Method for regulating and controlling content of nitrogen-containing heterocyclic ring substances in white spirit storage and aging process

Abstract

The invention discloses a method for regulating and controlling the content of nitrogen heterocyclic ring substances in the storage and aging process of white spirit, and belongs to the technical field of white spirit industry. According to the method for regulating and controlling the content of the nitrogen heterocyclic ring substances in the storage and aging process of the white spirit, Fe2O3 coated SiO2-Al2O3 is added into the white spirit in the storage and aging process of the white spirit, and the addition amount of the Fe2O3 coated SiO2-Al2O3 is 0-5% of the mass of the white spirit, but not 0. According to the method disclosed by the invention, after Fe2O3 coated SiO2-Al2O3 is added into the white spirit as a catalyst, the content of nitrogen heterocyclic ring substances in the white spirit stored for 6 months is increased by 1.1 times or more compared with that of the white spirit without Fe2O3 coated SiO2-Al2O3.

Description

Technical Field

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

[0002] Chinese liquor has a long history. It is made from cereals as the main raw materials, with Daqu, Xiaoqu or Fuqu as saccharification and fermentation agents, using solid, semi-solid or liquid fermentation methods, and through processes such as cooking, saccharification, fermentation, distillation, aging, and blending. Due to differences in the natural environment in which they are produced, brewing raw materials, saccharification and fermentation agents, production processes, and distillation, Chinese liquor has its own unique styles.

[0003] Pyrazine compounds are important compounds related to the flavor of Chinese liquor. They have a low aroma threshold and make an important contribution to the flavor of liquor. They are also substances beneficial to human health and have long received great attention from researchers.

[0004] The regulation of the content of pyrazine compounds in liquor is achieved through the selection of excellent strains and the application of fermentation engineering technology based on culture medium and fermentation process optimization to wine production. Most of the strain screening focuses on the screening of high-yield tetramethylpyrazine strains, and most of the strains screened are Bacillus subtilis and Bacillus licheniformis. The fermentation engineering technology based on culture medium and fermentation process optimization is based on the synthesis mechanism of tetramethylpyrazine microbial fermentation. The second stage of the metabolic reaction is carried out by acetoin and ammonium ions under the action of thermodynamics.

[0005] At present, there is no literature mentioning how to regulate the content of pyrazine compounds in liquor during the storage and aging process.

[0006] In the field of liquor, researchers still do not have a clear understanding of the chemical nature of liquor storage and aging flavor, making it difficult to effectively control the flavor quality of liquor during storage and aging. At the same time, pyrazine compounds that form liquor flavor often have the characteristics of low content and strong aroma intensity, and this type of substance shows a significant increase trend with the increase of liquor storage time. However, even in the storage process of up to 30 years, the change range of this type of substance is 1.5-5 times.

[0007] Therefore, how to regulate the content of pyrazine compounds in liquor during the storage and aging process is an urgent problem that needs to be solved. Summary of the invention

[0008] [Technical issues]

[0009] The regulation of the content of pyrazine compounds in liquor is achieved through the selection of excellent strains and the application of fermentation engineering technology based on culture medium and fermentation process optimization to wine production; there is no literature mentioning how to regulate the content of pyrazine compounds in liquor during storage and aging.

[0010] The flavor formation of conventional liquor during storage and aging relies on natural processes, and its quality is difficult to effectively control.

[0011] [Technical solution]

[0012] In order to solve the above problems, the present invention adds a catalyst Fe during the storage and aging process of liquor. 2 O 3 @SiO 2 -Al 2 O 3 Nanomaterials can be used to regulate the content of nitrogen-containing heterocyclic substances in liquor, especially the content of pyrazines.

[0013] The first object of the present invention is to provide a method for regulating the content of nitrogen-containing heterocyclic substances in the storage and aging process of liquor, wherein the method comprises adding Fe 2 O 3 @SiO 2 -Al 2 O 3 , Fe 2 O 3 @SiO 2 -Al 2 O 3 The amount added is 0-5% of the mass of the liquor, but not 0.

[0014] In one embodiment of the present invention, Fe 2 O 3 @SiO 2 -Al 2 O 3 It is a nano material with a particle size of 0.01mm-1mm.

