Method for regulating and controlling furanone substance content in white spirit storage and aging process

Abstract

The invention discloses a method for regulating and controlling the content of furanone substances in the storage and aging process of white spirit, and belongs to the technical field of white spirit industry. The method for regulating and controlling the content of the furanone substances in the storage and aging process of the white spirit comprises the step of adding a catalyst CuO coated SiO2-Al2O3 nano material into the white spirit in the storage and aging process of the white spirit, wherein the addition amount of the catalyst CuO coated SiO2-Al2O3 nano material is 0-5% of the mass of the white spirit, but not 0. After the catalyst CuO coated SiO2-Al2O3 is added, the content of fenugreek lactone in the Maotai-flavor liquor stored and aged for 6 months is increased by more than 2.5 times compared with that of Maotai-flavor liquor without the catalyst, the content of furanone is increased by more than 2.8 times, and the content of ethyl furanone is increased by more than 4.2 times.

Description

Technical Field

[0001] The invention relates to a method for regulating the content of furanone substances in the storage and aging process of liquor, and belongs to the technical field of liquor industry. Background Art

[0002] The older Chinese liquor is, the more fragrant it is. Flavor is a key factor in determining the quality of liquor products. "Aging" is a major process for improving the flavor quality of liquor products. Newly brewed liquor tastes rough and has an uncoordinated aroma. After a period of storage and aging, the flavor is significantly improved, the irritation and pungency are reduced, and the aroma is more delicate, elegant, full and pleasant. The sensory characteristics of liquor aroma formed during the "aging" process are essential characteristics for high-quality liquor products.

[0003] At present, the understanding of the chemical nature of the aged flavor of liquor is still not very clear, making it difficult to effectively control the flavor quality of liquor during the storage and aging process. At the same time, the compounds that form the aged flavor of liquor often have the characteristics of low content and strong aroma intensity. Based on the previous research of the inventor's team, it was found that furanones, including fenugreek lactone, furanone HDMF, and ethyl furanone HEMF, are important compounds that form the aged flavor of liquor. And this type of substance shows a significant increase trend with the increase of liquor storage time. However, despite the storage process of up to 30 years, the change range of this type of substance is only 50-200μg / L.

[0004] Therefore, there is an urgent need for a method for regulating the content of furanones during the storage and aging process of liquor. Summary of the invention

[0005] [Technical issues]

[0006] Since liquor production can only use the traditional pottery jar storage process, which is labor-intensive, time-consuming, wasteful and costly, it has become a bottleneck restricting the modernization and upgrading of my country's traditional liquor industry;

[0007] The flavor chemical quality of liquor during storage and aging is difficult to effectively control.

[0008] [Technical solution]

[0009] In order to solve the above problems, the present invention adds the catalyst CuO@SiO during the storage and aging process of liquor. 2 -Al 2 O 3 Nanomaterials can be used to regulate the content of furanone substances in liquor and shorten the storage and aging time of liquor.

[0010] The first object of the present invention is to provide a method for regulating the content of furanones in the storage and aging process of liquor, wherein the method comprises adding a catalyst CuO@SiO 2 -Al 2 O 3 Nanomaterials; among them, the catalyst CuO@SiO 2 -Al 2 O 3 The amount of nanomaterial added is 0 to 5% of the mass of the liquor, but not 0.

[0011] In one embodiment of the present invention, the catalyst CuO@SiO 2 -Al 2 O 3 The particle size of nanomaterials is 0.01 to 1 mm.

[0012] In one embodiment of the present invention, the furanone substance is one of fenugreek lactone, furanone and ethyl furanone.

[0013] In one embodiment of the present invention, the catalyst CuO@SiO 2 -Al 2 O 3 The preparation method of nanomaterials is as follows:

[0014] (1) mixing 1-methyl-2-pyrrolidone, polyethersulfone and polyvinylpyrrolidone to obtain a light yellow viscous liquid;

[0015] (2) Add SiO2 to the light yellow viscous liquid. 2 , alumina monohydrate, and CuO are fully dispersed to obtain a dispersion;

[0016] (3) Extruding the dispersion into spherical particles, and then soaking them in water to cause phase transformation to form solid small particles;

[0017] (4) Sintering the solid small particles to obtain the catalyst CuO@SiO 2 -Al 2 O 3 Nanomaterials.

