CN112410144A

CN112410144A - Processing technology of grape wine

Info

Publication number: CN112410144A
Application number: CN202011424205.4A
Authority: CN
Inventors: 邓卫平; 罗光辉
Original assignee: Individual
Current assignee: Individual
Priority date: 2020-12-09
Filing date: 2020-12-09
Publication date: 2021-02-26

Abstract

The invention belongs to the technical field of wine processing, and particularly relates to a wine processing technology which is characterized by comprising the following components in parts by mass: 96.65-98.85 parts of grape juice, 1-3 parts of activated yeast, 0.1-0.2 part of oxidized cellulose porphyrin cerium complex microspheres and 0.05-0.15 part of quaternary ammonium salt modified hawthorn-grape residue extract. The invention also provides a processing technology of the wine. The invention discloses a method for preparing wine by adding a clarifying agent which has strong lipid solubility and avoids the loss of wine in the processing technology for preparing wine, and is especially important for preparing wine by adding a safe additive which has double functions of sterilization and antioxidation.

Description

Processing technology of grape wine

Technical Field

The invention belongs to the technical field of wine processing, and particularly relates to a processing technology and a brewing formula of wine.

Background

Since the state of 2005 opened general trade and imported wine, the imported amount of wine in China is as short as 15 years, the growth is rapid, the cognition of Chinese consumers to wine is gradually changed and clear, the development of Chinese wine is in a long stage, and the yield and the industrial structure of the wine industry are greatly changed from the first without attention to the fact that most people accept wine today. In recent two years, with the rapid development of economy, the living standard and the consumption standard of people are rapidly improved, and the wine becomes a frequent visitor at home of common people.

The grape wine is an alcoholic beverage prepared by fermenting fresh grapes or grape juice, is a health alcoholic beverage which is recognized in the world and beneficial to human bodies, is rich in nutrition and complex in components, contains various chemical substances, exists in a dissolved state, some of the chemical substances are close to a saturated state, and also contains various macromolecular colloidal substances such as protein, tannin, polyphenol, pigment, pectin and the like. However, when the protein and pectin in the wine coexist with polyphenols, turbid colloid is generated and even precipitation occurs, which affects the transparency of the wine, so that a clarifying agent is added in the production to remove a part or most of easily formed precipitation components, so that the wine obtains good flavor and clarity.

Common wine clarifying agents are oxidized cellulose, diatomite, bentonite, pectinase, chitosan and the like, and although the price of the diatomite, the bentonite and the oxidized cellulose is low, the clarifying effect on most wines is poor; pectinase can decompose pectin in wine, but if the pectin is not properly treated, the carboxyl methyl ester on the pectin can generate methanol toxic substances, so that health is harmed; the chitosan can hydrolyze protein to achieve the purpose of clarification, but the chitosan has water solubility, and is easy to cause wine loss when clarifying wine and filtering precipitates.

Although the wine is sterilized before bottling, when the unsealed wine is stored, microorganisms harmful to the body are generated and the wine is oxidized, the color of the wine is changed, the nutritional value of the wine is reduced, generally, a wine manufacturer adds a preservative to prevent the enrichment of harmful microorganisms and the oxidation of the wine before bottling, sulfur dioxide is used at most and is added into the wine in the form of sulfite, which can cause anaphylactic reaction of people, cause a series of symptoms including headache, nausea, stomach stimulation and dyspnea, and cause certain damage to the respiratory system, the circulatory system, the nervous system and the like of the human body after long-time excessive consumption of the sulfite.

Based on the above situation, the invention adds the clarifying agent which has strong lipid solubility and avoids the loss of the wine in the process of making the wine, and adds the safe additive which has double functions of sterilization and antioxidation, thereby making the wine more important.

Disclosure of Invention

In order to solve the technical problems that the existing wine clarifying agent has poor clarifying effect and strong water solubility, the wine is easy to lose when the wine is clarified and precipitates are filtered, and microorganisms harmful to the body and the wine are oxidized in the storage process of the wine, the clarifying agent with strong lipid solubility and capable of avoiding the loss of the wine is added in the wine making process, and the safe additive with double functions of sterilization and antioxidation is added to make the wine.

In order to achieve the purpose, the invention adopts the following technical scheme:

the processing technology of the wine is characterized by comprising the following steps:

(1) picking mature grapes, removing diseased fruits, rotten fruits and other impurities from the picked grapes, removing stalks, squeezing, filtering to obtain grape pomace and grape juice respectively, adding the grape juice into a fermentation tank, adding activated yeast, and fermenting at 18-30 ℃ for 10-15 days to obtain fermentation liquor;

(2) adding oxidized cellulose porphyrin cerium complex microspheres into the fermentation liquor obtained in the step (1), performing closed circulation on the fermentation liquor for 0.5-1h, clarifying for 18-30h at 4-8 ℃, naturally heating to 12-16 ℃, standing for 3-5d, filtering, adding a quaternary ammonium salt modified hawthorn-grape residue extract, uniformly mixing, filtering by using a filter membrane with the pore diameter of 0.3-0.5 micrometer, and aging, refrigerating and packaging at 0-4 ℃ under an indoor condition to obtain the grape wine.

Furthermore, the brewing formula of the wine is characterized by comprising the following components in parts by mass: 96.65-98.85 parts of grape juice, 1-3 parts of activated yeast, 0.1-0.2 part of oxidized cellulose porphyrin cerium complex microspheres and 0.05-0.15 part of quaternary ammonium salt modified hawthorn-grape residue extract.

