JPH08198616A - Silicon dioxide for stabilizing beer and its production - Google Patents

Abstract

PURPOSE: To obtain silicon dioxide for stabilizing beer, which give excellent stabilizing effect without dajnaging the foam property of the beer. CONSTITUTION: Silicon dioxide for stabilizing the beer, which has 500-800m<2> /g specific surface area by BET method, shows pH8.0-9.3 in 5wt.% aq. suspension, is <=+4.8 in acid strength H0 and 0.8-1.2μmol/m<2> in acid quantity, is obtained by adding simultaneously sodium silicate and a mineral acid into a salt aq. solution under stirring to allow to react with each other at pH3.0-7.0 and 80 deg.C, adjusting the pH of the resulting silica suspension to 3.0-7.0, filtering, washing and dispersing again the resulting silica hydrogel into water and after adjusting the pH to 5.5-8.5, filtering, washing and drying.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a silicon dioxide for stabilizing beer, which does not impair the foam characteristics of beer and has excellent performance for improving the stability of beer (preventing turbidity). The manufacturing method is related.

[0002]

Amber-colored and transparent beer is an important factor that determines the commercial value of beer together with its flavor and foam characteristics.

The commercialized beer then gradually becomes less transparent as protein in the beer aggregates with the number of days. Especially, when it is stored at a low temperature for a long period of time, turbidity occurs to the extent that it can be seen visually. This phenomenon is called cold turbidity.

It is generally considered that the cause of this turbidity is that a certain protein or colloidal component such as polyphenol derived from barley or hop which is a raw material of beer is associated or aggregated.

Therefore, in order to prevent turbidity of beer and increase its stability, it is necessary to remove or reduce the components that cause turbidity in the process of producing beer. For this purpose, Silicon dioxide (silica gel) has been widely used since it is relatively inexpensive and has little influence on beer flavor, foam, and other qualities.

Various proposals have heretofore been made to use this silicon dioxide as a stabilizing treatment agent for beer.

For example, British Patent No. 981715 discloses
Specific surface area 200 to 600 m ² / g, pore volume 0.5 to
Silicon dioxide, which has the physical properties of 1.5 ml / g, average pore size 40 to 180Å and pH of 5% water suspension of 4.0 to 8.0, is excellent in preventing beer turbidity (stabilization). It is described that the above effect is exhibited.

Further, Japanese Patent Publication No. 3-27483 discloses that
Specific surface area 530-720 used for stabilizing beer
m ² / g, pore volume 0.9 to 1.5 ml / g, average pore diameter 50 to 120Å, water content 7 to 25% by weight (wet amount basis), and 5% water suspension PH of 6.0
A hydrous silica gel for stabilizing beer is proposed, which is characterized in that it is ˜8.0. Further, in JP-A-1-165363, in a method of stabilizing beer by contacting beer with an adsorbent, a specific surface area of 300 to 700 m ² / g as an adsorbent for beer during low temperature aging,
Pore volume 1.0-2.0 ml / g, average pore size 100-
A method for stabilizing beer is proposed, which is characterized in that spherical silica gel having an average particle diameter of 5 to 20 μm is added and brought into contact with the mixture, followed by filtration. JP-A-4-79876 discloses a method for stabilizing a beer having a specific surface area by the BET method. 250 to 500 m ² /
In the range of g, the acidity function H ₀ has a solid acidity of ₀ or less at an acid strength of +1.5 or less, and the acidity function H ₀ has a solid acidity of 0.01 to ₀ at an acid strength of up to +4.8. .40m
A stabilizing agent for beer characterized by comprising fine powder of silica gel in the range of mol / g has been proposed.

These proposals are intended to selectively adsorb and remove proteins involved in turbidity in beer by mainly controlling the physical surface area of silicon dioxide and the physical structure such as pore diameter and pore volume. However, the proteins contained in beer include turbid proteins (proteins involved in beer turbidity) and foaming proteins (proteins that contribute to beer's foam characteristics) as described above, and turbid proteins are beer. Since it adversely affects the stability of beer, it is necessary to remove it, but foaming protein improves the beer's foam characteristics such as foam retention and stickiness, and if this is removed, the original characteristics of beer are impaired. It will be.