[0018] In one embodiment of the present invention, in step (1), the mass ratio of 1-methyl-2-pyrrolidone, polyethersulfone and polyvinylpyrrolidone is 1:1.5-2:1.5-3.5.

[0019] In one embodiment of the present invention, the mixing in step (1) is carried out by stirring at 70-80° C. and 50-70 rpm for 2-3 hours.

[0020] In one embodiment of the present invention, in step (2), SiO2 The mass ratio of alumina monohydrate and CuO is 1:2~3:1~2.

[0021] In one embodiment of the present invention, the dosage ratio of CuO to the light yellow viscous liquid in step (2) is 1800-2000 mg:15 mL.

[0022] In one embodiment of the present invention, the sufficient dispersion in step (2) is carried out by stirring at 20 to 50° C. and 150 to 300 rpm for 18 to 30 hours.

[0023] In one embodiment of the present invention, the extrusion in step (3) is to pour the dispersion (semi-solid state) into a special container and evenly extrude it into particles of uniform size.

[0024] In one embodiment of the present invention, the soaking in water in step (3) requires continuous water change to allow sufficient phase conversion to occur.

[0025] In one embodiment of the present invention, the soaking in water in step (3) is done at room temperature (20-40° C.) for 3-5 days.

[0026] In one embodiment of the present invention, the sintering in step (4) is divided into four stages, as follows:

[0027] The first stage (removal of free water): the temperature is raised to 95-105°C at a rate of 1-2°C / min and maintained for 2-3 hours.

[0028] The second stage (removal of bound water and some organic matter): heating from 95-105°C to 195-205°C at a heating rate of 1-2°C / min and maintaining for 2-3h;

[0029] The third stage (removal of organic matter): the temperature is increased from 195-205°C to 395-405°C at a heating rate of 1-2°C / min and maintained for 2-3h;

[0030] The fourth stage (conversion of alumina monohydrate into activated alumina): heating from 395-405°C to 595-605°C at a heating rate of 1-2°C / min and maintaining for 2-3h.

[0031] In one embodiment of the present invention, the catalyst CuO@SiO is prepared 2 -Al 2 O 3 The raw materials of nanomaterials need to be dried overnight before use.

[0032] In one embodiment of the present invention, the method for regulating the content of furanones during the storage and aging process of liquor comprises the following steps:

[0033] The newly distilled liquor is put into a storage container and the catalyst CuO@SiO is added. 2 -Al 2 O 3 Nanomaterials are stored and aged at room temperature to obtain liquor with a high content of furanones.

[0034] In one embodiment of the present invention, the liquor is one or more of the following: sauce-flavor liquor, light-flavor liquor, strong-flavor liquor, phoenix-flavor liquor, rice-flavor liquor, sesame-flavor liquor, special-flavor liquor, Laobaigan-flavor liquor, mixed-flavor liquor, Dong-flavor liquor, rich-flavor liquor, and soy-flavor liquor.

[0035] In one embodiment of the present invention, the storage container is a glass jar, a ceramic jar, a ceramic vat, or a stainless steel tank.

[0036] In one embodiment of the present invention, storage and aging at room temperature is storage and aging at 20-40° C. for more than 2 months.

[0037] The second object of the present invention is to prepare a liquor with a high furanone content using the method of the present invention.

[0038] The third object of the present invention is to provide a finished wine, which is obtained by blending the white wine with a high furanone content of the present invention.

[0039] The fourth objective of the present invention is to use the liquor with high furanone content in the liquor processing field.

[0040] [Beneficial Effects]

[0041] (1) The present invention adds the catalyst CuO@SiO 2 -Al 2 O 3 Afterwards, the content of fenugreek lactone in the Maotai-flavor liquor stored and aged for 6 months increased by more than 2.5 times, furanone increased by more than 2.8 times, and ethyl furanone increased by more than 4.2 times compared with the Maotai-flavor liquor without adding catalyst.