Furthermore, the preparation method of the oxidized cellulose porphyrin cerium complex microsphere comprises the following steps:

step I, preparation of porphyrin oxidized cellulose: adding oxidized cellulose into water, soaking for 12-24h, heating to 40-60 ℃, stirring for 2-6h, cooling to room temperature to obtain oxidized cellulose solution for later use, adding 5- (4-hydroxyphenyl) -10, 15, 20-triphenylporphyrin into tetrahydrofuran, stirring until the mixture is completely dissolved, adding 4-hydroxy-2-piperidinecarboxylic acid, reacting for 2-6h at 50-70 ℃, cooling to room temperature, concentrating, adding chloroform, stirring until the mixture is dissolved, adding the oxidized cellulose solution and tetrabutylammonium bromide, reacting for 4-8h at 50-70 ℃, cooling to room temperature, performing suction filtration, washing the precipitate with chloroform until the precipitate is colorless, washing the precipitate with water, and drying to obtain porphyrized oxidized cellulose;

step II, preparation of the porphyrized oxidized cellulose microspheres: adding the porphyrized oxidized cellulose obtained in the step I into water, performing ultrasonic treatment for 20-40min, adding liquid paraffin and SP-80, stirring for 0.5-1h, slowly adding glutaric acid, reacting for 1-3h at 50-70 ℃, filtering, and washing precipitates with petroleum ether, absolute ethyl alcohol and water in sequence to obtain porphyrized oxidized cellulose microspheres;

step III, preparing oxidized cellulose porphyrin cerium complex microspheres: and (3) adding the porphyrized oxidized cellulose microspheres obtained in the step (II) and cerium nitrate into 0.2-0.6mol/L acetic acid solution, reacting for 6-10h at 40-60 ℃, cooling to room temperature, adjusting the pH to be neutral by using citric acid-sodium citrate, performing suction filtration, sequentially washing and precipitating for 2-4 times by using water and absolute ethyl alcohol, and drying to obtain the oxidized cellulose porphyrin cerium complex microspheres.

Furthermore, in the step I, the mass ratio of the 5- (4-hydroxyphenyl) -10, 15, 20-triphenylporphyrin to the 4-hydroxy-2-piperidinecarboxylic acid to the oxidized cellulose to the tetrabutylammonium bromide is 1: (5-7): (1-3): (0.01-0.03).

Furthermore, in the step II, the mass ratio of the porphyrized oxidized cellulose to the liquid paraffin to the SP-80 to the glutaric acid is 0.1: (120-180): (2-4): (0.8-1.2).

Furthermore, in the step III, the mass ratio of the porphyrized oxidized cellulose microspheres to the cerium nitrate to the acetic acid solution is (4-6): 1: (80-120).

Furthermore, the preparation method of the quaternary ammonium salt modified hawthorn-grape pomace extract comprises the following steps:

step I, preparing hawthorn-grape residue powder: drying and crushing hawthorn and grape residue obtained in the step (1) of the grape wine processing technology, sieving by using a sieve with the aperture of 50-100 meshes, adding petroleum ether, refluxing for 2-4h at the temperature of 60-80 ℃, cooling to room temperature, concentrating and drying to obtain hawthorn-grape residue powder;

step II, preparing the hawthorn-grape pomace extract: adding the hawthorn-grape residue powder obtained in the step I into an ethanol solution with the mass fraction of 70%, placing the mixture into an ultrasonic reactor, carrying out ultrasonic treatment for 20-40min at 40-60 ℃, filtering while the mixture is hot, repeating the ultrasonic treatment for 2-4 times, collecting and combining filtrate, concentrating to obtain a concentrated solution, extracting with ethyl acetate, collecting an organic phase, concentrating, adding anhydrous methanol, decoloring with AB-8 macroporous resin, concentrating, purifying with a silica gel column, and using dichloromethane and ethanol according to the volume ratio of 10: 1. 2: 1, sequentially carrying out gradient elution, and collecting dichloromethane and ethanol in a volume ratio of 2: 1, concentrating the eluent to obtain a hawthorn-grape residue extract;

step III, preparing the quaternary ammonium salt modified hawthorn-grape pomace extract: and (3) adding the hawthorn-grape residue extract obtained in the step (II) into dichloromethane, slowly adding thionyl chloride at the temperature of-5-0 ℃, heating to 20-30 ℃, reacting for 0.5-1h, concentrating, adding triethylamine and isopropanol, reacting for 5-7h at the temperature of 70-90 ℃, cooling to room temperature, and concentrating to obtain the quaternary ammonium salt modified hawthorn-grape residue extract.

Furthermore, the mass ratio of the hawthorn to the grape pomace in the step I is 1: (5-7).

Furthermore, the feed-liquid ratio of the hawthorn-grape residue powder to the ethanol solution in the step II is 1 g: (10-30) ml.

Furthermore, in the step III, the mass ratio of the hawthorn-grape pomace extract to the thionyl chloride to the triethylamine is (2-6): 1: (0.2-0.3).

Furthermore, the invention also protects a wine clarifying agent with strong fat solubility, which is the oxidized cellulose porphyrin cerium complex microsphere.

Furthermore, the invention also discloses a cationic flocculant for brewing wine, which is also the oxidized cellulose porphyrin cerium complex microsphere.

Furthermore, the invention also discloses a grape wine additive with sterilization and oxidation resistance, which is the quaternary ammonium salt modified hawthorn-grape residue extract.

The beneficial effects of the invention are shown in the following aspects:

1. the method comprises the steps of picking, selecting, removing impurities, removing stalks, squeezing, filtering, fermenting and the like of ripe grapes to obtain fermentation liquor, adding a clarifying agent for clarification and filtration, adding an antioxidant and a bactericide, performing fine filtration by using a microfiltration membrane, and finally aging, refrigerating and packaging at low temperature to obtain the wine. The wine clarified by adding the clarifying agent into the fermentation liquor before aging has good clarity, and the wine is not easy to be oxidized by adding the antioxidant and the bactericide, does not generate microorganisms harmful to the body, and has strong stability and good quality.

