JPH02227065A - Agent for keeping quality of liquors - Google Patents

Abstract

PURPOSE:To improve dispersibility to liquors to which urea decomposition treatment is carried out by subjecting an aqueous solution containing an acidic urease and dextrin having >=20 dextrose equivalent to drying treatment and preparing an agent for keeping quality of liquors. CONSTITUTION:An aqueous solution containing an acidic urease and dextrin having >=20 dextrose equivalent is prepared. Then the aqueous solution is subjected to drying treatment such as spray drying, freeze drying or heating and vacuum drying to prepare the agent for keeping quality of liquors. A dextrin in which a dextrin having >=9 glucose residue is contained at an amount of <=15wt.% is preferably used as the above-mentioned dextrin. The weight ratio of dextrin having >=20 dextrose equivalent to acidic urease is normally 1-5. When the above-mentioned agent for keeping quality of liquors is further blended with a filtration auxiliary such as diatomaceous earth or natural vegetable fibers, dispersibility in addition to liquors is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an agent for preserving the quality of alcoholic beverages using acid urease.

BACKGROUND ART Conventionally, when producing enzyme preparations for food, for example, in the case of microbial origin, the enzyme obtained after purifying the fermentation liquid is either in the form of a solution (e.g. extracellular enzyme) or in the form of a suspension ( (e.g. enzymes inside bacteria), wet precipitates (e.g. solvent sedimentation filtration products), wet precipitates (e.g. centrifuged salt folded products) It is customary to subject these items to a drying operation. As this drying operation, spray drying, freeze drying, vacuum drying, etc. are usually applied. During drying, excipients may be present in the presence of excipients, but the purpose of this is to improve handling by stabilizing or increasing the amount of the enzyme (e.g., Japanese Patent Publication No. 63-31446.
stable urease formulation).

Problems to be Solved by the Invention When the above-described dried enzyme and the undried enzyme are made to have the same titer and are added to a food, a difference may be observed in the expression of enzyme action in the food. This phenomenon is particularly likely to occur when the target food is different from water (for example, alcoholic beverages).

For example, in the case of acid urease for brewing, the urease suspension (A), its spray-dried powder (B), and its freeze-dried powder (C) are added to sake and the urea decomposition power in the sake is compared. Even when the same titer is added, the ranking is: (A) ≧ Addition of aqueous dispersion of (B) or (C) > Addition of liquor dispersion of (B) or (C), and a difference in decomposition power is recognized. In this case, since the amount of acid urease added is small, it is added after being dispersed with water or sake.

That is, when drying a food enzyme, there is a problem that the drying operation deteriorates compatibility with the target food and inhibits the expression of enzyme action.

To avoid this problem, enzyme preparations for brewing can be dispersed in water before being added to alcoholic beverages to improve the wetness (for example, when dispersing alcoholic beverages, strong agitation is applied and mechanical However, in any case, this method is difficult to adopt in actual use due to the time-consuming process and contamination of water.

Means for Solving the Problems As mentioned above, the present inventors have developed a mainly effective excipient in order to solve the problems when using dry powder of acid urease for the purpose of maintaining the quality of alcoholic beverages. After conducting studies from a selection standpoint, we found that the use of dextrins with specific properties was extremely effective, and after further studies, we completed the present invention.

That is, the present invention provides 1) an alcoholic beverage quality preservation agent obtained by drying an aqueous liquid containing acid urease and a dextrin having a dextrose equivalent of 20 or more; 2) a dextrin having 9 or more glucose residues among its components; is about 15 times 1
% or less, and 3) The above l) and 2 further contain a filtering agent.
This is a method for improving the quality of alcoholic beverages, which comprises treating alcoholic beverages with the alcoholic beverage quality preserving agent described in item (1) above and the alcoholic beverage quality preserving agent described in item (1) above.

The acid urease used in the present invention is an optimal pt-r
pH is in the acidic range, particularly in the pH range of 2 to 5.5. Such acid ureases are usually
Those produced by culturing a microbial strain capable of producing acid urease, such as European Patent Publication No. 0266088 or Patent Application No. 16 of 1988.
Acid urease cultured and purified by the method described in No. 9761 can be used.

In other words, target foods include intracellular enzymes that contain acid urease inside the cell or in cell fragments, water-soluble extracellular enzymes, and enzymes that have been purified into a single protein or several types of proteins through various purification procedures. Any form of acid urease that is added in a batch manner can be used as a raw material for the preparation of the present invention.

