Method for regulating and controlling content of vanillin and acetovanillin in white spirit

Abstract

The invention discloses a method for regulating and controlling the content of vanillin and acetovanillin in white spirit, and belongs to the technical field of white spirit industry. According to the method for regulating and controlling the content of vanillin and acetovanillone in the storage and aging process of the white spirit, a catalyst PtPb coated SiO2-Al2O3 nano material is added in the storage and aging process of the white spirit, and the addition amount of the catalyst PtPb coated SiO2-Al2O3 nano material is 0-5% of the mass of the white spirit, but not 0. After the catalyst PtPb coated SiO2-Al2O3 nano material is added, the content of vanillin in the Baijiu stored and aged for 6 months is increased by 1.1 times or above compared with that of Baijiu without the catalyst, and the content of acetovanillin is increased by 1.3 times or above.

Description

Technical Field

[0001] The invention relates to a method for regulating the contents of vanillin and vanillyl acetone in liquor, and belongs to the technical field of liquor industry. Background Art

[0002] Chinese liquor has a long history and is a world-renowned distilled liquor. The unique brewing process and the microbial system in the koji give the liquor a rich aroma and flavor substances and bioactive ingredients. Among them, phenols, aldehydes and ketones, as an important type of trace components in liquor, play an important role in the aroma, taste and stability of liquor. More and more studies have shown that phenols, aldehydes and ketones also have certain physiological activities.

[0003] At present, researchers' research on phenols, aldehydes and ketones is only about how to identify them, or how to regulate the content of phenols, aldehydes and ketones through the early fermentation process, but there is no mention of how to regulate the content of phenols, aldehydes and ketones during the storage and aging process.

[0004] Moreover, researchers still do not have a clear understanding of the chemical nature of the aged flavor of liquor, 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 among phenols, aldehydes and ketones, vanillin and vanillyl acetone 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.

[0005] Therefore, there is an urgent need for a method for regulating the content of vanillin and vanillyl acetone during the storage and aging process of liquor. Summary of the invention

[0006] [Technical issues]

[0007] The flavor chemical quality of liquor during storage and aging is difficult to effectively control, and there is no literature mentioning how to regulate the content of vanillin and vanillyl acetone during storage and aging of liquor.

[0008] [Technical solution]

[0009] In order to solve the above problems, the present invention adds a catalyst PtPb@SiO 2 -Al 2 O 3 Nanomaterials are used to control the content of vanillin and vanillin acetone in liquor; the method of the invention is beneficial to controlling the formation of flavor quality of liquor during storage and aging, thereby shortening 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 vanillin and vanillin acetone during the storage and aging of liquor, wherein the method comprises adding a catalyst PtPb@SiO 2 -Al 2 O 3 Nanomaterials, Catalyst PtPb@SiO 2 -Al 2 O 3 The amount of nanomaterial added is 0-5% of the mass of the liquor, but not 0.

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

[0012] In one embodiment of the present invention, the catalyst PtPb@SiO 2 -Al 2 O 3 The preparation method of nanomaterials is as follows:

[0013] (1) mixing a mixed solution of aluminum sec-butoxide and sec-butanol, tetramethyl orthosilicate, acetic acid and ethyl acetoacetate to obtain a mixed solution A;

[0014] (2) Chloroplatinic acid (H 2 PtCl 6 6H 2 O) and PdCl 2 Dissolve in a dilute hydrochloric acid solution to obtain a mixed solution B, and then mix the mixed solution B with the mixed solution A to obtain a mixed solution C;

[0015] (3) Drying and calcining the mixed solution C to obtain the catalyst PtPb@SiO 2 -Al 2 O 3 Nanomaterials.

[0016] In one embodiment of the present invention, the mixed solution of aluminum sec-butoxide and sec-butanol in step (1) is prepared by dispersing aluminum sec-butoxide in sec-butanol, and the dosage ratio of aluminum sec-butoxide to sec-butanol is 0.01 g:150 μL.