2. The oxidized cellulose molecule contains a large amount of hydroxyl and carboxyl, the water solubility is strong, the hydroxyl on 5- (4-hydroxyphenyl) -10, 15, 20-triphenyl porphyrin and the carboxyl on 4-hydroxyl-2-piperidine formic acid are subjected to esterification reaction to obtain porphyrin with piperidine ring and hydroxyl, the hydroxyl on the porphyrin and the carboxyl on the oxidized cellulose molecule are subjected to esterification reaction to obtain porphyrin oxidized cellulose with piperidine ring, the porphyrin oxidized cellulose and glutaric acid are subjected to crosslinking through a reversed phase suspension crosslinking method to obtain porphyrin oxidized cellulose microspheres, and the porphyrin oxidized cellulose microspheres and cerium ions in a cerium nitrate solution are subjected to a coordination reaction to obtain the oxidized cellulose porphyrin cerium complex microspheres. Cerium ions are stably chelated in the microspheres, the microspheres have a large number of micropores and a large specific surface area, the formation of the oxidized cellulose porphyrin cerium complex microspheres reduces the number of hydroxyl groups and carboxyl groups on oxidized cellulose, reduces the water solubility of the oxidized cellulose, and increases the lipid solubility of the oxidized cellulose by modifying the oxidized cellulose with porphyrin rings.

3. The microporous structure on the oxidized cellulose porphyrin cerium complex microspheres increases the contact surface area of the oxidized cellulose porphyrin cerium complex microspheres and the wine, and can adsorb polyphenol substances in the wine; the surface and internal functional groups of the oxidized cellulose porphyrin cerium complex microsphere can adsorb protein in the wine through hydrogen bond action and hydrophobic action; the oxidized cellulose porphyrin cerium complex microsphere contains porphyrin cerium complexes on the surface, cerium ions on the porphyrin cerium complexes contain empty orbitals and nitrogen atoms and oxygen atoms which can provide lone pair electrons in protein to form coordination bonds; the piperidine ring contained in the oxidized cellulose porphyrin cerium complex microspheres is protonated to obtain nitrogen positive ions which can be used as a cationic flocculant to adsorb anions in the wine and have good aggregation capability on total protein and pectin of the wine; the oxidized cellulose porphyrin cerium complex microspheres reduce the flocculation of polyphenol and protein or pectin in the wine through the action mode, so that the purpose of clarifying the wine is achieved, and the oxidized cellulose porphyrin cerium complex microspheres have good clarification effect and poor water solubility, and reduce the loss of the wine when being used as a clarifying agent to treat the wine.

4. The method takes grape pomace and hawthorn filtered in the process of making the grape wine as raw materials to obtain a quaternary ammonium salt modified hawthorn-grape pomace extract, and utilizes the grape pomace waste; firstly, drying, crushing and degreasing grape pomace and hawthorn to obtain hawthorn-grape pomace powder, then separating and purifying the hawthorn-grape pomace powder to obtain flavonoids without alcoholic hydroxyl groups and flavonoids containing alcoholic hydroxyl groups, wherein the alcoholic hydroxyl groups of the flavonoids are chlorinated and then subjected to quaternization to obtain a quaternary ammonium salt modified hawthorn-grape pomace extract which has nitrogen-containing cations and high positive charge density, has negative charges on the surface of bacteria and can be adsorbed by the negative charges on the surface of cells, and the quaternary ammonium salt modified hawthorn-grape pomace extract enters the cells through cell wall diffusion and interacts with the cell membranes to destroy the cell membranes and release substances in the cells to cause cell death and achieve the aim of sterilization; the flavonoids have oxidation resistance and bactericidal property, prevent the wine from generating microorganisms harmful to the body, inhibit the wine from being oxidized, and do not cause allergic reaction of people, thus being a safe and nontoxic bactericide.

Detailed Description

In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.

The raw materials used in the following examples of the present invention were all purchased commercially or obtained in daily agricultural production and life, and the unit d used was day and h was hour.

Example 1

(1) picking mature grapes, removing diseased fruits, rotten fruits and other impurities from the picked grapes, removing stalks, squeezing, filtering to obtain grape pomace and grape juice respectively, adding the grape juice into a fermentation tank, adding activated yeast, and fermenting at 18 ℃ for 10 days to obtain fermentation liquor;

(2) adding oxidized cellulose porphyrin cerium complex microspheres into the fermentation liquor obtained in the step (1), performing closed circulation on the fermentation liquor for 0.5h, clarifying for 18h at 4 ℃, naturally heating to 12 ℃, standing for 3d, filtering, adding the quaternary ammonium salt modified hawthorn-grape residue extract, uniformly mixing, filtering by using a filter membrane with the pore diameter of 0.3 micron, and aging, refrigerating and packaging at 0 ℃ in a room to obtain the grape wine.

Furthermore, the brewing formula of the wine is characterized by comprising the following components in parts by mass: 96.65 parts of grape juice, 3 parts of activated yeast, 0.2 part of oxidized cellulose porphyrin cerium complex microspheres and 0.15 part of quaternary ammonium salt modified hawthorn-grape residue extract.

step I, preparation of porphyrin oxidized cellulose: adding oxidized cellulose into water, soaking for 12h, heating to 40 ℃, stirring for 2h, cooling to room temperature to obtain oxidized cellulose solution for later use, adding 5- (4-hydroxyphenyl) -10, 15, 20-triphenylporphyrin into tetrahydrofuran, stirring to completely dissolve, adding 4-hydroxy-2-piperidinecarboxylic acid, reacting for 2h at 50 ℃, cooling to room temperature, concentrating, adding chloroform, stirring to dissolve, adding oxidized cellulose solution and tetrabutylammonium bromide, reacting for 4h at 50 ℃, cooling to room temperature, performing suction filtration, washing precipitate with chloroform to colorless, washing precipitate with water, drying to obtain porphyrized oxidized cellulose;

step II, preparation of the porphyrized oxidized cellulose microspheres: adding the porphyrized oxidized cellulose obtained in the step I into water, performing ultrasonic treatment for 20min, adding liquid paraffin and SP-80, stirring for 0.5h, slowly adding glutaric acid, reacting for 1h at 50 ℃, filtering, and washing precipitates with petroleum ether, absolute ethyl alcohol and water in sequence to obtain porphyrized oxidized cellulose microspheres;

step III, preparing oxidized cellulose porphyrin cerium complex microspheres: and (3) adding the porphyrized oxidized cellulose microspheres obtained in the step (II) and cerium nitrate into 0.2mol/L acetic acid solution, reacting for 6 hours at 40 ℃, cooling to room temperature, adjusting the pH to be neutral by using citric acid-sodium citrate, performing suction filtration, sequentially washing and precipitating for 2 times by using water and absolute ethyl alcohol, and drying to obtain the oxidized cellulose porphyrin cerium complex microspheres.