In the following, when the activity of acid urease is expressed, the unit (1) refers to the amount of enzyme that decomposes urea and releases 1 micromole of ammonia per unit time (1 minute) at 37°C. Hereinafter, the ■unit will be expressed as lU.

Next, the dextrin having a dextrose equivalent of 20 or more in the present invention is obtained by hydrolyzing starch by a method known per se. Here, dextrose equivalent.

DE (commonly abbreviated as DE) is generally used as an indicator of the degree of hydrolysis, and is the value obtained by measuring the reducing sugar in dextrin, which is produced as glucose, and calculating the percentage relative to the solid content.

In the present invention, a dextrin having a DE of 20 or higher and prepared such that the number of glucose residues of the dextrin is 9 or more is about 15% by weight or less is preferably used. In addition to this, the total amount of glucose, maltose and maltotriose in the dextrin is approximately 5
Those having a weight of 0% by weight or less can be more preferably used.

The alcoholic beverage quality preservation agent of the present invention comprises acid urease and DE20.
After preparing an aqueous solution containing the above dextrin,
Obtained by drying using an appropriate method.

Dextrin/acid urease fff with DE20 or higher
If the ffi ratio is about 0.5 or more, the desired effects of the present invention will be exhibited, but this optimal weight ratio is usually 1 to 5. At this time, the titer of acid urease after excipientation with dextrin of DE20 or higher is about 1 to 50 U/
It is adjusted so that s+g. Dextrin with a DE of 20 or more and acid urease are dissolved or dispersed in water in the above-mentioned ratio, but they may be mixed after making each into an aqueous liquid in advance, or by mixing one in an aqueous liquid with the other as a solid. It may be added as a substance, as long as these two components are mixed uniformly in an aqueous system. The first condition is that the amount of water is sufficient to uniformly dissolve or disperse dextrin with a DE of 20 or more and acid urease, and an appropriate amount may be added taking into consideration the effect on the subsequent drying operation. For example, 1000 mL of acid urease enzyme solution (3,000 U/
mL) and 390 g of dextrin with a DE of 20 or higher, the appropriate amount of water to be used is 1 to 3 L. However, there is no problem with adding more water than this range, except that the drying efficiency will be lowered.

The aqueous solution thus prepared is dried, and any conventional method for preparing enzyme preparations can be used as long as the drying method and conditions are such that the activity of acid urease is maintained. For example, spray drying, freeze drying, heated vacuum drying, etc. can be advantageously used. After drying, for example, those that have been freeze-dried or heated and vacuum-dried may be further pulverized, sieved, etc., and sized.

The liquor quality preservation agent prepared as above can be increased in quantity by further adding a filter aid, and its dispersibility is further improved when added to products, resulting in 7P! It is advantageous in terms of work because it can be uniformly suspended in type i in a short time.

The filter aid mentioned here can be used without particular limitation as long as it is normally used to enhance the filtration effect in the filtration process of alcoholic beverage production.

For example, mineral filter aids such as diatomaceous, natural vegetable fibers such as short pulp fibers and short cottonseed fibers (linter pulp), natural animal fibers such as short silk fibers, synthetic short fibers such as polyethylene short fibers, etc. Fibers and the like can be used alone or in combination of two or more.

The particle size or fiber length of these filter aids is 2 to 20μ in the case of mineral filter aids such as diatomaceous.
m, in the case of pulp short fibers, the fiber length is 0.05 to 1
Ill+m, in the case of short cottonseed fibers, the fiber length is 0.
2 to 5 mm, in the case of short silk fibers, the length of the fibers is Ol~
IonIIl, 0.3 to 3 for polyethylene staple fibers
mm can generally be used.

Among these filter aids, short pulp fibers have advantages such as good miscibility with the above acid urease preparation and less separation of the preparation components even if the resulting preparation is subjected to vibrations due to transportation or other operations. The most practical.

The short pulp fibers may be produced by a method known per se, and may be obtained by partially depolymerizing purified wood pulp with a mineral acid, refining it, and then mechanically crushing it.

The particle size of the short pulp fibers is preferably one that passes through a 50-mesh sieve and has a main fiber length of 150 μm or less. Commercially available products can be used as such short pulp fibers,
For example, KC Flock W-50 (90% or more that passes through a 50 mesh sieve), KC Flock W-100 (90% or more that passes 100 mesh), or KC Flock W-200.
(90% or more passed through a 200-mesh sieve) (both sold by Shikinichi Yakuhin Kogyo Co., Ltd.).

