RU2243992C2 - Method for preparing aqueous-alcoholic solution and alcoholic, pharmaceutical and cosmetic products prepared with its using - Google Patents

Abstract

FIELD: food industry.

SUBSTANCE: method involves the separate protonation of purified drinking water by addition to its 0.05-0.2 wt.-% of proton donors that are stronger than water and ethyl alcohol, by addition to its 0.1-0.5 wt.-% of proton donors that are stronger than ethyl alcohol, additional protonation of water and alcohol. For this purpose water and ethyl alcohol are fed by separate flows into two cylindrical glass or porcelain vessels wherein stirring is carried out for 1-5 min using, respectively, glass or porcelain mixers rotating at the rate 1000-3000 rev/min followed by separate filtration of water and alcohol flows and their mixing. Alcoholic product comprises the solution prepared by the proposed method as an aqueous-alcoholic solution. Pharmaceutical product contains effective dose of curative substance and pharmaceutically acceptable medium wherein product comprises an aqueous-alcoholic solution prepared by indicated method. Cosmetic product contains effective dose of active substance and cosmetically acceptable medium wherein it comprises an aqueous-alcoholic solution. Invention provides enhancing quality of the end product. Invention can be used for manufacturing alcoholic production and in pharmacology and cosmetology.

EFFECT: improved preparing method.

6 cl, 1 tbl, 8 ex

Description

The invention relates to the field of food industry, where it can be used for the production of alcoholic beverages, to pharmacology - for the production of tinctures and extracts or preparations containing hydroalcoholic solutions as pharmaceutically acceptable media, and also cosmetology - for the production of cosmetic products containing hydroalcoholic solutions as cosmetically acceptable environments.

The fundamental processes for the production of water-alcohol solutions and products based on them are the physicochemical processes of adsorption, diffusion and dissolution. The first two of these are widely used in the practice of manufacturing water-alcohol liquids and products from them, which cannot be said about the dissolution process - the mutual dissolution of alcohol and water, dissolution or non-dissolution (precipitation) of impurities present both in the initial water and alcohol, and formed in the process of mixing them; this is especially true of alcohol containing numerous impurities that worsen the taste and smell of alcohol, many of which are highly toxic: among the volatile impurities found more than 70 different compounds - higher alcohols with a burning taste and pungent odor, fusel oil alcohols, including n-propyl, n-butyl, n-amyl, etc., to nonyl and the corresponding iso alcohols, mainly isoamyl and isobutyl alcohols, aldehydes (acetic, formaldehyde, butyric, propionic, isovalerianic, crotonic, f rfurol, etc.), ketones, esters (mainly acetic ethyl), acids (acetic, propionic, butyric, etc.), alcohols (methyl and propyl, are not tasted in small quantities, but, being toxic, when accumulated they cause serious poisoning in the body) and others (“Examination of drinks”, edited by V. Poznyakovsky, Novosibirsk, publ. Novosibirsk University, 1999, p.17, 18).

Problems of improving the mutual dissolution of alcohol and water relate to patents No. 2157832, C 12 G 3/06, publ. in 2000 and No. 2169185, C 12 G 3/06, publ. in 2001, protecting the method of producing vodka.

In accordance with patent No. 2157832, an aqueous-alcoholic solution is prepared by mixing rectified ethyl alcohol with softened drinking water and then purifying it through a coal-cleaning battery and filtering, moreover, alcohol and water are mixed under turbulent conditions when there is countercurrent movement in a pipe-type mixer pipe ”or in a special mixer of alcohol and water flows in a volume ratio of 1: 1.38-1.44; water-alcohol solution is cleaned with activated carbon under the conditions of its pseudo-boiling layer, and filtration is carried out in three stages - first in a hydrocyclone, then through coarse frame flannel filters and, finally, through a fine filter (hydro-compressed layer of quartz sand). The creation of turbulence as a result of the oncoming movement of the jets provides favorable hydrodynamic conditions for the mixing and dissolution of alcohol in water. According to patent No. 2169185, mixing in turbulent conditions does not contain anything new, it is only noted that mixing is carried out in the mixer until the alcohol is completely dissolved in water.

