JP2017209062A - Method for purifying alcohol-containing liquid and apparatus for purifying alcohol-containing liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and an apparatus for purifying an alcohol-containing liquid having both removal performance of an aldehyde compound in the alcohol-containing liquid and desalination performance.SOLUTION: An apparatus 1 for purifying an alcohol-containing liquid includes an ion exchange system having an anion exchange tower 10 filled with free base-type primary amine and/or secondary amine weakly basic anion exchange resin and a cation exchange tower 12 filled with an H-shaped strongly acidic cation exchange resin, where the alcohol-containing liquid passes through the anion exchange tower 10 and then passes the liquid through the cation cationic tower 12.SELECTED DRAWING: Figure 1

Description

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

  Alcohol-containing liquids, for example, alcohol and water are the main components of alcoholic beverages, but as other ingredients in wine and sake such as sake, sugars derived from raw materials, amino acids, minerals derived from feed water, esters of fermentation products, Organic acids, aldehydes and the like are included. Distilled spirits such as shochu and whiskey contain non-volatile components such as esters, aldehyde compounds, organic acids, and minerals due to splashing, which are volatile substances among fermentation products. In particular, when an aldehyde compound is contained, it causes an unpleasant scent, and salts such as minerals cause a miscellaneous taste.

  For example, Patent Document 1 discloses that an aldehyde in an alcohol-containing liquid is obtained by contacting the alcohol-containing liquid with a primary amine and / or a free base weakly basic anion exchange resin containing a secondary amine as a functional group. A method of removing a compound is 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 is retained in the resin layer as a complex. The compound is removed from the alcohol-containing liquid.

  Further, for example, Patent Document 2 discloses a method in which an alcohol-containing liquid is passed through a mixed resin of the above free base type weakly basic anion exchange resin and an H type weakly acidic cation exchange resin, and the above free base type weakly basic substance. A method is disclosed in which after passing through an anion exchange resin, the solution is passed through an H-type weakly acidic cation exchange resin. When the alcohol-containing liquid is passed through a free base weakly basic anion exchange resin, the pH is inclined to the alkaline side, so that the taste and aroma may be impaired in alcoholic beverages or the like. With the weakly acidic cation exchange resin, it is possible to adjust the pH of the alcohol-containing liquid from a weakly acidic to a neutral range to suppress a change 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 miscellaneous taste than the H-type strongly acidic cation exchange resin, the flavor improving effect is not sufficient.

  Then, an object of this invention is to provide the purification method and refiner | purifier of an alcohol containing liquid which have the desalting performance with the removal performance of the aldehyde compound in an alcohol containing liquid.

  One aspect of this embodiment is the purification of an alcohol-containing liquid in which the alcohol-containing liquid is contacted with a free base primary amine and / or a secondary amine weakly basic anion exchange resin and an H-form strongly acidic cation exchange resin. Is the method.

  In the method for purifying the alcohol-containing liquid, it is preferable that the alcohol-containing liquid is contacted with the weakly basic anion exchange resin and then contacted with the H-type strongly acidic cation exchange resin.

  In the method for purifying the alcohol-containing liquid, it is preferable that the alcohol-containing liquid is brought into contact with an ion exchange resin obtained by mixing the weakly basic anion exchange resin and the H-type strongly acidic cation exchange resin.

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

  One aspect of this embodiment includes an ion exchange system having a primary amine in a free base form and / or a secondary amine weakly basic anion exchange resin and an H-form strongly acidic cation exchange resin, and an alcohol-containing liquid Is an apparatus for purifying an alcohol-containing liquid to be passed through the ion exchange system.

  In the apparatus for purifying an alcohol-containing liquid, the ion exchange system 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 is preferably passed through the anion exchange tower and then through the cation exchange tower.

  In the apparatus for purifying an alcohol-containing liquid, the ion exchange system includes a mixed bed column in which the weakly basic anion exchange resin and the H-type strongly acidic cation exchange resin are mixed and packed, and the alcohol-containing liquid includes: It is preferable to pass through the mixed bed tower.