[0017] In one embodiment of the present invention, in step (1), the volume ratio of the mixed solution of aluminum sec-butoxide and sec-butanol, tetramethyl orthosilicate, acetic acid and ethyl acetoacetate is 150:300:20:10.

[0018] In one embodiment of the present invention, in step (2), chloroplatinic acid (H 2PtCl 6 6H 2 O) and PdCl 2 The mass ratio is 1:1.

[0019] In one embodiment of the present invention, the dilute hydrochloric acid solution in step (2) is a dilute hydrochloric acid aqueous solution with a concentration of 0.2 mol / L.

[0020] In one embodiment of the present invention, in step (2), chloroplatinic acid (H 2 PtCl 6 6H 2 O) and dilute hydrochloric acid solution in a dosage ratio of 5g:15mL.

[0021] In one embodiment of the present invention, the volume ratio of the mixed solution B to the mixed solution A in step (2) is 1:1.

[0022] In one embodiment of the present invention, the mixing in step (2) is carried out by stirring at 20-40° C. (normal temperature) and 500-1000 rpm for 2.5-3.5 hours.

[0023] In one embodiment of the present invention, the drying in step (3) is microwave drying.

[0024] In one embodiment of the present invention, the calcination in step (3) is carried out by increasing the temperature to 550° C. at 2° C. / min and maintaining the temperature for 5 hours.

[0025] In one embodiment of the present invention, the method for regulating the content of vanillin and ethylvanillin during the storage and aging of liquor comprises the following steps:

[0026] The newly distilled liquor is put into a storage container and the catalyst PtPb@SiO is added. 2 -Al 2 O 3 Nano materials are stored at room temperature and aged to obtain liquor with high vanillin and vanillyl acetone content.

[0027] 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.

[0028] 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.

[0029] In one embodiment of the present invention, the room temperature storage is storage at 20-40°C for more than 2 months.

[0030] The second object of the present invention is to obtain liquor with high vanillin and ethylvanillin content prepared by the method of the present invention.

[0031] The third object of the present invention is to use the liquor with high vanillin and ethylvanillin content in the liquor processing field.

[0032] The fourth object of the present invention is to provide a finished wine, which is obtained by blending the white wine with high vanillin and ethylvanillin content of the present invention.

[0033] [Beneficial Effects]

[0034] (1) The present invention adds the catalyst PtPb@SiO 2 -Al 2 O 3 After adding nanomaterials, the content of vanillin in the liquor stored and aged for 6 months increased by more than 1.1 times compared with the liquor without adding catalyst, and the content of vanillone increased by more than 1.3 times.

[0035] (2) The method of the present invention enables new wine to reach the level of 8-year storage aging after 6 months of storage. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is the GC-MS-SIM pattern spectrum of vanillin and vanillyl ethyl ketone in Example 1. DETAILED DESCRIPTION

[0037] 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.

[0038] Test method:

[0039] Detection of vanillin and vanillyl acetone content:

[0040] (1) Liquid-liquid extraction sample pretreatment:

[0041] 20 mL of liquor sample was diluted with saturated saline to an alcohol content of 10% vol, and then anisyl acetone was added as an internal standard, 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;

[0042] (2) Sample analysis using gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring mode (SIM)

[0043] The GC conditions are as follows:

[0044] Agilent 7890 gas chromatograph tandem with 5975 mass spectrometer was used;

[0045] The chromatographic column was DB-FFAP (60 m × 0.25 mm × 0.25 μm, Agilent, America);

[0046] Chromatographic column (DB-FFAP) temperature program: initial temperature was 45 °C for 2 min, then increased to 230 °C at 6 °C / min and maintained for 10 min;

[0047] He (>99.999%) was used as carrier gas, with a flow rate of 2 mL / min and an injection port temperature of 230 °C;

[0048] The MS conditions are as follows:

[0049] The sample solvent delay time was 8 min;

