JP6718309B2 - Method for purifying alcohol-containing liquid and apparatus for purifying alcohol-containing liquid - Google Patents

Description

The present invention relates to a method for purifying an alcohol-containing liquid and a technique for a device for purifying an alcohol-containing liquid.

Alcohol-containing liquid, for example, the main components of alcoholic beverages are alcohol and water, but as other components in brewed liquor such as wine and sake, sugars derived from raw materials, amino acids, minerals derived from charged water, esters of fermentation products, Organic acids, aldehydes, etc. are included. Distilled spirits such as shochu and whiskey contain non-volatile components such as volatile substances such as esters, aldehyde compounds, organic acids and minerals resulting from the inclusion of droplets in the fermentation products. In particular, when an aldehyde compound is contained, it causes an unpleasant scent, and salts such as minerals cause an unpleasant taste.

For example, in Patent Document 1, by contacting an alcohol-containing liquid with a free base form weakly basic anion exchange resin containing a primary amine and/or a secondary amine as a functional group, the aldehyde in the alcohol-containing liquid is Methods of removing compounds are disclosed. According to the method described in Patent Document 1, an aldehyde compound is dehydrated and condensed with a primary or secondary amine functional group of an ion-exchange resin to form a Schiff base, and the compound is retained in the resin layer as a complex. The compound is removed from the alcohol-containing liquid.

Further, for example, in Patent Document 2, a method of passing an alcohol-containing liquid through a mixed resin of the above-mentioned free base form weakly basic anion exchange resin and H form weakly acidic cation exchange resin, the above free base form weakly basic form A method is disclosed in which, after passing through the anion exchange resin, the H type weakly acidic cation exchange resin is passed through. When the alcohol-containing liquid is passed through the free base type weakly basic anion exchange resin, the pH tends to the alkaline side, so that the taste and aroma may be impaired in alcoholic beverages and the like, but according to the method of Patent Document 2, The weakly acidic cation exchange resin makes it possible to adjust the pH of the alcohol-containing liquid from a weakly acidic to a neutral range and suppress changes in flavor.

JP, 2009-118781, A JP, 2009-247284, A

However, since the H-type weakly acidic cation exchange resin has a lower desalting performance for removing salts such as minerals that cause an unpleasant taste than the H-type strongly acidic cation exchange resin, the flavor improving effect is not sufficient.

Therefore, an object of the present invention is to provide a purification method and a purification apparatus for an alcohol-containing liquid that has desalination performance as well as the ability to remove aldehyde compounds in the alcohol-containing liquid.

One aspect of this embodiment is that an alcohol-containing liquid is contacted with a single bed of an OH type strongly basic anion exchange resin, and then a free base type primary amine and/or a secondary amine weakly basic anion exchange resin is used. , And H-type strongly acidic cation exchange resin in contact with the alcohol-containing liquid.

In the method for purifying an alcohol-containing solution, it is preferable that the alcohol-containing solution after contacting with the single bed is contacted with the weakly basic anion exchange resin and then with the H-form strongly acidic cation exchange resin.

In the method for purifying an alcohol-containing liquid, the alcohol-containing liquid after contacting with the single bed may be contacted with an ion exchange resin obtained by mixing the weakly basic anion exchange resin and the H-form strongly acidic cation exchange resin. preferable.

In the method for purifying an alcohol-containing liquid, the alcohol-containing liquid is preferably distilled liquor.

One aspect of the present embodiment is: a first treatment part, which is a single bed of an OH type strongly basic anion exchange resin, a free base type primary amine, and/or a secondary amine weakly basic anion exchange resin, and An ion exchange system comprising: a second treatment section having an H-type strongly acidic cation exchange resin; and an alcohol-containing liquid that is passed through the first treatment section and then through the second treatment section. This is a device for purifying alcohol-containing liquid.

In the apparatus for purifying an alcohol-containing liquid, the second processing section includes an anion exchange column filled with the weakly basic anion exchange resin and a cation exchange column filled with the H-type strongly acidic cation exchange resin. It is preferable that the alcohol-containing liquid, which has been passed through the first processing section, is passed through the anion exchange column and then passed through the cation exchange column.

In the apparatus for purifying an alcohol-containing liquid, the second treatment section has a mixed bed column in which the weakly basic anion exchange resin and the H-form strongly acidic cation exchange resin are mixed and packed, and the first treatment section is provided. It is preferable that the alcohol-containing liquid that has passed through the column is passed through the mixed bed tower.

In the apparatus for purifying an alcohol-containing liquid, the second treatment section has a multi-bed column having the weakly basic anion exchange resin as an upper layer and the H-form strongly acidic cation exchange resin as a lower layer, and the first treatment It is preferable that the alcohol-containing liquid that has passed through the section is passed through the double bed column in a descending flow.

In the alcohol-containing liquid refining apparatus, the alcohol-containing liquid is preferably distilled liquor.