[0042] (2) The method of the present invention enables the newly prepared Maotai-flavor liquor to reach the level of conventional storage and aging for 5 years after storage and aging for 6 months. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 This is the spectrum of furanones in Example 1 (GC-MS-SIM mode spectrum). DETAILED DESCRIPTION

[0044] The preferred embodiments of the present invention are described below. It should be understood that the embodiments are for better explaining the present invention and are not used to limit the present invention.

[0045] Test method:

[0046] Detection of Furanone Substances:

[0047] (1) Liquid-liquid extraction sample pretreatment:

[0048] 20 mL of liquor sample was diluted with saturated saline to an alcohol content of 10% vol, and then the isotope internal standard of fenugreek lactone was added, followed by extraction with 20 mL of dichloromethane as an extractant, and extracted 3 times in total, each time for 5 min; 60 mL of the extracted components were collected, 30 g of anhydrous sodium sulfate was added thereto, and stored at -20°C overnight; 60 mL of the extracted components were then concentrated to 200 μL by nitrogen blowing and waited for injection;

[0049] (2) Sample analysis was performed using gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring mode (SIM);

[0050] The GC conditions are as follows:

[0051] Agilent 7890 gas chromatograph tandem with 5975 mass spectrometer was used;

[0052] The chromatographic column was DB-FFAP (60m×0.25mm×0.25μm, Agilent, America); the temperature program of the chromatographic column (DB-FFAP) was as follows: the initial temperature was 45°C and maintained for 2 min, then increased to 230°C at 6°C / min and maintained for 10 min; He (>99.999%) was used as the carrier gas, with a flow rate of 2mL / min and an injection port temperature of 230°C;

[0053] The MS conditions are as follows:

[0054] The sample solvent delay time was 8 min; the EI ionization source, ionization energy was 70 eV, ion source temperature was 230 °C, and mass spectrometry ion scanning range was 35-350 amu; the quantification of fenugreek lactone, furanone HDMF and ethyl furanone HEMF was carried out in the selective ions monitoring mode (SIM), and the characteristic ions were 128 m / z, 128 m / z, and 142 m / z, respectively;

[0055] (3) Drawing of standard curve:

[0056] A simulated liquor matrix solution (pH=3.5, alcohol content of 53% vol) is prepared with chromatographic grade ethanol and ultrapure water for later use; a certain mass of standard furanone compounds (trigonelline lactone, furanone HDMF and ethyl furanone HEMF) is accurately weighed and dissolved in the simulated liquor solution to prepare a series of standard solutions with different concentration gradients; the standard solutions are treated according to the sample pretreatment method of step (1), and instrumental analysis is performed according to step (2), and a standard curve is prepared according to the peak area ratio and concentration ratio of the target substance to the internal standard substance as the horizontal and vertical coordinates respectively;

[0057] (4) Detection:

[0058] The liquor to be tested is tested according to steps (1) and (2) to obtain the peak area, which is then substituted into the standard curve of step (3) to obtain the concentration of the substance to be tested.

[0059] The raw materials used in the examples are:

[0060] 1. Catalyst CuO@SiO 2 -Al 2 O 3 Preparation of Nanomaterials:

[0061] (1) 1-methyl-2-pyrrolidone, polyethersulfone and polyvinylpyrrolidone were mixed in a mass ratio of 1:1.5:1.5, and stirred at 60 rpm for 2.5 h in a sealed constant temperature water bath at 75°C to obtain a light yellow viscous liquid;

[0062] (2) Add 1500 mg SiO 2 , 3500 mg of alumina monohydrate, 2000 mg of CuO, fully dispersed at 25° C. and 180 rpm for 24 h to obtain a dispersion;

[0063] (3) The dispersion is squeezed into spherical particles of uniform size, and then immersed in water at 25°C for 3 days, during which the water is constantly changed, so that a phase transformation occurs to form small solid particles; wherein the squeezing is to pour the dispersion (semi-solid state) into a special container and evenly squeeze it into particles of uniform size;

[0064] (4) Sintering the solid small particles as follows:

