical compared to traditional synthetic silica gel chill proofing products.

[0177] From the foregoing, it will be apparent that certain embodiments are set forth for illustrative purposes and that alterations and modifications to the described embodiments will readily occur to those skilled in the art. These and other alterations and modifications are intended to be within the spirit and scope of the disclosure and the appended claims.

Claims

1. A product for reducing cold turbidity in a fermentation broth, the product comprising attapulgite or sepiolite, The particle size distribution of the product or the attapulgite or the sepiolite is d 50 5-19 microns or 10-19 microns, wherein the pore volume of the product or the attapulgite or the sepiolite is 0.5-1.9 mL / g or 0.7-1.5 mL / g, wherein the porosity of the product or the attapulgite or the sepiolite is 30-90% or 40-80% or 45-75%, wherein the attapulgite comprises particles having an intrinsic pore size in the range of 6-50 nm, or 10-50 nm, or 15-35 nm, or 20-30 nm, or the sepiolite comprises particles having an intrinsic pore size in the range of 6-50 nm, or 10-50 nm, or 15-35 nm, or 20-30 nm, in, When 20-200 g of the product is loaded per HL of fermentation broth, the stability of the product is 40-100%, or when 30-180 g of the product is loaded per HL of fermentation broth, the stability of the product is 50-100%, or when 35-100 g of the product is loaded per HL of fermentation broth, the stability of the product is 40-100%, or when 75-100 g of the product is loaded per HL of fermentation broth, the stability of the product is 50-100%.

2. The product of claim 1 , wherein the attapulgite or sepiolite has been treated with acetic acid, and wherein the product has a pH of 6-8 or 6.5-7.5 or 6.9-7.1 measured in a 2 wt% slurry in water.

3. The product of claim 1 , wherein the fermentation broth is beer and the product has no more than 1.5 ppm beer soluble iron, or no more than 1.2 ppm beer soluble iron, or 0.1-1.3 ppm beer soluble iron, each as measured by the modified ASBC method.

4. The product of claim 1, wherein the fermentation broth is beer, and the beer stabilization capacity of the product is 40-100% when 35-100 g of the product is loaded per HL of beer, or the beer stabilization capacity of the product is 50-100% when 75-100 g of the product is loaded per HL of beer.

5. The product according to claim 4, wherein the surface area of ​​the product or the attapulgite or the sepiolite is 90-130 m 2 / g or 90-150m 2 / g range.

6. The product according to claim 1, wherein the fermentation broth is beer, wine, cider or vinegar, The product does not contain 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. The product of claim 1, wherein the fermentation broth is beer, wherein the beer is an IPA, a lager, or a pilsner.

8. The product according to claim 1, wherein the ratio of Al2O3 to SiO2 of the product is in the range of 0.17-0.22, wherein the ratio of MgO to SiO2 of the product is in the range of 0.12-0.16, The product has a MgO to Al2O3 ratio in the range of 0.75-0.

85.

9. A method for producing a product for reducing cold turbidity in a fermentation broth, the method comprising: heat-treating attapulgite and / or sepiolite at a temperature of 200-600° C. or 250-600° C. to produce a heat-treated material; wherein said product comprises said heat-treated material, The particle size distribution of the product or heat-treated attapulgite or heat-treated sepiolite is d 50 5-19 microns or 10-19 microns, wherein the pore volume of the product or the heat-treated attapulgite or the heat-treated sepiolite is 0.5-1.9 mL / g or 0.7-1.5 mL / g, wherein the porosity of the product or heat-treated attapulgite or heat-treated sepiolite is 30-90% or 40-80% or 45-75%, wherein the heat-treated attapulgite comprises particles having an intrinsic pore size in the range of 6-50 nm, or 10-50 nm, or 15-35 nm, or 20-30 nm, or the heat-treated sepiolite comprises particles having an intrinsic pore size in the range of 6-50 nm, or 10-50 nm, or 15-35 nm, or 20-30 nm, When the product is loaded at 20-200 g per HL of fermentation broth, the stability of the product is 40-100%, when the product is loaded at 30-180 g per HL of fermentation broth, the stability of the product is 50-100%, when the product is loaded at 35-100 g per HL of fermentation broth, the stability of the product is 40-100%, and when the product is loaded at 75-100 g per HL of fermentation broth, the stability of the product is 50-100%.

