JPS63116685A - Improving method for quality of distilled liquor - Google Patents

Abstract

PURPOSE:To obtain the titled distilled liquor without containing causative substance for forming curdy precipitates and oily smell precursor substances in a short time at a low cost, by bringing a distilled liquor into contact with an adsorbent of a specific zeolite to remove higher fatty acids (esters). CONSTITUTION:(A) A distilled liquor is continuously brought into contact with (B) one or more of Y-type zeolite, having >=10 ratio (SiO2/Al2O3) and subjected to dealumination treatment and pentasil type zeolite having >=50 ratio (SiO2/Al2 O3) at room temperature by, e.g. fixed be method, to afford the aimed liquor. The used zeolite can be regenerated by bringing into contact with a solvent, e.g. aqueous solution of ethyl alcohol, etc., for reutilization.

Description

DETAILED DESCRIPTION OF THE INVENTION A.3 Objective of the Invention Industrial Application Field This invention relates to a method for improving the quality of distilled spirits.

Conventional technology Alcoholic beverages (shochu, whiskey, brandy, etc.) produced by funeral distillation contain higher fatty acids and their esters, and these components crystallize in cold weather and form flocculent precipitates. Or, it may be oxidized and cause an oily odor, reducing the product value. There are two methods currently available for removing higher fatty acids and their esters: (1) cooling filtration υ1 and (2) activated carbon adsorption method.

The cooling filtration method described in (2) is a method of filtering and removing the esters that crystallize out by cooling, but the equipment costs are high because a refrigerator and a large heat-insulating tank are required. There are disadvantages such as the fact that it takes a long time for the output to completely finish.

■The activated carbon adsorption method involves adding several hundred PPm of activated carbon to -1
- The esters are adsorbed and removed by filtration, but activated carbon lacks selectivity in adsorption, so the quality of liquor (taste, aroma, color)
has a large impact on Furthermore, since the activated carbon is disposable, it is costly.

Problems to be Solved by the Invention The present invention improves the quality of distilled spirits by selectively removing higher fatty acids and their esters while leaving lower fatty acids and their esters, which are flavor components of distilled spirits, remaining. The purpose of the present invention is to provide a method that can be used, has low equipment costs, and low running costs.

Means for Solving the Constituent Problems of the Invention The method for improving the quality of distilled spirits according to the present invention is a method for improving the quality of distilled spirits using one or more zeolites selected from the group consisting of dealuminated Y-type zeolites and pentasil-type zeolites. It is characterized by bringing distilled liquor into contact with an adsorbent consisting of:

The dealuminated Y-type zeolite is S i
It is preferable that the molar ratio of 02/AQ and 203 is 10 or more and 1-.

The pentasil type zeolite is a high silica zeolite represented by ZSM-5, and preferably has a SiO2/A1203 molar ratio of 50 or more.

The adsorbent may be used either by adding a predetermined amount to distilled liquor and treating it batchwise, or by continuously treating it in a fixed bed. The treatment temperature may be room temperature, and heating and cooling are not necessary.

The amount of adsorbent used depends on the amount of higher fatty acids and their esters, but is usually 500 to 11,000 for distilled spirits.
A ratio of about pp is preferable.

In any method, the used zeolite can be regenerated by contacting it with a suitable solvent, such as an aqueous solution of ethyl alcohol, propyl alcohol, butyl alcohol, or amyl alcohol, and can be used for 11f.

However, since the object is food, it is desirable to use an ethyl alcohol aqueous solution, which is harmless and non-toxic. When using an aqueous ethyl alcohol solution for regeneration, the alcohol concentration must be higher than the alcohol concentration of the distilled liquor, preferably 1.
It is desirable that it be higher than 0% because the amount of solvent used can be further reduced. There is no higher limit, but if it exceeds 60%, it is treated as a dangerous substance and is subject to legal restrictions, so it is preferably 60% or less.

The temperature at which spent zeolite is regenerated by contacting it with a solvent may be room temperature, but the regeneration time can be shortened by increasing the temperature. In that case, the heating temperature is 60
℃ or less is preferable from the viewpoint of saving energy consumption.

In addition, when using a fixed bed flow type adsorption tower, it is better to pass the regenerating liquid in the opposite direction to that during the adsorption treatment of distilled liquor.

The physical and chemical properties of higher fatty acids and their esters are as follows: a. Solubility in alcohol is highly temperature dependent.

b. Solubility is highly dependent on alcohol concentration.

It is hydrophobic because it has a long C3 alkyl group.

It has properties such as. Among these, the cooling method utilizes the property a, and the activated carbon adsorption method utilizes the property C. In the case of activated carbon, it adsorbs not only hydrophobic compounds but also compounds with polar groups, which has a very large effect on taste, aroma, and color, and if the wrong liquid is used, it will have a big impact on the quality of the alcoholic beverage. Since the adsorbent of the present invention selectively adsorbs strongly hydrophobic substances, the influence on alcohol quality is small.

It is well known that silica-rich zeolites exhibit hydrophobic properties. However, in relation to the present invention, ferrierite and dealuminated mordenite have no effect even if they have a large amount of silica, whereas dealuminated Y-type zeolite, which does not have much silica, shows high selectivity. It cannot be explained from the surface alone.

