CN111518664B - Method for accelerating aging of white spirit by electrochemical oxidation - Google Patents

Method for accelerating aging of white spirit by electrochemical oxidation Download PDF

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CN111518664B
CN111518664B CN202010439640.8A CN202010439640A CN111518664B CN 111518664 B CN111518664 B CN 111518664B CN 202010439640 A CN202010439640 A CN 202010439640A CN 111518664 B CN111518664 B CN 111518664B
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aging
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white spirit
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CN111518664A (en
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郑青
余有贵
熊阿媛
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Yami Technology Guangzhou Co ltd
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Shaoyang University
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12HPASTEURISATION, STERILISATION, PRESERVATION, PURIFICATION, CLARIFICATION OR AGEING OF ALCOHOLIC BEVERAGES; METHODS FOR ALTERING THE ALCOHOL CONTENT OF FERMENTED SOLUTIONS OR ALCOHOLIC BEVERAGES
    • C12H1/00Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages
    • C12H1/12Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages without precipitation
    • C12H1/16Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages without precipitation by physical means, e.g. irradiation
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12HPASTEURISATION, STERILISATION, PRESERVATION, PURIFICATION, CLARIFICATION OR AGEING OF ALCOHOLIC BEVERAGES; METHODS FOR ALTERING THE ALCOHOL CONTENT OF FERMENTED SOLUTIONS OR ALCOHOLIC BEVERAGES
    • C12H1/00Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages
    • C12H1/12Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages without precipitation
    • C12H1/14Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages without precipitation with non-precipitating compounds, e.g. sulfiting; Sequestration, e.g. with chelate-producing compounds

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  • Distillation Of Fermentation Liquor, Processing Of Alcohols, Vinegar And Beer (AREA)

Abstract

The invention discloses a method for catalyzing aging white spirit by electrochemical oxidation, which comprises the steps of immersing a gold electrode into self-assembly solution for reaction, utilizing a self-assembly film to modify the gold electrode as a working electrode, a silver/silver chloride reference electrode and a platinum mesh electrode counter electrode to jointly form a three-electrode system; placing the three-electrode system in a container containing fresh wine at [ -1V,0V]Testing volt-ampere spectrum in a section, and recording reduction potential Vre; placing the three-electrode system in a container containing new wine, and setting the oxidation voltage to Vre+0.7-0.9V by adopting a timing current method; recording initial potential response current as I 0 The method comprises the steps of carrying out a first treatment on the surface of the When the reaction current I 1 Increasing the I by 1.2 to 1.5 times 0 And stopping aging. The invention has the advantages that the self-assembled film is adopted to modify the gold electrode as the working electrode, proper oxidation potential is selected to oxidize the new wine, and the aging is stopped under proper reaction current condition. On the premise of ensuring the quality stability of the white spirit, the aging time of the white spirit is shortened.

