JP3021319B2 - Stabilizer for beer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilizing agent for beer comprising a specific amorphous silica, and more particularly, to an amorphous silica having a large negative zeta potential in the pH range of beer. And a stabilizing agent for beer.

[0002]

2. Description of the Related Art Beer is a fermented product obtained by fermenting barley malt and hops as main raw materials, and is an amber-colored, shiny transparent spirit drink. Therefore, the appearance, as well as the taste, aroma, and flavor of an alcoholic beverage, are important factors that determine the commercial value.

In fact, when beer is stored in bottles, cans, barrels or the like and stored for a long period of time, or when cooled for use in drinking, beer or turbidity may be generated in the beer, causing turbidity. is there. The beer having such turbidity is hated as a beer having poor durability, and impairs the commercial value of the beer.

There are three cases of this turbidity: cold turbidity, permanent turbidity, and frozen turbidity. In beer, cold turbidity is 1.4 to 8.1 mg / l, and permanent turbidity is 6.6 to 14.
It is reported that 1 mg / l is mixed. It has also been reported that cloudiness occurs on the order of 44 to 100 mg / l depending on the storage period and type of beer.

[0005] Cold turbidity occurs when beer is cooled to around 0 ° C, and dissolves again at 20 ° C. Permanent turbidity is also called oxidized turbidity and does not redissolve. Freeze turbidity occurs when the beer is frozen or near -5 ° C, which is close to freezing. It is said that such beer turbidity is caused by insolubilization of a part of proteins derived from barley and hops as raw materials, soluble components such as polyphenol, and association of these colloid components. In the present specification, a causative factor component of turbidity that is dissolved or colloidally decomposed in beer and generated when the beer is stored or cooled for a long time is referred to as a “turbidity precursor”. As described above, the turbidity of beer is derived from the turbid precursor that is universally present in beer, and as long as the turbid precursor remains in the beer, turbidity cannot be denied depending on the conditions at that time.

Therefore, prevention of cloudiness of beer (stabilization treatment)
Various methods have been tried, and at present, the turbid precursor remaining in the beer is separated and removed by various method techniques to prevent deterioration of the beer and improve durability.

[0007] As a conventional technique for separating and removing the turbid precursor, for example, beer is treated by adding a turbidity inhibitor such as papain (a vegetable proteolytic enzyme recovered from papaya fruit), tannic acid, polyvinylpyrrolidone, and silica gel. A method has been provided and done. Especially silica gel,
It has been widely used as a stabilizing agent because it has little effect on beer quality such as beer aroma, taste, flavor and foam.

As a silica gel (amorphous silica) for stabilizing beer, it has been known to use a hydrogel or xerogel, for example, Japanese Patent Publication No. 63-6191.
No. 4 discloses silica hydrogel particles having a BET specific surface area of 300 m ² / g or more, obtained by reacting an acidic silica sol and sodium silicate in the presence of an aqueous salt solution and having a water content of 60 to 90% by weight. For use in the stabilization process.

Also, Japanese Patent Publication No. 3-27483 discloses that
Specific surface area 530-720 m ² / g, pore volume 0.9-
1.5 ml / g, average pore size of 50 to 120 Å, water content of 7 to 25%, and pH of 6.0 to 8.0 when prepared as a 5% aqueous suspension, a hydrogel for beer stabilization treatment. Is described.

Further, as a device using xerogel, JP-B-63-38188 discloses a surface area in the range of 100 m ² / g to 450 m ² / g, at least 0.6 m ² / g.
It has a pore volume of 6 cc / g, an average pore diameter of greater than 100 Å, and a peak in the infrared spectrum at 3760 cm ⁻¹ indicating the presence of single surface silanol groups, at 1890 cm ⁻¹ . Contacting the calcined silica xerogel with beer, wherein the ratio of the extinction index at 3760 cm ^-1 to the extinction index is greater than 2.2, and separating the silica from the beer, A method for processing beer is described.

[0011]

In the above-mentioned method using a silica hydrogel or a hydrogel, during the production of the gel,
Microorganisms such as molds often grow during storage or transportation, and when an acid is added to the gel to prevent this, there is a disadvantage that this acid is mixed into beer.

