JP6566333B2 - Method for producing metal-supported zeolite for liquor, metal-supported zeolite for liquor, and method for producing liquor - Google Patents

Description

  The present invention relates to a method for producing a metal-supported zeolite for liquor that removes unnecessary components contained in liquor, a metal-supported zeolite for liquor, and a method for producing alcohol using a metal-supported zeolite for liquor.

Some alcoholic beverages, such as whiskey, are stored in barrels for a short period of 4-6 years, usually 7-10 years, and in the case of a long period of nearly 20 years, and are aged.
During storage, transpiration and extinction of immature components such as sulfur compounds, reaction of new pot-derived components (oxidation reaction, acetalization reaction, esterification reaction, etc.), decomposition reaction of raw material components of barrel, elution in barrel As a result of the reaction between the raw material-derived components and the raw sake, the state change between ethanol and water constituting the raw sake, a flavor unique to whiskey is extracted.
However, the amount of raw liquor naturally decreases because the raw liquor is absorbed into the barrel or volatilizes through the barrel during storage. For this reason, the prolonged storage period has led to an increase in product loss in terms of manufacturing efficiency.
Therefore, there is a method of positively removing unnecessary components for alcoholic beverages such as unripe components such as sulfur compounds, precipitation components during cold, unpleasant scent components, etc. without waiting for changes that occur naturally by storage. Yes.
As a method for removing unnecessary components from alcoholic beverages, for example, a method of bringing alcoholic beverages into contact with an adsorbent obtained by treating silica with an organic silane compound (see Patent Literature 1), a method of bringing alcoholic beverages into contact with activated carbon (see Patent Literature 2). ), A method using an ion exchange resin (see Patent Document 3), a method using a metal particle and a resin layer (see Patent Document 4), and the like have already been proposed.
In alcoholic beverages, from the viewpoint of selectively removing immature components such as sulfur compounds, it is preferable to use an adsorbent carrying a metal, particularly silver or copper oxide. However, when these adsorbents are used, umami components may be removed.
Further, depending on the preparation method of the adsorbent, aggregation of metal components may occur, and for example, silver may be eluted in liquor at a level that is not edible.
As described above, in the conventional technology described above, there is still room for further improvement in order to provide a product that satisfies a higher quality requirement.

JP-A-63-137668 Japanese Patent Laid-Open No. 03-187374 JP 2004-222567 A JP2012-016321A

  The present invention relates to a method for producing a metal-supported zeolite for liquor that can efficiently remove unnecessary components contained in liquor and reduce elution of silver, a metal-supported zeolite for liquor, and liquor using the metal-supported zeolite for liquor. It is an object to provide a manufacturing method.

The present inventors have found that by passing liquor through a specific metal-supported zeolite, unnecessary components contained in liquor can be removed, and the above problem can be solved.
That is, the gist of the present invention is as follows.
[1] A method for producing a metal-supported zeolite for liquors that removes unnecessary components contained in alcoholic beverages, using an aqueous solution containing ammonium ions, a zeolite containing Y-type zeolite as a main component and carrying metal ions A first ion exchange treatment step for exchanging metal ions and ammonium ions in the solution, and a zeolite carrying ammonium ions obtained by the ion exchange treatment step, using an acidic aqueous solution containing silver ions, A method for producing a metal-supported zeolite for liquor, comprising a second ion exchange treatment step for exchanging silver ions.