  In the apparatus for purifying an alcohol-containing liquid, the ion exchange system includes a multi-bed tower having the weakly basic anion exchange resin as an upper layer and the H-type strongly acidic cation exchange resin as a lower layer, and the alcohol-containing liquid is It is preferable that the liquid is passed through the multi-bed tower in a downward flow.

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

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

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

  Embodiments of the present invention will be described below. This 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 apparatus for purifying an alcohol-containing liquid 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 connection pipe 18, and a discharge pipe 20. The supply pipe 16 is connected to the anion exchange tower 10. One end of the connecting pipe 18 is connected to the anion exchange column 10, and the other end is connected to the cation exchange column 12. Further, the discharge pipe 20 is connected to the cation exchange tower 12.

  The anion exchange column 10 is filled with a primary amine in a free base form 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.

  Primary amine compounds and secondary amine compounds are known to nucleophilically add to aldehyde compounds to form imines. Then, in the free base form primary amine and / or secondary amine weak base anion exchange resin, the aldehyde compound is fixed to the resin layer by using the above reaction, and the aldehyde compound is removed from the alcohol-containing liquid. .

  Although it does not specifically limit as a primary amine weakly basic anion exchange resin of a free base form, For example, what has a structural unit represented by following formula (1) is mentioned.

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 form primary amine and secondary amine weakly basic anion exchange resin are not particularly limited, but the matrix represented by the following formula (2) is a styrene polymer, or the matrix is acrylic. The thing which is a polymer of a system is mentioned.

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 form primary amine and / or secondary amine weakly basic anion exchange resin include, for example, Levacit VPOC1065 (trade name), Lebatit A365 (trade name), and Lebatit 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), Relite MG1 (product name), and the like.

  The cation exchange column 12 is filled with H-type strongly acidic cation exchange resin. The H-type strongly acidic cation exchange resin is not particularly limited. For example, Amberlite 200CT (trade name), Amberlite 120B (trade name), Amberlite FPC11 (trade name), Amberlite FPC14 (trade name) manufactured by Dow Chemical Co., Ltd. ), DOWEX 88 (trade name), DOWEX MONOSSPHERE 88 (trade name), Purolite C100 (trade name), C150 (trade name), C160 (trade name), Diaion SK1B (trade name) manufactured by Mitsubishi Chemical Corporation SK112 (product name), PK212 (product name), PK216 (product name), and the like.

  An example of operation | movement of the refinement | purification apparatus 1 of FIG. 1 is demonstrated.

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 column 10 circulates while diffusing in the free base form primary amine and / or secondary amine weak base anion exchange resin. During this time, primary amine or secondary amine is nucleophilically added to the carbonyl group of the aldehyde component in the alcohol-containing liquid, and the hydrogen on the nitrogen of the amine moves to carbonyl oxygen to form a hydroxy group. The imine is formed by leaving the group protonated by an acid catalyst and leaving. Thus, the aldehyde compound is removed from the alcohol-containing liquid. In addition, the anion component in the alcohol-containing liquid is adsorbed as an acid to the weakly basic anion exchange resin, so that 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 tower 10 passes through the connecting pipe 18 and is sent to the cation exchange tower 12. The alcohol-containing liquid sent to the cation exchange column 12 circulates 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. Thus, minerals and the like are removed (desalted) from the alcohol-containing liquid. Further, the H ⁺ concentration in the alcohol-containing liquid is increased, and the pH is inclined toward the acidic side. As described above, the alcohol-containing liquid whose aldehyde compound has been removed, desalted, and whose pH has been adjusted 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. In addition, by bringing the alcohol-containing liquid into contact with the H-type 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 miscellaneous taste. . As a result, an unpleasant scent can be reduced and a purified alcohol-containing liquid having a mellow mouth feel can be obtained.

