JPH055469B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a composition that allows beverages such as beer to be cooled without causing any inconvenience. The present invention relates to the use of a combination of various hydrophilic adsorbents, such as silica gel, and partially water-blocking adsorbents to remove various colloidal components of draft beer that form haze on cooling. The term beer herein includes a wide variety of brewed beverages. Such beverages include, but are not limited to, lagers, pilsners, Dortmund, and München beers, as well as top flavored beverages such as Alas, Porters, and Stouts. Turbidity is an important and sometimes troublesome aspect of brewing operations. It is of biological or physicochemical origin. Gross turbidity caused by suspended solids above the substantially colloidal range can be overcome by filtration or other separation methods. Various filter aids called fining agents are used to agglomerate such coarse particles. A second and more subtle haze problem involves the haze problem that occurs when pre-filtered beer is aged or cooled. This haze is caused by the agglomeration of several organic substances in the beer. These substances are not removed by the filtration steps described above. A number of methods have been developed to remove at least some of what creates chill haze in beer. Some of these methods involve reacting with other organic substances to precipitate compounds that can be filtered. A number of adsorbents are used to remove certain fractions that cause cooling haze. Silica hydrogels and xerogels, calcium, aluminum and magnesium silicates, diatomaceous earth, several types of natural substances, and clays, and mixtures thereof, have been suggested and used as cooling fog inhibitors. U.S. patents disclosing such technology include 3163538, 3251693, 3436225,
3617301, 3940498 and 3958023. While these materials and methods have been successful with some types of beer, they are often less satisfactory with others. It is an object of the present invention to provide a combination of adsorbents that removes a wide range of chill haze components in a wide variety of beverages. Combinations of hydrophilic and partially water-blocking adsorbents are excellent at eliminating haze caused by thermal formation or cooling of a variety of beverages, including many types of beer and other brewed beverages. . Inclusion of partially water-blocking adsorbents provides superior results when compared to hydrophilic materials. The hydrophilic and partially water-blocking reagents can be added to the beverage separately or combined before use. Contact between the combination and the beer is maintained for a time sufficient to adsorb the cooling haze components.
Filtration now removes the adsorbent containing undesirable substances. The hydrophilic portion of the combinations of the present invention is various types of siliceous adsorbents, usually various types of silica gels. Silica hydrogels, silica xerogels and silica aerogels are useful. The water-blocking component can be any adsorbent that has been or can be treated to impart partial water-blocking properties. These materials include organic materials with appropriate surface properties as well as inorganic materials that can be coated or reacted with various water blocking reagents. Means for Solving the Problem The main component of the chilled antifogging combination of the present invention is a siliceous material capable of sorbing colloidal fractions in beer that combine to produce haze upon aging and/or cooling. It is. Generally, the siliceous material is a silica gel prepared by adding an acid to an alkali metal silicate solution under conditions that produce a hydrosol that solidifies completely upon aging. The properties of such a gel are the gel state,
Depends on the technique used for drying and other processing. Silica gels formed with enough acid to at least completely neutralize the alkali in the silicate are designated as regular density gels, which tend to have a larger surface area with smaller pores and pore volume. . If all alkali is not neutralized, medium density
gels are produced, which tend to have smaller surface areas with larger pores and pore volumes. Drying these gels using conventional techniques tends to shrink the pores and form what is known as a xerogel. Replacement of water in the pores of the gel with a solvent with high vapor pressure and drying of the flash yields an aerogel that exhibits no pore shrinkage. The surface area and density of the normal density gel can be varied by heating at various PH values and salt concentrations. A more detailed discussion of gel preparation can be found in Ller's The Chemistry of Silica (Wiley Interscience, New York 1979). Other types of silica gels may also be particularly useful in the combinations of the present invention. The silica has a surface area of at least 700 m ² /g, an average pore size of 30 to 120 Å,