Example 1 200cc of shochu (alcohol concentration 43vo1%) obtained by simple distillation of a predetermined amount of Y-type zeolite (Si02/A203 molar ratio 14) dealuminated by high-temperature steam treatment
After stirring at room temperature for 30 minutes [7], the mixture was filtered using 5B filter paper (Toyo Roshi).

The analysis was carried out by the casslometry method, and the selectivity of adsorption was determined from the removal rate of ethyl caprate, which is a lower fatty acid ester, and the removal rate of ethyl valmitate, which is a higher fatty acid ester.

In addition, ethyl caprate Ll in the raw materials 15 p p m
, palmitin m-ethyl was 6 ppm.

The results are shown in Table 1. In the dealuminated Y-type zeolite used in Example 1, ethyl valmitate was selectively adsorbed and removed. In addition, C Il+ which is an oil odor precursor
Ethyl unsaturated fatty acids could also be removed in the same way as ethyl palmitate.

Furthermore, 100 CC of 6 is added to 1 g of zeolite after adsorption treatment.
Add 0vo 1% ethyl alcohol aqueous solution and incubate at room temperature for 3
After stirring for 0 minutes, the mixture was filtered and dried.

After drying, we conducted an adsorption experiment again using zeolite].
There was no change in adsorption performance before and after regeneration.

That is, it has been completely regenerated.

Example 2 S i 02 /A1203MoJl/Ratio 80(7)ZS
An adsorption test was conducted using M'-5 in the same manner as in Example 1. Table 1 shows the results.

ZSI'1l-5 used in Example 2 as shown in Table 1
Ethyl balmitate was selectively adsorbed and removed by zeolite. Ethyl CI11 unsaturated fatty acid, which is an oil odor precursor, could also be removed in the same manner as citilate palmitate.

The used foil absorbing agent was regenerated and reused in the same manner as in Example 1, but the adsorption performance did not change at all before and after regeneration.

Table 1 Comparative Example 1 Commercially available (7) Y-type zeolite (S i 02 /Au2
An adsorption experiment was conducted in the same manner as in Example 1 using 0.03 molar ratio 4.8).

As shown in Table 2, the non-dealuminated Y-type zeolite did not adsorb ethyl balmitate at all even when 11,000 pp was added.

Comparative Example 2 Commercially available (7)% Rudenite (S i 02 /An
20s molar ratio 10) was dealuminated using hydrochloric acid to prepare mordenite with a high 5i02/Au203 ratio,
An adsorption experiment was conducted in the same manner as in Example 1.

Even though 7000 ppm of the filtrate shown in the ft52 table was used, hardly any ethyl valmitate was adsorbed.

Furthermore, even if the S i 02 /Al2O5 molar ratio was increased, the adsorption capacity for ethyl palmitate did not improve much, but rather ethyl caprate was adsorbed.

Comparative Example 3 Ferrierite (S
Even when the i02/Al2O3 molar ratio -17) was used, as shown in Table 2, only a very small amount of ethyl balmitate was adsorbed.

Comparative Example 4 When activated carbon was used from palms with a specific surface area of 900 m2/g and 20 to 50 meshes, as shown in Table 2, not only ethyl valmitate but also ethyl caprate was removed, resulting in poor selectivity. Ta.

(Margins below) Table 2 In addition, when the samples subjected to the adsorption treatment shown in 2 below and the untreated samples were kept at -5°C for an IF period and the turbidity was visually compared, the untreated samples and Comparative Examples 1 to 2 were visually compared. The sample treated with the adsorbent with low adsorption capacity shown in No. 3 developed turbidity, whereas the samples of Example 1.2 and Comparative Example 4 showed no turbidity at all.

C1. Effects of the invention - Only the substances that cause the formation of flocculent precipitates and the precursors of oily odor are selectively adsorbed, so the influence on alcohol quality is small.

■Since adsorption can be performed at room temperature, energy can be saved compared to cold filtration methods.

■Equipment costs are lower than the cooling filtration method.

■If you use a fixed bed type, you won't need to pay for filter paper, which will save you money.

■Processing time is shorter compared to the cooling filtration method. (In the cold filtration method, it must be kept at a low temperature for a long time to completely form crystals.) ■Since the adsorbent can be easily regenerated, the adsorbent can be easily regenerated; 'The cost of i-drugs is low.

Claims (1)

[Scope of Claims] 1. Quality improvement of distilled liquor characterized by bringing distilled liquor into contact with an adsorbent made of one or more zeolites selected from the group consisting of dealuminated Y-type zeolite and pentasil-type zeolite. Law. 2 The dealuminated Y-type zeolite is SiO
The method for improving the quality of distilled spirits according to claim 1, wherein the molar ratio of _2/Al_2O_3 is 10 or more. 3 Pentasil type zeolite is SiO_2/Al_2O
_3 The method for improving the quality of distilled liquor according to claim 1, wherein the molar ratio is 50 or more. 4. The distilled liquor according to claim 1, 2, or 3, wherein the zeolite used as an adsorbent is one obtained by regenerating a used zeolite that has been brought into contact with a distilled liquor and brought into contact with an aqueous solution of ethyl alcohol. quality improvement method.