  Generally, in liquors and the like, if the pH of liquors after purification is higher than the pH of liquors (raw liquor) before refining, miscellaneous tastes such as umami that could not be felt in the original liquor may occur. Even in the purification method of the present embodiment, the pH of liquor after purification may be higher than the pH of liquor (raw liquor) before purification, depending on the performance of each ion exchange resin and the difference in filling amount. However, in the purification method of this embodiment, since salts such as minerals that cause miscellaneous taste are removed, it is possible to suppress the occurrence of mischievous attributed to an increase in pH.

  The alcohol-containing liquid to be purified in this embodiment is not particularly limited, and examples thereof include sake, brewed sake such as beer and wine, distilled spirits such as shochu, whiskey, brandy, white liquor, and industrial alcohol. In these, it is preferable to apply the purification method of this embodiment to distilled liquor. Distilled liquor has a smaller amount of mineral components that cause miscellaneous taste than brewed liquor, but also has fewer components that serve as flavor elements such as amino acids and organic acids. Therefore, distilled liquor has a greater influence of mineral taste than brewed liquor. In particular, when the pH of distilled liquor increases without removing the minerals, there is a tendency for umami to occur and the flavor to be impaired. Therefore, as in this embodiment, by purifying distilled liquor in combination with a weakly basic anion exchange resin and an H-type strongly acidic cation exchange resin with high desalting performance, the removal of aldehyde compounds and desalting are performed. It becomes possible to suppress that the flavor of distilled liquor is impaired by two flavor improvement effects. On the other hand, the combined use of a weakly basic anion exchange resin and an H-type weakly acidic cation exchange resin with low desalting performance hardly eliminates minerals in distilled liquor, so it is considered that a sufficient flavor modification effect cannot be expected. . In addition, although the density | concentration of the mineral in industrial alcohol is about 50 ppm or less as a non volatile matter (evaporation residue) and is still smaller than distilled liquor, according to the purification method of this embodiment, the mineral concentration in industrial alcohol is It is considered that industrial alcohol with fewer impurities can be obtained because it can be removed.

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

  The temperature of the alcohol-containing liquid in the anion exchange tower 10 is not particularly limited, but 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 the contact efficiency between the alcohol-containing liquid and the weakly basic anion exchange resin is improved. The removal efficiency of the aldehyde compound may be increased. Further, when the liquid passing temperature is 40 ° C. or lower, the alcohol component in the alcohol-containing liquid is less likely to evaporate. Moreover, when an aroma component is contained in the alcohol-containing liquid, evaporation and denaturation of the aroma component are difficult to occur by setting the liquid passing temperature to 40 ° C. or lower. Further, 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 liquid passing rate of the alcohol-containing liquid in the anion exchange tower 10 is preferably SV = 0.1-50. If the liquid flow rate is SV = 0.1 or more, the liquid flow rate per hour can be increased. Further, when the liquid flow rate is SV = 50 or less, the contact efficiency between the alcohol-containing liquid and the weakly basic anion exchange resin is improved, and the removal efficiency of the aldehyde compound may be increased. Here, SV is a space velocity represented by L / LR · h ⁻¹ which is a flow rate (L) circulated in one hour with respect to a unit volume (LR) of the ion exchange resin. Further, the flow rate of the alcohol-containing liquid in the cation exchange column 12 is the same as the flow rate of the alcohol-containing liquid in the anion exchange column 10.

  In the present 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. Thereby, adsorption | suction of umami components and sour components, such as an amino acid and organic acid in an alcohol containing liquid, can be decreased, and it becomes possible to leave these components in a refined alcohol containing liquid. The pH of the alcohol-containing liquid is preferably in the range of 8-12, more preferably in the range of 9-10. Although the alkaline aqueous solution added to the alcohol-containing liquid is not particularly limited, for example, a sodium carbonate aqueous solution or a sodium hydroxide aqueous solution can be used. In addition, the pH of the purified alcohol-containing liquid is not particularly limited, and it is preferably adjusted according to the pH of the alcohol-containing liquid to be processed.