[0015] In one embodiment of the present invention, Fe 2 O 3 @SiO 2 -Al 2 O 3 The preparation method is as follows:

[0016] (1) Preparation of MIL-101-Fe (metallic iron framework):

[0017] 1,4-phthalic acid and ferric chloride hexahydrate were subjected to solvothermal reaction in N,N-dimethylformamide to obtain MIL-101-Fe;

[0018] The dosage ratio of 1,4-phthalic acid, ferric chloride hexahydrate and N,N-dimethylformamide is 166 mg: 675 mg: 15 mL; the solvent thermal reaction is carried out at 120°C-180°C for 10h-24h;

[0019] (2) Preparation of SiAl@MIL:

[0020] Tetramethyl orthosilicate, aluminum sec-butoxide solution, acetic acid and ethyl acetoacetate are uniformly mixed to obtain a mixed solution; after MIL-101-Fe is activated, it is immersed in the mixed solution for soaking, and after the soaking is completed, it is separated and dried to obtain SiAl@MIL;

[0021] The volume ratio of tetramethyl orthosilicate, aluminum sec-butoxide solution, acetic acid and ethyl acetoacetate is 30:15:2:1; the solvent of aluminum sec-butoxide solution is sec-butanol, and the amount ratio of aluminum sec-butoxide to sec-butanol is 0.01 g:150 μL; soaking is done at room temperature (20-40° C.) for 3 hours; drying is done at 70-90° C. for 1-20 hours;

[0022] (3) Preparation of Fe catalyst 2 O 3 @SiO 2 -Al 2 O 3 Nanomaterials:

[0023] SiAl@MIL is heat treated to obtain Fe 2 O 3 @SiO 2 -Al 2 O 3 Nanomaterials;

[0024] The heat treatment is carried out at 900-1000°C for 1-3h.

[0025] In one embodiment of the present invention, the nitrogen-containing heterocyclic substance is a pyrazine substance, specifically including one or more of 2-methylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 2-ethyl-6-methylpyrazine, 3-ethyl-2,5-dimethylpyrazine, 2,3-dimethyl-5-ethylpyrazine, 2,3,5-trimethylpyrazine, and 2,3,5,6-tetramethylpyrazine.

[0026] In one embodiment of the present invention, the method for regulating the content of nitrogen-containing heterocyclic substances during the storage and aging process of liquor comprises the following steps:

[0027] The newly distilled liquor and Fe 2 O 3 @SiO 2 -Al2 O 3 The mixture is loaded into a storage container and stored at room temperature, and a liquor with a high content of nitrogen-containing heterocyclic substances is obtained through storage aging.

[0028] 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.

[0029] 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.

[0030] In one embodiment of the present invention, storage at room temperature is storage at 20-40° C. for more than 2 months.

[0031] The second object of the present invention is to provide a liquor with a high content of nitrogen-containing heterocyclic substances prepared by the method described in the present invention.

[0032] The third object of the present invention is to provide a finished wine, which is obtained by blending the white wine with a high content of nitrogen-containing heterocyclic substances of the present invention.

[0033] The fourth objective of the present invention is to use the liquor with a high nitrogen-containing heterocyclic substance content in the liquor processing field.

[0034] [Beneficial Effects]

[0035] (1) The present invention adds Fe to liquor 2 O 3 @SiO 2 -Al 2 O 3 After being used as a catalyst, the content of nitrogen-containing heterocyclic substances in the liquor stored for 6 months was lower than that without Fe addition. 2 O 3 @SiO 2 -Al 2 O 3 The price of liquor has increased by more than 1.1 times.

[0036] (2) The method of the present invention enables the content of nitrogen-containing heterocyclic substances in new wine to reach the level of storage and aging for more than 3 years after storage for 6 months. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is the spectrum of the pyrazine substance test in Example 1 (GC×GC-TOFMS2D spectrum).

[0038] Figure 2This is the spectrum of the pyrazine substance test in Example 1 (GC×GC-TOFMS1D spectrum). DETAILED DESCRIPTION

[0039] 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.