Among the above-mentioned prior arts, the method using a calcined xerogel, which is found in the latter proposal, is significant as a solution to the inconvenience of using a hydrogel or a hydrogel. According to research, wave number 3
The infrared absorption peak at 760 cm ^-1 is specific to type A silica gel having a remarkably high specific surface area, and it was found that the type B silica gel used in the present invention did not show this infrared absorption peak at all.

The present inventors have found that the pH of the aqueous suspension is in the weakly acidic pH range, which is almost the same as that of beer, and that the zeta potential of this aqueous suspension is negative and its absolute value is 20 mV.
The above-mentioned amorphous silica has been found to be effective for removing the turbid precursor without lowering the foam retention of beer.

[0014] That is, an object of the present invention is to make it easy to handle and to maintain beer foam retention at an excellent level.
An object of the present invention is to provide an amorphous silica-based beer stabilizing agent capable of effectively removing a cloudy (origin) precursor generated during refrigeration.

[0015]

According to the present invention, the following formula a M_{2 / m}O ・ SiO_Two・ NH_TwoO (A) wherein M is an alkali metal and / or an alkaline earth metal
And m represents the valence of the metal M, and a represents 0 to 5 ×
10^-3, Especially 0 to 3 × 10^-3Where n is from 0 to
0.2, especially a number from 0 to 0.125
100 to 600 m^Two/ G, especially 250
~ 550m ^Two/ G specific surface area and 1.0 to 2.0cc
/ G, especially a pore volume of 1.0 to 1.6 cc / g.
And the following formula R_A= I₉₇₀/ I₁₁₀₀ ... (1) where I₉₇₀Is the wave number 970c of the infrared absorption spectrum
m^-1Is the absorbance of the peak of₁₁₀₀Is the infrared absorption spectrum
Wave number 1100cm^-1Is the absorbance of the peak of
Absorbance ratio (R_A) Is 0.02 or more, 0.2
It is composed of amorphous silica having a value of less than 0, especially 0.15 or less.
Aqueous suspension at a concentration of 1000 ppm and a temperature of 25 ° C.
pH is between 4 and 6.2, especially between 5 and 6.0 and the water
Zeta potential in a neutral suspension and its absolute value is 20
mV or more, especially 30 mV or more.
And a stabilizing agent for the steel.

According to the present invention, the number of OH groups on the surface of the amorphous silica is not more than 7 / nm ² , preferably not more than 6 / nm ² , and the surface thereof is O
A stabilizing agent for beer, which is hard to be H-based and is modified.

Further, according to the present invention, the above-mentioned amorphous silica has a median diameter of 5 to 8 by a Coulter counter method.
The present invention provides a stabilizing agent for beer, characterized in that the number distribution of fine secondary particles having a particle size of from 5.5 to 7 μm, particularly from 2.6 to μm is from 30 to 60%.

[0018]

The amorphous silica used in the present invention has a chemical composition represented by the above formula (A), and has a water content of 0.2 mol or less, preferably 0.14 mol or less per 1 mol of silica. One of the characteristics is that the amount is as small as 0.125 mol or less, which gives an advantage that microorganisms such as molds do not grow during production, storage, or transportation, and that handling is easy.

The amorphous silica may contain an alkali metal component such as Na and K or an alkaline earth metal component such as Ca and Mg. And to prevent a decrease in flavor due to
O ₂ 1 mole per 5 × 10 ^-3 mol or less, should be especially 3 × 10 ^-3 mol or less.

The amorphous silica used in the present invention has a concentration of 1
The pH of the aqueous suspension at 000 ppm and a temperature of 25 ° C. is 4 to 6.2, especially 5 to 6.0, and the zeta potential of the aqueous suspension is negative and its absolute value is 20 mV or more;
In particular, it is a remarkable feature that the voltage is 30 mV or more.

First, the amorphous silica used in the present invention has a low concentration (1) such as that actually used for stabilizing beer.
PH of beer in aqueous suspension
(3.5-5.0), indicating a weakly acidic pH, which indicates that the contained components are less eluted from the amorphous silica,
It means that it has excellent flavor retention.