In the descriptions of these patents, it is explained that the use of intensive mixing at a certain ratio of alcohol and water flows makes it possible to obtain a highly stable system. More specific information and characteristics of the resulting products are not available.

In the journal “Beer and Beverages”, 2000, No. 1, pp. 30-32 and No. 2, pages 50, 51, publications related to the production of alcoholic beverages address the issue of heat generation when mixing alcohol with water, which negatively affects the quality of the final product (in this case, additional fusel oils are released in the liquid volume): an aqueous-alcoholic solution is obtained by mixing rectified higher purification alcohol or “Extra” or “Lux” with drinking water (clarified, deodorized and softened) in a small ring device where after Due to the high turbulization of the flow in the annular part, optimal conditions are created for the dissolution of alcohol. The final dissolution of alcohol occurs in the cylindrical part of the apparatus, where the water-alcohol solution enters through the diaphragm from the annular part. The prepared water-alcohol mixture is filtered on sand filters to remove fine particles formed from salts introduced with water when mixed with alcohol, after which it is treated with an adsorbent (for example, activated carbon) to form a taste and aroma due to the adsorption of impurities released from alcohol . When alcohol is mixed with water, heat is generated. The fact of heat generation is explained by many authors the formation of hydrogen bonds in mixed associates - water-alcohol solutions: the occurrence of a hydrogen bond between the hydrogen atom of one molecule and the oxygen atom of another water molecule due to the electrostatic attraction of the proton (the hydrogen atom gives an electron to oxygen) on the electron shell of the oxygen atom another water molecule. Similar phenomena occur between alcohol molecules, because ethanol has an affinity for water and, like water, also refers to associated liquids. The magnitude of the thermal effect of mixing alcohol and water is due to the formation of crystalline hydrates, first mentioned by D. I. Mendeleev (“Solutions”. Collection of works. Edited by Mishchenko KP, Leningrad: Publishing House of the USSR Academy of Sciences, 1959, p. 1163) by mixing them with each other or with an excess of one of the components (water or alcohol). The authors give a calculation of the amounts of alcohol and water introduced into the mixing apparatus to obtain a certain strength, taking into account the compression of the water-alcohol solution (maximum compression in 53.0-56.0% solution, maximum heat generation with a volume fraction of alcohol 36, 25 vol.% (30 wt.%)); however, no techniques can be used to reduce the negative impact of harmful impurities in the starting products and formed during the heating of the water-alcohol mixture on the final properties of the products. Not presented and the qualitative characteristics of the products obtained.

In the same work, it is noted that the intensification of the process of mixing alcohol with water is also achieved by using other versions of mixer devices: the VNIIIPBT cylindrical inkjet structure, injection, first installed at the Poltava Distillery. Due to the small volume of the apparatus and the specificity of the component supply, the basic requirement for the preparation of an aqueous-alcoholic solution is fulfilled - a high degree of dissolution of alcohol in water.

No information is given regarding the details of obtaining the technology of water-alcohol solutions in literature and in patents relating to the pharmaceutical and cosmetic industries. Aqueous alcohol solutions are also widely used there as pharmaceutically or cosmetically acceptable media. So, patent No. 2124353, A 61 K 7/48, publ. in 1994, protects a pharmaceutical composition for the treatment and skin care of topical application, containing in a cosmetically acceptable medium - an aqueous-alcoholic solution, at least one product with a secondary irritant effect; patent No. 2174388, A 61 K 7/46, publ. in 2001, it offers a “Flavoring and refreshing composition”, including mono-succinate in a cosmetically acceptable liquid - an aqueous-alcoholic solution, the use of which is also protected for the preparation of alcoholic beverages without restriction (paragraph 15 of the formula). Water-alcohol solutions are also used as independent drugs (numerous tinctures, extracts, their combinations) (M.Palov, “Encyclopedia of Medicinal Plants”, M .: Publishing House “Mir”, 1988).

