Method for accelerating aging of white spirit through hydrothermal synergistic electro-catalysis process

Abstract

The invention belongs to the new technical field of white spirit brewing, and particularly relates to a method for accelerating aging of white spirit through a hydrothermal synergistic electro-catalysis process, which specifically comprises the following steps: introducing newly-brewed white spirit into an aging container, carrying out electro-catalysis treatment, selecting titanium-plated platinum as an electrode material, and carrying out hydrothermal reaction synergistic treatment at the same time; after electro-catalysis treatment, constant-temperature water bath treatment is conducted, the operation is repeated for 3-5 times, and the treatment interval is 30-50 min. The content of acetal in the white spirit treated by the method is increased, the content of ester substances such as ethyl hexanoate and ethyl acetate is obviously increased, and irritant components such as low-grade saturated fatty aldehyde and fusel oil are reduced. The treated white spirit has the aroma of aged white spirit, tastes soft and soft, contains typical aromatic odor of the white spirit, has prominent flavor and is mellow and pleasant during drinking, and is equivalent to natural ageing for 1-3 years, so that the ageing period of the white spirit is greatly shortened, and the ageing cost of the white spirit is reduced.

Description

Technical Field

[0001] This invention belongs to the field of new technologies in liquor brewing, and in particular relates to a method for accelerating the aging of liquor through a hydrothermal synergistic electrocatalytic process. Background Technology

[0002] Baijiu, one of the world's six major distilled spirits, is a distilled spirit made primarily from grains, using daqu (large koji), xiaoqu (small koji), bran koji, enzymes, and yeast as saccharification and fermentation agents. The process involves cooking, saccharification, fermentation, distillation, aging, and blending. Aging is a crucial step in the baijiu fermentation process. New baijiu has a strong pungent flavor; aging reduces this harshness, improves the taste, enhances the complexity of the aroma, elevates the overall quality, and imparts a aged character.

[0003] However, most methods of aging baijiu (Chinese liquor) rely on natural aging, such as aging in earthenware jars, storing in stainless steel tubes, or aging in bottles. These methods are costly, inefficient, require long aging times, occupy large areas, and result in significant storage losses. Furthermore, they are not conducive to equipment maintenance and transportation. Therefore, research into artificial methods of aging is urgently needed.

[0004] In recent years, researchers both domestically and internationally have attempted to accelerate the aging of baijiu (Chinese liquor) using physical, chemical, and biocatalyst methods. However, biocatalysis is less widely used due to its high technical difficulty and numerous uncertainties. Chemical aging methods may lead to flavor distortion, poor stability, and safety concerns. Compared to electric field aging, other physical aging methods are more difficult to control or more expensive. Therefore, most companies and researchers choose electrocatalysis to accelerate the aging of new baijiu.

[0005] However, single methods of accelerating aging are often inefficient and cannot achieve satisfactory results. CN119351184A discloses a method for aging baijiu (Chinese liquor) using electrochemical methods. The drawback of this method is its long processing time, making it difficult to guarantee consistent processing times for each batch and thus limiting its application to industrial production. CN104593214A discloses a device and method for accelerating aging baijiu by heating air with a heat source. However, this method requires introducing air into the tank for 10-20 minutes every 24-48 hours, without specifying the precision and uniformity of temperature control. Furthermore, this approach is susceptible to localized overheating or uneven temperature distribution, which could negatively impact the flavor and quality of the baijiu, such as damaging temperature-sensitive flavor compounds, thus hindering its application in large-scale industrial production. Increasingly, researchers are exploring combined methods for accelerating aging.

[0006] Therefore, the inventors focused their research on whether they could provide a simpler and more effective method for synergistically accelerating the aging of baijiu (Chinese liquor). Summary of the Invention

[0007] To address the problems existing in the prior art, this invention provides a method for accelerating the aging of baijiu (Chinese white liquor) through a hydrothermal synergistic electrocatalytic process. Specifically, newly brewed baijiu is introduced into an aging container for electrocatalytic treatment. The electrode material is titanium plated with platinum, and a hydrothermal reaction is employed simultaneously. After electrocatalytic treatment, the liquor is placed in a constant-temperature water bath for repeated treatment 3-5 times, with each treatment interval of 30-50 minutes. Baijiu treated using this method shows an increase in acetal content, a significant increase in the content of esters such as ethyl hexanoate and ethyl acetate, and a decrease in irritating components such as lower saturated fatty aldehydes and fusel oils. The treated baijiu possesses the aroma of aged baijiu, a smooth and mellow taste, and the typical aromatic flavor of baijiu. When drinking, it has a prominent, mellow, and pleasant flavor, equivalent to 1-3 years of natural aging, thus shortening the aging cycle and reducing the aging cost of baijiu.