Furthermore, in the step I, the mass ratio of the 5- (4-hydroxyphenyl) -10, 15, 20-triphenylporphyrin to the 4-hydroxy-2-piperidinecarboxylic acid to the oxidized cellulose to the tetrabutylammonium bromide is 1: 5: 1: 0.01.

furthermore, in the step II, the mass ratio of the porphyrized oxidized cellulose to the liquid paraffin to the SP-80 to the glutaric acid is 0.1: 120: 2: 0.8.

furthermore, in the step III, the mass ratio of the porphyrized oxidized cellulose microspheres to the cerium nitrate to the acetic acid solution is 4: 1: 80.

step I, preparing hawthorn-grape residue powder: drying and crushing hawthorn and grape pomace obtained in the step (1) of the grape wine processing technology, sieving by using a sieve with the aperture of 50 meshes, adding petroleum ether, refluxing for 2 hours at the temperature of 60 ℃, cooling to room temperature, concentrating and drying to obtain hawthorn-grape pomace powder;

step II, preparing the hawthorn-grape pomace extract: adding the hawthorn-grape residue powder obtained in the step I into an ethanol solution with the mass fraction of 70%, placing the mixture into an ultrasonic reactor, carrying out ultrasonic treatment for 20min at 40 ℃, filtering while the mixture is hot, repeating the ultrasonic treatment for 2 times, collecting and combining filtrate, concentrating to obtain a concentrated solution, extracting with ethyl acetate, collecting an organic phase, concentrating, adding anhydrous methanol, decoloring with AB-8 macroporous resin, concentrating, purifying with a silica gel column, and purifying with dichloromethane and ethanol according to the volume ratio of 10: 1. 2: 1, sequentially carrying out gradient elution, and collecting dichloromethane and ethanol in a volume ratio of 2: 1, concentrating the eluent to obtain a hawthorn-grape residue extract;

step III, preparing the quaternary ammonium salt modified hawthorn-grape pomace extract: and (3) adding the hawthorn-grape pomace extract obtained in the step (II) into dichloromethane, slowly adding thionyl chloride at the temperature of-5 ℃, heating to 20 ℃, reacting for 0.5h, concentrating, adding triethylamine and isopropanol, reacting for 5h at the temperature of 70 ℃, cooling to room temperature, and concentrating to obtain the quaternary ammonium salt modified hawthorn-grape pomace extract.

Furthermore, the mass ratio of the hawthorn to the grape pomace in the step I is 1: 5.

furthermore, the feed-liquid ratio of the hawthorn-grape residue powder to the ethanol solution in the step II is 1 g: 10 ml.

Furthermore, in the step III, the mass ratio of the hawthorn-grape pomace extract to the thionyl chloride to the triethylamine is 2: 1: 0.2.

example 2

(1) picking mature grapes, removing diseased fruits, rotten fruits and other impurities from the picked grapes, removing stalks, squeezing, filtering to obtain grape pomace and grape juice respectively, adding the grape juice into a fermentation tank, adding activated yeast, and fermenting at 22 ℃ for 11 days to obtain fermentation liquor;

(2) adding oxidized cellulose porphyrin cerium complex microspheres into the fermentation liquor obtained in the step (1), performing closed circulation on the fermentation liquor for 0.6h, clarifying for 21h at 5 ℃, naturally heating to 13 ℃, standing for 3.5d, filtering, adding the quaternary ammonium salt modified hawthorn-grape residue extract, uniformly mixing, filtering by using a filtering membrane with the pore diameter of 0.3 micron, and aging, refrigerating and packaging at 1 ℃ under indoor conditions to obtain the grape wine.

Furthermore, the brewing formula of the wine is characterized by comprising the following components in parts by mass: 95.23 parts of grape juice, 2.5 parts of activated yeast, 0.18 part of oxidized cellulose porphyrin cerium complex microspheres and 0.13 part of quaternary ammonium salt modified hawthorn-grape residue extract.

step I, preparation of porphyrin oxidized cellulose: adding oxidized cellulose into water, soaking for 15h, heating to 45 ℃, stirring for 3h, cooling to room temperature to obtain oxidized cellulose solution for later use, adding 5- (4-hydroxyphenyl) -10, 15, 20-triphenylporphyrin into tetrahydrofuran, stirring to completely dissolve, adding 4-hydroxy-2-piperidinecarboxylic acid, reacting for 3h at 55 ℃, cooling to room temperature, concentrating, adding chloroform, stirring to dissolve, adding oxidized cellulose solution and tetrabutylammonium bromide, reacting for 5h at 55 ℃, cooling to room temperature, performing suction filtration, washing precipitate with chloroform to colorless, washing precipitate with water, drying to obtain porphyrized oxidized cellulose;

step II, preparation of the porphyrized oxidized cellulose microspheres: adding the porphyrized oxidized cellulose obtained in the step I into water, performing ultrasonic treatment for 25min, adding liquid paraffin and SP-80, stirring for 0.6h, slowly adding glutaric acid, reacting for 1.5h at 55 ℃, filtering, and washing precipitates with petroleum ether, absolute ethyl alcohol and water in sequence to obtain porphyrized oxidized cellulose microspheres;

step III, preparing oxidized cellulose porphyrin cerium complex microspheres: and (3) adding the porphyrized oxidized cellulose microspheres obtained in the step (II) and cerium nitrate into 0.3mol/L acetic acid solution, reacting for 7 hours at 45 ℃, cooling to room temperature, adjusting the pH to be neutral by using citric acid-sodium citrate, performing suction filtration, sequentially washing and precipitating for 2 times by using water and absolute ethyl alcohol, and drying to obtain the oxidized cellulose porphyrin cerium complex microspheres.