Currently, studies are being carried out regarding proton-containing water-alcohol systems: it has been shown that the nature of the acid-base interactions in ROH-H ₂ O-H ⁺ systems, where R = H, C _n H _{2n + 1} or C ₂ H ₄ OH, determines the possibility of the simultaneous presence of a proton in various solvate forms of ROH $\genfrac{}{}{0ex}{}{\text{+}}{\text{2}}$ and H ₃ O ⁺ and their relative concentration; a method for calculating the proton re-solvation constants in mixed solvents, in particular in water-alcohol systems, as a function of temperature and the nature of the solvent, was proposed and expanded, and the dependence of the proton concentration in various solvate forms on the concentration of water, the degree of electrolytic dissociation of Na _p and temperature was obtained (Journal of Physical Chemistry 1998, 72 (5), pp. 841-845); Complicated water structures are studied in aqueous-alcohol mixed solutions, including the water-ethanol system (I. Phys. Org. Chem., 1998, 11 (3), pp. 185-192), etc.

However, the targeted protonation of separately water and alcohol in relation to the production of water-alcohol solutions, as far as we know, has not been previously described.

The closest in technical essence to the solution proposed, adopted as a prototype, is the process of preparing an aqueous-alcoholic solution described in detail above, described in the journal “Beer and Beverages”, 2000, No. 1, p.30-32 and No. 2, p.50 -51.

The technical task of the invention is to develop a method for producing aqueous-alcoholic solutions of improved quality, as well as alcohol-based pharmaceutical and cosmetic products of improved quality, by increasing the dynamics of solutions and eliminating the heating of a mixture of water and alcohol, which to a large extent leads to an increase in the content of toxic products in water-alcohol solutions.

The technical result of the development is to reduce the content of harmful impurities - concentrations of fusel oils, aldehydes and ethers - in aqueous-alcoholic solutions.

The specified technical result is achieved by the fact that in the method for producing an aqueous-alcoholic solution based on purified drinking water and rectified ethyl alcohol, the water is separately protonated by introducing into it 0.05-0.2 wt.% Proton donors stronger than water, and ethyl alcohol by introducing into it 0.1-0.5 wt.% proton donors stronger than ethyl alcohol, additional protonation of water and ethyl alcohol, for which water and ethyl alcohol are sent in separate streams to two cylindrical or porcelain vessels a, in which stirring is carried out for 1-5 minutes using respectively glass or porcelain mixers at a stirrer speed of 1000-3000 rpm, separately filtering the protonated water and alcohol and mixing them.

The technical result in terms of improving the quality of alcoholic, pharmaceutical and cosmetic products is achieved by the use of water-alcohol solutions obtained by the above technology using methods of protonation and additional protonation.

Water is protonated by introducing into it donors of protons stronger than water, in particular inorganic acids, preferably orthophosphoric or carbonic acid, and alcohol is protonated by introducing proton donors stronger than alcohol, in particular organic or inorganic acids, preferably hydrochloric acid, or citric acid, or ascorbic acid, or oxalic acid.

With additional protonation, you can use any mixer - paddle, propeller or anchor types, preferably paddle with one or more blades mounted on the axis of the mixer.

The essence of the processes occurring in a water-alcohol system at the first stage of protonation with the introduction of proton donors is, in the authors' opinion, reduced to the following:

- in the presence of both water and alcohol in the system, a proton transfers from alcohol to water with the formation of a hydroxonium ion H ₃ O ⁺ ,

