WO2025160637A1 - Additive composition for alcohol products, method for applying the additive composition and use of the additive composition - Google Patents

Abstract

The present invention refers to an additive composition for reducing the undesirable impurities in alcohol, thus, directly improving the Barbet (or permanganate) Index and providing a better stability for the final product. The additive composition mainly comprises EDTA. The additive composition of the present invention can be applied in in any type of alcohol containing impurities and, after its application, the alcohol product can be used in various type of industry, allowing the use in pharmaceuticals, parfums, fragrances, fine chemicals and alcohol beverages. A method for applying the additive composition in alcohol product and the use of said additive composition for preparing an alcohol product are also disclosed herein.

Description

ADDITIVE COMPOSITION FOR ALCOHOL PRODUCTS, METHOD FOR APPLYING THE ADDITIVE COMPOSITION AND USE OF THE ADDITIVE COMPOSITION TECHNICAL FIELD 5 The present invention refers to an additive composition for reducing the undesirable impurities in alcohol, thus, directly improving the Barbet (or permanganate) Index and providing a better stability for the final product. The additive composition mainly comprises EDTA. The additive composition of the present invention can be applied in in 10 any type of alcohol containing impurities and, after its application, the alcohol product can be used in various type of industry, allowing the use in pharmaceuticals, parfums, fragrances, fine chemicals and alcohol beverages. The additive composition of the invention has no toxicity, harm, corrosion or oxidation and can be applied safely in food, pharmaceutical or beverage industries. 15 A method for applying the additive composition in alcohol product and the use of said additive composition for preparing an alcohol product are also disclosed herein. BACKGROUND OF THE INVENTION One concern to be faced by alcohol industries refers to the 20 aggressiveness of the alcohol due to undesirable impurities, affecting the properties of the final product, such as color, stability and the shelf life. For example, in the ethanol industry, the impurities present in the ethanol occurs due to the organic and inorganic origin of hydroalcoholic mixture, which may produce variation in the ethanol or bioethanol. 25 One common method used in industry to measure the aggressiveness level in alcohols is called Barbet test or Permanganate test. The Barbet test is used for identifying the undesirable impurities in alcohol/ethanol, in which the potassium permanganate (KMnO⁴) is the reactant used to provide the qualitative information regarding the presence of impurities. The 30 potassium permanganate is a strongly oxidizing reagent and substances, such as aldehydes, react with permanganate and oxidize to carboxylic acids. Other impurities that can be identified in the Barbet test are the acetaldehydes, methanol and all substances that reduce permanganate. After the consumption of potassium permanganate during the Barbet test, it is possible to verify that the solution changes color to salmon pink, with the elapsed time (in minutes) being the Barbet or Permanganate time. In this method, the shorter the time for color change, the greater the amount of impurities, such as aldehydes and other substances, present in ethanol. One of main technical problems observed in the ethanol production, is that the ethanol produced contains a greater number of contaminants and the Barbet test provides a low Barbet time due to the high contamination. The production of alcohol with high concentration of impurities limits the commercial value of the final product, as the alcohol could not be used in different technical fields such as fine chemicals, cosmetic, pharmaceuticals or alcoholic beverages. Since the fine chemical, cosmetic, pharmaceuticals or beverages industries require high degree of alcohols purity and less aggressiveness, it was identified a need to find solutions that can minimize impurities in alcohols and, consequently, to increase the Barbet Index. According to the state of the art, it is possible to find some developments involving methods to try to minimize ethanol impurities and, consequently, to increase the Barbet Index. For example, SALATA, C et al¹, propose a system for purification of ethanol with some contaminants from the fermentation of cassava starch, using physical-chemical processes, such as the addition of activated charcoal, in which the average of the Barbet test was about 10 minutes at 15ºC. However, according to this study, it was concluded that the addition of 