Furthermore, in the step I, the mass ratio of the 5- (4-hydroxyphenyl) -10, 15, 20-triphenylporphyrin to the 4-hydroxy-2-piperidinecarboxylic acid to the oxidized cellulose to the tetrabutylammonium bromide is 1: 5.5: 1.3: 0.015.

furthermore, in the step II, the mass ratio of the porphyrized oxidized cellulose to the liquid paraffin to the SP-80 to the glutaric acid is 0.1: 135: 2.5: 0.9.

furthermore, in the step III, the mass ratio of the porphyrized oxidized cellulose microspheres to the cerium nitrate to the acetic acid solution is 4.5: 1: 90.

step I, preparing hawthorn-grape residue powder: drying and crushing hawthorn and grape pomace obtained in the step (1) of the grape wine processing technology, sieving by using a sieve with the aperture of 60 meshes, adding petroleum ether, refluxing for 2.5 hours at the temperature of 65 ℃, cooling to room temperature, concentrating, and drying to obtain hawthorn-grape pomace powder;

step II, preparing the hawthorn-grape pomace extract: adding the hawthorn-grape residue powder obtained in the step I into an ethanol solution with the mass fraction of 70%, placing the mixture into an ultrasonic reactor, carrying out ultrasonic treatment for 25min at 45 ℃, filtering while the mixture is hot, repeating the ultrasonic treatment for 2 times, collecting and combining filtrate, concentrating to obtain a concentrated solution, extracting with ethyl acetate, collecting an organic phase, concentrating, adding anhydrous methanol, decoloring with AB-8 macroporous resin, concentrating, purifying with a silica gel column, and purifying with dichloromethane and ethanol according to the volume ratio of 10: 1. 2: 1, sequentially carrying out gradient elution, and collecting dichloromethane and ethanol in a volume ratio of 2: 1, concentrating the eluent to obtain a hawthorn-grape residue extract;

step III, preparing the quaternary ammonium salt modified hawthorn-grape pomace extract: and (3) adding the hawthorn-grape pomace extract obtained in the step (II) into dichloromethane, slowly adding thionyl chloride at the temperature of-4 ℃, heating to 22 ℃, reacting for 0.6h, concentrating, adding triethylamine and isopropanol, reacting for 5.5h at the temperature of 75 ℃, cooling to room temperature, and concentrating to obtain the quaternary ammonium salt modified hawthorn-grape pomace extract.

Furthermore, the mass ratio of the hawthorn to the grape pomace in the step I is 1: 5.5.

furthermore, the feed-liquid ratio of the hawthorn-grape residue powder to the ethanol solution in the step II is 1 g: 15 ml.

Furthermore, in the step III, the mass ratio of the hawthorn-grape pomace extract to the thionyl chloride to the triethylamine is 3: 1: 0.22.

example 3

(1) picking mature grapes, removing diseased fruits, rotten fruits and other impurities from the picked grapes, removing stalks, squeezing, filtering to obtain grape pomace and grape juice respectively, adding the grape juice into a fermentation tank, adding activated yeast, and fermenting at 25 ℃ for 13 days to obtain fermentation liquor;

(2) adding oxidized cellulose porphyrin cerium complex microspheres into the fermentation liquor obtained in the step (1), performing closed circulation on the fermentation liquor for 0.8h, clarifying for 24h at 6 ℃, naturally heating to 14 ℃, standing for 4d, filtering, adding the quaternary ammonium salt modified hawthorn-grape residue extract, uniformly mixing, filtering by using a filter membrane with the pore diameter of 0.4 micron, and aging, refrigerating and packaging at 2 ℃ in a room to obtain the grape wine.

Furthermore, the brewing formula of the wine is characterized by comprising the following components in parts by mass: 92.35 parts of grape juice, 2 parts of activated yeast, 0.15 part of oxidized cellulose porphyrin cerium complex microspheres and 0.1 part of quaternary ammonium salt modified hawthorn-grape residue extract.

step I, preparation of porphyrin oxidized cellulose: adding oxidized cellulose into water, soaking for 18h, heating to 50 ℃, stirring for 4h, cooling to room temperature to obtain oxidized cellulose solution for later use, adding 5- (4-hydroxyphenyl) -10, 15, 20-triphenylporphyrin into tetrahydrofuran, stirring until the mixture is completely dissolved, adding 4-hydroxy-2-piperidinecarboxylic acid, reacting for 4h at 60 ℃, cooling to room temperature, concentrating, adding chloroform, stirring until the mixture is dissolved, adding the oxidized cellulose solution and tetrabutylammonium bromide, reacting for 6h at 60 ℃, cooling to room temperature, performing suction filtration, washing the precipitate with chloroform until the precipitate is colorless, washing the precipitate with water, and drying to obtain the porphyrized oxidized cellulose;

step II, preparation of the porphyrized oxidized cellulose microspheres: adding the porphyrized oxidized cellulose obtained in the step I into water, performing ultrasonic treatment for 30min, adding liquid paraffin and SP-80, stirring for 0.8h, slowly adding glutaric acid, reacting for 2h at the temperature of 60 ℃, filtering, and washing precipitates by using petroleum ether, absolute ethyl alcohol and water in sequence to obtain porphyrized oxidized cellulose microspheres;

step III, preparing oxidized cellulose porphyrin cerium complex microspheres: and (3) adding the porphyrized oxidized cellulose microspheres obtained in the step (II) and cerium nitrate into 0.4mol/L acetic acid solution, reacting for 8 hours at 50 ℃, cooling to room temperature, adjusting the pH to be neutral by using citric acid-sodium citrate, performing suction filtration, sequentially washing and precipitating for 3 times by using water and absolute ethyl alcohol, and drying to obtain the oxidized cellulose porphyrin cerium complex microspheres.