The above-mentioned conventional proposals do not give sufficient consideration to the foaming protein when removing the cloudy protein, because the foaming protein differs from the cloudy protein in molecular weight and physical size. However, in reality, cloudy proteins and foaming proteins are not simply separated by their molecular weight and physical size, so controlling the pore structure of silicon dioxide fairly strictly. Also, a part of the foaming protein is adsorbed and removed, and there is a problem that foam characteristics such as foam retention and foaming are deteriorated.

The present invention has been made in view of the above circumstances, and it is possible to obtain a beer having good foam retention and foaming and high stability by stabilizing the beer without impairing the foam characteristics of the beer. An object of the present invention is to provide silicon dioxide for stabilizing beer and a method for producing the same.

[0012]

Means and Action for Solving the Problems The present inventors have
As a result of earnest studies to achieve the above object, as a result of silicon dioxide, the specific surface area by the BET method is 500 to 80.
When suspended in water at a concentration of 0 m ² / g, 5% by weight, the suspension pH is 8.0 to 9.3, the acid strength H ₀ is +4.8 or less, and the acid amount is 0.8 to 1 By using ² μmol / m ² for stabilizing beer, turbidity after long-term storage is effectively prevented, stability is high, and foam retention and foaming are good and beer foam characteristics are improved. It was found that sustained beer could be obtained.

Further, in this case, sodium silicate and mineral acid are simultaneously added to the aqueous solution of salt with stirring to carry out the reaction to obtain silicon dioxide.
7.0, the reaction temperature is set to 80 ° C. or lower, and the obtained silica suspension is first adjusted to pH 3.0 to 7.0, and then filtered and washed with water to obtain silica hydrogel. By redispersing the silica hydrogel in water and adjusting the pH of the silica hydrogel to 5.5 to 8.5, two-step pH adjustment is performed without impairing the foam characteristics of beer as described above, and The present invention has been completed by finding that silicon dioxide having excellent performance for improving the stability of beer (preventing turbidity) can be obtained.

Therefore, according to the present invention, (1) the specific surface area according to the BET method is 500 to 800 m ² / g, and the pH of a 5% by weight aqueous suspension is 8.0 to 9.3. And acid strength H ₀ is +4.8 or less and the amount of acid is 0.8 to 1.2 μ.
mol / m ² of silicon dioxide for stabilizing beer, and (2) sodium silicate and mineral acid are simultaneously added to an aqueous solution of a salt with stirring to obtain a pH.
After performing the reaction at 80 to 80 ° C. in 3.0 to 7.0,
The obtained silica suspension was adjusted to pH 3.0 to 7.0,
Then, the beer is characterized by being filtered and washed with water, redispersing the obtained silica hydrogel in water, adjusting the pH thereof to 5.5 to 8.5, filtering this, washing with water, and then drying. The present invention provides a method for producing silicon dioxide for stabilizing treatment of.

The present invention will be described in more detail below.
The silicon dioxide for stabilizing beer of the present invention has a specific surface area of 500 to 800 m ² / g, preferably 520 to 78.
It is 0 m ² / g. When the specific surface area is less than 500 m ² / g, the function of stabilizing beer (preventing turbidity) against beer is not sufficiently exerted, and the object of the present invention cannot be achieved. Further, when the specific surface area exceeds 800 m ² / g, there are many fine pores in which high molecular weight proteins cannot physically enter and tend not to contribute to adsorption of cloudy proteins.

Further, the silicon dioxide for beer stabilization treatment of the present invention has a pH (5%
Aqueous suspension pH) is 8.0 to 9.3, preferably 8.2.
Its characteristic is that it is 9.0, and the pH on the alkaline side weakens the surface acidity of silicon dioxide, and when added to beer, the interaction between the surface of silicon dioxide and turbid proteins or foam proteins. The (affinity) is controlled, and as a result, it has excellent performance for improving the stability of beer without impairing the foam characteristics of beer. On the other hand, when the pH is lower than 8.0, the beer foam characteristics (foam holding and foaming) are inferior, and the object of the present invention cannot be achieved. Further, if the pH is higher than 9.3, it is feared that the alkaline component in silicon dioxide is dissolved in beer and adversely affects the flavor.