2% activated charcoal at temperatures of 20, 30 and 40ºC wasn’t sufficient to remove the contaminants of alcohol. For reference, one typical Barbet test in ethanol production of a neutral ethanol with usual content of impurity compounds, such as aldehydes and methanol, should take more than 25 minutes for the permanganate to change color. In this sense, it is still desired by industries to obtain a product that could improve the time (in minutes) of the Barbet test to assure a good quality in the final alcohol product. Based on the above, the purpose of the present invention is to provide an additive composition for reducing the degree of impurities of alcohol/ethanol, ¹ SALATA, Cristiane da Cunha and CABELLO, Claudio- v. 5 (2009): Remoção de Substâncias Contaminantes do Álcool Etílico por adição de carvão ativado; Revista Raízes e Amidos Tropicais (unexp.br); Volume Especial- XIII Congresso Brasileiro da Mandioca- Botucatu - Resumos Expandidos. Website: REMOÇÃO DE SUBSTÂNCIAS CONTAMINANTES DO ÁLCOOL ETÍLICO POR ADIÇÃO DE CARVÃO ATIVADO | Revista Raízes e Amidos Tropicais (unesp.br) improving the Barbet Index. In this regard, the inventors of the present invention surprisingly found that the addition of an additive composition containing EDTA can reduce considerably the impurities present in alcohol and, consequently, increasing the time during the 5 Barbet Test. The additive of the present invention can be inserted safely into food or pharmaceutical products containing alcohol without harming human or animal health. SUMMARY OF THE INVENTION The present invention refers to an additive to be applied in alcohols in which the Barbet Index indicates a low time (in minutes) by the presence of impurities. 10 The additive composition of the present invention provides a final alcohol product that can be used in several industries that require a higher quality of alcohol. Particularly, the present invention is directed to a composition comprising EDTA (Ethylenediamine tetra acetic acid) and water. Specifically, the additive composition of the present invention comprises 15 the following components: - 0.1 to 5% by weight of EDTA or salts thereof; and - 95% to 99.9% by weight of water. The additive composition is applied directly in the alcohol produced in a conventional process, particularly, in a concentration varying from 500 ppm to 1500 20 ppm of the solution. Consequently, the impurities rate will be reduced, as it can be proved by the Barbet index, which is improved through the result obtained (increase in time in minutes). The present invention also refers to the use of the composition to be applied in alcohol (specially alcohols that contain low Barbet Index, i.e., less than 25 25 minutes) and, after its application, it is obtained an alcohol product with less aggressivity, that can be used in several types of industry, allowing the use in pharmaceuticals, parfums, fragrances, fine chemicals, and alcoholic beverages. The additive composition of the invention has no toxicity, harm, corrosion, or oxidation and can be applied safely in food, pharmaceutical or beverage industries. 30 A method for applying the additive composition an alcohol product and the use of said additive composition are also disclosed herein. DETAILED DESCRIPTION OF THE INVENTION Many technologies have been developed in the state of the art to try to increase the degree of purity in the production of alcohol, for example ethanol. Among them, the most common technologies refer to improvements in the production process, new raw materials, or new devices for purifying or distilling alcohol. However, the present inventors surprisingly found that a composition containing EDTA is capable to significantly reduce the number of contaminants in the 5 final alcohol product and, consequently, it improves the Barbet Index of the alcohol product without having to modify the process or reaction steps. This achievement was obtained by the addition of the composition of the present invention directly into the final alcohol product. The additive composition of the present invention comprises the following 10 components. - 0.1 to 5% by weight of EDTA or salts thereof; and - 95% to 99.9% by weight of water; in relation to the total weight of the composition. The salts of EDTA used in the present invention are selected from: 15 disodium EDTA tetrasodium EDTA, or mixtures thereof. The additive composition of the present invention may further comprise other sequestering components, selected from: sodium tripolyphosphate, hexametaphosphate, hydroxyethylene diphosphonic acid (HEDP) and citric acid, or mixtures thereof, in an amount varying from 0.1 to 5% by weight in relation to the total 20 weight of the composition. The additive composition is applied directly in the alcohol produced, which immediately reduce the impurities present in the alcohol and improve the Barbet index. The inclusion of the additive composition of the present invention also improves the stability, and sensorial properties of the final product. 