Further, according to the present invention, the zeta potential of the amorphous silica fine particles in the aqueous suspension is set to a negative value and the absolute value of the zeta potential is set in the above range, so that the beer foam retention is maintained in a good state. Meanwhile, the cold durability can be significantly improved. See Table 1 below. That is, there is a close relationship between the zeta potential of amorphous silica and the cold durability of the beer after the treatment, and the cold durability can be improved as the zeta potential is negative and its absolute value is higher. It is obvious.

It is said that the formation of cold turbidity (ori) in beer is caused by oxidative polymerization of protein and polyphenol in beer, but the amorphous silica used in the present invention has a negatively increased zeta potential. Therefore, it is recognized that the formation of cold turbidity is prevented because the protein colloid particles having a positive charge are effectively adsorbed.

In the present invention, an amorphous silicon having a specified zeta potential is used.
In Rica, the chemical composition is in the above range and the formula (1)
Absorbance ratio (R_A) Is 0.02 or more and 0.20
Less than 0.15
all right. The absorbance ratio (R_A) Is the infrared absorption spectrum
As shown in FIG. 1, each absorbance I₉₇₀And I
₁₁₀₀Can be calculated by calculating

FIG. 2 shows an infrared absorption spectrum of a typical amorphous silica used in the present invention. From Figure 2, the amorphous silica not have exactly the absorption at a wave number of 3760cm ^-1, it is found to have a small absorption in the large absorption and wavenumber 970 cm ^-1 in wave number 1100 cm ^-1. The characteristic absorption at the wave number of 1100 cm ^-1 is based on the stretching vibration of Si-O, while the characteristic absorption at the wave number of 970 cm ^-1 is considered to be based on the stretching vibration of Si-OH.

FIG. 3 shows the change in the characteristic absorption when the calcination temperature of the B-type amorphous silica is changed. As the calcination temperature increases, the absorption at the wave number of 970 cm ^-1 decreases. It is clear that the absorption at 800 ° C. has finally disappeared.

In the present invention, the zeta potential can be adjusted to the range of the present invention by subjecting the amorphous silica to a heat treatment so that the absorbance ratio (R _A ) falls within the above range.

FIG. 4 to be described later shows a conventional amorphous silica which is a stabilizing agent for various beers including the amorphous silica used in the present invention at a temperature of 25.degree.
With the values of the pH and the zeta potential when suspended in water at pm as the origin, hydrochloric acid was added thereto and the pH of the suspension was adjusted.
Is a display of the change in zeta potential when is shifted to the acidic side.

In the figure, a (sample No. H-1) is a conventional hydrogel type, and b (sample No. 1), d (sample No. 2), and e (sample No. 3) are according to the present invention. It is a xerogel type, and c (sample No. H-3) is a conventional xerogel type. It can be particularly said from FIG. 4 that the origin pH of the amorphous silica according to the present invention is b =
5.78, d = 5.6, e = 5.5, all of which are 6 or less;
In particular, it is 5.7 or less, and exhibits a pH closer to that of the above-described beer as compared with c = 6.27 of the conventional product.

It can furthermore be said that, in particular, d,
The zeta potential of e is not limited to the value at the origin, but the zeta potential for pH shift also includes the pH range of beer.
It shows a remarkable feature that the shift up to 3.5 is always negative and its absolute value is negatively stabilized and changes at a value of 30 mV or more.

Although the details of these behaviors are unknown, the amorphous silica particles according to the present invention have a pore distribution,
The number of OH groups on the silica surface, which will be described later, is lower than that of conventional silica (7 / nm ² or less, especially 6 / OH) although it depends on structural factors such as pore volume and specific surface area.
nm ² or less), the surface is likely to be negatively charged, and the silanol groups on the silica surface are stabilized so that they are not easily converted to OH groups. It is believed that the amorphous silica according to the present invention over a wide acidic pH range is liable to be electrically negatively charged.