Description

Method for accelerating aging of white spirit by electrochemical oxidation
Technical Field
The invention relates to white spirit catalysis Chen Lingyu, in particular to a method for catalyzing and ageing white spirit by electrochemical oxidation.
Background
The new wine just produced has pungency and can only be calculated as a semi-finished product. Similar to brandy and whiskey, white spirit generally needs to be stored for a certain time to be aged, so that the irritation and pungency of new wine are reduced, the wine body is soft and palatable, mellow and strong, and the taste is coordinated, and the phenomenon is called "aging" or "aging" in the white spirit industry. The ageing time is 3 to 5 years, even 10 years, and the long-time ageing greatly increases the brewing cost and the selling price of the white spirit. Therefore, the white spirit industry is in urgent need of a manual ageing accelerating technology, so that the white spirit ageing time is shortened.
In the prior art, an electrocatalytic method (publication number: CN 86103016C) for accelerating aging of wine is adopted to perform electrocatalytic by adopting a Pt-Pt electrode with catalytic activity, a reference electrode and a constant potential polarization power supply system so as to complete the aging accelerating process of the wine. However, by controlling the platinum potential of the working electrode of the oxidation and reduction groups, the catalytic effect is unstable, and the difference of the liquor samples processed in different batches is large, so that the stability of the quality of the white liquor is affected. Therefore, development of an electrocatalytic method for accelerating aging and curing of white spirit with stable catalytic effect is needed to ensure the quality and stability of white spirit.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the invention provides a method for accelerating aging of white spirit by electrochemical oxidation, which utilizes an electrochemical method of modifying a gold electrode by a self-assembled film as a working electrode to oxidize reducing substances in the white spirit, and accelerates the aging of the white spirit and shortens the aging time on the premise of ensuring the quality stability of the white spirit.
The technical scheme adopted by the invention is as follows:
a method for accelerating the aging of white spirit by electrochemical oxidation, which comprises the following steps:
preparation of a self-assembled film modified gold electrode: polishing the gold electrode into a mirror surface by polishing powder, cleaning the surface of the gold electrode, and preparing self-assembly solution by the volume ratio of 2-10: 100:200, immersing a gold electrode into a self-assembly solution, reacting for 20-28 hours at room temperature, and cleaning the surface of the gold electrode;
new wine test: the self-assembled film is used for modifying a gold electrode as a working electrode, a silver/silver chloride reference electrode and a platinum mesh electrode as a counter electrode to jointly form a three-electrode system, the three-electrode system is placed in a container containing new wine, the voltammogram is tested in the range of [ -1V,0V ], and the reduction potential Vre is recorded;
oxidation and aging: placing the three-electrode system in a container containing new wine, wherein the new wine loading capacity is 40-60% of the container volume, adopting a timing current method, setting the oxidation voltage as Vre+ (0.7-0.9) V, and recording the initial potential reaction current as I 0
Chen Tingzhi: when the reaction current I 1 The increment is 1.2 to 1.5 times of I 0 And stopping aging.
The method for electrochemically oxidizing and aging white spirit provided by the invention comprises the steps of preparing a self-assembled film modified gold electrode, testing new white spirit, and stopping oxidizing and aging Chen He. Wherein, the self-assembled film modifies the gold electrode preparation step, and forms the L-cysteine self-assembled film on the gold electrode surface. The self-assembly solution is prepared from L-cysteine, ethanol and butanol, and ensures the film formation uniformity of the gold electrode. The self-assembly solution is L-cysteine which is common amino acid in organisms, so that the safety of the white spirit is ensured. Using the oxidation current of the self-assembled film as a judgment condition for the aging stop time: the reducing substance and the modified self-assembled film in the new wine can be oxidized to form a competition reaction, but the reducing substance has low oxidation potential and is oxidized first. When the self-assembled film starts to oxidize, the reducing substances in the new wine are obviously consumed, and the current generated at the moment when the self-assembled film starts to oxidize is greatly increased, so that the oxidation reaction is stopped, excessive oxidation of the new wine is avoided, excessive acid substances are generated, the ethyl caproate exceeds the standard, and the quality of the white wine is influenced.
Preferably, the self-assembly solution consists of a volume ratio of 2 to 10:100:200, ethanol and butanol.
Specifically, the polishing step is to sequentially polish the gold electrode into a mirror surface by using aluminum oxide polishing powder with the particle sizes of 0.2-0.4 microns and 0.04-0.06 microns, so that the polishing effect of the surface of the gold electrode is ensured.
Specifically, the surface of the gold electrode is cleaned by sequentially using 8-15% by volume of dilute hydrochloric acid aqueous solution, 40-60% by volume of ethanol aqueous solution and deionized water, so that the surface of the gold electrode is kept clean and then subjected to film forming reaction.
Specifically, after immersing in the self-assembly solution for reaction, cleaning the surface of the gold electrode, sequentially cleaning the surface of the self-assembly film by using an aqueous solution of 40-60% ethanol and deionized water in volume fraction, and cleaning the residual solution on the surface of the self-assembly film.
In the invention, the new wine testing step provides reducibility identification for new wines in different batches, provides guidance for setting oxidation voltage, and avoids insufficient or excessive aging. And an oxidation catalyst Chen Buzhou, which rapidly oxidizes the reducing substances in the new wine by utilizing the catalysis of the working electrode, so that the new wine is rapidly aged. And stopping the ageing, namely stopping the reaction according to the reaction current in time, so as to ensure the stability of the quality of the white spirit.
The invention has the advantages that the self-assembled film is adopted to modify the gold electrode as the working electrode, proper oxidation potential is selected to oxidize the new wine, and the aging is stopped under proper reaction current condition. On the premise of ensuring the quality stability of the white spirit, the aging time of the white spirit is shortened, and the method has important significance for promoting the sustainable development of the white spirit industry.
Drawings
FIG. 1 is a voltammogram of the test in example 1;
FIG. 2 is a graph of the timing current spectrum tested in example 1.
Detailed description of the preferred embodiments
In order to better understand the above technical solutions, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
Example 1