Furthermore, the beer stabilizing silicon dioxide of the present invention has an acid strength H ₀ of +4.8 or less and an acid amount of 0.8 to 0.8.
It needs to be 1.2 μmol / m ² , and having such an acid strength can give a favorable result to the foam retention of beer. On the other hand, when the acid strength exceeds 1.2 μmol / m ² , the foam retention of beer becomes poor, and when it falls below 0.8 μmol / m ² , the residual alkali component in silicon dioxide increases, and as described above. The alkali content dissolves in beer and adversely affects the flavor of beer, and the physical stability of beer decreases.

FIG. 1 is a plot of the relationship between the foam retention of beer and the above-mentioned acid strength of silicon dioxide, which was measured by the method shown in Examples described later. From this result, the acid strength H ₀ is +4.8. It can be seen that when the following acid amount exceeds 1.2 μmol / m ² as a boundary, the foam retention is obviously deteriorated. The reason for this has not been sufficiently clarified at present, but the present inventors presume that the reason is as follows.

That is, the pH of beer is about 4 to 4.2, and the isoelectric point of silicon dioxide is 2, or a little higher than that due to the influence of impurities (from Chemical Handbook). Therefore, in beer, the surface of silicon dioxide has a negative charge. On the other hand, the turbid protein and foam protein in beer are said to have isoelectric points around 4 and 7 and above, respectively (“Stabilization of beer”).
using silica gel ”Proc. Cn
ov. of Inst. Brew. Therefore, it is considered that in beer, cloudy proteins are almost neutral in charge and foam proteins have a positive charge. Therefore, it is considered that the surface of silicon dioxide, which has a negative charge in beer, has a larger interaction (adsorption) with the foam protein, which has a positive charge, than the electrically neutral turbid protein.

From the above, it is considered that cloudy proteins are selectively adsorbed and removed by the physical pore structure (specific surface area, pore diameter, etc.) of silicon dioxide rather than electrical interaction ( gel-permiation effect), the amount of negative charges on the surface of silicon dioxide is large,
That is, when the above-mentioned acid strength (surface acidity) is high, the adsorption property of the foam protein becomes high, so that the foam characteristic of beer is considered to be deteriorated. Therefore, the silicon dioxide according to the present invention is 5
Not only has a large specific surface area of 00 to 800 m ² / g, but also weakens its surface acidity, that is, the acid amount having an acid strength H ₀ of +4.8 or less is 1.2 μmol / m ² or less. Thus, it is considered that the beer exhibits excellent performance for improving the stability of beer without deteriorating the foam characteristics of beer.

Here, in the proposal of Japanese Patent Laid-Open No. 4-79876, the acid strength (surface acidity) of silicon dioxide is also an important item, but the meaning of controlling the surface acidity in this proposal has been specified. When silica gel having a solid acid amount of acid strength distribution is mixed in beer, the catalyst of this silica gel rapidly forms a complex between protein and tannin in beer at room temperature, and as a result,
The tannins involved in beer turbidity can be effectively removed.According to acid strength only from the viewpoint of removing turbid proteins and stabilizing beer, the retention of foam proteins and the retention of beer foam. Therefore, it does not focus on the acid strength. On the other hand, the present invention relates to the interaction (affinity) between silicon dioxide and various proteins in beer.
In the above, the adsorption of the foam protein is minimized and the surface acidity is controlled in order to selectively adsorb and remove only the turbid protein. In fact, in the above proposal, the unit of surface acidity is mmol / g, that is, the amount of acid per unit weight, whereas in the present invention, μmol / m ² , that is, the amount of acid per unit surface area is It is defined. Therefore, in the case of the above proposal, while it is simply the total amount of acidic sites on the silica surface, the present invention means the solid acid density on the silica surface, which means that various proteins and silica in beer are present. It is closely related to the interaction with, the adsorption (orientation) state, etc., and is capable of more selectively adsorbing and removing the cloudy protein in beer.