Another physical property required for the amorphous silica for beer stabilization treatment is a specific surface area of 100 to 600 m ^2.
/ G, especially from 250 to 550 m ² / g. When the specific surface area is smaller than the above range, the removal of the cold turbid precursor tends to be insufficient, and when the specific surface area is larger than the above range, adsorption of a flavor component or the like occurs, thereby reducing the flavor retention of the beer after the treatment. Tend.

The pore volume is 1.0 to 2.0 cc /
g, especially in the range of 1.0 to 1.6 cc / g, below which the removal of the cold turbid precursor may still be inadequate, while more than the above range And the beer after treatment tends to have reduced foam retention.

The amorphous silica has a median diameter (volume basis, Coulter counter method) of 5.0 to 8.0 μm.
m, especially in the range of 5.5 to 7.0 μm. If the particle size is smaller than the above range, the particles will agglomerate with each other. Are not sufficient, the adsorbability of the turbid precursor decreases.

In the present invention, as described above, the median diameter is relatively large, but fine secondary particles of 2.6 μm or less according to the Coulter counter method have a number distribution of 30 to 60% around the large particles. Another characteristic is that they are grouped together.

This means that the beer lowering process of the actual beer is more suitable and effective as the amount of added silica is smaller and the processing time is shorter. Therefore, in the present invention, it is presumed that at the time of processing, negatively charged fine particles in the aqueous dispersion system are electrically repelled by the similarly negatively charged large particles and are quickly dispersed to accelerate the lowering speed of the orifice and effectively act. Is done.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION The stabilizing agent for beer of the present invention comprises:
A hydro- or xero silica gel produced by various methods, which has a specific absorbance ratio (R) starting from silica gel that passes silicon dioxide (silica gel) described in “Food Additive Official Specification” D-681. _A ) and heat-treated to have a zeta potential. Regarding a method for producing hydro or xero silica gel as a raw material of the silica gel of the present invention, the following method may be mentioned as an example.

As a general method for producing silica gel, an alkali silicate as a raw material and a mineral acid are subjected to a neutralization reaction by contact mixing to form a hydrogel, the hydrogel is crushed, further aged, and then the above-mentioned aging is performed. After washing and removing salts by-produced by the reaction, there is a method of drying, heat-treating, pulverizing and classifying.

Alkali silicate as a raw material is converted into easily reactive silica recovered from clay raw materials such as sodium silicate or potassium silicate of water glass, which is JIS standardized as an industrial product, and alkali metal to alkali metal. An alkali silicate or the like reacted with a hydroxide solution can be used.

As the mineral acid used for the neutralization reaction, hydrochloric acid, sulfuric acid and the like are generally used, but a mixed acid thereof can also be used. The neutralization reaction of contacting both raw materials, which are an aqueous solution or an aqueous dispersion, can be carried out by adding one of the two raw materials to the other raw material with stirring, or by subjecting the aqueous liquid of both raw materials to certain conditions. There is a method of contacting at the same time. In any case, in order to specify the specific surface area of the silica gel within the scope of the present invention, it is preferable to adjust the pH of the reaction mixture on the acidic side. Reaction conditions for adjusting physical properties such as the specific surface area and pore volume of silica gel to the intended range are as follows:
It can be easily determined by a simple preliminary experiment performed in advance.

In general, the hydrogel or xero silica gel prepared by the above method is subjected to hydrothermal treatment at 100 to 140 ° C. for a certain period of time to adjust the specific surface area and pore volume of the silica gel. The silica gel after the hydrothermal treatment is dried and heat-treated, and then pulverized and classified so as to have the above particle size. Grinding and classification may be performed after drying and prior to heat treatment.

The heat treatment of the silica gel is carried out according to the above formula (A).
Composition, absorbance ratio (R _A) And the aforementioned z
Data potential should be satisfied. Heat treatment temperature
The degree depends on the specific surface area of silica, but generally
120-1000 ° C, especially 150-900 ° C, most
Preferably, the range of 200 to 800 ° C. is appropriate. heating
The processing time varies depending on the temperature and the firing method,
In general, the above requirements are satisfied within the range of several seconds to several hours.
It's a good idea to choose a time. For the heat treatment, use an electric furnace,
Fixed floor, moving floor, such as tari kiln, hot air flash firing
A fluidized bed type heat treatment apparatus can be used.