25 More specifically, the additive composition of the present invention can be inserted in any type of alcohol that contains contaminants. In one embodiment, the alcohol may contain one, two, three or more hydroxyl groups. In a preferred embodiment, the alcohol is ethyl alcohol, denatured alcohol (SDA) benzyl alcohol, isopropyl alcohol or fatty alcohols (such as caprylic, cetearyl, cetyl, decyl, isostearyl, 30 lauryl, myristyl, oleyl and stearyl alcohols). In a more preferred embodiment, the alcohol is an ethanol. In a preferred embodiment, the composition of the present invention comprises 0.1% of EDTA and 99.9% of water, based on the total weight of the composition. As an example, the composition of the invention can be prepared by adding 1g of EDTA in 1000g of water. In another embodiment, the composition of the present invention comprises 0.5% of EDTA and 99.5% of water, based on the total weight of the composition. 5 The additive composition of the present invention is applied directly in the alcohol product, in a concentration varying from 300 ppm to 1500 ppm based on the solution. Consequently, after the application of the additive composition of the present invention, it is possible to verify that the alcohol has become less aggressive, 10 and the Barbet time will be increased (increase in time in minutes). The inventors of the present invention believe that, after the insertion of the composition in the alcohol, the EDTA acts by sequestering the metallic ions present in the alcohol, such as iron, magnesium, calcium and heavy metals, as they are considered pro-oxidants, thus, preventing them from causing any unwanted interaction 15 with other components of the product, increasing the product stability. The present invention also refers to a method for applying the additive composition of the invention. The method refers to the insertion of the additive composition in an alcohol product, wherein it comprises the following steps: - Adding the additive composition of the present invention, comprising: 20 From 0.1 to 5% by weight of EDTA or salts thereof; and From 95% to 99.9% by weight of water; in an alcohol product, in a concentration varying from 300 ppm to 1500 ppm; - Mixing the additive composition and the alcohol product until 25 complete homogenization; and - Carrying out the Barbet Test to verify the Index, in minutes, obtained after the dosing. The Barbet test is basically a qualitative/quantitative reaction that indicates the presence of impurities of organic and inorganic origin in the 30 hydroalcoholic mixture, by producing color variation of permanganate through comparison of color with a standard solution. A typical Barbet test in an alcohol product could be found in the Brazilian standard method ABNT (Brazilian Association of Technical Standards) -NBR 9866. As an example, the Barbet test comprises the following steps: - To transfer the sample to a test tube; - To place the tube in a water bath at a temperature of 15ºC to 20ºC and wait for the temperature to stabilize; - To add 2 mL of potassium permanganate (KMnO4) at 0.02% in the 5 test tube and start the timer; and - Read the time until the sample acquires the standard Barbet color, which is a salmon pink color. After the reduction of KMnO⁴ in Barbet test, the solution changes color to salmon pink and the elapsed time (in minutes) to achieve this color refers to the Barbet 10 time. Therefore, the shorter the time for color change, the greater the amount of contaminants, such as aldehydes, present in the ethanol. In an alcohol product, such as neutral alcohol, the Barbet time can vary from 22 to 29 minutes. Usually, one typical Barbet test in ethanol production of a neutral ethanol with a routine content of impurity compounds should take about 25 minutes for ¹⁵ the reduction of KMnO⁴ to occur. Considering a neutral ethanol product containing a Barbet Index from 22 to 29 minutes, the present inventors verified that it is possible to achieve a Barbet Index from 30 to until 100 minutes by inserting the composition of the present invention, significantly reducing the impurities from the alcohol product. 