10. The method of claim 9, further comprising classifying the attapulgite and / or sepiolite into particle size distributions d 50 The particle size is 5-19 μm, wherein the classification comprises agglomeration and / or wind classification and / or screening, and wherein the fermentation broth comprises beer, wine, cider or vinegar.

11. The method of claim 9, further comprising mixing the attapulgite and / or sepiolite with acetic acid prior to heat treatment, The heat treatment temperature is 300-400°C. The fermentation broth comprises beer, wine, cider or vinegar.

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

13. The method according to claim 12, wherein the fermentation liquid is beer, wherein said product has no more than 1.5 ppm beer soluble iron or no more than 1.2 ppm beer soluble iron, each as measured by a modified ASBC method, When each HL of fermentation liquid is loaded with 35-100 g of the product, the beer stabilization capacity of the product is 40-100%, or when each HL of fermentation liquid is loaded with 75-100 g of the product, the beer stabilization capacity of the product is 50-100%.

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

15. The method according to claim 9, wherein the fermentation liquid is beer, The permeability of the product is 0.1-1 Darcy, When each HL of fermentation liquid is loaded with 35-100 g of the product, the beer stabilization capacity of the product is 40-100%, or when each HL of fermentation liquid is loaded with 75-100 g of the product, the beer stabilization capacity of the product is 50-100%.

16. The method according to claim 9, wherein the fermentation broth comprises beer, wine, cider or vinegar, wherein the product does not contain a composite material comprising: (a) attapulgite agglomerated with a first material that is not attapulgite or sepiolite, or (b) sepiolite agglomerated with said first material that is not attapulgite or sepiolite, wherein the ratio of Al2O3 to SiO2 of the product is in the range of 0.17-0.22, wherein the ratio of MgO to SiO2 of the product is in the range of 0.12-0.16, The product has a MgO to Al2O3 ratio in the range of 0.75-0.

85.

17. A method for reducing cold turbidity in a fermentation broth comprising beer, wine, cider, or vinegar, the method comprising: contacting or mixing the fermentation broth with a product comprising heat-treated attapulgite or heat-treated sepiolite; and recovering the product from the fermentation broth to obtain a resulting fermentation broth having lower cold haze or having lower protein and / or polyphenol content than the fermentation broth prior to said contacting or mixing, When the product is loaded at 20-200 g per HL of fermentation liquid, the stability of the product is 40-100%, or when the product is loaded at 30-180 g per HL of fermentation liquid, the stability of the product is 50-100%, or when the product is loaded at 35-100 g per HL of fermentation liquid, the stability of the product is 40-100%, or when the product is loaded at 75-100 g per HL of fermentation liquid, the stability of the product is 50-100%. wherein the heat-treated attapulgite comprises particles having an intrinsic pore size in the range of 6-50 nm, 10-50 nm, 15-35 nm, or 20-30 nm, or the heat-treated sepiolite comprises particles having an intrinsic pore size in the range of 6-50 nm, 10-50 nm, 15-35 nm, or 20-30 nm, wherein the particle size distribution of the product or the heat-treated attapulgite or the heat-treated sepiolite is d 50 5-19 microns or 10-19 microns, wherein the pore volume of the product or the heat-treated attapulgite or the heat-treated sepiolite is 0.5-1.9 mL / g or 0.7-1.5 mL / g, The porosity of the product or the heat-treated attapulgite or the heat-treated sepiolite is 30-90% or 40-80% or 45-75%.

18. The method according to claim 17, The fermentation broth is beer, wherein the beer is IPA, lager or pilsner, When the product is loaded at 35-100 g per HL of beer, the beer stabilization capability of the product is 40-100%, or when the product is loaded at 75-100 g per HL of beer, the beer stabilization capability of the product is 50-100%.

19. The method according to 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% slurry in water, wherein the product has no more than 1.5 ppm beer soluble iron or no more than 1.2 ppm beer soluble iron, each as measured by the modified ASBC method.

20. The method of claim 18, wherein the product has a permeability in water of 0.1 to 1 Darcy, wherein the product does not contain 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, wherein the ratio of Al2O3 to SiO2 of the product is in the range of 0.17-0.22, wherein the ratio of MgO to SiO2 of the product is in the range of 0.12-0.16, The product has a MgO to Al2O3 ratio in the range of 0.75-0.85.

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