The method of processing a mixture of ethanol and water

 

(57) Abstract:

The invention concerns a method of processing a mixture of ethanol and water to remove impurities, involving contacting the mixture with several layers of activated carbon, at a temperature of from -45 to -22oC in the first stage and contacting the mixture with several layers of activated carbon at a temperature from -22 to +5oC in the second stage. 8 C.p. f-crystals., table 2.

The invention relates to methods for processing mixtures of ethanol and water to remove impurities. More specifically the invention relates to a water purification technology of ethanol obtained by fermentation of grain, from certain impurities that lower the organoleptic characteristics of produced vodka.

Ethyl alcohol is produced from prehistoric times yeast fermentation of sugars, converting sugar into alcohol and carbon dioxide. Source of sugar are root crops such as potatoes and grains (wheat, corn and the like). In the fermentation process produces not only ethanol, but also other substances, including fusel oil, glycerin and various organic acids. The products of fermentation, provided the RT but also removes a large amount of undesirable impurities. However, the repeated distillation purification to remove unwanted impurities also removes flavor elements in food drinks. Therefore, the distillation process to remove unwanted impurities from food drinks should be completed in such a way as to preserve the desirable flavor elements. Then use other methods to remove unwanted impurities.

The removal of undesirable impurities is particularly important for vodka, which is a pure drink without flavorings, masking the taste of impurities. Vodka high quality is uniform, timeless, colorless mixture with a weak odor of alcohol containing 40-50 % alcohol and 50-60 % of water and has a very distinctive mild taste.

For further purification of vodka initial distillate is passed through a sequence of columns filled with activated carbon. Traditionally, activated carbon produced from hard wood such as beech, maple, oak and pecan. In U.S. patent N 2,946,687 described using a modified and partially activated charcoal from hard wood. Despite the decline in various examples, the precipitate, reducing its marketability. The source of this sediment is used activated carbon containing polyvalent ions of calcium and magnesium. U.S. patent N 3,914,442 solves this problem by processing coal alcohol with polysterene cation exchange resins having a high content of sulfur cross ties, while maintaining the pH of vodka from 7.2 to 9.0.

Closest to the invention, the technical solution is U.S. patent 5,370,891, which describes a method of reducing the content of impurities in vodka with bandwidth spirtovodnogo mixture through three layers of activated carbon at the 5oC - 20oC.

All the known methods, however, not to eliminate completely the specific taste of vodka and even vodka high quality recommended to use very cold.

The objective of the invention is to improve the taste of the final product and further reduce the content of undesirable impurities.

The invention is based on the discovery of a previously unknown effect, namely, that in the process of spirtovodnogo mixture at temperatures below 5oC achieved a significant improvement in taste obtained vodka.

their aspects intends simplified for clarity and brevity.

Vodka is widely used in the world of food product. A very important quality, which are characterized by organoleptic characteristics and physico-chemical properties. The basic technology of production of vodka have been developed in the last century and since then has changed slightly.

Due to the interaction of molecules of ethanol and water, vodnoetanolnyh mixture is a complex system. Change the properties of this system depend on the ratio of the number of molecules of ethanol and water in the mixture, and the temperature of the mixture.

Water (H2O) and ethyl alcohol are associated liquids in which the molecules form associates.

Because of the great structural similarity of these liquids, ethanol is miscible with water in any ratio. Ethyl alcohol freezes at -117oC and water at 0oC. a Mixture of ethyl alcohol with water depending on the concentration of alcohol freezes at a temperature above (-117oC) and lower than the 0oC, as shown in the table.1.