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the refinement|purification method and refinement|purification apparatus of the alcohol containing liquid which have the removal performance of the aldehyde compound in an alcohol containing liquid, and desalination performance.

It is a schematic block diagram of the refiner|purifier of the alcohol containing liquid which concerns on this embodiment. It is a schematic block diagram of the refinement|purification apparatus of the alcohol containing liquid which concerns on other embodiment. It is a schematic block diagram of the refinement|purification apparatus of the alcohol containing liquid which concerns on other embodiment. It is a schematic block diagram of the refinement|purification apparatus of the alcohol containing liquid which concerns on other embodiment.

Embodiments of the present invention will be described below. The present embodiment is an example for carrying out the present invention, and the present invention is not limited to this embodiment.

FIG. 1 is a schematic configuration diagram of an alcohol-containing liquid purification device according to the present embodiment. The purification apparatus 1 shown in FIG. 1 includes an ion exchange system having an anion exchange column 10 and a cation exchange column 12, a supply pipe 16, a connecting pipe 18, and an exhaust pipe 20. The supply pipe 16 is connected to the anion exchange tower 10. Further, one end of the connecting pipe 18 is connected to the anion exchange tower 10, and the other end is connected to the cation exchange tower 12. Further, the discharge pipe 20 is connected to the cation exchange tower 12.

The anion exchange column 10 is filled with a free base type primary amine, and/or a secondary amine weakly basic anion exchange resin (hereinafter sometimes simply referred to as a weakly basic anion exchange resin). The weakly basic anion exchange resin may contain a tertiary amine or the like as long as it contains at least one of a primary amine and a secondary amine.

It is known that primary amine compounds and secondary amine compounds are nucleophilically added to aldehyde compounds to form imines. Then, in the free base form of the primary amine and/or secondary amine weakly basic anion exchange resin, the above reaction is utilized to fix the aldehyde compound on the resin layer and remove the aldehyde compound from the alcohol-containing liquid. ..

The free base type primary amine weakly basic anion exchange resin is not particularly limited, and examples thereof include those having a structural unit represented by the following formula (1).

式中、ａ、ｂ、ｃは重合度を示す１以上の整数である。

In the formula, a, b, and c are integers of 1 or more indicating the degree of polymerization.

The free base type primary amine and secondary amine weakly basic anion exchange resin are not particularly limited, but those represented by the following formula (2) are styrene-based polymers, or the matrix is acrylic. Examples thereof include those that are polymer of the system.

式中、ｎ、ｄ、ｅ、ｆは重合度を示す１以上の整数である。

In the formula, n, d, e, and f are integers of 1 or more indicating the degree of polymerization.

Examples of the free base type primary amine and/or secondary amine weakly basic anion exchange resin include, for example, Levacit VPOC1065 (trade name), Levatit A365 (trade name), Levatit S 5221 (trade name) manufactured by LANXESS. Purolite A109 (trade name), Purolite A830 (trade name), Duolite A365 (trade name) manufactured by Rohm and Haas, DIAION WA20 (trade name), WA21J manufactured by Mitsubishi Chemical Corporation. (Product name), Rewrite MG1 (Product name) and the like.

The cation exchange column 12 is filled with H-type strong acid cation exchange resin. The H-type strongly acidic cation exchange resin is not particularly limited, and examples thereof include Amberlite 200CT (trade name), Amberlite 120B (tradename), Amberlite FPC11 (tradename), and Amberlite FPC14 (tradename) manufactured by Dow Chemical Company. ), DOWEX88 (trade name), DOWEX MONOSPHERE88 (trade name), Purolite Co., Ltd. Purolite C100 (trade name), C150 (trade name), C160 (trade name), Mitsubishi Chemical Corporation Diaion SK1B (trade name) , SK112 (product name), PK212 (product name), PK216 (product name), and the like.

An example of the operation of the refining device 1 in FIG. 1 will be described.

The alcohol-containing liquid is sent to the supply pipe 16 and supplied to the anion exchange tower 10. The alcohol-containing liquid supplied to the anion exchange tower 10 flows while diffusing in the free base form of the primary amine and/or secondary amine weakly basic anion exchange resin. During this period, the primary amine or secondary amine undergoes nucleophilic addition to the carbonyl group of the aldehyde component in the alcohol-containing liquid, and hydrogen on the nitrogen of the amine moves to carbonyl oxygen to form a hydroxy group. An imine is formed when the group is protonated by an acid catalyst and eliminated. Thus, the aldehyde compound is removed from the alcohol-containing liquid. Further, the weakly basic anion exchange resin adsorbs the anion component in the alcohol-containing liquid as an acid, whereby the OH ⁻ concentration of the alcohol-containing liquid is increased and the pH is inclined toward the alkaline side.