Furthermore, in the step I, the mass ratio of the 5- (4-hydroxyphenyl) -10, 15, 20-triphenylporphyrin to the 4-hydroxy-2-piperidinecarboxylic acid to the oxidized cellulose to the tetrabutylammonium bromide is 1: 6: 2: 0.02.

furthermore, in the step II, the mass ratio of the porphyrized oxidized cellulose to the liquid paraffin to the SP-80 to the glutaric acid is 0.1: 150: 3: 1.

furthermore, in the step III, the mass ratio of the porphyrized oxidized cellulose microspheres to the cerium nitrate to the acetic acid solution is 5: 1: 100.

step I, preparing hawthorn-grape residue powder: drying and crushing hawthorn and grape pomace obtained in the step (1) of the grape wine processing technology, sieving by using a sieve with the aperture of 80 meshes, adding petroleum ether, refluxing for 3 hours at 70 ℃, cooling to room temperature, concentrating and drying to obtain hawthorn-grape pomace powder;

step II, preparing the hawthorn-grape pomace extract: adding the hawthorn-grape residue powder obtained in the step I into an ethanol solution with the mass fraction of 70%, placing the mixture into an ultrasonic reactor, carrying out ultrasonic treatment for 30min at 50 ℃, filtering while the mixture is hot, repeating the ultrasonic treatment for 3 times, collecting and combining filtrate, concentrating to obtain a concentrated solution, extracting with ethyl acetate, collecting an organic phase, concentrating, adding anhydrous methanol, decoloring with AB-8 macroporous resin, concentrating, purifying with a silica gel column, and purifying with dichloromethane and ethanol according to the volume ratio of 10: 1. 2: 1, sequentially carrying out gradient elution, and collecting dichloromethane and ethanol in a volume ratio of 2: 1, concentrating the eluent to obtain a hawthorn-grape residue extract;

step III, preparing the quaternary ammonium salt modified hawthorn-grape pomace extract: and (3) adding the hawthorn-grape pomace extract obtained in the step (II) into dichloromethane, slowly adding thionyl chloride at the temperature of-3 ℃, heating to 25 ℃, reacting for 0.7h, concentrating, adding triethylamine and isopropanol, reacting for 6h at the temperature of 80 ℃, cooling to room temperature, and concentrating to obtain the quaternary ammonium salt modified hawthorn-grape pomace extract.

Furthermore, the mass ratio of the hawthorn to the grape pomace in the step I is 1: 6.

furthermore, the feed-liquid ratio of the hawthorn-grape residue powder to the ethanol solution in the step II is 1 g: 20 ml.

Furthermore, in the step III, the mass ratio of the hawthorn-grape pomace extract to the thionyl chloride to the triethylamine is 4: 1: 0.25.

example 4

(1) picking mature grapes, removing diseased fruits, rotten fruits and other impurities from the picked grapes, removing stalks, squeezing, filtering to obtain grape pomace and grape juice respectively, adding the grape juice into a fermentation tank, adding activated yeast, and fermenting at 28 ℃ for 14 days to obtain fermentation liquor;

(2) adding oxidized cellulose porphyrin cerium complex microspheres into the fermentation liquor obtained in the step (1), performing closed circulation on the fermentation liquor for 0.9h, clarifying for 27h at 7 ℃, naturally heating to 15 ℃, standing for 4.5d, filtering, adding the quaternary ammonium salt modified hawthorn-grape residue extract, uniformly mixing, filtering by using a filtering membrane with the pore diameter of 0.5 micron, and aging, refrigerating and packaging at 3 ℃ under indoor conditions to obtain the grape wine.

Furthermore, the brewing formula of the wine is characterized by comprising the following components in parts by mass: 93.65 parts of grape juice, 1.5 parts of activated yeast, 0.13 part of oxidized cellulose porphyrin cerium complex microspheres and 0.08 part of quaternary ammonium salt modified hawthorn-grape residue extract.

step I, preparation of porphyrin oxidized cellulose: adding oxidized cellulose into water, soaking for 21h, heating to 55 ℃, stirring for 5h, cooling to room temperature to obtain oxidized cellulose solution for later use, adding 5- (4-hydroxyphenyl) -10, 15, 20-triphenylporphyrin into tetrahydrofuran, stirring until the mixture is completely dissolved, adding 4-hydroxy-2-piperidinecarboxylic acid, reacting for 5h at 65 ℃, cooling to room temperature, concentrating, adding chloroform, stirring until the mixture is dissolved, adding the oxidized cellulose solution and tetrabutylammonium bromide, reacting for 7h at 65 ℃, cooling to room temperature, performing suction filtration, washing the precipitate with chloroform until the precipitate is colorless, washing the precipitate with water, and drying to obtain the porphyrized oxidized cellulose;

step II, preparation of the porphyrized oxidized cellulose microspheres: adding the porphyrized oxidized cellulose obtained in the step I into water, performing ultrasonic treatment for 35min, adding liquid paraffin and SP-80, stirring for 0.9h, slowly adding glutaric acid, reacting for 2.5h at 65 ℃, filtering, and washing precipitates with petroleum ether, absolute ethyl alcohol and water in sequence to obtain porphyrized oxidized cellulose microspheres;

step III, preparing oxidized cellulose porphyrin cerium complex microspheres: and (3) adding the porphyrized oxidized cellulose microspheres obtained in the step (II) and cerium nitrate into 0.5mol/L acetic acid solution, reacting for 9 hours at 55 ℃, cooling to room temperature, adjusting the pH to be neutral by using citric acid-sodium citrate, performing suction filtration, sequentially washing and precipitating for 4 times by using water and absolute ethyl alcohol, and drying to obtain the oxidized cellulose porphyrin cerium complex microspheres.

Furthermore, in the step I, the mass ratio of the 5- (4-hydroxyphenyl) -10, 15, 20-triphenylporphyrin to the 4-hydroxy-2-piperidinecarboxylic acid to the oxidized cellulose to the tetrabutylammonium bromide is 1: 6.5: 2.5: 0.025.

furthermore, in the step II, the mass ratio of the porphyrized oxidized cellulose to the liquid paraffin to the SP-80 to the glutaric acid is 0.1: 165: 3.5: 1.1.

furthermore, in the step III, the mass ratio of the porphyrized oxidized cellulose microspheres to the cerium nitrate to the acetic acid solution is 5.5: 1: 110.