The linter pulp used in the present invention preferably has an α-cellulose content of 98% or more and a beating degree of 20 to 70. This linter pulp is obtained by cooking, bleaching, and beating the linter pulp obtained from cottonseed by a method known per se, and has an α-cellulose content of 98% or more and a beating degree of
~70. It is preferable to use linter pulp having a fiber length of 1.5 am, particularly llllIn or less.

In the present invention, activated carbon for sake brewing may be used in combination with a filter aid, and the activated carbon includes plant-based raw materials (for example, wood, wood flour, wood carbonized product, charcoal, fruit shells, lignin, etc.) and mineral-based raw materials. (For example, coal 1 coal coke, stone AIr
It is acceptable as long as it uses coke, pitch, etc.) and is manufactured for food use. Activated carbon is classified into powdered activated carbon and granular activated carbon based on its particle shape. In the present invention, powdered activated carbon is used, and the particle size is preferably one that passes 100 mesh. Further, methods for producing activated carbon include a chemical activation method and a gas activation method, and activated carbon may be produced using either of the activation methods. Specifically, for example, Tokusen Shirasagi, Tokusei Shirasagi, Shirasagi RM (Shikiichi Yakuhin Kogyo Co., Ltd.)
Commercial products such as those manufactured by Co., Ltd.) can be mentioned. When using activated carbon for sake brewing, generally about 10 parts by weight per 100 parts by weight of filter aid.
It is preferable to mix in a proportion of 300 parts by weight.

When adding a filter aid to the above preparation obtained using acid urease and dextrin with a DE of 20 or higher, the acid urease titer in the preparation should be approximately 0.1 = 10 U/mg.
It is blended so that The blending may be carried out using a conventional rotary mixer or stationary mixer.

From the viewpoint of urease stability, etc., the preparation of the present invention usually contains
It is preferable to adjust the water content to 10% or less.

Next, the alcoholic beverage targeted by the present invention is sake.

Beer, wine, aged sake, mirin, etc., brandy moromi, rum moromi, whiskey moromi, spirits (e.g., gin, vodka, tequila, etc.) moromi, roasted moromi, etc., as long as they contain urea, can be used. It can also be used as an intermediate process product during manufacturing. This preparation can be used in the same way as conventional filter aids in the filtration process of alcoholic beverage production, and can also be used to achieve the purpose of urea decomposition. May be used in For example, in the case of sake, this preparation is added to fermented moromi, new sake after pressing and filtering the moromi, raw sake, stored sake after pasteurization, sake before bottling, etc., and after leaving it until the urea disappears, by the usual method. Just filter it. The amount of this preparation is approximately 0.00% of acid urease per 1 liter of fermented moromi, new sake, raw sake, storage layer, sake before bottling, etc. OIU to 1.000U, more preferably about 0.00U. l
Advantageously, the amount is between U and 500 U. As a more specific example of how to use this preparation, in the case of sake, approximately 50 U or more of acid urease is added to 5 kiloliters of new or unpasteurized sake by pressing and filtering the fermented moromi and pasteurization. Add this preparation to preferably 500 U or more, more preferably 5.0 OOU or more, leave it at about 10°C to 30°C, and then follow conventional manufacturing methods such as filtration, pasteurization, storage, and bottling. Manufacture. For example, at 15℃ urease is 130,0OOU
When this preparation is added, the leaving period is 3 days,
When this preparation is added so that the urease concentration is 130.0 OOU at 50C, the standing period is 8 days.

During this standing period, urea can be decomposed.

Effects and Examples The present invention will be explained in detail below using experimental examples, and then the present invention will be explained more specifically with reference to examples. In the following, urea was quantified using FKinod (urea/ammonia UV method) manufactured by Boehringer Mannheim. Also, G l+ G,, G.

Alternatively, each symbol G indicates the number of glucose residues in the component in dextrin, and these contents are determined by calculating the area of each peak on the chart when measured by high performance liquid chromatography (HPLC) and calculating its relative value. expressed.

Experimental Example 1 Lactobacillus fermentum (Lactobacillus fermentum)
us fermentum) I F 0 1451
A spray-dried product of an aqueous solution (1,850 U/+nL, solid content 15%) containing purified acid urease obtained by culturing No. 1 was used as sake (a commercially available product, however, ethanol 20% (V/V)).

Each pretreatment shown in Table 1 was applied to urea (adjusted to 30 ppm) and added, and the mixture was left at 10oC and the amount of urea was measured over time. The results are shown in Table 1.