20 The present invention also foresees the use of the composition of the present invention to be applied in alcohol product to improve the Barbet Index, obtaining a final alcohol product with high quality and less impurities. In one embodiment, the additive composition of the present invention can be used for preparing an ethanol product that provides a Barbet Index higher than 38 25 minutes until 100 minutes. Therefore, the additive composition can be used simply and effectively in alcohols with high amount of impurities and with low Barbet Index. After the application of the additive composition, the final alcohol product could be used in various type of industry, allowing the use in pharmaceuticals, parfums, 30 fragrances, fine chemicals and alcohol beverages. As used herein, all ranges provided are meant to include every specific range within, and combination of sub ranges between, the given ranges. Thus, a range from 1-5, includes specifically 1, 2, 3, 4 and 5, as well as sub ranges such as 2-5, 3-5, 2-3, 2-4, 1-4, etc. All ranges and values disclosed herein are inclusive and combinable. For examples, any value or point described herein that falls within a range described herein can serve as a minimum or maximum value to derive a sub-range, etc. Throughout the disclosure, the term “mixtures thereof” may be used following a list of elements as shown in the following example where letters A-F 5 represent the elements: “one or more elements selected from the group consisting of A, B, C, D, E, F, and a combination thereof.” The cited chemical compounds contain synonyms, respective CAS number, IUPAC names and should be considered therein. Those skilled in the art should appreciated that the examples and 10 embodiments described herein are for illustrate purposes only and not to limit the scope of the present invention. Various of modifications, combination and sub- combinations and changes can be made, if necessary, all of modifications, combinations, sub-combinations, changes, and equivalents are fallen in the scope of the following claims. 15 By way of non-limiting illustration, the invention will now be described with reference to the following examples. EXAMPLE 1: Comparative test of a sample obtained directly from ethanol production in relation to a sample containing the additive composition of the present invention. 20 A comparative test was performed to verify the technical effect achieved by the additive composition of the present invention. Initially, 10 samples of ethanol were collected. Such samples were obtained from conventional distillation plant and contains a routinely number of impurities. 25 Such 10 samples were submitted to a Barbet test, following the methodology described below: ^ Barbet test: Determination of KMnO4 reduction time in minutes ^ Reagents and Solutions used in the test: - Potassium permanganate solution 0.02% 30 - Standard color solution ^ Solution Preparation a) KMnO4 at 0.02% solution: Firstly, weight 0.2g of KMnO4, then, to dissolve in a small amount of distilled water and transfer it to a 1000mL flask. Completing the volume with distilled water b) Color-Barbet standard solution: to weight 0.25g of cobalt chloride hexahydrate, dissolve in a small amount of distilled water and transfer it to a 50mL volumetric flask, completing to the final volume with distilled water. Place this solution in a test tube with a screw cap. The color of this solution is salmon, under normal conditions and it is stable for one year. ^ Methodology i. Pipette 50mL of the sample and transfer to a test tube; ii. To place the tube in a bath at 15ºC and after stabilizing the sample temperature. To add 2ml of 0.02% KMnO4 solution and then, starting the timer. iii. Periodically compare the color developed in the sample with that of the Barbet standard solution (salmon colour); iv. When the 0.02% KMnO⁴ solutions have the same color as the standard color solution (salmon), stop the timer. This time corresponds to the Barbet time of the alcoholic solution. The Table 1 below shows the variation of the colors of permanganate depending on the oxidation state of manganese. Table 1: Variation of the colors of permanganate Oxidation state Colors Observation MnO4 (^-1) +7 VIOLET Permanganate MnO4 (^-2) +6 GREEN Manganate MnO² +4 BROWN Manganese dioxide Mn2O3 +3 RED Manganês trioxide Mn(⁺²) +2 COLORLESS Manganese The KMnO4 is highly reactive and can oxidize a wide variety of organic and inorganic substances. In the oxidation process, KMNO⁴ (Mn⁺⁷) can be reduced to MnO4(^-2)(Mn⁺⁶), MnO2(Mn⁺⁴ ), Mn2O3(Mn⁺³) and Mn(⁺²). The KMnO4 can react with different types of reducing substances, such as metals, hydrogen, sulfides, aldehydes, ketones, alcohols, organic acids, among others. The composition of the invention used in this example was prepared as follows: - 0.1 % of EDTA; and - 99.9% of Water. The additive composition of the invention was then added into the ethanol 5 samples in different dosages: 