[0050] EI ionization source, ionization energy of 70 eV, ion source temperature of 230 ° C, mass spectrometry ion scanning range of 35-350 amu;

[0051] Selective ions monitoring (SIM) mode was used for the quantification of vanillin and vanillyl ethyl ketone, and the characteristic ions were 152 m / z and 166 m / z, respectively;

[0052] (3) Standard curve drawing:

[0053] 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 phenolic ketone compound standard (vanillin and vanillyl ethyl ketone) is accurately weighed and dissolved in the simulated liquor solution to prepare a series of standard solutions with different concentration gradients; the standard solution is 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;

[0054] (4) Detection:

[0055] 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.

[0056] The raw materials used in the embodiment:

[0057] 1. Catalyst PtPb@SiO 2 -Al 2 O 3 The preparation method of nanomaterials is as follows:

[0058] (1) 150 μL of a mixed solution of aluminum sec-butoxide and sec-butanol (0.01 g of aluminum sec-butoxide dispersed in 150 μL of sec-butanol), 300 μL of tetramethyl orthosilicate, 20 μL of acetic acid, and 10 μL of ethyl acetoacetate were mixed to obtain a mixed solution A;

[0059] (2) Add 5 g of chloroplatinic acid (H 2 PtCl 6 6H 2 O) and 5g PdCl 2 Dissolve in 15 mL of 0.2 mol / L dilute hydrochloric acid aqueous solution to obtain mixed solution B, then mix mixed solution B with mixed solution A at a volume ratio of 1:1, and stir at 25°C (normal temperature) and 500 rpm for 3 h to obtain mixed solution C;

[0060] (3) The mixed solution C was dried under microwave for 30 min and then calcined in a muffle furnace (heated to 550 °C at 2 °C / min and maintained for 5 h) to obtain the catalyst PtPb@SiO 2 -Al 2 O 3 Nanomaterials.

[0061] 2. Catalyst PtPb@SiO 2 -Al 2 O 3 The amount of nanomaterial added (%) is the mass percentage relative to the newly distilled liquor.

[0062] 3. Pottery powder and pottery fragments come from pottery jars (commercially available pottery jars commonly used to store liquor). Pottery powder is the powder obtained by grinding the pottery jars, and pottery fragments are fragments of the pottery jars.

[0063] 4. Maotai-flavor liquor, light-flavor liquor, strong-flavor liquor, and mixed-flavor liquor are new liquors that have not been stored.

[0064] Example 1

[0065] A method for regulating the contents of vanillin and vanillone during the storage and aging process of liquor, comprising the following steps:

[0066] The newly distilled liquor (Jiangxiang liquor) was put into a stainless steel tank and 1% catalyst PtPb@SiO was added. 2 -Al 2 O 3 Nanomaterials (0.1 mm) were stored and aged at room temperature (25°C) for 6 months to obtain liquor with high vanillin and vanillyl acetone content.

[0067] Example 2 Optimization of catalyst dosage

[0068] Adjust the catalyst PtPb@SiO in Example 12 -Al 2 O 3 The addition amount of the nano material is 0, 0.1%, 2%, and 3%, and the others are consistent with Example 1, to obtain a liquor with high vanillin and vanillyl acetone content.

[0069] The obtained liquor with high vanillin and vanillin acetone content was subjected to performance tests, and the test results are as follows:

[0070] Table 1

[0071] Catalyst dosage (%) Vanillin(μg / L) Vanillyl acetone (μg / L) 1 (Example 1) 411±26 70±12 0 280±19 36±8 0.1 308±15 49±11 2 392±26 63±17 3 406±21 66±10

[0072] Example 3 Optimization of storage container

[0073] The storage container (stainless steel tank) in Example 1 is adjusted to a ceramic jar, and the other contents are kept consistent with Example 1 to obtain a liquor with high vanillin and vanillyl acetone content.