The method for accelerating aging of white spirit by electrochemical oxidation specifically comprises the following steps:
preparation of a self-assembled film modified gold electrode: sequentially polishing the gold electrode into a mirror surface by using aluminum oxide polishing powder with the particle sizes of 0.3 micron and 0.05 micron, and sequentially cleaning the gold electrode by using a dilute hydrochloric acid aqueous solution with the volume fraction of 10 percent, an ethanol aqueous solution with the volume fraction of 50 percent and deionized water; the self-assembly solution comprises the following components in percentage by volume: 100:200, immersing the gold electrode into a self-assembly solution, reacting for 24 hours at room temperature, and then sequentially cleaning with 50% ethanol water solution and deionized water;
new wine test: the self-assembled film is used for modifying a gold electrode as a working electrode, a silver/silver chloride reference electrode and a platinum mesh electrode counter electrode to jointly form a three-electrode system. The three-electrode system was placed in a vessel containing fresh wine and the voltammogram was tested in the [ -1v,0v ] interval and its reduction potential Vre was recorded.
Oxidation and aging: the self-assembled film is used for modifying a gold electrode as a working electrode, a silver/silver chloride reference electrode and a platinum mesh electrode counter electrode to jointly form a three-electrode system. The three electrode system was placed in a vessel containing fresh wine with a loading of 50% of the vessel volume, and a chronoamperometry was used to set the oxidation voltage to vre+0.8v. As shown in fig. 1, vre is-0.61V, the oxidation voltage is vre+0.8v, i.e., the oxidation potential is-0.61v+0.8v=0.19V. Recording initial potential response current as I 0
Chen Tingzhi: when the reaction current I 1 The increase is 1.2 times of I 0 And stopping aging. As shown in FIG. 2, the initial potential reaction current I 0 At a reaction current I of 3.5 1 The increment is I 0 The aging is stopped at 1.2 times, i.e. 1.2 x 3.5=4.2 nanoamperes.
Example 2
The method for accelerating aging of white spirit by electrochemical oxidation specifically comprises the following steps:
preparation of a self-assembled film modified gold electrode: sequentially polishing the gold electrode into a mirror surface by using aluminum oxide polishing powder with the particle sizes of 0.3 micron and 0.05 micron, and sequentially cleaning the gold electrode by using a dilute hydrochloric acid aqueous solution with the volume fraction of 10 percent, an ethanol aqueous solution with the volume fraction of 50 percent and deionized water; the self-assembly solution comprises the following components in percentage by volume: 100:200, immersing the gold electrode into a self-assembly solution, reacting for 24 hours at room temperature, and then sequentially cleaning with 50% ethanol water solution and deionized water;
new wine test: the self-assembled film is used for modifying a gold electrode as a working electrode, a silver/silver chloride reference electrode and a platinum mesh electrode counter electrode to jointly form a three-electrode system. Placing the three-electrode system in a container containing new wine, testing volt-ampere spectrum in the range of [ -1V,0V ], and recording the reduction potential Vre;
oxidation and aging: the self-assembled film is used for modifying a gold electrode as a working electrode, a silver/silver chloride reference electrode and a platinum mesh electrode counter electrode to jointly form a three-electrode system. Three electrodes are arrangedThe system is placed in a container containing new wine, the loading capacity of the new wine is 50% of the volume of the container, a timing current method is adopted, and the oxidation voltage is set to Vre+0.8V; recording initial potential response current as I 0
Chen Tingzhi: when the reaction current I 1 The increase is 1.4 times of I 0 And stopping aging.
Example 3
The method for accelerating aging of white spirit by electrochemical oxidation specifically comprises the following steps:
preparation of a self-assembled film modified gold electrode: sequentially polishing the gold electrode into a mirror surface by using aluminum oxide polishing powder with the particle sizes of 0.3 micron and 0.05 micron, and sequentially cleaning the gold electrode by using a dilute hydrochloric acid aqueous solution with the volume fraction of 10 percent, an ethanol aqueous solution with the volume fraction of 50 percent and deionized water; the self-assembly solution comprises the following components in percentage by volume: 100:200, immersing the gold electrode into a self-assembly solution, reacting for 24 hours at room temperature, and then sequentially cleaning with 50% ethanol water solution and deionized water;
new wine test: the self-assembled film is used for modifying a gold electrode as a working electrode, a silver/silver chloride reference electrode and a platinum mesh electrode counter electrode to jointly form a three-electrode system. Placing the three-electrode system in a container containing new wine, testing volt-ampere spectrum in the range of [ -1V,0V ], and recording the reduction potential Vre;
oxidation and aging: the self-assembled film is used for modifying a gold electrode as a working electrode, a silver/silver chloride reference electrode and a platinum mesh electrode counter electrode to jointly form a three-electrode system. Placing the three-electrode system in a container containing new wine, wherein the loading capacity of the new wine is 50% of the volume of the container, and setting the oxidation voltage to Vre+0.8V by adopting a chronoamperometry; recording initial potential response current as I 0
Chen Tingzhi: when the reaction current I 1 The increase is 1.5 times of I 0 And stopping aging.
Comparative example 1
Comparative example 1 differs from example 1 in that the self-assembling solution consists of a volume ratio of 20:100:200, ethanol and butanol.
Comparative example 2
Comparative example 2 differs from example 1 in that when the reaction current I 1 The increment is 2 times of I 0 And stopping aging.
The electrochemical oxidation catalysts Chen Baijiu obtained in examples 1 to 3 and comparative examples 1 to 2 were subjected to ethyl caproate content detection, and whether the ethyl caproate content was out of standard was determined by referring to the national standard.
TABLE 1 catalysis Chen Xiaoguo of white spirit in examples 1-3, comparative examples 1-2
Ethyl caproate content Whether or not to exceed the standard
Example 1 2.3g/L Whether or not
Example 2 3.2g/L Whether or not
Example 3 2.8g/L Whether or not
Comparative example 1 3.6g/L Is that
Comparative example 2 3.8g/L Is that
As can be seen from Table 1, the ethyl caproate content of examples 1-3 was lower than that of comparative examples 1-2, and the ethyl caproate content was prevented from exceeding the standard. The difference between the comparative example 1 and the example 1 is that the self-assembled solutions with different concentrations are adopted, the difference between the comparative example 2 and the example 1 is that the ethyl caproate content of the white spirit after the aging in the comparative example 1 and the comparative example 2 exceeds the standard, and the result proves that the ethyl caproate content up to the standard can be obtained by adopting the corresponding self-assembled solution proportion and the aging time in the examples 1-3 in the preparation process.