[2] The method for producing a metal-supported zeolite for liquor according to [1], wherein the aqueous solution containing ammonium ions is selected from an aqueous ammonium nitrate solution, an aqueous ammonium chloride solution, an aqueous ammonium sulfate solution, an aqueous ammonium phosphate solution, an aqueous ammonium acetate solution, and an aqueous ammonia solution. .
[3] The method for producing a metal-supported zeolite for liquor according to [1] or [2], wherein the acidic aqueous solution containing silver ions is a silver nitrate aqueous solution.
[4] A metal-supported zeolite for liquor that carries silver ions as a metal component and removes unnecessary components contained in alcoholic beverages, comprising Y-type zeolite as a main component, and the visible-ultraviolet of the metal-supported zeolite for alcoholic beverages According to the spectroscopic observation, the height UV1 of the absorption peak observed between 250 and 270 nm and the height UV2 of the absorption peak observed between 210 nm ± 10 nm satisfy (UV1 / UV2) ≦ 0.2. And the supported amount of silver ions is 10% or more and 20% or less in terms of oxide, the supported amount of silver with respect to 1 g of zeolite is 0.15 g or more, and the usage rate of silver is 85% or more. Metal-supported zeolite for liquors.
Here, the usage rate of silver is obtained by the following formula.
Usage rate (%) = {Amount of supported silver / Amount of charged silver (theoretical value)} × 100
[5] The metal-supported zeolite for liquor according to [4], wherein the Y-type zeolite is contained in an amount of 80% by mass or more based on the total mass of the metal-supported zeolite for liquor.
[6] A method for producing an alcoholic beverage, comprising a purification step for purifying the alcoholic beverage, and removing unnecessary components contained in the alcoholic beverage by the metal-supported zeolite for alcoholic beverage according to claim 4 or 5 in the purification step. A method for producing alcoholic beverages, characterized in that:
[7] The method for producing an alcoholic beverage according to [6], wherein the alcoholic beverage is a distilled liquor.
[8] The method for producing an alcoholic beverage according to [6], wherein the alcoholic beverage is a brewed alcoholic beverage.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the metal carrying | support zeolite for liquor which can remove efficiently the unnecessary component contained in liquor and can reduce elution of silver, the metal carrying | support zeolite for liquor, and this metal carrying | support zeolite for liquor are used. It is possible to provide a method for producing liquor.

It is a figure which shows the result of having performed visible ultraviolet spectroscopy measurement to the molded object obtained in the Example, and the molded object obtained in the comparative example.

[Method for producing metal-supported zeolite for liquors]
A method for producing a metal-supported zeolite for liquor according to an embodiment of the present invention is a method for producing a metal-supported zeolite for liquor that removes unnecessary components contained in liquor, using an aqueous solution containing ammonium ions, A first ion exchange treatment step of exchanging a metal ion and an ammonium ion of a zeolite containing a zeolite as a main component and carrying a metal ion; and a zeolite carrying an ammonium ion obtained by the ion exchange treatment step, A second ion exchange treatment step of exchanging ammonium ions and silver ions using an acidic aqueous solution containing silver ions.
In the method for producing a metal-supported zeolite for liquor according to the present embodiment, metal ions are supported inside the zeolite crystals by ion exchange. In the metal-supported zeolite for liquors according to the present embodiment, the metal ion finally supported on the zeolite is a silver (hereinafter sometimes referred to as Ag) ion.

In the first ion exchange treatment step, for example, when ammonium nitrate is used as the ammonium ion, the concentration of the ammonium nitrate aqueous solution is 1% by mass to 50% by mass, preferably 3% by mass to 20% by mass, more preferably 5%. It is 10% by mass or more.
Temperature conditions are 0 degreeC or more and 100 degrees C or less, Preferably they are 20 degreeC or more and 80 degrees C or less, More preferably, they are 40 degreeC or more and 60 degrees C or less. The treatment time is 1 hour or more and 10 hours or less, preferably 2 hours or more and 8 hours or less, more preferably 3 hours or more and 5 hours or less.
By exchanging the metal ions of the zeolite with ammonium ions in the first ion exchange treatment step, the dispersibility of the silver ions to be ion exchanged in the zeolite in the second ion exchange treatment step can be enhanced.