According to the present invention, as another method for modifying the silica surface, an alkali metal component such as sodium and potassium and / or an alkaline earth metal component such as Ca and Mg are secondarily added to the silica surface. Deposition may be performed to reduce the number of OH groups on the surface, and then heat treatment may be performed if necessary. In this case, a in the formula (A) is preferably a number of 5 × 10 ⁻³ or less from the viewpoint of the above-mentioned pH and elution into beer.

The proportion of the amorphous silica of the present invention to be added as a stabilizing agent for beer varies depending on the type of beer, fermentation conditions and production conditions. , And can be appropriately added and processed.

[0045]

EXAMPLE An amorphous silica-based stabilizing agent for beer according to the present invention was prepared as follows. As a raw material for preparing a silica hydrogel , JIS sodium silicate (SiO ₂ 22.3)
_{8%, Na 2 O 7.10%} , SG 1.294 / 15
° C) and a 45% strength sulfuric acid solution (specific gravity 1.352 / 15
° C) in a volume ratio of 4: 1, using a device capable of instantaneous contact between the two, simultaneously supplying sodium silicate and sulfuric acid solution to the device and reacting at 30-35 ° C. The reaction was adjusted to adjust the pH of the reaction system to 2.0 to 2.2 to produce silica, and then aged for 2 hours under the same conditions to recover a silica hydrogel. The aged silica hydrogel was crushed to a size of 2 to 5 mm, and washed with water to obtain a hydrogel having a water content of 68.5% (sample SG-1). The hydrogel is then redispersed in water and
, And dried at 110 ° C, pulverized, and classified to obtain a fine silica gel powder (sample No. SG-110).

(Examples 1 to 3) The sample Nos. Sample No. SG-110 was heat-treated at 200 ° C., 400 ° C., and 600 ° C. for 1 hour, respectively.
1, No. 2, No. 3, and evaluated as physical properties and a processing agent for beer by the test methods described below. Table 1 shows the results.

Example 4 Sample SG-1 was redispersed in water, subjected to hydrothermal treatment at 120 ° C. for 2 hours, dried, pulverized and classified at 110 ° C., and further heat-treated at 400 ° C. for 1 hour. Sample No. 4 and various properties were evaluated in the same manner as in Example 1. Table 1 shows the results.

(Examples 5 to 6) The sample SG-1 was re-dispersed in water, hydrothermally treated at 130 ° C. or 140 ° C. for 4 hours, dried at 110 ° C., pulverized and classified, and further at 400 ° C. for 1 hour. The sample subjected to the heat treatment was designated as Sample No. 5, no. 6, and various properties were evaluated in the same manner as in Example 1. Table 1 shows the results.

(Comparative Examples 1 and 2) SG-110
And sample no. Sample No. SG-1 was spray-dried at 110 ° C. Evaluation was performed similarly as H-1 and H-2. Table 2 shows the results.

Comparative Example 3 A commercially available silica gel was used for sample N
o. It was set to H-3 and evaluated similarly. Table 2 shows the results.

Comparative Example 4 Sample No. 4 which was not fired at 400.degree. It was set to H-4 and evaluated similarly. Table 2 shows the results.

(Comparative Examples 5 to 6) 400 of Examples 5 and 6
Samples that were not fired at ℃ H-5 and H-6 were evaluated in the same manner. Table 2 shows the results.

Alkali metal and alkaline earth metal deposition
Of sodium and / or calcium using NaOH and / or CaSO ₄ to a concentration of 5 × 10 ⁻³ mol based on SiO ₂ using sample SG-1 at 110 ° C. The sample dried with sample No. H-7, no. H-8.
The results are shown in Tables 2 and 3.

(Example 7) H-8 at 400 ° C
Baked for 1 hour. 7, and various properties were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 3.