step I, preparing hawthorn-grape residue powder: drying and crushing hawthorn and grape pomace obtained in the step (1) of the grape wine processing technology, sieving by using a sieve with the aperture of 90 meshes, adding petroleum ether, refluxing for 3.5 hours at the temperature of 75 ℃, cooling to room temperature, concentrating, and drying to obtain hawthorn-grape pomace powder;

step II, preparing the hawthorn-grape pomace extract: adding the hawthorn-grape residue powder obtained in the step I into an ethanol solution with the mass fraction of 70%, placing the mixture into an ultrasonic reactor, carrying out ultrasonic treatment for 35min at 55 ℃, filtering while the mixture is hot, repeating the ultrasonic treatment for 4 times, collecting and combining filtrate, concentrating to obtain a concentrated solution, extracting with ethyl acetate, collecting an organic phase, concentrating, adding anhydrous methanol, decoloring with AB-8 macroporous resin, concentrating, purifying with a silica gel column, and purifying with dichloromethane and ethanol according to the volume ratio of 10: 1. 2: 1, sequentially carrying out gradient elution, and collecting dichloromethane and ethanol in a volume ratio of 2: 1, concentrating the eluent to obtain a hawthorn-grape residue extract;

step III, preparing the quaternary ammonium salt modified hawthorn-grape pomace extract: and (3) adding the hawthorn-grape pomace extract obtained in the step (II) into dichloromethane, slowly adding thionyl chloride at the temperature of-2 ℃, heating to 28 ℃, reacting for 0.9h, concentrating, adding triethylamine and isopropanol, reacting for 6.5h at the temperature of 85 ℃, cooling to room temperature, and concentrating to obtain the quaternary ammonium salt modified hawthorn-grape pomace extract.

Furthermore, the mass ratio of the hawthorn to the grape pomace in the step I is 1: 6.5.

furthermore, the feed-liquid ratio of the hawthorn-grape residue powder to the ethanol solution in the step II is 1 g: 25 ml.

Furthermore, in the step III, the mass ratio of the hawthorn-grape pomace extract to the thionyl chloride to the triethylamine is 5: 1: 0.28.

example 5

(1) picking mature grapes, removing diseased fruits, rotten fruits and other impurities from the picked grapes, removing stalks, squeezing, filtering to obtain grape pomace and grape juice respectively, adding the grape juice into a fermentation tank, adding activated yeast, and fermenting at 30 ℃ for 15 days to obtain fermentation liquor;

(2) adding oxidized cellulose porphyrin cerium complex microspheres into the fermentation liquor obtained in the step (1), performing closed circulation on the fermentation liquor for 1h, clarifying for 30h at the temperature of 8 ℃, naturally heating to 16 ℃, standing for 5d, filtering, adding the quaternary ammonium salt modified hawthorn-grape residue extract, uniformly mixing, filtering by using a filter membrane with the pore diameter of 0.5 micron, and ageing, refrigerating and packaging at the indoor temperature of 4 ℃ to obtain the grape wine.

Furthermore, the brewing formula of the wine is characterized by comprising the following components in parts by mass: 90.55 parts of grape juice, 1 part of activated yeast, 0.1 part of oxidized cellulose porphyrin cerium complex microspheres and 0.05 part of quaternary ammonium salt modified hawthorn-grape residue extract.

step I, preparation of porphyrin oxidized cellulose: adding oxidized cellulose into water, soaking for 24h, heating to 60 ℃, stirring for 6h, cooling to room temperature to obtain oxidized cellulose solution for later use, adding 5- (4-hydroxyphenyl) -10, 15, 20-triphenylporphyrin into tetrahydrofuran, stirring to completely dissolve, adding 4-hydroxy-2-piperidinecarboxylic acid, reacting for 6h at 70 ℃, cooling to room temperature, concentrating, adding chloroform, stirring to dissolve, adding oxidized cellulose solution and tetrabutylammonium bromide, reacting for 8h at 70 ℃, cooling to room temperature, performing suction filtration, washing precipitate with chloroform to colorless, washing precipitate with water, drying to obtain porphyrized oxidized cellulose;

step II, preparation of the porphyrized oxidized cellulose microspheres: adding the porphyrized oxidized cellulose obtained in the step I into water, performing ultrasonic treatment for 40min, adding liquid paraffin and SP-80, stirring for 1h, slowly adding glutaric acid, reacting for 3h at 70 ℃, filtering, and washing precipitates by using petroleum ether, absolute ethyl alcohol and water in sequence to obtain porphyrized oxidized cellulose microspheres;

step III, preparing oxidized cellulose porphyrin cerium complex microspheres: and (3) adding the porphyrized oxidized cellulose microspheres obtained in the step (II) and cerium nitrate into 0.6mol/L acetic acid solution, reacting for 10 hours at the temperature of 60 ℃, cooling to room temperature, adjusting the pH to be neutral by using citric acid-sodium citrate, performing suction filtration, sequentially washing and precipitating for 4 times by using water and absolute ethyl alcohol, and drying to obtain the oxidized cellulose porphyrin cerium complex microspheres.

Furthermore, in the step I, the mass ratio of the 5- (4-hydroxyphenyl) -10, 15, 20-triphenylporphyrin to the 4-hydroxy-2-piperidinecarboxylic acid to the oxidized cellulose to the tetrabutylammonium bromide is 1: 7: 3: 0.03.

furthermore, in the step II, the mass ratio of the porphyrized oxidized cellulose to the liquid paraffin to the SP-80 to the glutaric acid is 0.1: 180: 4: 1.2.

furthermore, in the step III, the mass ratio of the porphyrized oxidized cellulose microspheres to the cerium nitrate to the acetic acid solution is 6: 1: 120.