The silicon dioxide for beer stabilization treatment of the present invention has a pore volume of 0.5 to 1.5 ml / in that the adsorbed cloudy protein must be retained in the pores.
g, particularly 0.6 to 1.2 ml / g, and the average pore diameter is 4 to 12 nm, particularly 5 to 10 nm from the viewpoint that the turbid protein more selectively enters the pores and is adsorbed and removed. Is preferred. Further, from the viewpoint of drying efficiency and workability, and from the viewpoint of suppressing the growth of microorganisms during storage, the water content is 3 to 15% by weight, particularly 5%.
It is preferably ˜12% by weight. The average particle size of the silicon dioxide used is usually 10 to 20 μm in view of the filterability for beer, and more preferably 12
-18 μm.

The silicon dioxide is prepared by simultaneously adding a sodium silicate solution and a mineral acid such as sulfuric acid or hydrochloric acid to an aqueous salt solution of sodium sulfate, sodium chloride, sodium phosphate or the like to precipitate silicon dioxide (simultaneous injection method). Can be obtained by In this case, the reaction is carried out at 80 ° C. or lower, preferably 75 ° C. or lower, more preferably 70 ° C. or lower, and the pH during the reaction is 3.0 to 7.0, preferably 3.5 to 6.0. If the reaction temperature is higher than 80 ° C,
The resulting silicon dioxide has a small specific surface area,
Moreover, the acid strength is also high. The reaction may be carried out at room temperature or lower, but in this case, the resulting reaction slurry has poor filterability, so that the efficiency of subsequent filtration (solid-liquid separation) / water washing is considerably deteriorated, and in particular, sodium silicate If the concentration is high, the entire liquid may solidify during the reaction, so 4
It is preferable to carry out the reaction at 0 ° C. or higher. Further, if the pH during the reaction is lower than 3.0, there is a material problem in acid resistance in ordinary industrial equipment. If the pH is higher than 7.0, the specific surface area of the finally obtained silicon dioxide will be smaller than the target, and a sufficient effect for improving the stability of beer cannot be obtained.

In the production method of the present invention, the pH of the silica suspension after the reaction is adjusted to 3.0 to 7.0, preferably 3.5 to 6.0 (first step pH adjustment). Is necessary for the same reason as the pH control during the reaction.

When the silica hydrogel obtained by filtering and washing the reaction product is redispersed in water, the pH of the suspension is 5.5 to 8.5, preferably 6.0 to 8. It is indispensable to adjust to 0.0 (second-step pH adjustment), and adjustment p
If H is out of this range, the product pH and acid strength (surface acidity) of the finally obtained silicon dioxide deviate from the target values, and thus the beer foam characteristics deteriorate.

That is, in the production method of the present invention, by performing the two-step pH adjustment as described above, and by setting the pH adjustment range as described above, the beer stabilization treatment having the above-mentioned characteristics is performed. It is possible to obtain silicon dioxide.

Here, the standing time after the first-step pH adjustment is preferably 30 minutes to 5 hours, and the standing time after the second-step pH adjustment is preferably 30 minutes to 3 hours. If the standing time is shorter than 30 minutes, the effect of pH adjustment does not sufficiently appear. On the contrary, if the standing time is too long, the effect of pH adjustment does not change so much and the productivity only decreases. Further, when the pH of the slurry is 7 or more, the specific surface area of the finally obtained silicon dioxide tends to be small if left for a long time.

The treatment after pH adjustment may be carried out by filtration, washing with water and drying by a known method for producing finely powdered silicon dioxide, and further pulverizing (and classifying) to a predetermined particle size if necessary. .

The beer-stabilizing silicon dioxide of the present invention can be used in the same manner as the known beer-stabilizing silicon dioxide, and is effectively used for filtering beer that has been post-fermented and aged. In this case, it can be used together with a filter aid such as diatomaceous earth.

The beer treated with silicon dioxide according to the present invention is excellent in stability and also has good foaming characteristics, and an excellent beer can be obtained as a whole.