[0065] The first stage (removal of free water): heating to 100 °C at a heating rate of 1.5 °C / min and maintaining for 2.5 h;

[0066] The second stage (removal of bound water and some organic matter): heating from 100°C to 200°C at a heating rate of 1.5°C / min and maintaining for 2.5h;

[0067] The third stage (removal of organic matter): heating from 200°C to 400°C at a heating rate of 1.5°C / min and maintaining for 2.5h;

[0068] The fourth stage (conversion of alumina monohydrate to activated alumina): finally, the temperature was increased from 400°C to 600°C at a heating rate of 1.5°C / min and maintained for 2.5h;

[0069] The catalyst CuO@SiO 2 -Al 2 O 3 Nanomaterials;

[0070] All the raw materials used were dried in an oven at 65°C overnight.

[0071] 2. Catalyst CuO@SiO 2 -Al 2 O 3 The amount of nanomaterial added (%) is the mass percentage relative to the newly distilled liquor.

[0072] 3. Pottery powder and pottery shards come from pottery jars. Pottery powder is the powder obtained by grinding the pottery jar, and pottery shards are fragments of the pottery jar.

[0073] 4. Maotai-flavor liquor, Qing-flavor liquor, Luzhou-flavor liquor, and mixed-flavor liquor are new liquors that have not been stored;

[0074] 5. Ceramic jars and stainless steel tanks: commercially available containers for storing liquor.

[0075] Example 1

[0076] A method for regulating the content of furanone substances during the storage and aging process of liquor comprises the following steps:

[0077] The newly distilled liquor (Jiangxiang liquor) was put into a stainless steel tank and 1% catalyst CuO@SiO was added. 2 -Al 2 O 3 The nanomaterial (0.1 mm) was stored and aged at room temperature (25°C) for 6 months to obtain a liquor with a high content of furanones.

[0078] Example 2 Optimization of catalyst dosage

[0079] Adjust the catalyst CuO@SiO in Example 1 2 -Al 2 O 3 The addition amount of the nano material is 0, 0.1%, 2%, and 3%, and the other contents are consistent with those in Example 1, thereby obtaining a liquor with a high content of furanone substances.

[0080] The obtained liquor with high furanone content was subjected to performance test, and the test results are as follows:

[0081] Table 1

[0082] Catalyst dosage (%) Trigonelline lactone (μg / L) Furanone (μg / L) Ethyl furanone (μg / L) 1 (Example 1) 52±9.0 13.1±1.4 7.0±1.0 0 15±1.5 1.8±0.8 1.0±0.1 0.1 38±6.6 5.2±1.3 4.2±0.9 2 50±10.0 10.3±2.5 8.2±1.1 3 51±11.0 11.5±3.0 7.3±1.3

[0083] Example 3 Optimization of storage container

[0084] The storage container in Example 1 is adjusted to a ceramic jar, and the other parts are kept consistent with Example 1 to obtain a liquor with a high content of furanone substances.

[0085] The obtained liquor with high furanone content was subjected to performance test, and the test results are as follows:

[0086] Table 2

[0087] Storage Container Trigonelline lactone (μg / L) Furanone (μg / L) Ethyl furanone (μg / L) Pottery jar 68±5.2 17.7±3.6 9.5±1.3 Stainless steel tank (Example 1) 52±9 13.1±1.4 7.0±1.0

[0088] Example 4 Optimization of liquor types

[0089] The types of liquor in Example 1 are adjusted to light-flavor liquor, strong-flavor liquor, and mixed-flavor liquor, and the rest are kept consistent with Example 1 to obtain liquor with a high content of furanones.

[0090] The obtained liquor with high furanone content was subjected to performance test, and the test results are as follows:

[0091] Table 3

[0092] Liquor Trigonelline lactone (μg / L) Furanone (μg / L) Ethyl furanone (μg / L) Maotai-flavor type (embodiment 1) 52±9 13.1±1.4 7±1 Strong aroma 26±2 5.3±0.3 - Light fragrance 14±5.2 - - Fragrance 5.5±0.8 4.1±1.2 -

[0093] Note: “-” means not detected.