Table 1 When the state of the spray-dried grains was observed under a microscope during the pretreatment shown in Table 1, it was found that the grains maintained their original shape with almost no change in shape when agitated with a magnetic cooler, but the strength of the grains with a household mixer was When stirring, the particles are broken into pieces and the original shape of the particles cannot be seen.

In other words, when dispersed in water, the original shape of the spray-dried particles is maintained, but the activity is best expressed, and when dispersed in alcohol,
If the original form remains, the effectiveness decreases, and if agitation is applied so strongly that the original form disappears, the effectiveness increases, but the relationship is slightly inferior to that of water dispersion.

This indicates that spray drying of acid urease reduces its affinity for sake, and that when it is added to sake without rehydration, its activity expression decreases.

Experimental Example 2 The same acidic urease solution as in Experimental Example 1 was spray-dried. On the other hand, in this acidic urease solution, DE1
8 dextrin 01 or more 22%.

G, +Gt+03= 18%) and DE32 (G, more than 9
%.

c, +G*+c, = 39%)] were dissolved in two times the weight ratio, and then spray-dried. The three types of preparations obtained were each made into sake [commercially available product: ethanol 20% (V/V)]
, 30 ppm 1 of urea (preparation)] was dispersed in water or dispersed in a portion of the test sake, and then added, and the urea decomposition power at 10°C was measured. The results are shown in Table 2.

Table 2 Urea decomposition constant at io℃ [k=-' 1n(C
L/Co).

Ct and Co represent t and urea concentration at day 0, respectively. ] Enzyme addition amount: 200/L As is clear from Table 2, the acid urease powder without dextrin becomes less compatible with sake due to the drying operation, and activity is expressed with or without prior rehydration (water dispersion). A big difference occurs. In acid urease powder dried using DElg dextrin as an excipient, the activity expression is constant regardless of the dispersion method, but when comparing water dispersions, the activity expression is inferior to that of acid urease powder without dextrin. On the other hand; after adding DE32 dextrin, the dried acid urease powder has improved compatibility with sake;
Both the water dispersion and the alcohol dispersion showed a significant increase in activity expression compared to acid urease powder without excipients.

Example 1 A purified acid urease solution 820 a+L (1,850 U/sL) obtained in the same manner as in Experimental Example 1 was divided into two parts, and one part was directly spray-dried. On the other 410@L, Amicol No. 3L (8 made by Deri Kagaku Co., Ltd., DE34.5
．． C,,+G! +0337%, G9 and above 10%) 158
A mixture of 400 aL of liquid was prepared by dissolving 400aL of the liquid in water, and this was spray-dried. The powder without dextrin had s l 3 , OU/ag, and the product containing this dextrin had 3,20/sg.

Add ethanol and urea to commercially available sake to make ethanol 2
To investigate the decomposition of urea at 10°C, we added each of the above acidic urease preparations to a total of 200 l to a model Kamitaru sake adjusted to 0% (V/V) and 30 pp- of urea (see Table 3).
.

Table 3 shows the superiority of dry powder with DE34.5 dextrin, especially before adding the powder to sake.
The effect is remarkable when it is added after being dispersed with sake, and the purpose of the present invention is to improve the decrease in compatibility with sake due to drying by adding a specific dextrin.
This is sufficiently proven in this example.

Example 2 The two types of acid urease preparations prepared in Example 1 were
The powder was mixed with cellulose fine powder (KC Flock W-200, manufactured by Dezumi Kokusaku Pulp Co., Ltd.), and the powder was mixed with 1.3 U/ag.
A formulation was prepared. After suspending 385+ ng of this preparation in water or 25-L of sake, 1 mL of it was added to model Kamitaru sake IL prepared from two types of commercially available sake in the same manner as in Example 1 (Additional amount: 1.3 U/agX 385mg/25mL
X 1 a+L/L=20 Ll/L). Then,
Table 4) to compare the decomposition of urea when stored at 10°C.

As shown in Table 4, the efficacy of the liquor quality preservation agent prepared according to the present invention is maintained without being affected by mixing with fine cellulose powder, which is a type of filtering agent.

Next, the effect of the fine cellulose powder used in this example is to improve the dispersibility when dispersing the acid urease preparation in sake.

In other words, when the acid urease preparation prepared using dextrin with a DE of 34.5 by the method described above is suspended in lh sake, a "mamako" phenomenon may be observed, and it takes a certain amount of time for uniform suspension. In short, if a fine cellulose powder is mixed with this, a uniform suspension can be instantaneously achieved, which is more advantageous in terms of work (Table 5).