The alcohol-containing liquid that has flowed through the anion exchange column 10 is sent to the cation exchange column 12 through the connecting pipe 18. The alcohol-containing liquid sent to the cation exchange tower 12 flows while diffusing in the H-type strongly acidic cation exchange resin. During this time, salts such as minerals such as Ca ²⁺ , Mg ²⁺ and Na ⁺ in the alcohol-containing liquid are adsorbed, and at the same time, H ⁺ is released from the H-type strongly acidic cation exchange resin. In this way, minerals and the like are removed (desalted) from the alcohol-containing liquid. Further, the H ⁺ concentration in the alcohol-containing liquid increases, and the pH tends to the acidic side. In this way, the alcohol-containing liquid from which the aldehyde compound has been removed, desalted, and adjusted in pH is discharged from the discharge pipe 20 as a purified alcohol-containing liquid.

Thus, according to this embodiment, the aldehyde compound can be removed by bringing the alcohol-containing liquid into contact with the weakly basic anion exchange resin. Further, by bringing the alcohol-containing liquid into contact with the H-form strongly acidic cation exchange resin, it becomes possible to adjust the pH to the acidic side, and it is also possible to remove salts such as minerals that cause a taste of miscellaneous taste. .. As a result, an unpleasant scent can be reduced, and a purified alcohol-containing liquid having a mellow mouthfeel can be obtained.

In general, in the case of alcoholic beverages, when the pH of alcoholic beverages after purification is higher than the pH of alcoholic alcohols before refinement (raw alcoholic beverages), an unpleasant taste such as acridness that is not felt in the original alcoholic beverages may occur. Even in the refining method of the present embodiment, the pH of the liquor after purification may be higher than the pH of the liquor (raw liquor) before refining depending on the performance of each ion exchange resin and the difference in the filling amount. However, in the refining method of the present embodiment, since salts such as minerals that cause the unpleasant taste are removed, it is possible to suppress the occurrence of unpleasant taste caused by the increase in pH.

The alcohol-containing liquid to be refined in the present embodiment is not particularly limited, and examples thereof include brewed sake such as sake, beer and wine, distilled liquor such as shochu, whiskey, brandy and white liquor, industrial alcohols and the like. Among these, it is preferable to apply the refining method of the present embodiment to distilled liquor. Compared to brewed liquor, distilled liquor has a smaller amount of mineral components that cause miscellaneous taste, but also has less components that serve as flavor elements such as amino acids and organic acids. For this reason, distilled liquor has a greater influence of the miscellaneous taste due to minerals than brewed liquor. In particular, when the pH of distilled liquor increases without removing the minerals, acridness tends to occur and the flavor tends to be impaired. Therefore, as in the present embodiment, by using a weakly basic anion exchange resin and an H-form strongly acidic cation exchange resin having high desalting performance in combination to purify distilled spirits, the aldehyde compound is removed and desalted. The two flavor improving effects make it possible to prevent the flavor of distilled liquor from being impaired. On the other hand, when the weakly basic anion exchange resin and the H-form weakly acidic cation exchange resin having low desalting performance are used in combination, the minerals in the distilled liquor are scarcely removed, and thus it is considered that a sufficient flavor-modifying effect cannot be expected. .. The concentration of minerals in industrial alcohol is about 50 ppm or less as non-volatile matter (evaporation residue), which is even lower than that of distilled liquor, but according to the purification method of the present embodiment, the concentration of minerals in industrial alcohol is Since it can be removed, it is considered that industrial alcohol with less impurities can be obtained.

The alcohol concentration of the alcohol-containing liquid is preferably 60% by mass or less. By setting the alcohol concentration to 60 mass% or less, the weakly basic anion exchange resin is in a hydrated state, so that the contact efficiency between the weakly basic anion exchange resin and the aldehyde compound in the alcohol-containing liquid is improved, The efficiency of removing the aldehyde compound may increase.

The temperature of the alcohol-containing liquid in the anion exchange column 10 is not particularly limited, but it is preferably -10 to 40°C. Although it depends on the alcohol concentration, if the liquid passing temperature is -10°C or higher, the freezing of the solution and the increase in viscosity are reduced, so that the contact efficiency between the alcohol-containing liquid and the weakly basic anion exchange resin is improved, The efficiency of removing the aldehyde compound may increase. Further, when the liquid passing temperature is 40° C. or lower, the alcohol component in the alcohol-containing liquid is hard to evaporate. Further, when the alcohol-containing liquid contains a fragrance component, the liquid passing temperature is set to 40° C. or lower to prevent evaporation or denaturation of the fragrance component. The temperature of the alcohol-containing liquid in the cation exchange column 12 is preferably the same as the temperature of the alcohol-containing liquid in the anion exchange column 10.