  The filling amount of the H-type strongly acidic cation exchange resin and the weakly basic anion exchange resin is adjusted, for example, from the neutral to acidic pH of the purified alcohol-containing liquid. : The weak base 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 an apparatus for purifying an alcohol-containing liquid that is passed through an anion exchange tower 10 after the alcohol-containing liquid is passed through a cation exchange tower 12. Also with the apparatus for purifying an alcohol-containing liquid, desalting of the alcohol-containing liquid and aldehyde compounds are removed. However, since the alcohol-containing liquid that has passed through the H-form strongly acidic cation exchange resin has a pH that is inclined toward 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 trend. Therefore, the apparatus for purifying an alcohol-containing liquid is suitable for purifying industrial alcohol in that impurities in the alcohol-containing liquid can be efficiently removed.

  FIG. 2 is a schematic configuration diagram of an apparatus for purifying an alcohol-containing liquid 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 a discharge pipe 20. The supply pipe 16 and the discharge pipe 20 are connected to the ion exchange tower 22.

  The ion exchange tower 22 is filled with a weakly basic anion exchange resin and an H-type strongly acidic cation exchange resin. The ion exchange tower is a mixed bed tower 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. Such as a packed double-bed tower.

  An example of operation | movement of the refiner | purifier 2 shown in FIG. 2 is demonstrated.

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 solution. When the ion exchange tower 22 is a multi-bed tower, the alcohol-containing liquid supplied to the ion exchange tower 22 flows in a downward flow while diffusing in the upper weakly basic anion exchange resin. During this time, aldehyde compounds 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 to 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 lower H-type strongly acidic cation exchange resin. During this time, the mineral components in the alcohol-containing liquid are adsorbed, and at the same time, H ⁺ is released, and the pH is inclined to the acidic side. Then, the alcohol-containing liquid whose aldehyde compound has been removed, desalted, and pH-adjusted is discharged from the discharge pipe 20 as a purified alcohol-containing liquid.

When the ion exchange tower 22 is a mixed bed tower, 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, the mineral components are adsorbed, and H ⁺ is released. Then, the alcohol-containing liquid whose aldehyde compound has been removed, desalted, and pH-adjusted is discharged from the discharge pipe 20 as a purified alcohol-containing liquid.

  As a modification of the purification apparatus 2 shown in FIG. 2, an alcohol-containing liquid comprising an ion exchange system comprising a multi-bed tower packed with an H-type strongly acidic cation exchange resin as an upper layer and a weakly basic anion exchange resin as a lower layer. Is an apparatus for purifying an alcohol-containing liquid which is passed through the multi-bed tower in a downward flow. Also with the apparatus for purifying an alcohol-containing liquid, desalting of the alcohol-containing liquid and aldehyde compounds are removed. However, since the alcohol-containing liquid whose pH is inclined toward the acidic side comes into contact with the weakly basic anion exchange resin, the removal rate of amino acids and organic acids other than aldehyde compounds tends to increase. Therefore, the apparatus for purifying an alcohol-containing liquid is suitable for purifying industrial alcohol in that impurities in the alcohol-containing liquid can be efficiently removed.

  The processing conditions of the purification apparatus 2 in FIG. 2 are preferably the same as the processing conditions of the purification apparatus 1 shown in FIG. The processing conditions of the purification apparatus shown below are also the same.

  FIG. 3 is a schematic configuration diagram of an apparatus for purifying an alcohol-containing liquid according to another embodiment. 3 includes an ion exchange system having a pretreatment anion exchange tower 24, an anion exchange tower 10, and a cation exchange tower 12, a supply pipe 16, connection pipes 18a and 18b, a discharge pipe 20, It has. The supply pipe 16 is connected to the pretreatment anion exchange tower 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. One end of the connecting pipe 18 b is connected to the anion exchange column 10, and the other end is connected to the cation exchange column 12. Further, the discharge pipe 20 is connected to the cation exchange tower 12.

