JPS5824114B2 - How to decolorize sake - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for decolorizing sake.

Sake is a beverage that is susceptible to microbial, chemical, or physical changes, and is therefore prone to discoloration during production or storage.

This coloring is not completely unrelated to taste or aroma, but is deeply connected directly or indirectly to the quality of sake.For example, volatile carbonyl compounds increase due to the aminocarbonyl reaction that causes browning of sake, resulting in overripeness of sake. It becomes a smell.

Furthermore, when bottled sake is exposed to light having a wavelength of 280 to 380 mμ, coloring progresses and the sake acquires an unusual odor called sunlight smell.

Coloring thus impairs the value of products, and the development of a method for removing coloration is strongly desired in this industry.

Coloring substances that are generally mixed into sake include (1) flapine pigments (L derived from raw rice and yeast), ferrichrome pigments (colorless deferichromes produced by Aspergillus aspergillus and iron ions) combine to form brown ferrichromes (ferricrysin).

Derived from iron.

L (3) Melanoidin pigments (brown pigments produced by the amino carbonyl reaction that occurs as sake ages), (4) Coloring due to sunlight (flavins and kynurenic acid act as photosensitizers) In addition, amino acids such as tryptophan and tyrosine, deferiferichromes, oxyacids, and manganese are mainly known to be involved in coloring.

Among these colored substances, mesinoidin and flavin can be easily decolored with activated carbon or ion exchange resin, whereas ferriclysin is a stable iron chelate compound and is said to be unable to be removed by normal decolorizing methods.

Furthermore, when activated carbon or ion exchange resin is used, there is a problem in that quality deteriorates as a result of adsorbing not only coloring substances but also other desirable components involved in taste, aroma, etc.

As a result of extensive research under such circumstances, the present inventors have discovered a new method for decolorizing sake coloring substances that can be universally applied to coloring substances and does not affect components such as desirable taste and aroma.

That is, according to the present invention, colored substances in sake can be removed by bringing the sake into contact with a water-insoluble tannin preparation in which a water-insoluble and hydrophilic polymer and a tannin component are bound together by covalent bonds. can.

The sake used in the present invention may be sake obtained at any stage before pasteurization or after long aging.

Further, the water-insoluble tannin preparation that is brought into contact with this sake is a substance in which a water-insoluble and hydrophilic polymer (carrier) and a tannin component are bonded by covalent bonds.

This substance can be produced by covalently bonding a tannin compound selected from tannins, aminoalkylated tannins, carboxyalkylated tannins, and hydroxyalkylated tannins to a water-insoluble and hydrophilic polymer.

The tannin used in the present invention may be pyrogallol tannin or catechol tannin.

Examples of pyrogallol tannins include gallic tannins and pentagram tannins, and examples of catechol tannins include catechol polymers obtained from tea, cacao, and the like.

Further, the tannins do not necessarily have to be purified, and may be impure tannins such as those commercially available as persimmon tannins.

Also, aminoalkylated tannins, carboxyl alkylated tannins, or hydroxyalkylated tannins,
A tannin is reacted with a cyanogen halide (e.g. cyanogen bromide) or an epoxy compound (e.g. epichlorohydrin) to produce a cyanogen halide activated tannin or an epoxy compound activated tannin, which is then reacted with an alkylene diamine (e.g. ethylene diamine). , tetramethylene diamine, hexamethylene diamine, dodecamethylene diamine), aminoalkyl carboxylic acids (e.g. ε-
Preferred examples include those obtained by reacting aminocaproic acid) or aminoalkanols (for example, 2-amine ethanol).

The reaction between tannins and cyanogen halides (e.g. evacuated cyanogen bromide) can be carried out, for example, in a suitable solvent (e.g. water) at a pH of about 8-8.
12. It can be suitably carried out at a temperature of about 15 to 30°C.

The reaction of the thus obtained logogenated cyanogen-activated tannin with alkylene cyamine, aminoalkyl carboxylic acid, aminoalkanol, etc., can be carried out, for example, in a suitable solvent (e.g., water) at a pH of about 8 to 12 and a temperature of about 15 to It can be suitably carried out at 30°C.

On the other hand, the reaction between tannins and epoxy compounds (e.g. epichlorohydrin) is carried out in a suitable solvent (e.g. water) at pH
It can be suitably carried out at a temperature of about 9-14°C and a temperature of about 30-100°C.