[0008] The specific technical solution of the present invention is as follows: A method for accelerating the aging of baijiu (Chinese white liquor) through a hydrothermal synergistic electrocatalytic process involves introducing newly brewed baijiu into an aging container for electrocatalytic treatment, while simultaneously employing a hydrothermal synergistic treatment. The two treatments are carried out in the order of "electrocatalysis-hydrothermal catalysis," and repeating this process 3 to 5 times can achieve the effect of natural aging for 1 to 3 years.

[0009] Preferably, the working electrode material selected in the electrocatalysis process is titanium platinum plated, and the ratio of the length, width and thickness of the working electrode is 2:1:0.02. The titanium platinum plated electrode has a higher cost performance and better aging effect than other inert material electrode plates. Compared with platinum metal plates, the effect is basically similar, but the cost of titanium platinum plated electrode is lower and it is suitable for industrial promotion and application.

[0010] Furthermore, the aforementioned electrode plate materials can prevent oxidation-reduction reactions of substances in the liquor on the electrode surface, ensuring that the composition and style of the liquor remain unchanged after aging. Since liquor is an acidic solution, using palladium as the electrode plate material can easily form soluble complexes, contaminating the liquor. If pure titanium is used as the electrode plate material, a passivation oxide layer easily forms on its surface, leading to reduced electrochemical activity and thus weakening catalytic activity.

[0011] Preferably, the hydrothermal catalytic reaction temperature is 30-50℃, the voltage of the uniform electric field electrocatalytic treatment is 10-15V, the total time for each "electrocatalysis-hydrothermal catalysis" is 30-35 minutes, and the single batch processing volume is 500ml-1000ml. To protect the electrode plates and avoid excessive heat generation from prolonged treatment affecting the aging effect, the time should not exceed 40 minutes. Corresponding to the above processing volume, the working electrode plate is 10cm long, 5cm wide, and 0.1cm thick; the distance between the working electrode plates is 2cm; the single batch processing volume can be increased by enlarging the electrode plate area, etc. The hydrothermal reaction time is the same as the electrocatalytic treatment time.

[0012] This application employs the following apparatus to achieve the above processing procedure: The device includes an aging container, a peristaltic pump, a wine container, a hydrothermal reaction unit, and a voltage regulating device; wherein the aging container includes a top cover, on which an anode plate and a cathode plate are inserted, and the two plates are electrically connected to the voltage regulating device, which can adjust the voltage between the two plates. The hydrothermal reaction unit is filled with a heat medium, preferably deionized water in this application. The unit includes a wine coil and a heater at its bottom. This heater heats the heat medium to a set temperature, thereby heating the wine coil. The wine provides the temperature required for the hydrothermal reaction. The aging container, peristaltic pump, wine container, and hydrothermal reaction unit are connected by piping.

[0013] In practical use, first ensure that all components are securely connected and that the electrical connections of the electrical units are normal, using an external power supply. Then, place the newly brewed liquor into the liquor container. Turn on the voltage regulator in advance to generate the target voltage on the anode and cathode plates. Start the peristaltic pump to send the liquor from the inlet of the aging container into the aging container. The liquor ages in a uniform electric field. After aging, the liquor is discharged from the outlet of the aging container and enters the inlet of the liquor coil. During its passage through the liquor coil, it is uniformly heated to the set temperature under the action of the heat medium. Then, it is returned to the liquor container through the outlet of the liquor coil. The peristaltic pump then continues the process. After the specified time, turn off the voltage regulator and heater, and use the peristaltic pump to transfer all the liquor from the system into the liquor container, completing one processing cycle. Repeat the above operation after the interval. The speed of the peristaltic pump is adjusted according to the amount of liquor being processed, ensuring that the liquor to be processed reaches the required processing time.