In mixtures of ethyl alcohol and water are formed associates and hydrates of type (C2H5OH) (12H2O), (C2H5OH) (3H2O) and 3(C2H2OH) (12H2O)

It is clear that the molecules of ethyl Speer is the culprit structure molecular associates water at high temperature, at the same time at a low temperature and low concentrations of ethanol in the mixture molecular structure is essentially preserved. Thermodynamic properties of ethanol-water mixtures, such as the entropy of mixing, heat of mixing and excess Isobaric heat capacity of the mixture, reflect an increase of ruined hydrogen bonds with increasing temperature. The heat of mixing together with the external temperature at which mixing occurs, is associated with the formation of undesirable chemical compounds, referred to here as clathrates. For the formation of clathrate compounds the molecules of ethyl alcohol penetrate into the space formed by the molecular structure of water. The behavior of clathrates formed ethyl alcohol with water, similar to the behavior of clathrates, capable of capturing other substances inside their own crystal lattice: oral primary molecules such as cells, tunnels or layers, grasp the construction of molecules with approximately the same size and shape, which are chemically similar to the primary molecules. Presumably, clathrate compounds, formed during blending of ethanol with water at high temperatures, also zahvat cavity clathrates these undesirable compounds are not removed or poorly removed by activated carbon. Hence, stir and consistently clear water-ethanol mixture required at lower temperatures than those used before.

In a preferred embodiment of the invention uses ultra-low temperature from -45 to -22oC for the first processing stage, and from -22 to 5oC for the second stage to minimize the content in vodka unpleasant taste compounds, such as acetale and Polyacetal. The ingredients that make up these undesirable compounds present in small quantities in the source water-ethanol mixture. The stage of purification of water-ethanol mixtures by activated carbon described in more detail below, but here we note that the surface activity of activated carbon increases from 1.5 to 2.5 for these low temperatures, therefore, the cleaning efficiency of ethanol-water mixtures at low temperatures is significantly increased.

In addition to low temperatures, as will be described below, the invention uses a specific activated carbon and optimum contact time to obtain high-purity water-ethanol mixture.

The first stage of processing.

After mixing ethanol is built in three layers of activated carbon at a temperature of from -45 to -22oC.

Typically, the granules of activated carbon have an internal surface from 500 to 1500 m2/g and an external surface of from 10 to 20 cm2/, Consequently, their inner surfaces 2105to 15105times greater than the external surface. A typical pore size of activated carbon from 0.5 to 1.5 nm, while the size of the molecules of impurities from 0.3 to 1.0 nm. Therefore, molecules of impurities penetrate into the internal pores of activated carbon and adsorbed on their surface. Surface activity depends on : (a) temperature activated charcoal and (b) the number of major oxides on its surface. Discovered that best results are obtained on the adsorber filled with three layers of activated charcoal with low, medium and high surface activity. Low surface activity is 2-3 mg-equivalent/l, average 3-4 mg-equivalent/liter and high 4-5,4 mg-equivalent/liter Solution first passes through the layer with low activity, then through a layer with medium activity, and finally through the layer with the highest activity at temperatures from -45 to -22oC.

For efficient processing of a mixture of activated carbon should preferably have a total pore volume of 0.9-1 cm3/g for micropores. The micropores were pores smaller than 2 nm, mesopores have a size of 2-50 nm macropores have a size greater than 50 nm.

The second stage of processing.

After addition obtained in the first stage a mixture of additional quantities of water and stirring the mixture in the second stage alcohol-water mixture is passed through an adsorber filled with three successive layers of activated carbon at a temperature from -22 to 5oC. Low surface activity is 1.2 to 1.8 mg-equivalent/liter, an average of 1.8-2.2 mg-equivalent/liter and high - 2,2-2,6 mg-equivalent/liter Mixture first passes through the layer with low activity, and then through the layer with medium activity, and finally - through the layer with the highest activity at temperatures from -22 to 5oC.

For efficient processing of activated carbon preferably has a total pore volume of 0.5-0.7 cm3/g and a distribution volume of pores of 0.1 - 0.15 cm3/g for the micropores of 0.1-0.2 cm3/g for mesopores and 0.2-0.3 cm3/g for micropores.

Activated carbon.