  The pretreatment anion exchange tower 24 is filled with OH type strong basic anion exchange resin. The OH type strongly basic anion exchange resin is not particularly limited. For example, acrylic type OH type strongly basic anion exchange resins such as Amberlite IRA958 and IRA458 manufactured by Dow Chemical Company, Purolite A860 and A850 manufactured by Purolite, Dow Chemical Company Examples thereof include styrene-based OH-type strongly basic anion exchange resins such as Amberlite IRA900, IRA402, IRA402BL, Purolite A500S manufactured by Purolite, Diaion SA10A manufactured by Mitsubishi Chemical Corporation, and PA308.

  An example of operation | movement of the refiner | purifier 3 shown in FIG. 3 is demonstrated.

The alcohol-containing liquid is sent to the supply pipe 16 and supplied to the pretreatment anion exchange tower 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 time, the anion component in the alcohol-containing liquid is adsorbed, and at the same time, OH ⁻ is released from the OH-type strongly basic anion exchange resin. Thus, the anion component is removed from the alcohol-containing liquid, and the pH is inclined to the alkaline side. The alcohol-containing liquid discharged from the pretreatment anion exchange tower 24 passes through the connecting pipe 18a and is sent to the anion exchange tower 10. The sent alcohol-containing liquid flows while diffusing in the weakly basic anion exchange resin in the anion exchange tower 10, and the aldehyde compound is removed.

The alcohol-containing liquid that has circulated through the anion exchange tower 10 passes through the connecting pipe 18b and is sent to the cation exchange tower 12. The alcohol-containing liquid sent to the cation exchange column 12 circulates while diffusing in the H-type strongly acidic cation exchange resin. During this time, 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 toward the acidic side. The alcohol-containing liquid whose aldehyde has been removed, desalted, and pH adjusted is discharged from the discharge pipe 20 as a purified alcohol-containing liquid.

  As in the purifying apparatus 3 in FIG. 3, the aldehyde compound is easily removed by the weakly basic anion exchange resin by performing the pretreatment for reducing the anion component in the alcohol-containing liquid. As a result, it is considered that a purified alcohol-containing liquid with reduced miscellaneous taste, acidity and the like can be obtained.

  Desirably, the treatment conditions such as the temperature and the water flow rate 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 tower 24, an anion exchange tower 10 and a cation exchange tower 12 is provided, and an alcohol-containing liquid is passed through the pretreatment anion exchange tower 24. After that, an apparatus for purifying an alcohol-containing liquid which is passed through the cation exchange tower 12 and then passed through the anion exchange tower 10 can be mentioned. Also with the apparatus for purifying an alcohol-containing liquid, desalting of the alcohol-containing liquid and aldehyde compounds are removed. In addition, as described above, since the removal rate of amino acids other than aldehyde compounds, organic acids and the like tends to increase, the apparatus for purifying an alcohol-containing liquid can efficiently remove impurities in the alcohol-containing liquid. This is suitable for the purification of industrial alcohol.

  FIG. 4 is a schematic configuration diagram of an apparatus for purifying an alcohol-containing liquid 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 connection pipe 18, and a discharge pipe 20. The supply pipe 16 is connected to the pretreatment anion exchange tower 24. 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 tower 22 is a mixed bed tower 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 multi-bed tower packed as

  An example of the operation of the purification apparatus 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 tower 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 time, the anion component in the alcohol-containing liquid is adsorbed, and at the same time, OH ⁻ is released from the OH-type strongly basic anion exchange resin. Thus, the anion component is removed from the alcohol-containing liquid, and the pH is inclined 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 tower 22 is a multi-bed tower, the alcohol-containing liquid supplied to the ion exchange tower 22 flows in a downward flow while diffusing in the upper weakly basic anion exchange resin. During this time, aldehyde compounds and the like in the alcohol-containing liquid are removed, and the pH is inclined toward the alkaline side. Subsequently, the H-type strongly acidic cation exchange resin is diffused and distributed. During this time, the mineral components in the alcohol-containing liquid are adsorbed, and at the same time, H ⁺ is released, and the pH is inclined to the acidic side. Then, the alcohol-containing liquid whose aldehyde compound has been removed, desalted, and pH-adjusted is discharged from the discharge pipe 20 as a purified alcohol-containing liquid.