Claims (2)

1. The method for accelerating the aging of the white spirit by electrochemical oxidation is characterized by comprising the following steps of:
preparation of a self-assembled film modified gold electrode: polishing the gold electrode into a mirror surface by polishing powder, cleaning the surface of the gold electrode, and preparing self-assembly solution by the volume ratio of 2-10: 100:200, immersing a gold electrode into a self-assembly solution, reacting for 20-28 hours at room temperature, and cleaning the surface of the gold electrode;
new wine test: the self-assembled film is used for modifying a gold electrode as a working electrode, a silver/silver chloride reference electrode and a platinum mesh electrode as a counter electrode to jointly form a three-electrode system, the three-electrode system is placed in a container containing new wine, the voltammogram is tested in the range of [ -1V,0V ], and the reduction potential Vre is recorded;
oxidation and aging: placing the three-electrode system in a container containing new wine, wherein the loading capacity of the new wine is 40-60% of the volume of the container, setting the oxidation voltage as Vre+ (0.7-0.9) V by adopting a timing current method, and recording the initial potential reaction current as I0;
chen Tingzhi: stopping aging when the reaction current I1 is increased to 1.2-1.5 times of I0;
the polishing step is to sequentially polish the gold electrode into a mirror surface by using alumina polishing powder with the particle sizes of 0.2-0.4 microns and 0.04-0.06 microns;
the surface of the cleaned gold electrode is washed by ethanol water solution with the volume fraction of 40-60% and deionized water sequentially after immersing in the self-assembly solution for reaction.
2. The method for electrochemically oxidizing aged white spirit according to claim 1, wherein: the surface of the polished clean gold electrode is sequentially cleaned by 8-15% by volume of dilute hydrochloric acid aqueous solution, 40-60% by volume of ethanol aqueous solution and deionized water.
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CN112029607B (en) * 2020-08-27 2022-12-02 邵阳学院 Electrochemical method for improving total ester content of liquid fermentation base wine and liquid fermentation base wine
CN112255302A (en) * 2020-09-30 2021-01-22 邵阳学院 Preparation method and application of bionic self-assembled membrane with anion switch function

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