Properties of activated carbon is described, for example, in : (1) Bansal, R. C., Donna B. and Stoeckli F., Active Carbons, Marcell Dekker, new York, (1988); (2) Patrick J. Century, IMIA Surfaces, Entertains, New York, (1986).

In the method according to the invention the activity of activated carbon improved by reducing the temperature. According to the Arrhenius equation (1) (see reference 2), the activity of coal increases with decreasing temperature T, i.e.

Acoal(T) = A0exp(-Ea/RT)

where

A0the pre - exponential factor,

Eathe activation energy of adsorption,

R is the gas constant,

T is the absolute temperature in degrees Kelvin.

Experimental data confirmed that the activity of coal increases from 1.5 if 5oC to 2.5 at -45oC.

Activated carbons are produced by many companies, for example: Environtal, Siwinski, Pennsylvania; APL industrial, Rivera beach, Florida; Norit Americas, Atlanta; Activated carbon Resorces, Ridgehill, Connecticut; carbon of Activated, Gardena, California; General carbon Corp., Paterson, New Jersey; North American Carbon, Columbus, Ohio.

At the first stage of processing, the optimal contact time between spirtovodnogo mixture and the activated carbon at a temperature of from -45 to -22oC should be 0.5 to 5 minutes, preferably 1 to 2 minutes, This duration contact a surprising lighting paint the Torah hours.

In the second stage of processing, the optimal contact time between spirtovodnogo mixture and the activated carbon at a temperature from -22 to 5oC should be 1-10 minutes, preferably 1-5 minutes

Further reduction in contact time affects the quality of the vodka, but exceeding a specified contact time should be avoided, because the catalytic process, taking place on charcoal in solution, will lead to the formation of aldehydes, ketones and other unexpected impurities that reduce the organoleptic characteristics of vodka.

Regeneration of activated carbon.

Also found that the activity of activated carbon can be restored to the starting with the simple procedure of passing hot dry air at 100-400oC through the layers of activated charcoal from the bottom up, layer with low activity to the upper layer with the most activity. Each layer of activated charcoal (low, medium, and highest level of activity) is regenerated using this procedure sufficiently for subsequent use.

The cooling.

The required temperature in the range from -45 to 5oC can be achieved and maintained in the ice. Technology such cooling is described, for example in : Walker,, Cricklade, including 1: Fundamentals, including 2: Applications, Plenum Press, new York, NY (1988) and Dean F. and Kokit F. H. , the Technique of Low Temperature, George Newnes limited, London (1989).

Example 1 illustrates the method according to the invention, example 2, comparative and made in the traditional way, example 3 - comparative carried out in example 2, but at a lower temperature.

Example 1. 76-77 about. % grain alcohol containing about 95-96. % ethanol, mixed with about 23-24. % demineralized water and cooled to a temperature of from -45 to -22oC. At the first stage of processing solution is passed through three layers of activated carbon with low, medium and high surface activity at temperatures from -45 to -22oC. the contact Time of about 1.5 minutes In the second stage of the processing solution is mixed with demineralized water to obtain a solution of about 40. % ethanol and about 60. % of water at temperatures from -22 to 5oC. the Solution is passed through three layers of activated carbon with low, medium and high surface activity at temperatures from -22 to 5oC. the contact Time of about 3.5 minutes the mixture is then filtered at 5-20oC to remove particles ACU is 7,1-7,5.

Example 2 (comparative). 41,8-42,2% vol. grain alcohol containing about 95-96. % ethanol was mixed with 57.8-58.2 about. % demineralized water at 20-25oC. the Solution was passed through three successive columns containing activated carbon, at 20-25oC. the contact Time of about 90 minutes the Solution was filtered to remove solid impurities.

Example 3 (comparative). Carried out a similar procedure for a similar amount of the mixture, as in example 2, but with 5-10oC.