The passage rate of the alcohol-containing liquid in the anion exchange tower 10 is preferably SV=0.1-50. If the liquid passing rate is SV=0.1 or more, the liquid passing amount per time can be increased. If the liquid passing rate is SV=50 or less, the contact efficiency between the alcohol-containing liquid and the weakly basic anion exchange resin may be improved, and the removal efficiency of the aldehyde compound may be increased. Here, the SV is a space velocity represented by L/LR-h- ¹ , which is a flow rate (L) of flowing per hour for a unit volume (LR) of the ion exchange resin. The liquid-passing speed of the alcohol-containing liquid in the cation exchange column 12 is the same as the liquid-flowing speed of the alcohol-containing liquid in the anion exchange column 10.

In this embodiment, it is preferable to add an alkaline aqueous solution to the alcohol-containing liquid in advance to make the pH alkaline, and then contact the weakly basic anion exchange resin. As a result, it is possible to reduce the adsorption of umami components and sour components such as amino acids and organic acids in the alcohol-containing liquid, and leave these components in the purified alcohol-containing liquid. The pH of the alcohol-containing liquid is preferably in the range of 8-12, more preferably 9-10. The alkaline aqueous solution added to the alcohol-containing solution is not particularly limited, but for example, an aqueous sodium carbonate solution or an aqueous sodium hydroxide solution can be used. The pH of the purified alcohol-containing liquid is not particularly limited, and it is preferable to adjust it according to the pH of the alcohol-containing liquid to be treated.

The filling amount of the H-type strongly acidic cation exchange resin and the weakly basic anion exchange resin is, for example, in order to adjust the pH of the purified alcohol-containing liquid from neutral to acidic. : The weakly basic anion exchange resin is preferably in the range of 1.5:0.5 to 0.5:1.5, more preferably in the range of 1.2:1 to 1:1.

As a modification of the purification apparatus 1 shown in FIG. 1, there is a purification apparatus for an alcohol-containing liquid that is passed through the anion exchange column 10 after the alcohol-containing liquid is passed through the cation exchange column 12. The alcohol-containing liquid purifying device also removes the salt-containing liquid and the aldehyde compound. However, since the pH of the alcohol-containing liquid that has passed through the H-form strongly acidic cation exchange resin is inclined to the acidic side, the removal rate of amino acids other than aldehyde compounds, organic acids and the like increases in the latter weakly basic anion exchange resin. It becomes a tendency. Therefore, the alcohol-containing liquid refining apparatus is suitable for refining industrial alcohols in that it can efficiently remove impurities in the alcohol-containing liquid.

FIG. 2 is a schematic configuration diagram of an alcohol-containing liquid purification device according to another embodiment. The purification apparatus 2 shown in FIG. 2 includes an ion exchange system including an ion exchange tower 22, a supply pipe 16 and an exhaust pipe 20. The supply pipe 16 and the discharge pipe 20 are connected to the ion exchange tower 22.

The ion exchange column 22 is filled with a weakly basic anion exchange resin and an H-type strongly acidic cation exchange resin. The ion exchange column may be a mixed bed column in which a weakly basic anion exchange resin and an H-type strongly acidic cation exchange resin are mixed, or a weakly basic anion exchange resin as an upper layer and an H type strongly acidic cation exchange resin as a lower layer. For example, a packed double bed tower.

An example of the operation of the refining device 2 shown in FIG. 2 will be described.

The alcohol-containing liquid is sent to the supply pipe 16 and supplied to the ion exchange tower 22. At this time, the pH may be adjusted by adding an alkaline aqueous solution to the alcohol-containing liquid. When the ion exchange column 22 is a double bed column, the alcohol-containing liquid supplied to the ion exchange column 22 flows in a downward flow while diffusing in the weakly basic anion exchange resin in the upper layer. During this period, the aldehyde compound and the like in the alcohol-containing liquid are mainly removed. Further, the anion component in the alcohol-containing liquid is adsorbed as an acid on the weakly basic anion exchange resin, so that the OH ⁻ concentration in the alcohol-containing liquid is increased and the pH is inclined toward the alkaline side. Next, the alcohol-containing liquid flows while diffusing in the H-type strongly acidic cation exchange resin in the lower layer. During this period, at the same time that the mineral components in the alcohol-containing liquid are adsorbed, H ⁺ is released and the pH is inclined to the acidic side. Then, the alcohol-containing liquid from which the aldehyde compound has been removed, desalted, and adjusted in pH is discharged from the discharge pipe 20 as a purified alcohol-containing liquid.

When the ion exchange column 22 is a mixed bed column, the alcohol-containing liquid comes into contact with the weakly basic anion exchange resin to remove the aldehyde compound and the anion component, while increasing the OH ⁻ concentration of the alcohol-containing liquid. The alcohol-containing liquid comes into contact with the H-type strongly acidic cation exchange resin to adsorb the mineral components and release H ⁺ . Then, the alcohol-containing liquid from which the aldehyde compound has been removed, desalted, and adjusted in pH is discharged from the discharge pipe 20 as a purified alcohol-containing liquid.