H ₂ O + C ₂ H ₅ OH → H ₃ O ⁺ + C ₂ H ₅ O ^-

The appearance of hydroxonium in an aqueous-alcoholic solution leads to the orientation of the liquid molecules around it and the formation of a hydrate-solvate shell, which causes loosening and destruction of the initial structure of the aqueous-alcoholic solution. The destroyed initial structure of water and alcohol, forming a hydrate-solvate shell around hydroxonium, enters into a chemical reaction with molecules of alcohol or water, accompanied by heat, forming a complete set of water complexes - H ₃ O ⁺ , H ₅ O $\genfrac{}{}{0ex}{}{\text{+}}{\text{2}}$ , H ₇ O $\genfrac{}{}{0ex}{}{\text{+}}{\text{3}}$ , H ₉ O $\genfrac{}{}{0ex}{}{\text{+}}{\text{4}}$ . These water complexes were first described by the German chemist E. Wicke. This information is given in the book of G. Remy “The course of inorganic chemistry”, v.1, M., 1963, p.100-102;

- when mixing separately protonated water and alcohol due to the presence of an excess of protons in the system, the proton transfer process from alcohol to water is suppressed and heating does not take place;

- in the absence of an excess of protons in the alcohol-water system, the complete mutual solubility of fusel oils and alcohol takes place, and with an excess of protons, systems are formed in which fusel oils are separated from alcohol and can be separated by filtration, for example, using reverse osmosis and Na- cationization.

At the stage of additional protonation, the essence of the processes is reduced to the formation of an additional number of protons as a result of the creation of turbulent fluid motion and the interaction of the solution components, in particular water and alcohol, with silicon dioxide (which is part of the vessel and stirrer material) with the formation of silicic acid H ₂ SiO ₃ , which is a source of protons in a turbulent system: Н ₂ SiO ₃ → Н ⁺ + НSiO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ .

When the stirrer rotates at a speed of less than 1000 rpm, sufficient turbulence is not created to increase the protonation efficiency, and at a speed exceeding 3000 rpm, the protonation efficiency no longer increases, i.e. it does not make sense to further increase the energy intensity of the process.

A similar picture takes place during the mixing process for less than 1 min (insufficient protonation) and more than 5 min (there is no noticeable effect of the activation of protonation).

Separately protonated streams are filtered using reverse osmosis technologies.

Information on examples is summarized in a table, which also shows data on two control examples and the norm according to GOST 5964-93:

examples 1-3 illustrate the method in accordance with the invention,

examples 4-5 are control (example 4 - the process of additional protonation was carried out in a stainless steel vessel; example 5 - a stainless steel vessel and a stirrer made of glass were used).

Examples 1-3 are made using, respectively, citric acid, oxalic acid and hydrochloric acid as a proton donor for alcohol in amounts of from 0.1 to 0.5 wt.% And using carbonic acid or phosphoric acid as a proton donor for water in the amount of 0.05-0.2 wt.%. The indicated amounts of both donors are also preferred. The ratio of alcohol to water is selected so that the strength of the obtained water-alcohol solutions (alcohol concentration in volume%) is from 10 vol.% To 40 vol.%, Which corresponds to drinks from low alcohol to vodka, although the method can be successfully applied as to weaker and stronger drinks.

The methods for all the examples presented are carried out as follows: to alcohol and water, placed in different containers (stainless steel), add with stirring the corresponding proton donors in the quantities necessary to achieve their concentrations indicated in the table. In all cases, 1 kg of a water-alcohol mixture was taken without taking into account the amounts of proton donors. Then, for example 1, the load of alcohol is 333.3 g, water is 666.7 g, and the load of citric acid and carbonic acid are 0.333 g (0.1 wt.%) And 0.333 g (0.05 wt.%), Respectively.

The conditions of additional protonation according to examples 1-3 (material of vessels and mixers, mixing time and rotation speed of the mixers) are presented in the table. Separate filtering of protonated alcohol and water is carried out using the technology of sodium cationization and reverse osmosis, after which the filtered solutions are mixed by pouring water into alcohol.

Tests of solutions were carried out in accordance with GOST 5964-93 according to the main indicators affecting the organoleptic characteristics of water-alcohol solutions: mass concentrations of aldehydes were determined (their reaction with a fuchsin sulphide reagent was based on), fusel oil (the analysis is based on the reaction of higher alcohols with a solution salicylic aldehyde in the presence of sulfuric acid) and esters - reaction products of alcohols and acids (titrimetric determination after saponification with a solution of sodium hydroxide) and volume d A methyl alcohol (by comparing the color of typical solutions with the color of the test solution is formed by the reaction of methanol oxidation by potassium permanganate and sulfuric acid).