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

  As a modification of the purification apparatus 4 shown in FIG. 4, an ion exchange system having a pretreatment anion exchange tower 24, a multi-bed tower packed with an H-type strongly acidic cation exchange resin as an upper layer and a weakly basic anion exchange resin as a lower layer. And an apparatus for purifying an alcohol-containing liquid in which the alcohol-containing liquid passed through the pretreatment anion exchange tower 24 is passed through the multi-bed tower in a downward flow. Also with the apparatus for purifying an alcohol-containing liquid, desalting of the alcohol-containing liquid and aldehyde compounds are removed. In addition, as described above, since the removal rate of amino acids other than aldehyde compounds, organic acids and the like tends to increase, the apparatus for purifying an alcohol-containing liquid can efficiently remove impurities in the alcohol-containing liquid. This is suitable for the purification of industrial alcohol.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail more concretely, this invention is not limited to a following example.

Example 1
As the alcohol-containing liquid, wheat shochu (pH 4.6, conductivity 45.1 μS / cm) containing 30 ppm acetaldehyde was used. As a primary amine in the free base form and / or as a secondary amine weakly basic anion exchange resin, Levacit A365 and Amberlite 200CT as a H-form strongly acidic cation exchange resin were mixed at a volume ratio of 2: 1. The mixture was packed in a glass column having an inner diameter of 10 mm to prepare a mixed bed tower.

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

(Example 2)
As a primary amine in the free base form and / or as a secondary amine weakly basic anion exchange resin, Purolite A830 and Amberlite 200CT as a H-form strongly acidic cation exchange resin were mixed at a volume ratio of 2: 1. The treatment solution 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. About the extract | collected processing liquid, acetaldehyde removal rate, electrical conductivity, pH, and flavor (fragrance, taste) were evaluated. The results are shown in Table 1.

(Example 3)
As a primary amine in the free base form and / or as a secondary amine weakly basic anion exchange resin, Diaion WA20 and Amberlite 200CT as a H-form strongly acidic cation exchange resin 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 a mixed column was prepared by filling a glass column having an inner diameter of 10 mm. About the extract | collected processing liquid, acetaldehyde removal rate, electrical conductivity, pH, and flavor (fragrance, taste) were evaluated. The results are shown in Table 1.

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

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

  In Example 1, the acetaldehyde removal rate was 80%. The flavor of the treatment liquid became a fruity fragrance while maintaining the mild taste of the original sake. On the other hand, although the comparative example 1 showed the acetaldehyde removal rate similar to Example 1, as a flavor of the process liquid, a little bitterness was felt in the aftertaste. This is considered to be because the mineral of the raw liquor was not removed in addition to the pH of Comparative Example 1 being higher than that of the raw liquor.

  The conductivity of the treatment liquid was reduced to 5.0 μS / cm in Example 1, but was reduced only to 21.3 μS / cm in Comparative Example 1. Here, it means that there are few salts, such as a mineral, in a process liquid, so that electrical conductivity is low. Therefore, although the purification method of Example 1 has sufficient desalting performance, it can be said that the purification method of Comparative Example 1 does not have sufficient desalting performance.

  In all of Examples 2 to 4, the aldehyde removal rate was 80% or more. As for the flavor, it became a fruity scent while maintaining the mellow taste of the original sake, or a refreshing taste and a fruity scent. In addition, about Example 2, 4, it was the same pH as the comparative example 1, but the gumminess was not felt in the aftertaste. As described above, when the pH is generally high, the flavor tends to be impaired. However, in the purification methods of the examples, minerals are sufficiently removed from the raw liquor. It is thought that it did not occur. And in the electrical conductivity of a process liquid, in Examples 2-4, the value of 5.5 microsiemens / cm or less is shown, and it can be said that all have sufficient desalting performance.