In the second ion exchange treatment step, for example, when silver nitrate is used as the acidic aqueous solution containing silver ions, the concentration of the aqueous silver nitrate solution used is 1% by mass to 50% by mass, preferably 3% by mass to 25% by mass. Hereinafter, it is more preferably 5% by mass or more and 15% by mass or less.
When an aqueous solution containing silver ions is inclined to basicity, a precipitate is usually generated. In order to dissolve silver in the basic aqueous solution, for example, it is necessary to form complex ions with ammonium ions. However, when ions such as ammonium ions are present, competitive ion exchange occurs in the ion exchange treatment step, and the supported amount of silver ions decreases. For this reason, it is preferable that the aqueous solution containing silver ions used for ion exchange is an acidic aqueous solution.
Temperature conditions are 0 degreeC or more and 100 degrees C or less, Preferably they are 20 degreeC or more and 80 degrees C or less, More preferably, they are 40 degreeC or more and 60 degrees C or less.
The time is 1 hour or more and 10 hours or less, preferably 2 hours or more and 8 hours or less, more preferably 3 hours or more and 5 hours or less.

Note that the operations of the first ion exchange treatment step and the second ion exchange treatment step may be repeated a plurality of times. Moreover, metal ions other than ammonium ions may be included in the first ion exchange treatment step, and metal ions other than silver ions may be included in the second ion exchange treatment step.
Further, after the second ion exchange treatment step, the zeolite carrying silver ions may be washed with water or the like and dried at a temperature of about 50 ° C. or more, preferably about 50 ° C. or more and 200 ° C. or less. Further, after drying, it may be further fired for several hours at a temperature of 500 ° C. or lower, preferably 200 ° C. or higher and 500 ° C. or lower.

[Metal-supported zeolite for liquors]
The metal-supported zeolite for liquor obtained by the production method according to the embodiment of the present invention removes unnecessary components contained in liquor. The unnecessary component to be removed is a component that hinders the flavor of alcoholic beverages, and mainly includes a tasteless component. Examples of the tasteless component include sulfur compounds such as dimethyl sulfide, dimethyl disulfide, and dimethyl trisulfide.
The metal-supported zeolite for liquor according to the present embodiment can remove the above-mentioned unnecessary components contained in liquor, while leaving umami components such as higher alcohols, fusels and esters in liquor.
The target alcoholic beverages are not particularly limited, and all alcoholic beverages can be applied. Specifically, all distilled liquors such as whiskey, brandy, gin, vodka, tequila, rum, white liquor, and arak are applicable. In addition, all brewed liquors and mixed liquors such as sake, beer, wine, fortified wine, and Chinese liquor are applicable. Among the brewed liquor and the mixed liquor, sake is preferably used. Furthermore, all shochus such as barley shochu, rice shochu, koji shochu, brown sugar liquor, buckwheat shochu, corn shochu, kojiri shochu, and awamori can be applied.

The metal ion supported on the alcohol-supported zeolite for liquor obtained by the production method according to the present embodiment is silver. The metal-supported zeolite for liquor may contain ions of at least one metal element selected from copper, zinc, nickel, iron, cerium, lanthanum, zirconium and titanium in addition to silver.
The metal-supported zeolite for liquor obtained by the production method according to the present embodiment is obtained by exchanging sodium ions and silver ions using sodium Y-type zeolite as a carrier based on the production method.
When the metal ion is a mononuclear ion, the sodium ion in the zeolite is easily exchanged for the mononuclear ion. For this reason, metal ions are easily supported in the zeolite, and the amount of sodium ions remaining in the zeolite is reduced. Thus, zeolite with a small amount of residual sodium ions has a high sulfur compound adsorption activity.
On the other hand, when the metal ions are cluster ions, they are not easily exchanged with sodium ions in the zeolite. For this reason, metal ions are hardly supported on the zeolite carrier, and the amount of sodium ions remaining in the zeolite increases. That is, when the amount of sodium ions remaining in the zeolite is large, the sulfur compound adsorption activity is low.
When sodium ions in zeolite are exchanged with ammonium ions, the metal ions to be ion-exchanged next are easily exchanged in a mononuclear state. Therefore, the sulfur compound adsorption activity can be increased by exchanging ammonium ions of zeolite that has been subjected to ion exchange treatment with ammonium ions with metal ions.
In addition, for example, an ultra-stabilized zeolite (USY zeolite) having a high Si / Al ratio in the zeolite and a low sodium ion amount in advance, even if the metal ions exist as mononuclear ions, Since the amount of sodium ions that can be exchanged with ions is small, it is considered that the adsorption activity of sulfur compounds is reduced.