The reaction between the epoxy compound-activated tannin thus obtained and alkylene diamine, aminoalkyl carboxylic acid, etc. is preferably carried out in a suitable solvent (e.g., water) at a pH of about 9 to 14 and a temperature of about 30 to 100°C. You can.

On the other hand, the polymer used in the present invention is one selected from the group consisting of hydroxyl group, amine group and carboxyl group.
Examples include water-insoluble and hydrophilic polymers having more than one type of functional group in the molecule.

Here, hydrophilicity means that the polymer has the property of being wetted or swollen in water.

Water-insoluble and hydrophilic polymers having hydroxyl groups in their molecules include, for example, cellulose, agarose, polysaccharides such as cross-linked dextran, or hydroxyalkylated polysaccharides (for example, hydroxypropylated cross-linked dextran).
Examples include polysaccharides into which a spacer having a hydroxyl group is introduced.

Next, water-insoluble and hydrophilic polymers having amino acids in their molecules include, for example, aminoalkylated polysaccharides (
(e.g. aminoethylated cellulose, aminehexylated cellulose, aminehexylated agarose), aminoaralkylated polysaccharides (e.g. aminobenzylated cellulose)
A polysaccharide into which a spacer having an amine group is introduced, such as;
Polyacrylamide; polyacrylamide into which a spacer having an amino group is introduced, such as aminoalkylated polyacrylamide (e.g., aminoethylated polyacrylamide); spacer having an amine group, such as p-aminobenzoylaminoglopylated porous glass Examples include porous glass into which a spacer having an amino group is introduced; fibrous scleroproteins such as wool and silk; fibrous scleroproteins into which a spacer having an amino group is introduced, such as aminoalkylated wool (for example, aminehexylated wool).

Next, water-insoluble and hydrophilic polymers having a carboxyl group in the molecule include, for example, carboxyl-alkylated polysaccharides (e.g., carboxymethylated cellulose, carboxyhexylated agarose, carboxypentylated agarose, carboxyl-methylated Examples include polysaccharides into which a spacer having a carboxyl group is introduced, such as crosslinked dextran), and polyacrylamide into which a spacer having a carboxyl group is introduced, such as carboxyalkylated polyacrylamide (for example, carboxyl methylated polyacrylamide).

In order to produce a water-insoluble tannin preparation by covalently bonding a tannin compound as described above to a water-insoluble and hydrophilic polymer, a known method employed for producing an immobilized enzyme by a covalent bonding method [ For example, Chibata Han, "Immobilized Enzyme", pH ~ 40, published by Kodansha (March 20, 1975)
Japan); Tobatsu Dezaki “Affinity Chromatography”,
p19-32, published by Kodansha (February 1, 1975)], for example, JP-A-55-3970.
It can be produced by the method described in Publication No. 7.

The water-insoluble tannin preparation thus obtained is brought into contact with sake to remove colored substances in the sake, which can be carried out by any of the column method, fluidized bed method, or batch method.

For example, in the case of carrying out the column method, a water-insoluble tannin preparation is packed into a column, washed with about 10 times the amount of water as eluted in the column, and then the sake is passed through the column and the sake that has passed through the column is collected.

Although the flow rate of sake can be arbitrarily selected, it is generally desirable that the space velocity (SV) is 0.1 to 30 (hr).

Further, although the operating temperature can be set arbitrarily, it is generally preferable to carry out the operation at a temperature of 70° C. or lower.

When the fluidized bed method is used, sake can be passed through a fluidized bed in which a water-insoluble tannin preparation washed with water is dispersed in the same manner as described above.

The flow rate of sake is generally a space velocity ('SV) of 0.1~
The treatment time is preferably 100 (hr), and the operation temperature is preferably 70°C or lower.

Furthermore, when carrying out a batch method, it can be carried out by washing the water-insoluble tannin preparation with about 10 volumes of water, and then adding sake and stirring.

The stirring time is preferably about 2 hours, and the shredding operation temperature is preferably 70°C or less, as described above.

Sake processed using Kempo can be collected as follows.

That is, since water-insoluble tannin preparations precipitate within a relatively short period of time, sake can be collected by collecting the supernatant liquid by decantation or by removing water-insoluble tannin preparations by filtration.