[0094] Comparative Example 1

[0095] Adjust the catalyst CuO@SiO in Example 1 2 -Al 2 O 3 The nano material is ceramic powder (particle size is 0.1 mm), and the other parameters are the same as those in Example 1, so as to obtain a liquor with a high content of furanone substances.

[0096] Comparative Example 2

[0097] Adjust the catalyst CuO@SiO in Example 1 2 -Al 2 O 3 The nanomaterial is a pottery fragment (size is 50×50 mm), and the other parts are consistent with Example 1, so as to obtain a liquor with a high content of furanone substances.

[0098] Comparative Example 3

[0099] Adjust the catalyst CuO@SiO in Example 1 2 -Al 2 O 3 The nanomaterials are CuO and SiO in a mass ratio of 1:10:20. 2 、Al 2 O 3 A mixture of nanomaterials (0.1 mm) and the other contents were the same as in Example 1 to obtain a liquor with a high content of furanones.

[0100] The obtained liquor with high furanone content was subjected to performance test, and the test results are as follows:

[0101] Table 4

[0102] example Trigonelline lactone (μg / L) Furanone (μg / L) Ethyl furanone (μg / L) Example 1 52±9 13.1±1.4 7±1 Comparative Example 1 26±2 5.8±1.3 3.6±0.9 Comparative Example 2 12±2 4.0±0.9 3.2±0.8 Comparative Example 3 33±5 8.2±2.6 5.5±1.9

[0103] Although the present invention has been disclosed as above in the form of a preferred embodiment, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the definition of the claims.

Claims

1. A method for regulating the content of furanones during the storage and aging process of liquor, It is characterized in that The method described is to add the catalyst CuO@SiO into the liquor during the storage and aging process. 2 -Al 2 O 3 Nanomaterials; among them, the catalyst CuO@SiO 2 -Al 2 O 3 The amount of nanomaterial added is 0 to 5% of the mass of the liquor, but not 0.

2. The method according to claim 1, It is characterized in that Catalyst CuO@SiO 2 -Al 2 O 3 The particle size of nanomaterials is 0.01 to 1 mm.

3. The method according to claim 1, It is characterized in that Furanone substances are one of fenugreek lactone, furanone, and ethyl furanone.

4. The method according to claim 1, It is characterized in that Catalyst CuO@SiO 2 -Al 2 O 3 The preparation method of nanomaterials is as follows: (1) mixing 1-methyl-2-pyrrolidone, polyethersulfone and polyvinylpyrrolidone to obtain a light yellow viscous liquid; (2) Add SiO2 to the light yellow viscous liquid. 2 , alumina monohydrate, and CuO are fully dispersed to obtain a dispersion; (3) Extruding the dispersion into spherical particles, and then soaking them in water to cause phase transformation to form solid small particles; (4) Sintering the solid small particles to obtain the catalyst CuO@SiO 2 -Al 2 O 3 Nanomaterials.

5. The method according to claim 1, It is characterized in that The method for regulating the content of furanone substances during the storage and aging process of liquor comprises the following steps: The newly distilled liquor is put into a storage container and the catalyst CuO@SiO is added. 2 -Al 2 O 3 Nanomaterials are stored and aged at room temperature to obtain liquor with a high content of furanones.

6. The method according to claim 1, It is characterized in that The liquor is one or more of the following: sauce-flavor liquor, light-flavor liquor, strong-flavor liquor, phoenix-flavor liquor, rice-flavor liquor, sesame-flavor liquor, special-flavor liquor, Laobaigan-flavor liquor, mixed-flavor liquor, Dong-flavor liquor, rich-flavor liquor, and soy-flavor liquor.

7. The method according to claim 1, It is characterized in that The storage container is a glass jar, a ceramic jar, a ceramic vat, or a stainless steel tank.

8. Liquor with high furanone content prepared by the method according to any one of claims 1 to 7.

9. A finished wine, It is characterized in that The product is obtained by blending the liquor with a high furanone content as claimed in claim 8.

10. Use of the liquor with high furanone content as claimed in claim 8 in the field of liquor processing.

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