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

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

  In Comparative Example 2, the acetaldehyde removal rate was 93%. As a flavor, the scent of the original sake, shochu shochu, is maintained, but the aftertaste was felt. This is thought to be because the pH of Comparative Example 2 was higher than that of the raw sake, and minerals were not removed from the raw sake. In Comparative Example 2, the conductivity of the treatment liquid was reduced only to 14.5 μS / cm. Therefore, it can be said that the purification method of Comparative Example 2 does not have sufficient desalting performance.

(Comparative Example 3)
Example 1 except that a free-base primary amine and / or secondary amine weakly basic anion exchange resin was filled with 20 mL of Levacit A365 into a glass column having an inner diameter of 10 mm to prepare a single bed column. The treatment liquid was collected under the same conditions as in. As a result of measuring the conductivity of the treatment liquid, it was 31.6 μS / cm. Since the raw liquor has a conductivity of 45.1 μS / cm, it can be said that the purification method of Comparative Example 3 does not have sufficient desalting performance.

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

  A sample solution having a volume 20 times the volume of the weakly basic anion exchange resin was passed through the mixed bed column at room temperature and water flow rate SV = 10. From the start of liquid flow, 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)
As a primary amine in the free base form and / or as a secondary amine weakly basic anion exchange resin, Purolite A830 and Amberjet 200CT as a H-form strongly acidic cation exchange resin 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 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 ion base amine and / or secondary amine weakly basic anion exchange resin, Diaion WA20, and H-form strongly acidic cation exchange resin, Amberjet 200CT, mixed at a volume ratio of 2: 1 Then, the treatment liquid was collected under the same conditions as in Example 5, except that a mixed 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.

  In Examples 5 to 7, the acetaldehyde removal rate was 89% or more. Thereby, even if it was high concentration alcohol, it turned out that a high acetaldehyde removal rate is shown.

  1-4 purification apparatus, 10 anion exchange tower, 12 cation exchange tower, 16 supply pipe, 18, 18a, 18b connection pipe, 20 discharge pipe, 22 ion exchange tower, 24 pretreatment anion exchange tower.

Claims (9)

  A method for purifying an alcohol-containing liquid, comprising bringing the alcohol-containing liquid into contact with a primary amine in a free base form and / or a secondary amine weakly basic anion exchange resin and an H-form strongly acidic cation exchange resin.   The method for purifying an alcohol-containing liquid according to claim 1, wherein the alcohol-containing liquid is brought into contact with the weakly basic anion exchange resin and then brought into contact with the H-type strongly acidic cation exchange resin.   The method for purifying an alcohol-containing liquid according to claim 1, wherein the alcohol-containing liquid is brought into contact with an ion exchange resin obtained by mixing the weakly basic anion exchange resin and the H-type strongly acidic cation exchange resin.   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.   It has an ion exchange system having a primary amine in a free base form and / or a secondary amine weakly basic anion exchange resin and an H-form strongly acidic cation exchange resin, and an alcohol-containing liquid is passed through the ion exchange system. An apparatus for purifying an alcohol-containing liquid, wherein The ion exchange system 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,
6. The apparatus for purifying an alcohol-containing liquid according to claim 5, wherein the alcohol-containing liquid is passed through the anion exchange tower and then through the cation exchange tower.   The ion exchange system has a mixed bed tower in which the weakly basic anion exchange resin and the H-type strongly acidic cation exchange resin are mixed and packed, and the alcohol-containing liquid is passed through the mixed bed tower. The apparatus for purifying an alcohol-containing liquid according to claim 5.   The ion exchange system has a multi-bed tower in which the weakly basic anion exchange resin is an upper layer and the H-type strongly acidic cation exchange resin is a lower layer, and the alcohol-containing liquid is flown down to the multi-bed tower. The apparatus for purifying an alcohol-containing liquid according to claim 5, wherein the liquid is passed. The apparatus for purifying an alcohol-containing liquid according to any one of claims 5 to 8, wherein the alcohol-containing liquid is distilled liquor.

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