In addition, once used water-insoluble tannin preparations can be regenerated and reused regardless of whether they are used in a column method, a fluidized bed method, or a batch method.

Regeneration is achieved by adding dilute acid soluble (e.g. 0.5
This can be easily carried out by contacting with N-hydrochloric acid).

Hereinafter, the present invention will be explained with reference to reference examples and examples.
They do not limit the invention in any way.

Reference example 1 (1) Filter pipe A4 (trade name manufactured by Toyo Kuchushi Co., Ltd.)
12 Sodium hydroxide solution 7 which cooled 25g to 4℃
Soaked in 501rLi for 30 minutes, added 1.51ml of water and
The mixture was stirred at 0°C for 30 minutes.

Add 250m of epichlorohydrin to this and 600C
After stirring for 30 minutes, the activated cellulose was collected by filtration and was optically washed with water.

The obtained epichlorohydrin-activated cellulose was dissolved in hexamethylene diamine solution 11 (hexamethylene diamine 6
．． 25g of the solution was dissolved in water and the pH was adjusted to 11), and the mixture was vigorously stirred at 60°C for 2 hours.

The produced aminehexylcellulose was collected by filtration, thoroughly washed with water, and then added with 0.25N sodium hydroxide solution 1.2
I was stunned at 51.

Add 125ml of epichlorohydrin to this suspension,
After stirring at 60°C for 30 minutes, the solid content was filtered off.
Epichlorohydrin-activated aminohexylcellulose was obtained by photo-cleaning with water.

(2) Five-fold tannin 31.2.9 water 500ml 1VC
Dissolve, 0. After adding 125 mL of IN aqueous sodium carbonate solution, the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution.

Water was added to this solution to make a total volume of 11, and the epichlorohydrin-activated aminehexyl cellulose obtained in (1) above was
00 g (wet weight) was suspended and stirred at 45°C for 2.5 hours.

After the reaction, the solid content was filtered and washed with water and 30% thiacetone water to obtain water-insoluble tannin preparation 1.
93 g (wet weight) was obtained.

This wet sample was further freeze-dried to obtain 36.5.9 as a dry powder.

Glue Example 2 (1) Cellulose Powder C (trade name manufactured by Toyo Kushi Co., Ltd.) 10I was mixed with 25% sodium hydroxide aqueous solution 500T11
1 for 30 minutes at 25°C, and then washed thoroughly with water.

25 g (wet weight) of the obtained alkali-treated cellulose was
．． The mixture was suspended in 200 m/' of 1M aqueous sodium hydrogen carbonate solution and adjusted to pH 11.5.

Cyanogen bromide 2.0.9 was added to the suspension to activate the cellulose.

(During the activation reaction, the pH was always maintained at 11 to 11.5, and the reaction temperature was not to exceed 30°C.

) After about 8 minutes, the activated cellulose was collected by filtration and washed with a previously cooled 0, 1M aqueous sodium bicarbonate solution and water.

The obtained cyanogen bromide-activated callose was dissolved in an aqueous solution (pH 10) containing hexamethylene diamine 57,5I.
The mixture was suspended at 0 m/min and reacted at 25°C for 2 hours.

After the reaction was completed, the solid content was collected by filtration and washed with a 0.1 M aqueous sodium bicarbonate solution and water to obtain aminohexylated cellulose.

(2) Five-fold tannin was dissolved in water at a ratio of 5%, and 500ml of the solution was adjusted to pH 11.5.

Jin's melting. 2.0 g of cyanogen bromide was added to the solution at 20°C, and the mixture was reacted for 8 minutes while maintaining the pH at 11 to 11.5 at the same temperature.

The obtained cyanogen bromide-activated five-fold tannin solution was added to the above (
In addition to the amine hexylated cellulose obtained in 1), at 25°C
The reaction was carried out for 2 hours.

After the reaction, the solid content was collected by filtration and washed with light using a 0.1 M aqueous sodium bicarbonate solution and water to obtain 32.3 g (wet weight) of a water-insoluble tannin preparation.

This wet sample was further freeze-dried to obtain 14.6 g of a dry powder product.

Reference Example 3 Epoxy-activated Sepharose 6B (trade name, manufactured by Pharmacia) 15I was sequentially washed with 500 m/l of water, 5001 rL/l of a 0.5 M aqueous sodium chloride solution, and 500 m/l/l of water.