From the viewpoint of the adsorption activity of the above-described sulfur compound, in the metal-supported zeolite for alcoholic beverages, sodium ions remaining without being exchanged for metal ions are less than 0.5% by mass in terms of Na ₂ O. Since the amount of sodium ions that can be exchanged with ions is too small, there is little room for metal ions to be exchanged, and sufficient adsorption activity for sulfur compounds cannot be obtained.
In addition, when sodium ion exceeds 7.0% by mass in terms of Na ₂ O, a large amount of sodium ion remains without being exchanged with metal ion in the zeolite, so that the sulfur compound adsorption activity does not sufficiently increase. .
From the above viewpoint, the Na ₂ O content is preferably 0.6% by mass or more and 6.5% by mass or less, and more preferably 0.7% by mass or more and 6.0% by mass or less.

  The supported amount of silver ions in the metal-supported zeolite for liquor according to this embodiment is preferably 10% or more and 20% or less. If it is less than 10%, the required desulfurization activity cannot be obtained. If it exceeds 20%, the elution amount of silver ions increases, which is not suitable.

In the metal-supported zeolite for liquor according to this embodiment, it is preferable that the supported amount of silver with respect to 1 g of zeolite as a carrier is 0.15 g or more and the usage rate of silver is 85% or more.
Here, the usage rate of silver is obtained by the following formula.
Usage rate (%) = {Amount of supported silver / Amount of charged silver (theoretical value)} × 100
If this usage rate is 85% or more, more silver can be supported on the zeolite, so the amount of loss for the introduced silver can be reduced, leading to a reduction in production cost and high desulfurization performance. Is obtained.

In addition, in the metal-supported zeolite for liquor according to the present embodiment, an absorption peak is observed between at least 180 nm and 250 nm by observation by visible ultraviolet spectroscopy (Ultraviolet / Visible Absorption Spectroscopy: UV-VIS).
In the visible ultraviolet spectroscopy, the absorption peak observed between 180 nm and 250 nm is attributed to mononuclear ions of silver (copper, zinc, nickel, iron, cerium, lanthanum, zirconium and titanium in some cases).
In the metal-supported zeolite for liquor according to the present embodiment, the observation of an absorption peak between 180 nm and 250 nm by observation by visible ultraviolet spectroscopy is silver (in some cases, copper, zinc, nickel, iron, cerium). , Lanthanum, zirconium and titanium) and the intensity of the absorption peak is large, there are many mononuclear metal ions, and the amount of metal supported in the zeolite is Many. That is, it means that the absorption capacity of the sulfur compound is high.

When the metal component is silver, an absorption peak is observed at least in the range of 210 nm ± 10 nm in the metal-supported zeolite for liquor according to the present embodiment by observation using visible ultraviolet spectroscopy.
Further, in the metal-supported zeolite for liquor according to the present embodiment, absorption peaks are observed between 210 nm ± 10 nm and 250 to 270 nm by observation by visible ultraviolet spectroscopy, which is the height of these two absorption peaks. It is preferable that UV1 (the height of an absorption peak between 250 to 270 nm) and UV2 (the height of an absorption peak between 210 nm ± 10 nm) satisfy (UV1 / UV2) ≦ 1.0.
In the visible ultraviolet spectroscopy, an absorption peak observed between 210 nm ± 10 nm belongs to mononuclear silver ions. Moreover, the absorption peak observed between 250-270 nm belongs to silver cluster ion.