step I, preparing hawthorn-grape residue powder: drying and crushing hawthorn and grape pomace obtained in the step (1) of the grape wine processing technology, sieving by using a sieve with the aperture of 100 meshes, adding petroleum ether, refluxing for 4 hours at the temperature of 80 ℃, cooling to room temperature, concentrating and drying to obtain hawthorn-grape pomace powder;

step II, preparing the hawthorn-grape pomace extract: adding the hawthorn-grape residue powder obtained in the step I into an ethanol solution with the mass fraction of 70%, placing the mixture into an ultrasonic reactor, carrying out ultrasonic treatment for 40min at 60 ℃, filtering while the mixture is hot, repeating the ultrasonic treatment for 4 times, collecting and combining filtrate, concentrating to obtain a concentrated solution, extracting with ethyl acetate, collecting an organic phase, concentrating, adding anhydrous methanol, decoloring with AB-8 macroporous resin, concentrating, purifying with a silica gel column, and purifying with dichloromethane and ethanol according to the volume ratio of 10: 1. 2: 1, sequentially carrying out gradient elution, and collecting dichloromethane and ethanol in a volume ratio of 2: 1, concentrating the eluent to obtain a hawthorn-grape residue extract;

step III, preparing the quaternary ammonium salt modified hawthorn-grape pomace extract: and (3) adding the hawthorn-grape pomace extract obtained in the step (II) into dichloromethane, slowly adding thionyl chloride at the temperature of 0 ℃, heating to 30 ℃, reacting for 1h, concentrating, adding triethylamine and isopropanol, reacting for 7h at the temperature of 90 ℃, cooling to room temperature, and concentrating to obtain the quaternary ammonium salt modified hawthorn-grape pomace extract.

Furthermore, the mass ratio of the hawthorn to the grape pomace in the step I is 1: 7.

furthermore, the feed-liquid ratio of the hawthorn-grape residue powder to the ethanol solution in the step II is 1 g: 30 ml.

Furthermore, in the step III, the mass ratio of the hawthorn-grape pomace extract to the thionyl chloride to the triethylamine is 6: 1: 0.3.

comparative example 1

A wine brewing formulation substantially as described in example 1, except that: no oxidized cellulose porphyrin cerium complex microspheres were added.

Comparative example 2

A wine brewing formulation substantially as described in example 1, except that: the hawthorn-grape pomace extract is not modified by adding quaternary ammonium salt.

Comparative example 3

A wine brewing formulation substantially as described in example 1, except that: oxidized cellulose is used to replace oxidized cellulose porphyrin cerium complex microspheres.

Comparative example 4

A wine brewing formulation substantially as described in example 1, except that: the hawthorn-grape residue extract is used for replacing the quaternary ammonium salt modified hawthorn-grape residue extract.

Comparative example 5

Common wine is sold in the market.

The experimental results are as follows:

the inhibition rates of the wines prepared in examples 1-5 and comparative examples 1-5 on golden yellow wine bacteria and escherichia coli are carried out according to WS/T650-2019 standard, and the test results are shown in Table 1.

TABLE 1 inhibition, Total Oxidation resistance and light transmittance of wine against Staphylococcus aureus and Escherichia coli in different examples

The method for measuring the total antioxidant capacity comprises the following steps: 1mL of a 4-fold diluted wine was mixed with 2.5mol/L of a phosphate buffer solution of pH 6.6, 2.5mL of a 10% trichloroacetic acid solution and 2.5mL of an 1% iron potassium chloride solution, reacted at 50 ℃ for 20min, and then centrifuged at 3000rpm for 10 min. 2.5mL of the supernatant was mixed with 2.5mL of distilled water and 0.5mL of a 0.1% ferric chloride solution, and absorbance at a wavelength of 700nm was measured, and a standard curve was prepared using ascorbic acid as a standard, and the value of mmol ascorbic acid/L (mmol AAE/L) was expressed based on the standard curve, and the test results are shown in Table 1.

The light transmittance test method comprises the following steps: the method comprises the steps of taking wine, measuring the absorbance at the position of 680nm of wavelength on a UV1901PC ultraviolet-visible spectrophotometer, calculating the light transmittance according to the absorbance, carrying out blank zero adjustment by using distilled water, and obtaining the test result shown in table 1.

As can be seen from the table 1, the wine prepared by the wine processing technology has the inhibition rate of more than or equal to 90% on golden yellow wine bacteria and escherichia coli, and has strong bacteriostatic effect; as can be seen from the example 1 and the comparative example 2, the total antioxidant capacity of the wine is improved by 30% by adding the quaternary ammonium salt modified hawthorn-grape pomace extract into the wine; the transparency is more than or equal to 70 percent, the transparency is good, and the addition amount of the oxidized cellulose porphyrin cerium complex microspheres in the wine can not be too much or too little, and the optimal amount is 0.15 percent as can be seen from examples 1-5.

The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims

1. The processing technology of the wine is characterized by comprising the following steps:

2. The wine processing technology as claimed in claim 1, wherein the wine brewing formula comprises the following components in parts by mass: 90.55-96.8 parts of grape juice, 1-3 parts of activated yeast, 0.1-0.2 part of oxidized cellulose porphyrin cerium complex microspheres and 0.05-0.15 part of quaternary ammonium salt modified hawthorn-grape residue extract.

3. The wine processing technology of claim 1, wherein the preparation method of the oxidized cellulose porphyrin cerium complex microspheres comprises the following steps:

4. A wine processing technology as claimed in claim 3, wherein the mass ratio of 5- (4-hydroxyphenyl) -10, 15, 20-triphenylporphyrin, 4-hydroxy-2-piperidinecarboxylic acid, oxidized cellulose and tetrabutylammonium bromide in the step I is 1: (5-7): (1-3): (0.01-0.03).

5. A wine processing technology as claimed in claim 3, wherein the mass ratio of the porphyrized oxidized cellulose, the liquid paraffin, the SP-80 and the glutaric acid in the step II is 0.1: (120-180): (2-4): (0.8-1.2).

6. A wine processing technology as claimed in claim 3, wherein the mass ratio of the porphyrized oxidized cellulose microspheres, the cerium nitrate and the acetic acid solution in the step III is (4-6): 1: (80-120).

7. The wine processing technology of claim 1, wherein the preparation of the quaternary ammonium salt modified hawthorn-grape pomace extract comprises the following steps:

8. The wine processing technology of claim 7, wherein the mass ratio of the hawthorn fruits to the grape pomace in the step I is 1: (5-7).

9. The wine processing technology of claim 7, wherein the feed-liquid ratio of the hawthorn-grape residue powder to the ethanol solution in the step II is 1 g: (10-30) ml.

10. The wine processing technology of claim 7, wherein the mass ratio of the hawthorn-grape pomace extract, the thionyl chloride and the triethylamine in the step III is (2-6): 1: (0.2-0.3).