[0040] Test method:

[0041] Detection of pyrazines:

[0042] (1) Pretreatment of liquor samples:

[0043] Dilute the liquor sample with ultrapure water to an alcohol content of 10% vol, then take 5 mL and add it to a 20 mL headspace bottle, then add 1.5 g NaCl and 10 μL of pyrazine isotope internal standard, 2-methylpyrazine-d6;

[0044] After the samples were mixed, HS-SPME was performed using a MPS2 (Gerstel, Germany) multifunctional autosampler. The conditions were as follows: the samples were equilibrated at 40°C for 5 minutes, stirred and extracted at 250 rpm for 40 minutes, and the extraction head model was DVB / CAR / PDMS (2 cm, 50 / 30 μm, Supelco, America). After the extraction, desorption was performed at 250°C for 5 minutes.

[0045] (2) Determination of the content of pyrazines in liquor samples by comprehensive two-dimensional gas chromatography:

[0046] Chromatographic conditions: The gas chromatograph was Agilent 7890B (Agilent, America), the first-dimension chromatographic column was a DB-FFAP capillary column (60m×0.25mm×0.25μm, Agilent, America), and the second-dimension chromatographic column was an Rx-17 Si capillary column (0.8m×0.25mm×0.36μm, Restek, America); the first-dimension chromatographic column and the second-dimension chromatographic column were connected in series through a four-nozzle two-stage thermal modulator, and the transmission temperature was 240°C; He (>99.999%) was used as the carrier gas, the flow rate was 1mL / min, and the injection port temperature was 250°C;

[0047] The temperature program of the one-dimensional column is mainly divided into four stages. The starting temperature of the first stage is set to 45℃ and maintained for 3min; the second stage is heated to 150℃ at a heating rate of 4℃ / min and then maintained for 2min; the third stage is heated to 200℃ at a heating rate of 6℃ / min; the last stage is heated to 230℃ at a heating rate of 10℃ / min and then maintained for 10min.

[0048] The total time of the entire analysis process was 53 minutes, and the temperature of the second-dimensional column oven was 5°C higher than that of the first-dimensional column oven throughout the process; the compensation temperature of the modulator was set to 20°C, the modulation cycle of the modulator was 4s, and the thermal pulse time was 0.8s. Mass spectrometry conditions: ion source voltage 70eV, temperature 230°C, transmission line temperature 240°C, ion scanning range 35-400amu, scanning frequency 100spestra / s.

[0049] (3) Standard curve drawing:

[0050] Use chromatographic grade ethanol and ultrapure water to prepare a simulated liquor matrix solution (pH = 3.5, alcohol content 53% vol) for later use;

[0051] Accurately weigh a certain amount of pyrazine compound standard and dissolve it in simulated liquor solution to prepare a series of standard solutions with different concentration gradients. The standard solution is treated according to the above sample pretreatment method and then analyzed by the instrument. The peak area ratio and concentration ratio of the target substance to the internal standard substance are used as the horizontal and vertical coordinates to prepare the standard curve;

[0052] (4) Detection:

[0053] 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.

[0054] The raw materials used in the examples are:

[0055] 1.Fe 2 O 3 @SiO 2 -Al 2 O 3 Preparation:

[0056] (1) 166 mg of 1,4-phthalic acid and 675 mg of ferric chloride hexahydrate were subjected to solvothermal reaction in 15 mL of N,N-dimethylformamide at 160° C. for 22 h to obtain MIL-101-Fe;

[0057] (2) dispersing 0.01 g of aluminum sec-butoxide in 150 μL of sec-butanol to obtain an aluminum sec-butoxide solution; mixing 300 μL of tetramethyl orthosilicate, 150 μL of the aluminum sec-butoxide solution, 20 μL of acetic acid and 10 μL of ethyl acetoacetate to obtain a mixed solution;

[0058] MIL-101-Fe was vacuum activated, then immersed in the mixed solution at room temperature (25°C) for 3 h, taken out, filtered, and the obtained solid was dried at 80°C for 12 h to form SiAl@MIL;

[0059] (3) SiAl@MIL was heat treated at 950℃ for 2h to obtain Fe 2 O 3 @SiO 2 -Al 2 O 3 .

[0060] 2.Fe 2 O 3 @SiO 2 -Al 2 O 3 The amount added (%) is the mass percentage relative to the newly distilled liquor.

[0061] 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.