From this, in the metal-supported zeolite for liquor according to this embodiment, the observation of an absorption peak between 210 nm ± 10 nm by observation by visible ultraviolet spectroscopy means that mononuclear silver ions are included. The high intensity of the absorption peak means that there are many mononuclear metal ions.
In addition, in the metal-supported zeolite for liquor according to the present embodiment, the absorption peak height between 210 nm ± 10 nm and the absorption peak height (intensity) of 250 to 270 nm (intensity) is 210 nm ± 10 nm. (Height) and UV1 (height of absorption peak between 250 to 270 nm) satisfy (UV1 / UV2) ≦ 1.0, that is, mononuclear silver ions rather than silver cluster ions This means that a large amount of is present, and the adsorption ability of the sulfur compound at a low temperature (room temperature) is improved.
From the above viewpoint, (UV1 / UV2) ≦ 0.4 is more preferable, and (UV1 / UV2) ≦ 0.2 is more preferable.

[Zeolite]
The carrier constituting the metal-supported zeolite for liquor according to the present embodiment is mainly a zeolite having 12-membered rings or 10-membered ring pores. Zeolite having pores smaller than this (eight-membered ring pores, etc.) is not suitable because the organic compound that is a tasteless component cannot diffuse through the pores, and thus cannot exhibit removal performance. Zeolite having large pores (such as 14-membered ring pores) is a production method that requires a special structure-directing agent, so that the zeolite itself is very expensive and unsuitable.
Among zeolites having 12-membered rings or 10-membered ring pores, zeolites having a FAU or BEA structure are preferable, and zeolites having a FAU structure are particularly preferable. Zeolite having a FAU structure is classified into X-type zeolite and Y-type zeolite according to the ratio of Si and Al elements.
Among these, those containing 80% by mass or more of Y-type zeolite based on the total mass of the metal-supported zeolite for liquor are preferable.
The composition formula of a zeolite having the FAU structure _is a _{Na n Al n Si 192-n} O 384 · xH 2 O. Among these, if n = 48-76, it will become Y type zeolite, and if n = 77-96, it will become X type zeolite.

The BET specific surface area of the zeolite as the carrier constituting the metal-supported zeolite for liquor according to the present embodiment is preferably 500 m ² / g or more and 900 m ² / g, more preferably 550 m ² / g or more and 850 m ² / g. It is as follows.
Moreover, it is preferable that the micropore volume of a zeolite is 0.05 cc / g or more and 0.40 cc / g or less, More preferably, it is 0.10 cc / g or more and 0.35 cc / g.
Furthermore, the average particle diameter of zeolite is preferably 0.1 mm or more and 5 mm or less, more preferably 0.3 mm or more and 3 mm or less, and further preferably 0.5 mm or more and 2 mm or less.

The metal-supported zeolite for liquor according to the present embodiment may be used after being molded by adding a binder component. The amount of the binder component added is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 30% by mass, based on the total amount of the metal-supported zeolite for liquor. Is desirable.
As a usable binder component, alumina, silica and the like are preferable. From the viewpoint of facilitating molding, clay minerals such as bentonite and vermiculite, and organic additives such as cellulose may be added. The above-mentioned binder component can be added to zeolite, and a metal-supported zeolite for alcoholic beverages can be molded by conventional methods such as extrusion molding, tableting molding, rolling granulation, spray drying and the like.