As a modified example of the purifying apparatus 2 shown in FIG. 2, an H-type strong acid cation exchange resin is provided as an upper layer, and an ion exchange system including a double bed column filled with a weakly basic anion exchange resin as a lower layer is provided, and an alcohol-containing liquid is provided. An apparatus for purifying an alcohol-containing liquid in which is passed through the double bed tower in a descending flow can be mentioned. The alcohol-containing liquid purifying device also removes the salt-containing liquid and the aldehyde compound. However, since the alcohol-containing liquid whose pH is inclined to the acidic side comes into contact with the weakly basic anion exchange resin, the removal rate of amino acids other than aldehyde compounds and organic acids tends to increase. Therefore, the alcohol-containing liquid refining apparatus is suitable for refining industrial alcohols in that it can efficiently remove impurities in the alcohol-containing liquid.

The processing conditions of the refining device 2 in FIG. 2 are preferably the same as the processing conditions of the refining device 1 shown in FIG. The processing conditions of the purifying device shown below are also the same.

FIG. 3 is a schematic configuration diagram of an alcohol-containing liquid purification device according to another embodiment. The purification apparatus 3 shown in FIG. 3 includes an ion exchange system having a pretreatment anion exchange column 24, an anion exchange column 10, and a cation exchange column 12, a supply pipe 16, connecting pipes 18a and 18b, and an exhaust pipe 20. Equipped with. The supply pipe 16 is connected to the pretreatment anion exchange column 24. Further, one end of the connecting pipe 18 a is connected to the pretreatment anion exchange tower 24, and the other end is connected to the anion exchange tower 10. Further, one end of the connecting pipe 18b is connected to the anion exchange tower 10, and the other end is connected to the cation exchange tower 12. Further, the discharge pipe 20 is connected to the cation exchange tower 12.

The pretreatment anion exchange tower 24 is filled with an OH type strongly basic anion exchange resin. The OH type strongly basic anion exchange resin is not particularly limited, but for example, acrylic type OH type strongly basic anion exchange resin such as Amberlite IRA958, IRA458 manufactured by Dow Chemical Co., Purolite A860, A850 manufactured by Purolite Co., Dow Chemical Co. Amberlite IRA900, IRA402, IRA402BL manufactured by Purolite Co., Purolite A500S manufactured by Purolite Co., DIAION SA10A manufactured by Mitsubishi Chemical Co., PA308, and other styrene-based strongly basic anion exchange resins.

An example of the operation of the refining device 3 shown in FIG. 3 will be described.

The alcohol-containing liquid is sent to the supply pipe 16 and supplied to the pretreatment anion exchange column 24. The supplied alcohol-containing liquid flows while diffusing in the OH-type strongly basic anion exchange resin in the pretreatment anion exchange tower 24. During this period, at the same time as the anion component in the alcohol-containing liquid is adsorbed, OH ⁻ is released from the OH type strongly basic anion exchange resin. In this way, the anion component is removed from the alcohol-containing liquid, and the pH tends to the alkaline side. The alcohol-containing liquid discharged from the pretreatment anion exchange tower 24 is sent to the anion exchange tower 10 through the connecting pipe 18a. The fed alcohol-containing liquid flows while diffusing in the weakly basic anion exchange resin in the anion exchange tower 10 to remove the aldehyde compound.

The alcohol-containing liquid flowing through the anion exchange tower 10 is sent to the cation exchange tower 12 through the connecting pipe 18b. The alcohol-containing liquid sent to the cation exchange tower 12 flows while diffusing in the H-type strongly acidic cation exchange resin. During this period, mineral components such as Ca ²⁺ , Mg ²⁺ and Na ⁺ in the alcohol-containing liquid are adsorbed, and at the same time, H ⁺ is released from the H-type strongly acidic cation exchange resin, and the pH is inclined to the acidic side. Then, the alcohol-containing liquid from which the aldehyde has been removed, desalted, and adjusted in pH is discharged from the discharge pipe 20 as a purified alcohol-containing liquid.

By performing the pretreatment for reducing the anion component in the alcohol-containing liquid as in the purifying apparatus 3 in FIG. 3, the weakly basic anion exchange resin facilitates the removal of the aldehyde compound. As a result, it is considered that a purified alcohol-containing liquid with reduced sourness and sourness can be obtained.

It is desirable that the treatment conditions such as the liquid passing temperature and the water passing speed of the alcohol-containing liquid in the pretreatment anion exchange tower 24 are the same as those in the anion exchange tower 10 and the cation exchange tower 12. The same applies to the embodiments described below.

As a modification of the purification apparatus 3 shown in FIG. 3, an ion exchange system having a pretreatment anion exchange column 24, anion exchange column 10 and a cation exchange column 12 is provided, and an alcohol-containing liquid is passed through the pretreatment anion exchange column 24. After that, an apparatus for purifying the alcohol-containing liquid, which is passed through the cation exchange tower 12 and then passed through the anion exchange tower 10, can be mentioned. The alcohol-containing liquid purifying device also removes the salt-containing liquid and the aldehyde compound. Further, as described above, since the removal rate of amino acids and organic acids other than aldehyde compounds tends to increase, the alcohol-containing liquid purification device can efficiently remove impurities in the alcohol-containing liquid. It is suitable for the purification of industrial alcohols because it is possible.