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

[Table 3]

Measurement method 1. Specific surface area by BET method The specific surface area is measured by an automatic BET specific surface area measuring device (CARLO-ERB)
Using Sorptomatic Series 1800 manufactured by Company A), samples prepared under the following conditions were measured by the BET method using a nitrogen adsorption method. The measuring method referred to the following literature. S.Brunaue
r, PHEmmettand E. Teller. J. Am. Chem. Soc., 60 , 309
(1938) 0.5-0.6 sample dried sufficiently at 150 ° C
g in a weighing bottle, dried at 150 ° C. for 1 hour, and precisely weighed. This sample is placed in an adsorption sample tube, heated to 200 ° C., degassed until the degree of vacuum in the adsorption sample tube reaches 10 mm ⁻⁴ Hg, allowed to cool, and then placed in liquid nitrogen at about −196 ° C. , PN ₂ /po=0.05 to 0.30
pN ₂ : nitrogen gas pressure, po: atmospheric pressure at the time of measurement, 4
Convert the amount of nitrogen gas adsorbed to 5 points into an adsorbed amount of 0 ° C. and 1 atm and substitute it into the BET equation to obtain Vm [cc / g] And the specific surface area is determined by the following equation (2). Specific surface area SA = 4.35 × Vm [m ² / g] (2)

2. Pore volume by BET method 1 automatic BET specific surface area measuring device (CARLO-ER)
Using the Sorptomatic Series 1800 manufactured by BA, the nitrogen adsorption method was used to perform the same operation as in section 1 to obtain a sample with a pore radius of 0 to 0.
The gas volume [(Vs) (cc)] adsorbed at a saturation pressure at 300 angstroms was determined, and the pore volume (Vp) (cc / g) was determined by equation (3). Vp (cc / g) = Vs × 0.00155 / w (3) w: sample weight (g)

3 Bulk density Measured according to the method described in 6.8 of JIS K 6220.

4 pH of Aqueous Suspension A 5 g sample was suspended in 100 ml of ion-exchanged water, stirred for 10 minutes, and measured at 25 ° C. with a pH meter.

5 Electric Conductivity The pH measurement suspension was measured with a conductivity meter model DS-12 manufactured by Horiba Co., Ltd.

6 Moisture Measurement Water content was measured by determining the weight loss of the sample when dried at 110 ° C. for 2.0 hours in an electric dryer.

7 Median Diameter and Number Distribution A sample of 0.5 g was suspended in 100 ml of ion-exchanged water, subjected to ultrasonic treatment for 1 minute, and a 100 μm aperture tube was attached thereto, followed by measurement by a Coulter method. The number% was calculated for those having a particle size of 2.6 μm or less from the above measurement results.

8 Loss on ignition (Ig. Loss) and number of OH groups on the surface The silica powder is preliminarily dried at 110 ° C. to remove adsorbed water. Thereafter, the weight loss of the sample when heated to a constant weight at 1000 ° C. in an electric furnace was determined, and the ignition loss was measured. The number of surface OH groups was determined by the following equation.

9 Zeta potential The value obtained when 0.2 g of a sample is suspended in 200 ml of ion-exchanged water is defined as the origin, and then the pH is adjusted using a 0.5N HCl solution. The suspension was subjected to ultrasonic dispersion for 30 seconds, and a LAZER ZEE METER manufactured by Benchem Co., Ltd.
Each zeta potential was measured with MODEL 501.

10 IR Measurement An IR spectrophotometer A-302 manufactured by JASCO Corporation was used for measurement. The measurement sample was 0.1 mg for 100 mg of KBr.
4 mg of silica powder was added, and the mixture was prepared using a tablet press.

11 Definition of _{RA In} the method shown in FIG.
0 cm ^-1 peak intensity (I ₉₇₀ ) and wavelength 1100 cm
The ratio of ^-1 peak intensity (I ₁₁₀₀₎ of (I ₉₇₀ / I _{11 00)} calculated was R _A.