[Liquor production method]
The method for producing an alcoholic beverage according to an embodiment of the present invention includes a purification step for purifying an alcoholic beverage. In the purification step, by using the above-described metal-supported zeolite for alcoholic beverage, unnecessary components contained in the alcoholic beverage are removed.
The purification conditions using the metal-supported zeolite for liquor are as follows.
If the concentration of the sulfur compound in the raw liquor is 100 ppm by volume or less, it can be desulfurized with the above-mentioned metal-supported zeolite for liquors. The concentration of the sulfur compound is preferably 10 ppm by volume or less.
The temperature range is −50 ° C. or higher and 150 ° C. or lower, more preferably −50 ° C. or higher and 120 ° C. or lower, and further preferably −20 ° C. or higher and 100 ° C. or lower.
When the method of distributing liquor to the alcoholic liquor metal loaded zeolite described above, the flow velocity (LHSV) range is at 0.1 h ^-1 or more 100h ^-1 or less, more preferably 0.5 or more 50h ^{- 1} or less, more preferably 1 or more and 30 h ⁻¹ or less.
According to the said refinement | purification conditions, an unnecessary component can be removed, hold | maintaining umami components, such as higher alcohols, fusels, and esters, in liquor.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples.
[Evaluation method]
The components of the sample liquor described later were evaluated by the following methods.
<Quantification of the amount of silver supported on metal-supported zeolite for liquors>
The amount of silver supported in the metal-supported zeolite for liquor was quantified using an ICP emission spectroscopic analyzer 720-ES manufactured by Agilent Technologies. The silver carrying amount is the silver carrying amount in terms of silver oxide (hereinafter the same). In addition, an alkali melting method was used as a pretreatment for converting the metal-supported zeolite for liquor into an aqueous solution.

<Silver usage rate>
The usage rate of silver was calculated by the following formula using the value of the amount of silver supported in the above-determined metal-supported zeolite for alcohol.
Utilization rate (%) = {Amount of supported silver in oxide in zeolite / Amount of charged silver in terms of oxide (theoretical value)} × 100

<Evaluation of ingredients in liquors>
Sulfur compounds in the sample liquor (dimethyl sulfide (DMS) and dimethyl disulfide (DMDS), GC-SCD apparatus (gas chromatography with chemiluminescence sulfur detector), GC: 6890N / SCD: 355 manufactured by Agilent Technologies, Inc. And analyzed.
The test method for the desulfurization rate was a flow-through method. Using 2.5 liters of test liquor, it was circulated through a 1 cm diameter column in which 18 cm ³ of the test desulfurizing agent was enclosed. Thereafter, the components in the sample liquor were analyzed again. The distribution conditions were LHSV = 20 h ⁻¹ and the analysis was performed by collecting the treatment liquid after 7 hours.
The desulfurization rate (%) was calculated by the following formula.
[(Sulfur compound concentration before introduction-sulfur compound concentration after desulfurization) / Sulfur compound concentration before introduction] × 100

<Measurement of visible ultraviolet spectroscopy>
Using V-650 manufactured by JASCO Corporation, the measurement was performed at a measurement range of 800 to 200 nm by a diffuse reflection method.

<Solubility of silver>
The solubility of silver was measured as follows. First, a sulfuric acid treatment and an ashing treatment were sequentially performed using the aqueous solution after the desulfurization treatment as a pretreatment, and then an alkali melting method was performed to obtain a uniform aqueous solution. The silver contained in this aqueous solution was quantified using an ICP emission spectroscopic analyzer (720-ES manufactured by Agilent Technologies).

[Production example of desulfurization agent]
The desulfurization agent was manufactured by the following manufacture examples 1-5.
<Production Example 1>
A commercially available sodium Y-type zeolite molding (HSZ-320NAD1A manufactured by Tosoh Corporation) was crushed to have an average particle size of 1.0 to 1.5 mm. 264 g of ammonium nitrate was dissolved in 3.3 L of water, 1 kg of the zeolite was added, the liquid was stirred for 3 hours, and ion exchange treatment was performed to obtain NH ₄ Y-type zeolite. After washing with water, 1 kg of NH ₄ Y-type zeolite was added to a silver nitrate aqueous solution in which 394 g of silver nitrate was dissolved in 3 L of water, the liquid was stirred for 3 hours, silver ion exchange was performed, and water washing and drying were further performed. Thereafter, firing was performed at 400 ° C. for 3 hours to obtain AgY-type zeolite 1.