Obtained in example 1 and in comparative examples 2 and 3, the samples were analyzed by chromatographic method described in journal of Chyromatography, 198 (1980) 347-353. The results are shown in table.2, in which:

column 1 shows the impurity concentration in mg/l in grain alcohol for mixing, i.e., grain alcohol used in examples 1, 2 and 3;

in column IIA and IIB shows the impurity concentration in mg/l in aqueous alcoholic solution obtained by 20-25oC (example 2), and at 5-10oC (example 3), respectively;

in column IIIA and IIIB shows the impurity concentration in mg/l in water-ethanol solution after its passage through activated carbon at 20-25oC (example 2) 5-10oC (example 3 after the first and second stages of processing water-alcohol mixtures at temperatures from -45 to -22oC and -22 to 5oC.

In the invention two receiving ethanol can be any carbohydrate raw materials such as grains, potatoes and beets, of which the fermentation is obtained ethyl alcohol.

It is clear that the invention describes a process for the production of vodka can also be used to improve other strong alcoholic beverages, not freezing at low temperatures, to reduce them in the content of undesirable impurities, the method according to the invention allows to improve the taste and color quality of the product and provides desirable organoleptic characteristics and appearance.

1. The method of processing a mixture of ethanol and water to reduce the content of impurities, providing at least one stage of purification of the mixture by passing through at least one layer of activated carbon, characterized in that the treatment is carried out at a temperature below 5oWith in two stages, the first of which is indicated the temperature of the mixture is from -22 -45oWith, and the second is from -22 to about 5oC.

2. The method according to p. 1, characterized in that the first processing stage includes:

a) mixing 65 - 75% this is opuskanie the resulting solution at temperatures from -45 to -22oWith three layers of activated carbon in the adsorber with the following surface activities, respectively:

1) of 2.0 - 3.0 mg/l,

2) 3,0 - 4,0 mg/l,

3) of 4.0 - 5.4 mg/l,

moreover, the activated carbon in the adsorber has a total pore volume of 0.9 - 1.5 cm3/g, and the duration of contact of the solution with activated charcoal adsorber is 0.5 to 5 minutes,

b) mixing an aqueous-ethanol solution obtained in the first processing stage, with water to obtain a water-ethanol solution containing 35 to about 45. % ethanol and 55 - 65% water at a temperature of from 22 to 5oC;

the transmittance of the obtained solution at a temperature from -22 to 5oWith three layers of activating carbon adsorber with the following surface activities, respectively:

4) of 1.2 - 1.8 mg/l,

5) of 1.8 - 2.2 mg/l,

6) of 2.2 - 2.6 mg/l,

moreover, the activated carbon in the adsorber has a total pore volume of 0.9 - 0.7 cm3/g, and the duration of contact of the solution with activated charcoal adsorber is 0.5 - 10 minutes

3. The method according to p. 1, wherein the total pore volume of activated carbon in the adsorber used in the first processing stage is: micropore volume of 0.1 - 0.15, the volume of mesopores of 0.1 - 0.2 and the amount of poppy the water-alcohol solution to remove particles of charcoal.

5. The method according to p. 1, characterized in that the recovery of the initial activity of activated charcoal in the canister through a purge flow of dry air with a temperature of 100 - 400oWith through the layers of activated charcoal.

6. The method according to p. 2, characterized in that the duration of contact of the solution with activated charcoal adsorber is 1 to 2 minutes on the first stage of treatment and 1 to 3 minutes in the second stage.

7. The method according to p. 6, wherein the total pore volume of activated carbon in the adsorber in the second stage processing is respectively: the micropores of 0.1 - 0.15, mesopores of 0.1 - 0.2 and macropores of 0.2 - 0.3 cm3/,

8. The method according to p. 6, characterized in that will filter the purified water-alcohol solution to remove particles of charcoal.

9. The method according to p. 6, characterized in that is carried out restoration of the initial activity of activated charcoal in the canister through a purge flow of dry air with a temperature of 100 - 400oWith through the layers of activated charcoal.

 

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