FIG. 4 is a schematic configuration diagram of an alcohol-containing liquid purification device according to another embodiment. The purification apparatus 4 shown in FIG. 4 includes an ion exchange system having a pretreatment anion exchange tower 24 and an ion exchange tower 22, a supply pipe 16, a connecting pipe 18, and an exhaust pipe 20. The supply pipe 16 is connected to the pretreatment anion exchange column 24. Further, one end of the connecting pipe 18 is connected to the pretreatment anion exchange tower 24, and the other end is connected to the ion exchange tower 22. Further, the discharge pipe 20 is connected to the ion exchange tower 22.

The ion exchange column 22 is a mixed bed column in which a weakly basic anion exchange resin and an H-type strongly acidic cation exchange resin are mixed, or a weakly basic anion exchange resin as an upper layer and an H-type strongly acidic cation exchange resin as a lower layer. A double-bed tower, etc.

An example of the operation of the refining device 4 shown in FIG. 4 will be described.

The alcohol-containing liquid is sent to the supply pipe 16 and supplied to the pretreatment anion exchange column 24. The supplied alcohol-containing liquid flows while diffusing in the OH-type strongly basic anion exchange resin in the pretreatment anion exchange tower 24. During this period, at the same time as the anion component in the alcohol-containing liquid is adsorbed, OH ⁻ is released from the OH type strongly basic anion exchange resin. In this way, the anion component is removed from the alcohol-containing liquid, and the pH tends to the alkaline side. The alcohol-containing liquid discharged from the pretreatment anion exchange tower 24 passes through the connecting pipe 18 and is sent to the ion exchange tower 22.

When the ion exchange column 22 is a double bed column, the alcohol-containing liquid supplied to the ion exchange column 22 flows in a downward flow while diffusing in the weakly basic anion exchange resin in the upper layer. During this period, the aldehyde compound and the like in the alcohol-containing liquid are removed, and the pH tends to the alkaline side. Then, the H-form strong acidic cation exchange resin is diffused and distributed. During this period, at the same time as the mineral components in the alcohol-containing liquid are adsorbed, H ⁺ is released and the pH is inclined to the acidic side. Then, the alcohol-containing liquid from which the aldehyde compound has been removed, desalted, and adjusted in pH is discharged from the discharge pipe 20 as a purified alcohol-containing liquid.

When the ion exchange column 22 is a mixed bed column, the alcohol-containing liquid flows while diffusing in the ion exchange resin in the mixed bed column. During this period, aldehyde compounds, mineral components, etc. are removed and the pH is adjusted. Then, the alcohol-containing liquid from which the aldehyde compound has been removed, desalted, and adjusted in pH is discharged from the discharge pipe 20 as a purified alcohol-containing liquid.

As a modification of the purifying apparatus 4 shown in FIG. 4, an ion exchange system having a pretreatment anion exchange column 24, a double bed column in which an H-type strongly acidic cation exchange resin is used as an upper layer and a weakly basic anion exchange resin is used as a lower layer. An apparatus for purifying an alcohol-containing liquid, which is provided and in which the alcohol-containing liquid passed through the pretreatment anion exchange column 24 is passed through the double bed column in a descending flow, may be mentioned. The alcohol-containing liquid purifying device also removes the salt-containing liquid and the aldehyde compound. Further, as described above, since the removal rate of amino acids and organic acids other than aldehyde compounds tends to increase, the alcohol-containing liquid purification device can efficiently remove impurities in the alcohol-containing liquid. It is suitable for the purification of industrial alcohols because it is possible.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

(Example 1)
As the alcohol-containing liquid, barley shochu (pH 4.6, conductivity 45.1 μS/cm) containing 30 ppm of acetaldehyde was used. A free base type primary amine and/or a secondary amine weakly basic anion exchange resin, Levatit A365, and H type strongly acidic cation exchange resin, Amberlite 200CT, were mixed at a volume ratio of 2:1. A mixed bed tower was prepared by filling a glass column having an inner diameter of 10 mm.

At room temperature, water flow rate SV=9, and a volume of 30 times the volume of the weakly basic anion exchange resin, barley shochu was passed through the mixed bed tower. From the start of the passage of the liquid, the treatment liquid of 4 times the volume of the weakly basic anion exchange resin was discarded, and the remaining treatment liquid was collected. The collected treatment liquid was evaluated for acetaldehyde removal rate, conductivity, pH, and flavor (fragrance, taste). The results are shown in Table 1.