[0014] More preferably, the above-mentioned method for accelerating the aging of Baijiu through electrocatalysis and hydrothermal reaction adopts the following steps: The newly brewed baijiu is subjected to a uniform electric field treatment, with titanium-plated platinum material as the electrode, a voltage of 10V, and a treatment time of 30 minutes to perform an electrocatalytic process on the baijiu. The baijiu after electrocatalytic treatment is transported to a hydrothermal treatment unit through a preset delivery pump, where it continues to age under constant temperature hydrothermal treatment. The constant temperature hydrothermal temperature is selected as 40℃, and the hydrothermal reaction time is the same as the electrocatalytic treatment time.

[0015] In a preferred embodiment of the present invention, the electrocatalytic process combined with hydrothermal reaction accelerates aging for 30 minutes per cycle and 700 ml per batch; the temperature of the hydrothermal unit is set to 40°C; the treatment is repeated 3 times, with an interval of 30-50 minutes between each treatment.

[0016] Compared with the prior art, the present invention has the following beneficial effects: (1) This invention effectively shortens the time required for aging of liquor. The actual total processing time of this aging process is 1-3 hours, and the liquor can achieve the effect of natural aging for 1-3 years. The most prominent change is the significant increase of esters, especially ethyl acetate and ethyl hexanoate, while aldehydes are significantly reduced and acetals are significantly increased, so that the liquor presents the high-quality characteristics of prominent aged aroma, mellow and rich taste, and clean finish.

[0017] (2) The aging method provided by the present invention can effectively improve the aggregation of flavor substances in baijiu and accelerate the combination rate of ethanol and water molecules, making the baijiu more mellow. At the same time, it can effectively reduce the irritating components such as low-grade saturated fatty aldehydes and fusel oils in newly brewed baijiu, making the baijiu with a more prominent flavor and a purer body.

[0018] (3) The method provided by the present invention can greatly reduce the materials and costs required for aging, and the aging time is short and energy consumption is low, with high processing efficiency.

[0019] (4) Most existing electrolytic aging experiments use pulsed electric fields. The principle is to accelerate the molecular motion and chemical reaction inside the liquor by inputting energy from a high-voltage short-pulse electric field, thus quickly achieving the flavor optimization and quality improvement that natural aging requires a long period of time. However, high-voltage pulsed electric fields have instantaneous high-intensity peaks, which can easily lead to excessive electrolysis of local liquor, producing off-flavor substances such as methanol and high-carbon aldehydes, which can damage the flavor harmony of the liquor. This invention uses a uniform electric field with a continuous low intensity, which only targets undesirable components such as low-grade saturated aldehydes and free fatty acids, without damaging core flavor substances such as ethyl acetate and ethyl lactate. Compared with the instantaneous high voltage of pulsed electric fields, which can easily cause the molecular chain of the liquor to break, potentially leading to ester hydrolysis and excessive oxidation of alcohols, resulting in flavor loss or liquor deterioration, this invention is a significant improvement. Moreover, when the uniform electric field of this application is applied to the liquor, the electric field intensity is consistent throughout the treatment area, which can allow target substances such as aldehydes and esters in the liquor to undergo uniform condensation and oxidation reactions. Attached Figure Description

[0020] Figure 1 This is a flowchart of the equipment used in the hydrothermal synergistic electrocatalytic process for aging baijiu as described in this application. In the diagram, 1 is the aging container, 1-1 is the top cover of the aging container, 1-2 is the anode plate, 1-3 is the cathode plate, 1-4 is the liquid inlet of the aging container, 1-5 is the liquid outlet of the aging container, 2 is the peristaltic pump, 3 is the wine container, 3-1 is the liquid inlet of the wine container, 3-2 is the liquid outlet of the wine container, 4 is the hydrothermal reaction unit, 4-1 is the liquid inlet of the wine coil, 4-2 is the wine coil, 4-3 is the heater, 4-4 is the liquid outlet of the wine coil, and 5 is the voltage regulating device. Detailed Implementation

[0021] The technical solution of the present invention will be further described below with reference to specific embodiments. These embodiments are only used to illustrate the technical solution of the present invention in more detail and should not be construed as limiting the scope of protection of the present invention.