[0062] 4. Pottery jar: a commercially available pottery jar used to store liquor.

[0063] 5. 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 content of nitrogen-containing heterocyclic substances during the storage and aging process of liquor comprises the following steps:

[0066] The newly distilled liquor (sauce-flavor liquor) and Fe 2 O 3 @SiO 2 -Al 2 O 3 Nanomaterials (0.1m m ) into a stainless steel tank, Fe 2 O 3 @SiO 2 -Al 2 O 3 The mass of the nanometer material is 1% of the mass of the liquor, and the liquor is stored and aged at room temperature (30° C.) for 6 months to obtain the liquor containing nitrogen heterocyclic substances.

[0067] Example 2 Optimization of catalyst dosage

[0068] Adjust the Fe in Example 1 2 O 3 @SiO 2 -Al 2 O 3 The addition amount of the nano material is 0, 0.1%, 2%, and 3% of the mass of the liquor, and the other contents are consistent with those in Example 1, so as to obtain liquor with a high content of nitrogen-containing heterocyclic substances.

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

[0070] Table 1

[0071]

[0072] Example 3 Optimization of storage container

[0073] The stainless steel tank 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 nitrogen-containing heterocyclic substances.

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

[0075] Table 2

[0076]

[0077]

[0078] Example 4 Optimization of liquor types

[0079] The sauce-flavor liquor in Example 1 is adjusted to be a light-flavor liquor, a strong-flavor liquor, or a mixed-flavor liquor, and the rest is kept consistent with Example 1, that is, a liquor with a high content of nitrogen-containing heterocyclic substances.

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

[0081] Table 3

[0082]

[0083] Comparative Example 1

[0084] Adjust the Fe in Example 1 2 O 3 @SiO 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.

[0085] Comparative Example 2

[0086] Adjust the Fe in Example 1 2 O 3 @SiO 2 -Al 2 O 3 The nanomaterial is a pottery piece (size is 50×50 mm), and the rest is consistent with Example 1 to obtain white wine.

[0087] Comparative Example 3

[0088] Adjust the Fe in Example 1 2 O 3 @SiO 2 -Al 2 O 3 The nanomaterial is Fe in a mass ratio of 1:10:20 2 O 3 、SiO 2 、Al 2 O 3 A mixture of powders (0.1 mm) and the rest of the mixture was the same as in Example 1 to obtain liquor.

[0089] The obtained liquor was subjected to performance test, and the test results are as follows:

[0090] Table 4

[0091]

[0092] 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 nitrogen-containing heterocyclic substances during the storage and aging process of liquor, It is characterized in that The method described is to add Fe to the liquor during the storage and aging process. 2 O 3 @SiO 2 -Al 2 O 3 , Fe 2 O 3 @SiO 2 -Al 2 O 3 The amount 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 Fe 2 O 3 @SiO 2 -Al 2 O 3 It is a nano material with a particle size of 0.01mm-1mm.

3. The method according to claim 1, It is characterized in that The method for regulating the content of nitrogen-containing heterocyclic substances during the storage and aging process of liquor comprises the following steps: The newly distilled liquor and Fe 2 O 3 @SiO 2 -Al 2 O 3 The mixture is loaded into a storage container and stored at room temperature, and a liquor with a high content of nitrogen-containing heterocyclic substances is obtained through storage aging.

4. 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.

5. The method according to claim 1, It is characterized in that The nitrogen-containing heterocyclic substances are pyrazine substances, including one or more of 2-methylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 2-ethyl-6-methylpyrazine, 3-ethyl-2,5-dimethylpyrazine, 2,3-dimethyl-5-ethylpyrazine, 2,3,5-trimethylpyrazine, and 2,3,5,6-tetramethylpyrazine.

6. 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.

7. The method according to claim 1, It is characterized in that Storage at room temperature is 20-40℃ for more than 2 months.

8. Liquor with high nitrogen heterocyclic content prepared by the method described in claims 1-7.

9. A finished wine, It is characterized in that The liquor is obtained by blending the liquor having a high content of nitrogen-containing heterocyclic substances as described in claim 8.

10. Use of the liquor with a high content of nitrogen-containing heterocyclic substances as claimed in claim 8 in the field of liquor processing.

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