Table 5 Example 3 for cellulose fine powder mixed preparation/liquor dispersion Using 500 mL each of the acid urease purified liquid used as the raw material in Example 1, add DE24 dextrin (G, 5% or more, G1 + (g + 03 =39%.

Amifur No, IB), DE16 dextrin (G
, more than 24%, G, 10 G, +03 = 16%, Amycol No, l) and DC2,4 dextrin (G.

The above is 95% or more, G + + G t + a 3<
Add aqueous solutions of 1% and Pine Index 100) and spray dry.

Dry powders shaped with each dextrin were prepared.

Same as the previous examples (20 tl for model Kamitaru sake)
The urea decomposition power at 1O'c was investigated by adding /L at a time (
Table 6).

7 Stirring time with a magnetic stirrer until a uniform suspension is obtained when 1 g of the above mixed preparation is mixed with 25 mL of sake.

As can be seen from Table 6, the dextrin used in the present invention is effective if it has a DE of 20 or more, and exhibits a function different from that of a mere excipient or filler.

Example 4 Using the acid urease preparation shown in Example 2, it was added to Jotansake at a Japanese sake manufacturing site to examine the effects of the present invention (Table 7).

Jotanzake is 500L, and the amount added is each log (26υL).

The storage temperature was 4°C.

Table 7 Example 5 The acidic urease solution obtained in the same manner as in Experimental Example 2 was spray-dried. On the other hand, in the acid urease solution, DE32 dextrin [G, at least 9%
, G, +c, +c3=39%] and then spray-dried to obtain a preparation. These two preparations were respectively dispersed in old wine [China-made Shaoxing wine, 17-18% ethanol (V/V), 30 ppm urea] and added after dispersing in water or a part of the test old wine. The urea decomposition power was measured. The results are shown in Table 8.

Table 8 Urea decomposition constant at 20°C [k=-' In(CL
/Co)1 in enzyme addition amount + 280/L The product of the present invention decomposed urea much faster than the control product.

As is clear from Table 8, after adding DE32 dextrin, the dried acid urease powder has improved compatibility with old sake compared to acid urease powder without dextrin, and the activity expression has been improved in both water dispersion and old sake dispersion. It is increasing dramatically.

Example 6 An acidic urease solution obtained in the same manner as in Experimental Example 2 was spray-dried. On the other hand, add DE32 dextrin [aSS or more 9 by weight] to the acid urease solution twice the solid content of the acid urease solution.
After dissolving G+ + c t 10 G a =39 G+, the mixture was spray-dried to obtain a preparation. These two formulations were added to white wine [commercial product, ethanol less than 14% (V/V), urea 30 ppm prepared in a water dispersion or a portion of the test wine and then added to the urea solution at 10°C. The decomposition power was measured. The results are shown in Table 9.

Table 9 Urea decomposition constant at 1°C [k--↓1・(CL/C
o)] Enzyme addition amount: 100 u/L As is clear from Table 9, after adding DE32 dextrin, the dried acid urease powder had a higher dispersion rate in both water and wine dispersion than the acid urease powder without dextrin. The activity expression has increased significantly.

Effects of the Invention When the alcoholic beverage quality preservation agent of the present invention is used to decompose and remove urea from alcoholic beverages, it has good dispersibility in the target alcoholic beverage and does not require strong mechanical affinity promoting operation or pre-watering. There is no need to go through the trouble of adding it back. That is, this preparation can sufficiently exhibit its urea-decomposing power by adding it directly to the target alcoholic beverage or by adding it after dispersing a portion of the target alcoholic beverage. Therefore, the present formulation offers great convenience in use in alcohol production sites compared to conventional acid urease formulations.

Claims (1)

[Scope of Claims] 1) An alcoholic beverage quality preservation agent obtained by drying an aqueous liquid containing acid urease and dextrin having a dextrose equivalent of 20 or more. 2) The liquor quality preservation agent according to claim 1, wherein the dextrin contains about 15% by weight or less of dextrin having 9 or more glucose residues. 3) Claims 1) and 2 further comprising a filter aid.
) Alcoholic beverage quality preservation agent. 4) A method for improving the quality of alcoholic beverages, which comprises treating alcoholic beverages with an alcoholic beverage quality preservation agent obtained by drying an aqueous liquid containing acid urease and dextrin having a dextrose equivalent of 20 or more.