[0022] Unless otherwise specified, the content of each substance in the liquor samples in the following examples was detected and analyzed as follows: GC conditions: RTX-WAX capillary column (30m×0.25μm×0.25mm); carrier gas was high-purity helium; splitless injection, injection port temperature 250℃; column temperature was programmed: the programmed temperature was 40℃ held for 3 min, increased to 130℃ at 2℃ / min, increased to 220℃ at 10℃ / min, and held for 4 min.

[0023] MS conditions: transfer line temperature 250 ℃; ion source temperature 230 ℃; quadrupole temperature 150 ℃; electromagnetic source EI; ion source EI; ionization energy 70 eV; scan mass range 15~500 amu; mass spectrometry scan mode: full scan (SCAN).

[0024] Data processing: The detected volatile components were analyzed qualitatively and quantitatively by mass spectrometry and NIST2020 spectral library search; the matching factor was greater than 80 for qualitative analysis; and the internal standard method was used for quantitative analysis.

[0025] The method described in the following embodiments is implemented using the following apparatus: like Figure 1 As shown, the device includes an aging container 1, a peristaltic pump 2, a wine container 3, a hydrothermal reaction unit 4, and a voltage regulating device 5; wherein the aging container 1 includes a top cover 1-1, an anode plate 1-2 and a cathode plate 1-3 are inserted into the top cover, and the two plates are connected to the voltage regulating device 5, which can adjust the voltage between the two plates. The hydrothermal reaction unit 4 is filled with a heat medium, preferably deionized water in this application. A wine liquid coil is installed inside the hydrothermal reaction unit 4, and a heater 4-3 is located at the bottom of the unit. This heater heats the heat medium to a set temperature, thereby heating the wine liquid coil. The wine liquid provides the temperature required for the hydrothermal reaction. The aging container 1, peristaltic pump 2, wine liquid container 3, and hydrothermal reaction unit 4 are connected by pipelines.

[0026] In practical use, first ensure that the connections between all components are secure and the electrical connections of the electrical units are normal, using an external power supply. Then, place the newly brewed liquor into the liquor container 3. Turn on the voltage regulator 5 in advance to generate the target voltage on the anode and cathode plates. Turn on the peristaltic pump 2 to send the liquor from the inlet of the aging container into the aging container. The liquor ages in a uniform electric field. After aging, the liquor is discharged from the outlets 1-5 of the aging container and enters the inlet of the liquor coil. During the process in the liquor coil, it is uniformly heated to the set temperature under the action of the heat medium. Then, it is sent back to the liquor container 3 through the outlet of the liquor coil. The peristaltic pump then continues the process. After the specified time is reached, turn off the voltage regulator and the heater. The peristaltic pump then transfers all the liquor from the system into the liquor container, completing one processing cycle. Repeat the above operation after the interval time. The speed of the peristaltic pump is adjusted according to the amount of liquor being processed, thus ensuring that the liquor to be processed reaches the required processing time.

[0027] Example 1: A method for accelerating the aging of Baijiu (Chinese liquor) using a hydrothermal synergistic electrocatalytic process, the specific steps of which are as follows: 700ml of newly brewed light-aroma baijiu from the liquor container is introduced into the aging container, and an electric current is applied. The voltage of the uniform electric field is 15V. After electrocatalytic treatment in the aging container, the liquor is sent to a hydrothermal reaction unit with a set temperature of 40℃ through a pipeline. The hydrothermal reaction time is the same as the electrocatalytic time. After the hydrothermal reaction is completed, the liquor is returned to the liquor container and then sent to the aging container again by a peristaltic pump for repeated treatment, forming a circulation path. This process lasts for 30 minutes. The above process is repeated 3 times, with a 40-minute interval between each "electrocatalysis-hydrothermal reaction" synergistic treatment, and finally aged light-aroma baijiu is obtained.