[0031]

EXAMPLES The present invention will be described below in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[Example 1] A commercially available solution of diluted JIS No. 3 sodium silicate and dilute sulfuric acid were simultaneously added to a sodium sulfate solution while stirring, and the pH during the reaction was adjusted to 5.0 to 5.0.
The reaction is carried out at 65 ° C, keeping it between 5.5.

Next, the pH of the silica suspension after the reaction was adjusted to 5.
It was adjusted to 0 and left for 1 hour, then filtered and washed with water, the obtained silica hydrogel was redispersed in water, the pH of the suspension at that time was adjusted to 7.0, and left for 1 hour.

The treatment after pH adjustment was generally carried out by filtration, washing with water and drying by a known method for producing finely powdered silicon dioxide, and further pulverization (and classification) to adjust to a predetermined particle size.

[Example 2, Comparative Examples 1 to 7] Reaction temperature, pH of silica suspension after reaction (first step pH adjustment), suspension obtained by redispersing the obtained hydrogel in water PH of
The same operation as in Example 1 was performed except that (second step pH adjustment) was as shown in Table 1.

Comparative Examples 8 and 9 As in Example 1 except that the reaction temperature was as shown in Table 1, the first-step pH adjustment was performed at the pH shown in Table 1, and the second-step pH adjustment was not performed. The same operation was performed.

Table 1 also shows the physical properties of the obtained silicon dioxide and the results of beer evaluation when the beer was stabilized with these materials. The physical properties of silicon dioxide and beer were evaluated by the following methods. Method for measuring physical properties of silicon dioxide [specific surface area] The specific surface area was measured by a nitrogen adsorption method (BET method) using a fully automatic specific surface area / pore distribution measuring device (BELSORP 28) manufactured by Nippon Bell Co., Ltd. The sample was pretreated by vacuum degassing at 160 ° C. for 2 hours. (Reference: S. Brunauer, PH Emme.
tt, E.I. Teller, J .; Amer. Chem. S
oc. , 60, 309 (1938)) [Product pH] Disperse 5 g of a sample in 100 ml of ion-exchanged water, boil once, cool to room temperature, and measure the pH of the slurry. [Acid Strength (Surface Acidity)] The surface acidity is defined as the number of acid points or the number of moles per unit weight or unit volume. Put the sample in an Erlenmeyer flask with a ground stopper, 140 ~ 15
After drying at 0 ° C. for 3 hours, the sample weight at that time is precisely weighed. Purified benzene is added, methyl red (pKa = + 4.8) is added as an indicator (Hamet indicator), and then titrated with n-butylamine. The acidity per unit surface area [the amount of acid having an acid strength H ₀ of +4.8 or less] was calculated from the titration amount (number of moles) at this time and the specific surface area described above. (Reference: "Adsorption", Tominaga Keiitoshi, Kyoritsu Zensho, p.7.
2 and 2, Catalytic Engineering Course 4, "Catalyst Basic Measurement Method", edited by The Catalysis Society of Japan, p. 161-) [Pore volume] The adsorption isotherm of nitrogen was obtained using the above-mentioned BELSORP 28, and the pore volume having a pore diameter of 2 to 60 nm was obtained by the analysis method of Dorymore heel according to JIS-K1150. [Average Pore Diameter] The average pore diameter was calculated from the above-mentioned specific surface area and pore volume by the following formula. Average pore diameter (nm) = 4000 × pore volume (ml / g)
/ Specific surface area (m ² / g) [Water content] The water content was defined as the weight loss when dried at 105 ° C for 4 hours.