(Example 2)
A free base type primary amine and/or a secondary amine weakly basic anion exchange resin, Purolite A830, and H type strongly acidic cation exchange resin, Amberlite 200CT were mixed at a volume ratio of 2:1. The treatment liquid was collected under the same conditions as in Example 1 except that a mixed column was prepared by filling a glass column having an inner diameter of 10 mm. The collected treatment liquid was evaluated for acetaldehyde removal rate, conductivity, pH, and flavor (fragrance, taste). The results are shown in Table 1.

(Example 3)
Free base type primary amine and/or secondary amine Weakly basic anion exchange resin, Diaion WA20, and H type strongly acidic cation exchange resin, Amberlite 200CT are mixed at a volume ratio of 2:1. Then, the treatment liquid was collected under the same conditions as in Example 1 except that the mixed bed column was prepared by packing the glass column having an inner diameter of 10 mm. The collected treatment liquid was evaluated for acetaldehyde removal rate, conductivity, pH, and flavor (fragrance, taste). The results are shown in Table 1.

(Example 4)
Free base primary amine weakly basic anion exchange resin and H type strongly acidic cation exchange resin Amberlite 200CT were mixed at a volume ratio of 2:1 and packed in a glass column having an inner diameter of 10 mm to form a mixed bed. The treatment liquid was collected under the same conditions as in Example 1 except that the tower was prepared. The collected treatment liquid was evaluated for acetaldehyde removal rate, conductivity, pH, and flavor (fragrance, taste). The results are shown in Table 1.

(Comparative Example 1)
Free base form primary amine and/or secondary amine weak basic anion exchange resin, Levatit A365, and H form weak acidic cation exchange resin, Amberlite IRC76-HG at a volume ratio of 2:1. A treatment liquid was collected under the same conditions as in Example 1 except that the mixed column was prepared by mixing and filling a glass column having an inner diameter of 10 mm. The collected treatment liquid was evaluated for acetaldehyde removal rate, conductivity, pH, and flavor (fragrance, taste). The results are shown in Table 1.

In Example 1, the acetaldehyde removal rate was 80%. Regarding the flavor of the treatment liquid, the fruity aroma was obtained while maintaining the mellow taste of the original sake. On the other hand, Comparative Example 1 showed the same acetaldehyde removal rate as that of Example 1, but the treatment liquid had a slightly edgy aftertaste. It is considered that this is because the pH of Comparative Example 1 was higher than the pH of the original sake and the minerals were not removed from the original sake.

The conductivity of the treatment liquid was reduced to 5.0 μS/cm in Example 1, but was reduced to only 21.3 μS/cm in Comparative Example 1. Here, the lower the conductivity, the less the amount of salts such as minerals in the treatment liquid. Therefore, it can be said that the purification method of Example 1 has sufficient desalination performance, but the purification method of Comparative Example 1 does not have sufficient desalination performance.

In each of Examples 2 to 4, the aldehyde removal rate was 80% or more. As for the flavor, the fruity aroma was maintained while maintaining the mellow taste of the original sake, and the taste was refreshing and fruity. In addition, in Examples 2 and 4, the pH was the same as that of Comparative Example 1, but no acclimation was felt in the aftertaste. As described above, generally, when the pH is high, the flavor tends to be impaired, but in the refining method of the example, since the minerals are sufficiently removed from the raw sake, even if the pH is high, the acridness is It is thought that it did not occur. Then, in the conductivity of the treatment liquid, in Examples 2 to 4, a value of 5.5 μS/cm or less is shown, and it can be said that all have sufficient desalination performance.

(Comparative example 2)
As the alcohol-containing liquid, potato shochu (pH 4.7, conductivity 23.0 μS/cm) containing 18 ppm of acetaldehyde was used. As a free base type primary amine and/or secondary amine weakly basic anion exchange resin, 20 mL of Levatit A365 was packed in a glass column having an inner diameter of 10 mm to prepare a single bed column.

Room temperature, water flow rate SV=10, and 20 times the volume of the weakly basic anion exchange resin of potato shochu were passed through the single bed column. From the start of the passage of the liquid, the treatment liquid of 4 times the volume of the weakly basic anion exchange resin was discarded, and the remaining treatment liquid was collected. The collected treatment liquid was evaluated for acetaldehyde removal rate, pH, conductivity, and flavor (fragrance, taste). The results are shown in Table 2.

In Comparative Example 2, the acetaldehyde removal rate was 93%. As for the flavor, it retains the scent of sweet potato shochu, which is the original sake, but it has an aftertaste of acridness. It is considered that this is because the pH of Comparative Example 2 was higher than that of the raw liquor and the minerals were not removed from the raw liquor. In Comparative Example 2, the conductivity of the treatment liquid was reduced to only 14.5 μS/cm. Therefore, it can be said that the purification method of Comparative Example 2 does not have sufficient desalination performance.