[0028] Example 2: A method for accelerating the aging of Baijiu (Chinese liquor) using a hydrothermal synergistic electrocatalytic process, the specific steps of which are as follows: 500ml of newly brewed strong-aroma baijiu from the liquor container is introduced into the aging container, and an electric current is applied. The voltage of the uniform electric field is 10V. After electrolysis in the aging container, the liquor is introduced into a hydrothermal reaction unit with a set temperature of 45℃. The hydrothermal reaction time is the same as the electrocatalytic time. After the hydrothermal reaction is completed, the liquor is returned to the liquor container and then fed into the aging container again by a peristaltic pump for repeated processing, forming a circulation path. This process lasts for 30 minutes. The above process is repeated 3 times, with a 40-minute interval between each "electrocatalytic-hydrothermal reaction" synergistic treatment, and finally aged strong-aroma baijiu is obtained.

[0029] Example 3: A method for accelerating the aging of Baijiu (Chinese liquor) using a hydrothermal synergistic electrocatalytic process, the specific steps of which are as follows: 700ml of newly brewed Maotai-flavor liquor from the liquor container is introduced into the aging container, and an electric current is applied. The voltage of the uniform electric field is 10V. After electrolysis in the aging container, the liquor is introduced into a hydrothermal reaction unit at a set temperature of 30℃. The hydrothermal reaction time is the same as the electrocatalysis time, and no stirring or other treatment is required during this period. After the hydrothermal reaction is completed, the liquor is returned to the liquor container and then fed into the aging container again by a peristaltic pump for repeated treatment, forming a circulation path. This process lasts for 30 minutes. The above process is repeated 5 times, with a 40-minute interval between each "electrocatalysis-hydrothermal reaction" synergistic treatment, and finally aged Maotai-flavor liquor is obtained.

[0030] Experimental Example (1) The contents of various substances in the newly brewed light-aroma baijiu before and after the treatment in Example 1, and the light-aroma baijiu samples that have been naturally aged for 6 months, 12 months and 18 months respectively, were detected and analyzed by GC-MS. The results are shown in Table 1: Table 1 compares the content of various substances in newly brewed light-aroma baijiu samples before and after treatment in Example 1 with light-aroma baijiu samples that have been naturally aged for 6 months, 12 months, and 18 months, respectively. As shown in Table 1, the content of esters such as ethyl acetate in the light-aroma baijiu treated with this method is effectively increased, while the content of acids such as acetic acid and hexanoic acid is reduced. Furthermore, the content of lower saturated fatty aldehydes such as acetaldehyde and fusel oils such as n-butanol and isoamyl alcohol is effectively reduced. The baijiu possesses a unique aroma after aging, and has a smooth and refreshing taste, achieving the effect of aging for 1 to 3 years.

[0031] (2) The contents of various substances in the newly brewed strong-aroma baijiu before and after the treatment in Example 2, as well as the strong-aroma baijiu samples that have been naturally aged for 6 months, 12 months, and 18 months, were detected and analyzed by GC-MS. The results are shown in Table 2: Table 2 shows the content of various substances in the newly brewed strong-aroma baijiu and strong-aroma baijiu samples that were naturally aged for 6 months, 12 months and 18 months before and after the treatment in Example 2. As shown in Table 2, the content of esters such as ethyl acetate in the strong-aroma baijiu treated with this method is effectively increased, while the content of acids such as acetic acid and hexanoic acid is reduced. Furthermore, the content of lower saturated fatty aldehydes such as acetaldehyde and fusel oils such as n-butanol and isoamyl alcohol is effectively reduced, significantly reducing the "spicy and harsh" taste of newly brewed strong-aroma baijiu.

[0032] (3) The contents of various substances in the newly brewed Maotai-flavor liquor before and after the treatment in Example 3, and the Maotai-flavor liquor samples that have been naturally aged for 6 months, 12 months, and 18 months, respectively, were detected and analyzed by GC-MS. The results are shown in Table 3: Table 3 shows the content of various substances in the newly brewed Maotai-flavor liquor and the Maotai-flavor liquor samples that were naturally aged for 6 months, 12 months, and 18 months before and after the treatment in Example 3. As shown in Table 3, the content of esters such as ethyl acetate in the liquor treated with this method is effectively increased, while the content of acids such as acetic acid and hexanoic acid is reduced; the content of acetal is significantly increased, which can effectively improve the taste and remove the irritation of new liquor; the content of fusel oils such as n-butanol and isoamyl alcohol is significantly reduced, which significantly reduces the "spicy and throat-pungent" taste of newly brewed strong-aroma liquor, achieving the effect of aging for 1 to 2 years.