12 Durability of Beer Beer (sample) packed in a bottle (can) was subjected to 60 ± 1
Immersed in standing water at a constant temperature of 72 ° C. for 72 hours, cooled with water, and then placed in an ice bath at 0 ° C. (Cooling Bath) for 24 hours.
After soaking for an hour, the sample is transferred to a cell of a turbidimeter and the turbidity is measured at 0 ° C. ◎ Unit: EBC unit

13 Foam retention Using the sigma value obtained in accordance with the sigma value method described in the analysis method of the American Society of Brewing Chemists (ASBC), the foam retention was determined from the following equation. Foam retention = (Sigma value of control beer) − (Sigma value of Comparative Example H-2)

Measurement of sigma value In an 800 ml separating funnel, at a temperature of 20 ° C., 225 to 2
In 30 seconds (t), the volume of the control beer where the foam was broken and liquefied and the remaining foam were liquefied, and the sigma value was calculated from the following formula from the volume c. Sigma value = t / ｛2.302 log [(b + c) /
c)｝ * Integer after rounding off

[0072]

According to the present invention, the use of heat-treated amorphous silica fine particles exhibiting a large negative zeta potential in a weakly acidic pH range close to the pH of beer as a stabilizing agent for beer allows the foaming of beer to be improved. While maintaining the durability at a good level, it was possible to effectively remove the cold turbid precursor and improve the flavor retention of beer.

[Brief description of the drawings]

FIG. 1 is a graph showing the R _{A of the} formula (1) from the infrared absorption spectrum.
The method of measuring the absorption peak whose value is to be calculated will be described.

FIG. 2 shows the infrared absorption spectrum of the entire region of a typical amorphous silica according to the present invention.

FIG. 3 shows the heat treatment temperature of amorphous silica and 1000c.
7 shows a change in an infrared absorption spectrum near m ⁻¹ .

FIG. 4 shows the relationship between pH and zeta potential of various amorphous silica aqueous suspensions.

FIG. 5 shows infrared absorption spectra of amorphous silica obtained in Examples and Comparative Examples of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tatsuji Morimoto 4-20-1, Ebisu, Shibuya-ku, Tokyo Inside Sapporo Beer Co., Ltd. (72) Inventor Akira Sukebe 4-2-1-1, Ebisu, Shibuya-ku, Tokyo Sapporo Beer (56) References JP-A-5-70120 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C12H 1/00-1/22 C12C 1/00-13 / 10 C01H 33/113-33/193

Claims (5)

(57) [Claims] During 1. A formula _{a M 2 / m O · SiO} 2 · nH 2 O ... (A) formula, M represents an alkali metal and / or alkaline earth metal, m represents the valence of the metal M , A is 0 to 5 ×
Is a number of 10 ^-3 and n is a number of 0 to 0.2. It has a composition represented by the following formula, and has a specific surface area of 100 to 600 m ² / g and a pore of 1.0 to 2.0 cc / g. And the following formula: _RA = I ₉₇₀ / I ₁₁₀₀ (1) where I ₉₇₀ is the wave number 970c of the infrared absorption spectrum
m ¹ is the absorbance of the peak, and I ₁₁₀₀ is the absorbance of the peak at a wave number of 1100 cm ^{−1 in} the infrared absorption spectrum. The absorbance ratio (R _A ) defined by
Consisting of amorphous silica less than 0, with a concentration of 1000 pp
wherein the aqueous suspension has a pH of 4 to 6.2 at 25 ° C. and a temperature of 25 ° C., and has a negative zeta potential and an absolute value of 20 mV or more. Agent. 2. The stabilizing agent for beer according to claim 1, wherein the amorphous silica has no absorption peak at 3760 cm ^-1 in the absorption spectrum of the infrared absorption spectrum. 3. The stabilizing agent for beer according to claim 1, wherein in the formula (A), the alkali metal is sodium and / or the alkaline earth metal is calcium. 4. The amorphous silica having a surface OH group number of 7
^{2. The} stabilizing agent for beer according to claim 1, wherein the number is not more than the number of particles / nm ² . 5. The amorphous silica has a median diameter measured by a Coulter counter method of 5 to 8 μm and 2.6 μm.
The stabilizing agent for beer according to claim 1, wherein the number distribution of the following secondary particles is 30 to 60%.