300 ppm (0.3 mL/ 1L of alcohol), 500 ppm (0.5 mL/ 1L of alcohol), 1000 ppm (1 mL/ 1L of alcohol), and 1500 pm (1.5 mL/ 1L of alcohol). After the homogenization of the additive composition with ethanol, the samples were submitted to Barbet test. The results are described in the tables 2 to 5 below: Table 2: Comparative test of Barbet Index at 300 ppm SAMPLES DOSAGE (PPM) BARBET INDEX (minutes) Initial Ethanol after dosing the additive ethanol composition of the invention 1 300 27,0 41,0 2 300 29,0 39,0 3 300 24,0 38,0 10 Table 3: Comparative test of Barbet Index at 500 ppm SAMPLES DOSAGE (PPM) BARBET INDEX (minutes) Initial Ethanol after dosing the additive ethanol composition of the invention 4 500 22,0 42,0 5 500 29,0 46,0 6 500 20,0 38,0 7 500 25,0 39,0 Table 4: Comparative test of Barbet Index at 1000 ppm SAMPLES DOSAGE (PPM) BARBET INDEX (minutes) Initial Ethanol after dosing the additive ethanol composition of the invention 8 1.000 25,0 51,0 9 1.000 24,0 62,0 15 Table 5: Comparative test of Barbet Index at 1500 ppm SAMPLES DOSAGE (^PPM) _{BARBET INDEX (minutes)} Initial Ethanol after dosing the additive ethanol composition of the invention 10 1.500 27,0 100,0 As it can be seen in tables 1 to 5 above, the additive composition of the invention provides a surprising effect in reducing aggressiveness and impurities in ethanol, as prove by Barbet time. 5 For dosages of 300 ppm, the Barbet Index was improved from 24 -29 minutes to 38-41 minutes. The increase of approximately 10 to 14 minutes obtained in the Barbet test using the additive composition of the present invention indicates that there was a significant reduction in aggressiveness and impurity content in ethanol. For dosages of 500 ppm, the Barbet Index was improved from 20-29 10 minutes to 38-42 minutes. The increase of approximately 14 to 20 minutes obtained in the Barbet test by the additive composition of the present invention demonstrates a significant reduction in the aggressiveness and impurity content in the ethanol. For dosages of 1000 ppm, the Barbet Index was improved from 24 -24 minutes to 51 to 62 minutes, which indicates that there was a highly significant 15 reduction in the aggressiveness and impurity content in the ethanol. Finally, for dosages of 1500 ppm, the Barbet Index was improved from 27 minutes to 100 minutes, which demonstrates that the additive composition of the present invention had an even more significant reduction in aggressiveness and impurity content in ethanol at this concentration. 20 The above test indicates that the greater the dosage of the additive composition of the present invention, the greater the reduction in the aggressiveness and impurity content of the alcohol, and this content can be adapted according to the purpose of the product and the required purity of the alcohol to be used.

Claims

SET OF CLAIMS 1. An additive composition for alcohol products, wherein it comprises: from 0.1 to 5% by weight of ethylenediamine tetra acetic acid (EDTA) or 5 salts thereof; and from 95% to 99.9% by weight of water, in relation to the total weight of the composition. 2. Composition, according to claim 1, wherein the EDTA salts are selected from disodium EDTA, tetrasodium EDTA, or mixtures thereof. 0 3. Composition, according to claim 1, wherein the composition further comprises other sequestering components selected from: sodium tripolyphosphate, hexametaphosphate, hydroxyethylene diphosphonic acid (HEDP) and citric acid, or mixtures thereof. 4. Composition, according to claim 3, wherein sequestering5 component is present in an amount varying from 0.1 to 5% by weight, in relation to the total weight of the composition. 5. Method for applying the additive composition, as defined in claim 1, in an alcohol product, wherein it comprises the following steps: - Adding the additive composition directly in an alcohol product, in a0 concentration varying from 300 ppm to 1500 ppm; - Mixing the additive composition and the alcohol product until complete homogenization; and - Carrying out Barbet Test to verify the Index (in minutes) obtained after the dosing. 5 6. Method, according to claim 1, wherein the alcohol product is selected from ethyl alcohol, denatured alcohol (SDA) benzyl alcohol, isopropyl alcohol or fatty alcohols. 7. Method, according to claim 5, wherein the alcohol product is ethanol. 0 8. Use of the additive composition, as defined in claim 1, wherein said composition is for preparing an alcohol product that provides a Barbet Index higher than 30 minutes. 9. Use, according to claim 8, wherein such additive composition is for preparing an alcohol product to be used in pharmaceutical products, parfums, cosmetics products or alcoholic beverages.