<Production Example 2>
A commercially available sodium Y-type zeolite molding (HSZ-320NAD1A manufactured by Tosoh Corporation) was crushed to have an average particle size of 1.0 to 1.5 mm. 1 kg of this sodium Y-type zeolite was put into a silver nitrate aqueous solution in which 394 g of silver nitrate was dissolved in 3 L of water, the liquid was stirred for 3 hours, silver ion exchange was performed, and further, washing and drying were performed. Thereafter, firing was performed at 400 ° C. for 3 hours to obtain AgY-type zeolite 2.

<Production Example 3>
A commercially available sodium Y-type zeolite molding (HSZ-320NAD1A manufactured by Tosoh Corporation) was crushed to have an average particle size of 1.0 to 1.5 mm. 264 g of ammonium nitrate was dissolved in 3.3 L of water, 1 kg of the zeolite was added, the liquid was stirred for 3 hours, and ion exchange treatment was performed to obtain NH ₄ Y-type zeolite. After washing with water, 1 kg of NH ₄ Y-type zeolite was added to a silver nitrate aqueous solution in which 315.2 g of silver nitrate was dissolved in 3 L of water, the liquid was stirred for 3 hours, silver ion exchange was performed, and further, water washing and drying were performed. Thereafter, firing was performed at 400 ° C. for 3 hours to obtain AgY-type zeolite 3.

<Production Example 4>
A commercially available sodium Y-type zeolite molding (HSZ-320NAD1A manufactured by Tosoh Corporation) was crushed to have an average particle size of 1.0 to 1.5 mm. 264 g of ammonium nitrate was dissolved in 3.3 L of water, 1 kg of the zeolite was added, the liquid was stirred for 3 hours, and ion exchange treatment was performed to obtain NH ₄ Y-type zeolite. After washing with water, 1 kg of NH ₄ Y-type zeolite was added to a silver nitrate aqueous solution in which 157.6 g of silver nitrate was dissolved in 3 L of water, the liquid was stirred for 3 hours, silver ion exchange was performed, and further, water washing and drying were performed. Thereafter, firing was performed at 400 ° C. for 3 hours to obtain AgY-type zeolite 4.

<Production Example 5>
A commercially available NaX-type zeolite molding (Zeoram F-9 manufactured by Tosoh Corporation) was crushed to have an average particle size of 1.0 to 1.5 mm. 528 g of ammonium nitrate was dissolved in 3.3 L of water, 1 kg of the zeolite was added, the liquid was stirred for 3 hours, and ion exchange treatment was performed to obtain NH ₄ X-type zeolite. After washing with water, 1 kg of NH ₄ X-type zeolite was added to a silver nitrate aqueous solution in which 315.2 g of silver nitrate was dissolved in 3 L of water, the liquid was stirred for 3 hours, silver ion exchange was performed, and water washing and drying were further performed. Thereafter, calcination was performed at 400 ° C. for 3 hours to obtain AgX-type zeolite 1.

[Examples and Comparative Examples]
<Example 1>
Whiskey (malt whiskey (alcohol content: 62%)) was passed through AgY-type zeolite 1 obtained in Production Example 1, and the components before and after passing were compared based on the above evaluation test. The whiskey before treatment contained 1.7816 ppm of DMS and 0.4226 ppm of DMDS. The results are shown in Table 1.
<Example 2>
Whiskey (malt whiskey (alcohol content: 62%)) was passed through AgY-type zeolite 3 obtained in Production Example 3, and the components before and after passing were compared based on an evaluation test. The whiskey before treatment contained 1.7816 ppm of DMS and 0.4226 ppm of DMDS. The results are shown in Table 1.
<Comparative Example 1>
Whiskey (malt whiskey (alcohol content: 62%)) was passed through AgY-type zeolite 2 obtained in Production Example 2, and the components before and after passing were compared based on the above evaluation test. The results are shown in Table 1.
<Comparative Example 2>
Whiskey (malt whiskey (alcohol content: 62%)) was passed through AgY-type zeolite 4 obtained in Production Example 4, and the components before and after passing were compared based on the above evaluation methods. The results are shown in Table 1.
<Comparative Example 3>
Whiskey (malt whiskey (alcohol content: 62%)) was passed through AgX-type zeolite 1 obtained in Production Example 5, and the components before and after passing were compared based on the above evaluation methods. The results are shown in Table 1.