A specially prepared silica hydrogel having an average particle size of 20μ or less and an ignition source amount of at least 50% by weight. The preparation and properties of this hydrogel are disclosed in US Pat. No. 3,617,301. Reference is made to this patent here. The second component of the combination of the present invention is any of a number of adsorbents that have partially water-blocking properties. This adsorbent actually requires a certain balance of water-repellent and hydrophilic properties. The water-blocking moiety provides improved interaction between the adsorbent and the organic material being adsorbed. The hydrophilic portion is required to provide sufficient and continuous contact between the adsorbent particles and the aqueous environment of the beer. The balance required is probably described as no more water-blocking than conditions that allow the adsorbent to remain in an aqueous suspension under mild agitation. Any adsorbent that can be partially water-blocking, retains its ability to adsorb the desired organic species, and remains stable with the silica hydrogel can be used in the combinations of the present invention. Dextran and other organic polymers that are partially water-blocking or can be made water-blocking can be used. Various silicates, such as aluminosilicates, magnesium silicates, and silicas, can be partially water-blocking and can be used. Partial silanization can be used, among other methods, to provide the required balance of properties. More than one such partially water-blocking adsorbent can be used. As required by the present invention, precipitated silica is a good water inhibiting adsorbent. This and other materials can be partially water-blocked by reacting the material with silanes, silicones, or others. Water blocking agents must have stable organic groups that can withstand exposure to curing and drinking. The adsorbent must be treated with sufficient water-blocking agent to obtain partially water-blocking properties. Up to about 5-7% will give the required activity. Reactions with about 10% or more of the reagent appear to result in decreased efficacy. In the present invention, the water blocking agent ultimately accounts for about 0.5 to 5.0% of the partially water blocking adsorbent.
It is preferable that The cooling-free combinations of the present invention contain from about 1 to 80 parts by weight of a partially water-blocking adsorbent (or adsorbents) per 100 parts by weight of silica gel;
That is, it contains 0.9 to 45% by weight of partially water-blocking substances. In the present invention, the combination contains about 2 to 60 parts by weight of partially water-blocking adsorbent(s) per 100 parts of gel, or about 1.9-38% of partially water-blocking material. It is preferable to do so. In the present invention, approximately
Most preferably, it contains 5 to 40 parts by weight of partially water-blocking material, corresponding to a partial water-blocking property of 4.7 to 29%. Although the combinations may be added to the beer separately, it is preferred to add them as a blend or a product that is gelled together. The required formulation can be achieved by any method, but during grinding of the gel. The combination can be contacted with the beer in any convenient manner and removed by any suitable separation technique.
The level of treatment should be sufficient to remove chill haze components, which are generally between 20 and 2000 ppm of beer. About 200 of the combinations according to the invention
Preferably, ~800 ppm is used. The chilled anti-clouding combination of the present invention is added to the beverage in any convenient manner. This is maintained in contact for a time sufficient to adsorb the desired substance and separated by filtration or centrifugation. The combinations of the invention can be used with other beer processing agents, if desired, such as filter aids, magnesium silicates, and polyvinylpyrrolidone. EXAMPLES The following examples are some embodiments of the invention.
They should not be considered as establishing the scope of the invention. The scope of the invention is defined by the claims. Unless otherwise indicated, percentages are parts by weight, percentages by weight (%w/w), and ppm
It is. Cooling fog protection was measured in a laboratory simulation of cooling fog formation. This simulation is
K. Asano, K. Shinagawa and H. Presented at the 48th Annual Meeting of the American Society for Brewing Chemistry, Kansas City, Missouri, May 1982.
This is a modified method of the phasing test of ``Characterization of Phase Formation of Proteins and Their Inchyl Haze Formation'' reported by Hashimoto. Crude beer protein was obtained by ammonium sulfate precipitation (100% saturation) from chilled non-fog beer. 15 parts by weight of the above protein dispersion was added to a solution of (±) cathecin (800 mg/l) in several containers.
parts by weight. The mixture was heated at 100°C for 20 minutes. After cooling to room temperature, 0.5 parts by weight of the hydrogel/water-blocking adsorbent composition and equal amounts of each component were added separately with vigorous stirring. Contact was held for 5 minutes before filtration. The filtrate was then cooled at 0° C. for 40 minutes and the formation of haze was measured in a Formazine Nephelometer Turbidity Unit (NTU) corrected to the blank value. Example 1 A blend of hydrogel and Cephadex LH-20 with a surface area of 800 m ² /g, an ignition source amount of 66.5%, and an average pore size of 87 Å was made by compounding the two components. These materials were tested as previously described. Hydrogels were also tested separately. The results are as follows.