To this was added a solution of 1 g of five-fold tannin dissolved in 100 m of 0.1M aqueous sodium bicarbonate solution, and after adjusting p and Hlo to 5 with sodium hydroxide, the mixture was heated at 37°C for 2 hours.
The reaction was allowed to take place while shaking for 6 hours.

After the reaction, the solid content was collected by filtration and mixed with water 1/2 and carbonate buffer (p
By sequentially washing with 500 ml of H10) and water 11, the water-insoluble tannin preparation 4o, ii! (wet weight) was obtained.

This wet sample was further freeze-dried to obtain 8 g of a dry powder product.

Example 1 The water-insoluble tannin preparation prepared by the method of Reference Example 1 was tested in 5. ! 9 (wet weight) each was suspended in distilled water, packed into a column, adjusted to 10vt13, and further washed with distilled water.

Sake from brewery A was added to this column at 10°C and 6°C, respectively.
The flow rate was 40 mjl'/hour at 0°C.

The effluent was fractionated at 100m/each, and the color tone of each fraction was 430.
It was determined by measuring the absorbance at nm.

The results are shown in Table 1 below, and it is clear that the method of the present invention is effective in removing colored substances from sake.

Table 1 (Removal of colored substances using water-insoluble tannin preparations) Example 2 5 g (wet weight) of each of the water-insoluble tannin preparations prepared by the method of Reference Example 1 was suspended in distilled water, and packed into a column of 10 m/min. It was further washed with distilled water.

40 d/s of sake from brewery B was added to this column at a temperature of 60°C.
200M of effluent flowing down at a speed of 200g/hour
The color tone of each fraction was determined by measuring the absorbance at 430 Mm.

The results are shown in Table 2 below.

Table 2 (Removal of colored substances using water-insoluble tannin preparation) Example 3 2 g of water-insoluble tannin preparation prepared by the method of Reference Example 2 (
Wet weight) was washed with distilled water, collected and drained.

This was suspended in 200M sake from brewery A heated to 60°C and shaken at the same temperature.

The color tone of the filtrate was determined by measuring the absorbance at 430 Mm.

As a control, decolorizing charcoal for sake 1. ! 9 was suspended in sake 11 similar to that used above, and the absorbance was measured in the same manner using the supernatant liquid that was left to stand at 10° C. for 7 days.

The results are shown in Table 3 below, and it is clear that the method of the present invention can efficiently decolorize in a short time.Example 4 40g of water-insoluble tannin preparation prepared by the method of Reference Example 3
(wet weight) was washed with distilled water, drained and drained.

This was heated to 30°C and stirred for 2 hours.

The absorbance of the solution after filtration was found.

Example 5 Water-insoluble tannin preparation prepared by the method of Reference Example 1; Agent 50
I (wet weight) was suspended in distilled water, packed into a column, and further washed with distilled water at 100 m/bin.

=0.171) was flowed down at 60° C. at a speed of 400 m//hour.

4 after discarding the first 100 ml of flowing liquid, and the decolorization rate was 68%.

Add 1 g of decolorizing charcoal for sake to this sampled liquid 11 and press out 10
After 7 days at ℃, the temperature decreased to 0.034.

Claims (1)

[Claims] 1. Coloring components in sake are removed by bringing the sake into contact with a water-insoluble tannin preparation formed by covalently bonding a water-insoluble and hydrophilic polymer to a tannin component. A method for decolorizing sake. 2. The water-insoluble tannin preparation contains a polymer having in its molecule one or more functional groups selected from the group consisting of hydroxyl group, amine group, and carboxyl group, and tannin, aminoalkylated tannin, carboxyalkylated tannin, and hydroxyalkylated tannin. 2. The decolorizing method according to claim 1, wherein the tannin compound selected from the group consisting of: is a substance bound by a covalent bond. 3. The decolorization method according to claim 1 or 2, wherein the contacting operation is carried out by a column method in which sake is passed through a column filled with a water-insoluble tannin preparation. 4. The decolorization method according to claim 1 or 2, wherein the contacting operation is carried out in a fluidized bed in which sake is passed through a fluidized bed in which a water-insoluble tannin preparation is dispersed. 5. The decolorization method according to claim 1 or 2, wherein the contacting operation is carried out by a batch method in which a water-insoluble tannin preparation is added to and dispersed in sake in a reaction tank.