In addition, the above-described visible ultraviolet spectroscopic measurement was performed on the molded body obtained in Example 1 and the molded body obtained in Comparative Example 1. The result is shown in FIG.
As shown in FIG. 1, the silver ion-exchanged Y-type zeolite moldings obtained in Example 1 and Example 2 had a peak observed at around 210 nm, but around 270 nm observed in Comparative Example 1. Almost no peak was observed. The peak intensity ratio between the observed peak near 210 nm and the absorption peak near 270 nm was 0.18 to 0.19.
The silver ion exchange Y-type zeolite molding obtained in Comparative Example 1 showed strong absorption peaks at around 210 nm and around 270 nm by visible ultraviolet spectroscopy. The peak intensity ratio between the observed peak near 210 nm and the absorption peak near 270 nm was 0.63.
The X-type zeolite of Comparative Example 3 showed a behavior in which the absorption increased near 280 nm. This is considered to be derived from the X-type zeolite and the binder constituting the carrier supporting silver ions. When X-type zeolite was used, the peak intensity ratio between the observed peak near 210 nm and the absorption peak near 270 nm exceeded 0.2. As a result, the DMS desulfurization rate and the DMDS desulfurization rate were lower than those in Examples 1 and 2.

[Evaluation results]
According to observation by visible ultraviolet spectroscopy, the height UV1 of the absorption peak observed between 250 and 270 nm and the height UV2 of the absorption peak observed between 210 nm ± 10 nm are (UV1 / UV2) ≦ 0. 2, the supported amount of silver ions is 10% or more and 20% or less in terms of oxide, the supported amount of silver with respect to 1 g of zeolite is 0.15 g or more, and the usage rate of silver is 85% or more. It has been found that the zeolite molded body of a certain example can achieve both a high desulfurization rate and a reduction in the elution amount of silver.

Claims (5)

A metal-supported zeolite for shortening the storage period of alcoholic beverages , which is used for producing alcoholic beverages that shorten the storage period by removing unnecessary components contained in alcoholic beverages, with silver ions supported as a metal component,
Y-type zeolite as a main component,
According to observation of the metal-supported zeolite for liquor by visible ultraviolet spectroscopy, the absorption peak height UV1 observed between 250 and 270 nm and the absorption peak height UV2 observed between 210 nm ± 10 nm are ( UV1 / UV2) ≦ 0.2,
A metal-supported zeolite for shortening the storage period of alcoholic beverages, wherein the supported amount of silver ions is 10% by mass or more and 20% by mass or less as an oxide. The Y-type zeolite, alcohol shelf life shortened metal loaded zeolite of claim 1 which contains 80 wt% or more based on the total mass of the storage period shortened metal loaded zeolite of該酒class. A method for producing liquor,
A purification step for purifying the liquor,
Method for producing alcoholic beverages and removing an unnecessary component included in the liquor with liquor storage period shortened metal loaded zeolite of claim 1 or 2 in the purification process. The method for producing an alcoholic beverage according to claim 3 , wherein the alcoholic beverage is a distilled alcoholic beverage. The method for producing an alcoholic beverage according to claim 3 , wherein the alcoholic beverage is a brewed alcoholic beverage.