(Comparative example 3)
Example 1 except that Levatit A365 was charged as a free base type primary amine and/or secondary amine weakly basic anion exchange resin in a glass column having an inner diameter of 10 mm in an amount of 20 mL to prepare a single bed tower. The treatment liquid was collected under the same conditions as in. The conductivity of the treatment liquid was measured and found to be 31.6 μS/cm. Since the electric conductivity of the sake is 45.1 μS/cm, it can be said that the refining method of Comparative Example 3 does not have sufficient desalination performance.

(Example 5)
A sample solution in which 50 ppm of acetaldehyde was added to a 99.5% ethanol solution was used as the alcohol-containing solution. A free base type primary amine and/or a secondary amine weakly basic anion exchange resin, Levatit A365, and H type strongly acidic cation exchange resin, Amberjet 200CT, were mixed at a volume ratio of 2:1. A mixed bed tower was prepared by filling a glass column having an inner diameter of 10 mm.

At room temperature, water flow rate SV=10, and 20 times the volume of the weakly basic anion exchange resin sample solution was passed through the mixed bed column. From the start of the passage of the liquid, the treatment liquid of 4 times the volume of the weakly basic anion exchange resin was discarded, and the remaining treatment liquid was collected. The acetaldehyde removal rate was measured for the collected treatment liquid. The results are shown in Table 3.

(Example 6)
A free base type primary amine and/or a secondary amine weakly basic anion exchange resin, Purolite A830, and H type strong acid cation exchange resin, Amberjet 200CT, were mixed at a volume ratio of 2:1. The treatment liquid was collected under the same conditions as in Example 5, except that a mixed bed column was prepared by filling a glass column having an inner diameter of 10 mm. The acetaldehyde removal rate was measured for the collected treatment liquid. The results are shown in Table 3.

(Example 7)
Free base type primary amine and/or secondary amine Weakly basic anion exchange resin, Diaion WA20, and H type strongly acidic cation exchange resin, Amberjet 200CT, are mixed at a volume ratio of 2:1. Then, the treatment liquid was collected under the same conditions as in Example 5 except that the mixed bed column was prepared by packing the glass column having an inner diameter of 10 mm. The acetaldehyde removal rate was measured for the collected treatment liquid. The results are shown in Table 3.

In Examples 5 to 7, the acetaldehyde removal rate was 89% or more. From this, it was found that even a high-concentration alcohol shows a high acetaldehyde removal rate.

1 to 4 purification device, 10 anion exchange column, 12 cation exchange column, 16 supply pipe, 18, 18a, 18b connection pipe, 20 discharge pipe, 22 ion exchange column, 24 pretreatment anion exchange column.

Claims (9)

After contacting the alcohol-containing liquid with a single bed of the OH type strongly basic anion exchange resin, a free base type primary amine and/or secondary amine weakly basic anion exchange resin, and H type strongly acidic cation exchange resin A method for purifying an alcohol-containing liquid, which comprises contacting with a resin. The alcohol-containing solution according to claim 1, wherein the alcohol-containing liquid after contacting with the single bed is contacted with the weakly basic anion exchange resin and then with the H-form strongly acidic cation exchange resin. Liquid purification method. The alcohol-containing liquid after contacting with the single bed is contacted with an ion exchange resin obtained by mixing the weakly basic anion exchange resin and the H-form strongly acidic cation exchange resin. Method for purifying alcohol-containing liquid. The method for purifying an alcohol-containing liquid according to any one of claims 1 to 3, wherein the alcohol-containing liquid is distilled liquor. The first treatment section, which is a single bed of the OH type strongly basic anion exchange resin, and the free base type primary amine and/or secondary amine weakly basic anion exchange resin, and the H type strongly acidic cation exchange resin are used. An alcohol-containing liquid, comprising: an ion exchange system including: a second processing unit having; and an alcohol-containing liquid being passed through the second processing unit after the alcohol-containing liquid is passed through the first processing unit. Refining equipment. The second processing section has an anion exchange column filled with the weakly basic anion exchange resin, and a cation exchange column filled with the H-type strongly acidic cation exchange resin,
The alcohol-containing liquid that has passed through the first treatment unit is passed through the anion exchange column and then through the cation exchange column, and the alcohol-containing liquid according to claim 5, wherein Liquid purification equipment. The second treatment section has a mixed bed column in which the weakly basic anion exchange resin and the H-form strongly acidic cation exchange resin are mixed and packed, and contains alcohol after being passed through the first treatment section. The apparatus for purifying an alcohol-containing liquid according to claim 5, wherein the liquid is passed through the mixed bed tower. The second treatment section has a double bed column having the weakly basic anion exchange resin as an upper layer and the H-form strongly acidic cation exchange resin as a lower layer, and the alcohol after being passed through the first treatment section. The apparatus for purifying an alcohol-containing liquid according to claim 5, wherein the contained liquid is passed through the double bed column in a descending flow. The alcohol-containing liquid purifying device according to claim 5, wherein the alcohol-containing liquid is distilled liquor.

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