Method for evaluating performance with beer [Method for treating beer with silicon dioxide] 3 L of stored beer (young beer) was tested with 1.5 g of silicon dioxide.
And diatomaceous earth (3.0 g) were added and stirred for 30 minutes,
Diatomaceous earth precoat filtration was performed with a filter press. The obtained beer after filtration was subjected to the following various analyses. [Bubbling] Beer is degassed and then kept at 20 ° C
It was measured according to the udin method (Institute
of Brewing magazine). That is, beer is bubbled with carbon dioxide, and the time required for bubbles of a certain height to return to beer is measured. Therefore, beer with good foam lasts longer. [Bubbling] The measurement was carried out by modifying the Bamforth method (Institute of Brewing). That is, beer degassed in a cup is bubbled with carbon dioxide, left for a certain period of time, and then the bubbles adhering to the wall of the cup are collected with water, and the absorbance is calculated. Therefore, the larger this value is, the better the bubbles are. [SASPL value] A saturated ammonium sulfate solution is added to degassed beer in fixed amounts, and the precipitation limit amount is determined from the turbidity increase curve due to protein insolubilization. Therefore, the larger this value, the less likely turbidity occurs. [Forced deterioration turbidity] Beer is stored at 50 ° C for 1 week immediately after filtration, and turbidity after 24 hours at 0 ° C (EBC turbidity unit)
To measure.

[0039]

[Table 1]

From the results shown in Table 1, the silicon dioxide according to the present invention (Examples 1 and 2) had good foam retention and foaming, and SA
It is recognized that the SPL is large and the forced deterioration turbidity is small.

On the other hand, the silicon dioxide of Comparative Example 1 is
The adjusted pH of the second step is as low as 4.0, the product pH is low, and
The high surface acidity also results in poor beer foam properties. The reaction temperature of the silicon dioxide of Comparative Example 2 was as high as 85 ° C., and the pH of the silicon dioxide of Comparative Example 3 was as high as 8.0 in the first step, and both of them have a small specific surface area and a large surface acidity. As a result, the foam retention is poor and the stability of beer is poor. Comparative Example 4 has a too large specific surface area,
In addition, since the product pH is low, foam retention and foaming are poor. In Comparative Example 5, the adjusted pH of the first step and the second step deviates from the conditions of the present invention, and the specific surface area, product pH, and surface acidity are all outside the ranges of the present invention, so the foam characteristics of beer are stable. Is also bad. Comparative Example 6 has high surface acidity, poor foam retention, and poor beer stability. In Comparative Example 7, the product pH is low and the foam property is deteriorated. Furthermore, in Comparative Examples 8 and 9, the pH adjustment was carried out in a single step. The silicon dioxide of Comparative Example 8 had a low product pH, had poor foam characteristics, and had insufficient beer stability. Silicon has a small specific surface area and has poor beer stability.

[0042]

EFFECT OF THE INVENTION The silicon dioxide for stabilizing beer of the present invention provides an excellent effect of stabilizing beer (preventing turbidity) without impairing the foam characteristics of beer. Moreover, according to the manufacturing method of the present invention, such silicon dioxide can be reliably manufactured.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the acid amount of silicon dioxide having H ₀ of +4.8 or less and the foam retention of beer.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Seiichi Horiuchi 2-13-1, Omorikita, Ota-ku, Tokyo Asahi Biru Co., Ltd. Alcoholic Beverages Research Institute (72) Inventor Hiroaki Kaku 129 Grandform, Miyagawa-cho, Kurayoshi-shi, Tottori Prefecture Kurayoshi 405

Claims (3)

[Claims] 1. A specific surface area according to the BET method of 500 to 80.
0 m ² / g, p when 5% by weight of water suspension
H is 8.0 to 9.3, and acid strength H ₀ is +4.8.
The following acid amount is 0.8-1.2 micromol / m < ² >, The silicon dioxide for stabilization processing of beer characterized by the above-mentioned. 2. A pore volume of 0.5 to 1.5 ml / g, an average pore diameter of 4 to 12 nm, and a water content of 3 to 15% by weight.
The silicon dioxide for stabilizing beer according to claim 1, which is 3. A solution of sodium silicate and a mineral acid are simultaneously added to an aqueous salt solution with stirring to carry out a reaction at a temperature of 3.0 to 7.0 at 80 ° C. or lower, and then the obtained silica suspension is adjusted to pH 3 It is adjusted to 0.0 to 7.0, then filtered and washed with water to redisperse the obtained silica hydrogel in water, and its pH is adjusted to 5.5 to 8.5, which is filtered,
A method for producing silicon dioxide for stabilizing beer, which comprises washing with water and then drying.