[0033] Comparative Example 1 According to the method described in CN201410778172.1, 500ml of newly brewed strong-aroma baijiu was passed through a high-voltage pulsed electric field, the current was turned on, and a sodium carbonate solution with a concentration of 3 mol / L was added. The pulsed electric field frequency was 30Hz, the electric field strength was 25kV / cm, and the treatment time was 1200μs to obtain strong-aroma baijiu aged under high-voltage pulsed electric field. The result was compared with the sample treated in Example 2.

[0034] The contents of various substances in the newly brewed strong-aroma baijiu before and after treatment in Comparative Example 1, the strong-aroma baijiu aged under high voltage pulse electric field, and the sample treated in Example 2 were analyzed by GC-MS. The results are shown in Table 4. Table 4 As shown in Table 4, the content of esters such as ethyl acetate in the liquor of strong-aroma baijiu is effectively increased after high-voltage pulsed electric field treatment, but the content of acids such as acetic acid and hexanoic acid is significantly reduced, which easily makes the baijiu greasy and causes an imbalance of esters and acids; and it cannot effectively remove fusel oils such as n-butanol and isoamyl alcohol; therefore, high-voltage pulsed electric field treatment can easily damage the sensory quality of the liquor and cause it to lose its typical style. The quality of the treated sample described in Example 2 of this application is significantly improved compared to the former.

[0035] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any equivalent substitutions or modifications made by those skilled in the art within the spirit and principle of the present invention without any creative effort should be included within the protection scope of the present invention.

Claims

1. A method for accelerating the aging of Baijiu (Chinese liquor) using a hydrothermal synergistic electrocatalytic process, characterized in that, The specific steps are as follows: The newly brewed liquor is introduced into an aging container for electrocatalytic treatment, while a hydrothermal reaction is used for synergistic treatment. The two treatments are carried out in the order of "electrocatalysis-hydrothermal catalysis" and repeated 3 to 5 times. The hydrothermal catalytic reaction temperature is 30-50℃, the voltage of the uniform electric field electrocatalytic treatment is 10-15V, and the total time of each "electrocatalysis-hydrothermal catalysis" is 30-35min.

2. The method for accelerating the aging of Baijiu (Chinese liquor) using a hydrothermal synergistic electrocatalytic process according to claim 1, characterized in that, The working electrode material selected for the electrocatalytic process is titanium plated with platinum, and the ratio of the length, width and thickness of the working electrode is 2:1:0.

02.

3. The method for accelerating the aging of Baijiu (Chinese liquor) using a hydrothermal synergistic electrocatalytic process according to claim 1 or 2, characterized in that, The working electrode plate is 10cm long, 5cm wide, and 0.1cm thick; the distance between the working electrodes is 2cm, and the single batch processing volume is 500ml-1000ml.

4. The method for accelerating the aging of Baijiu (Chinese liquor) using a hydrothermal synergistic electrocatalytic process according to claim 1, characterized in that, The hydrothermal catalytic reaction time is the same as the electrocatalytic treatment time.

5. The method for accelerating the aging of Baijiu (Chinese liquor) using a hydrothermal synergistic electrocatalytic process according to claim 1, characterized in that, The repeated processing is performed at intervals of 30-50 minutes.

6. The method for accelerating the aging of Baijiu (Chinese liquor) using a hydrothermal synergistic electrocatalytic process according to claim 1, characterized in that, The hydrothermal catalytic reaction temperature is 40℃, the voltage of the uniform electric field electrocatalytic treatment is 10V, and the total time for each "electrocatalysis-hydrothermal catalysis" is 30min.

7. The method for accelerating the aging of Baijiu (Chinese liquor) using a hydrothermal synergistic electrocatalytic process according to claim 3, characterized in that, The processing volume per batch is 700ml.

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