As can be seen from the table, the technical result of the proposed method consists in improving the quality of the obtained aqueous-alcoholic solutions (and therefore products using them) by reducing the content of harmful impurities in the solutions - for 40% (vol.) Solution:

- a decrease in the concentration of fusel oil is 40%,

- a decrease in the concentration of esters is 40%,

- reduction in the proportion of aldehydes is 50%.

The proposed method allows to obtain a more structured solutions, which creates a soft taste. In this case, water-alcohol solutions obtained in accordance with the proposed method can be widely used in the alcoholic beverage industry, in the production of low-alcohol products; they can find application in pharmacology in the preparation of preparations in the form of aqueous-alcoholic solutions, tinctures and extracts, as well as in the cosmetic industry as cosmetically acceptable media, since the requirements for aqueous-alcoholic solutions used for the indicated purpose are similar.

Claims (6)

1. A method of obtaining a water-alcohol solution based on purified drinking water and rectified ethyl alcohol, characterized in that the water is separately protonated by introducing 0.05-0.2 wt.% Of proton donors stronger than water and ethyl alcohol into it. the introduction of 0.1-0.5 wt.% donors, protons stronger than ethyl alcohol, additional protonation of water and ethyl alcohol, for which water and ethyl alcohol are sent in separate streams into two cylindrical glass or porcelain vessels, in which stirring for 1-5 minutes using glass or porcelain stirrers at a stirrer speed of 1000-3000 rpm, separate filtering of protonated water and ethyl alcohol, and mixing them. 2. The method according to claim 1, characterized in that inorganic acids selected from the group consisting of phosphoric or carbonic acid are used as proton donors for water. 3. The method according to claim 1, characterized in that organic or inorganic acids selected from the group consisting of hydrochloric acid, citric acid, ascorbic acid or oxalic acid are used as proton donors for ethanol. 4. Alcohol product in the form of a water-alcohol solution, characterized in that it contains a water-alcohol solution obtained by separate protonation of purified drinking water and ethyl alcohol rectified by introducing into the water 0.05-0.2 wt.% Proton donors stronger, than water, and into ethyl alcohol - 0.1-0.5 wt.% proton donors stronger than ethyl alcohol, by additional separate protonation of water and ethyl alcohol by mixing in glass or porcelain cylindrical vessels for 1-5 minutes using respectively glass or porcelain mixers at a stirrer speed of 1000-3000 rpm, followed by their separate filtering and mixing. 5. A pharmaceutical product comprising an effective amount of a therapeutic substance and a pharmaceutically acceptable medium, characterized in that the latter product contains a water-alcohol solution obtained by separate protonation of purified drinking water and rectified ethyl alcohol by adding 0.05-0.2 wt. .% of proton donors stronger than water, and in ethyl alcohol - 0.1-0.5 wt.% of proton donors stronger than ethyl alcohol, and additional separate protonation of water and ethyl alcohol by mixing I a cylindrical glass or porcelain vessels over 1-5 minutes respectively using glass or porcelain stirrers at a speed stirrers 1000-3000 rev / min, followed by filtration and separate them by mixing. 6. A cosmetic product comprising an effective amount of the active substance and a cosmetically acceptable medium, characterized in that the latter product contains a water-alcohol solution obtained by separate protonation of purified drinking water and rectified ethyl alcohol by adding 0.05-0.2 wt. .% of proton donors stronger than water, and in ethyl alcohol - 0.1-0.5 wt.% of proton donors stronger than ethyl alcohol, and additional separate protonation of water and ethyl alcohol by stirring in teklyannyh or porcelain cylindrical vessel for about 1-5 minutes, respectively, using glass or porcelain stirrers at a speed stirrers 1000-3000 rev / min, followed by filtration and separate them by mixing.