[0074] The obtained liquor with high vanillin and vanillin acetone content was subjected to performance tests, and the test results are as follows:

[0075] Table 2

[0076] Storage container Vanillin(μg / L) Vanillyl acetone (μg / L) Pottery jar 567±38 91±28 Stainless steel tank (Example 1) 411±26 70±12

[0077] Example 4 Optimization of liquor types

[0078] 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 high vanillin and vanillyl acetone content.

[0079] The obtained liquor with high vanillin and vanillin acetone content was subjected to performance tests, and the test results are as follows:

[0080] Table 3

[0081] Liquor Type Vanillin(μg / L) Vanillyl acetone (μg / L) Maotai-flavor type (embodiment 1) 411±26 70±12 Strong aroma 251±32 50±15 Light fragrance 309±24 29±12 Fragrance 322±19 42±20

[0082] Comparative Example 1

[0083] Adjust the catalyst PtPb@SiO in Example 1 2 -Al 2 O 3 The nano material is ceramic powder (particle size is 0.1 mm), and the rest is consistent with Example 1 to obtain white wine.

[0084] Comparative Example 2

[0085] Adjust the catalyst PtPb@SiO in Example 1 2 -Al 2 O 3The nanomaterial is a pottery piece (size is 50×50 mm), and the rest is consistent with Example 1 to obtain white wine.

[0086] Comparative Example 3

[0087] Adjust the catalyst PtPb@SiO in Example 1 2 -Al 2 O 3 The nanomaterials are PtPb and SiO in a mass ratio of 1:10:20. 2 、Al 2 O 3 A mixture of nanomaterials (0.1 mm) and other conditions are consistent with those in Example 1 to obtain white wine.

[0088] The obtained liquor was subjected to performance test, and the test results are as follows:

[0089] Table 4

[0090] example Vanillin(μg / L) Vanillyl acetone (μg / L) Example 1 411±26 70±12 Comparative Example 1 300±19 36±11 Comparative Example 2 280±13 29±9 Comparative Example 3 336±18 42±13

[0091] 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 vanillin and vanillyl acetone during the storage and aging process of liquor. It is characterized in that The method described is to add the catalyst PtPb@SiO 2 -Al 2 O 3 Nanomaterials, Catalyst PtPb@SiO 2 -Al 2 O 3 The amount of nanomaterial added is 0-5% of the mass of the liquor, but not 0.

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

3. 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.

4. The method according to claim 1, It is characterized in that The method for regulating the content of vanillin and vanillyl acetone 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 PtPb@SiO is added. 2 -Al 2 O 3 Nano materials are stored at room temperature and aged to obtain liquor with high vanillin and vanillyl acetone content.

5. The method according to claim 1, It is characterized in that The storage container is one of a glass jar, a pottery jar, a pottery cylinder and a stainless steel tank.

6. The method according to claim 1, It is characterized in that The room temperature storage is storage at 20-40°C for more than 2 months.

7. The method according to claim 1, It is characterized in that The catalyst PtPb@SiO 2 -Al 2 O 3 The preparation method of nanomaterials is as follows: (1) mixing a mixed solution of aluminum sec-butoxide and sec-butanol, tetramethyl orthosilicate, acetic acid and ethyl acetoacetate to obtain a mixed solution A; (2) Chloroplatinic acid and PdCl 2 Dissolve in a dilute hydrochloric acid solution to obtain a mixed solution B, and then mix the mixed solution B with the mixed solution A to obtain a mixed solution C; (3) Drying and calcining the mixed solution C to obtain the catalyst PtPb@SiO 2 -Al 2 O 3 Nanomaterials.

8. A liquor with high vanillin and ethylvanillin content prepared by the method according to any one of claims 1 to 7.

9. Use of the liquor with high vanillin and ethylvanillin content as claimed in claim 8 in the field of liquor processing.

10. A finished wine, It is characterized in that The product is obtained by blending the liquor with high vanillin and ethylvanillin content as claimed in claim 8.

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