TABLE These results clearly demonstrate the improved performance obtained using the combination of the invention. There is significant haze reduction when Cephadex LH-20 is combined with hydrogels. Example 2 Three batches of precipitated silica were treated with silicone oil as follows. The silica was slurried with diethyl ether and then silicone oil (dimethylsiloxane) was added to the slurry. Diethyl ether was evaporated before curing for 20 hours at 300°C. Processing yielded a product containing approximately 2.5 and 10% silicone. Precipitated silica has a surface area of approx.
190 m ² /g, an ignition source amount (1000° C. for 2 hours) of 5%, and an average agglomerate size of about 7 μ. Five parts by weight of each of these materials were combined with 95 parts by weight of the hydrogel described above and tested as described above. The results are summarized in Table 2.

Table: Example 3 The procedure of Example 2 was carried out using the same silicone oil from a different supplier. The results are summarized in Table 3.

[Table] These results were almost the same as those of Example 2.

Claims (1)

Claims: 1. A beer treatment composition for preventing cooling haze, comprising 1 to 80 parts by weight (pbw) of a partially water-blocking adsorbent and 100 parts by weight of silica gel. 2. A composition according to claim 1, wherein the partially water-blocking adsorbent is a precipitated silica reacted with up to 7% by weight of silane or silicone. 3. A composition according to claim 2, wherein the precipitated silica is reacted with 0.5 to 5.0% by weight of silane or silicon. 4. The composition according to claim 2, wherein the silica gel is a normal density xerogel or a medium density xerogel. 5 silica gel has a surface area of at least 700 m ² /g;
Average pore size of 30-120 Å, average grain size of 20 μ or less, and loss on ignition of at least 50% (w/w)
The composition according to claim 2, which is a hydrogel having w). 6. In a method for treating beer to prevent chill haze, (a) the beer is treated with 1 to 80 parts by weight of a partially water-blocking adsorbent and 100 parts by weight of silica gel in an amount sufficient to remove chill haze components; (b) maintaining said contact for a period sufficient to remove the cooling haze components from the beer; and (c) separating the combination from the beer. 7. The method of claim 6, wherein the partially water-blocking adsorbent is precipitated silica reacted with up to 7% w/w silane or silicone. 8. The method of claim 7, wherein the precipitated silica is reacted with 0.5 to 5.0% by weight of silane or silicone. 9. The method according to claim 7, wherein the silica gel is a normal density xerogel or a medium density xerogel. 10. The method of claim 8, wherein the silica gel is a normal density xerogel or a medium density xerogel. 11 The silica gel has a surface area of at least 700 m ² /g,
8. The method of claim 7, wherein the silica hydrogel has an average pore size of 30 to 120 Å, an average particle size of 20 microns or less, and an ignition source amount of at least 50% (w/w). 12 The silica gel has a surface area of at least 700 m ² /g,
9. The method of claim 8, wherein the silica hydrogel has an average pore size of 30 to 120 Å, an average particle size of 20 μ or less, and an ignition source amount of at least 50% (w/w). 13 The amount of combination that comes into contact with beer is 20~
7. The method according to claim 7, wherein the amount is 2000 ppm. 14 The amount of combination that comes into contact with beer is 20~
The method according to claim 8, wherein the amount is 2000 ppm. 15 The amount of combination that comes into contact with beer is 20~
The method according to claim 9, wherein the amount is 2000 ppm. 16 The amount of combination that comes into contact with beer is 20~
11. The method according to claim 10, wherein the amount is 2000 ppm. 17 The amount of combination that comes into contact with beer is 20~
12. The method according to claim 11, wherein the amount is 2000 ppm. 18 The amount of combination that comes into contact with beer is 20~
13. The method according to claim 12, wherein the amount is 2000 ppm.