Preparation method of chewable tablet food

Abstract

The invention discloses a preparation method of a chewable tablet food, and belongs to the technical field of chewable tablet processing. Comprising the following steps: pretreating raw materials to obtain juice and pomace; performing enzymolysis; performing fermentation; adsorption and enrichment: introducing the fermentation liquor into an adsorption and enrichment material, then concentrating the fermentation liquor which is not adsorbed to obtain concentrated fruit vinegar, desorbing adsorbed components, and performing post-treatment to obtain an enriched product; the adsorption enrichment material comprises modified chitosan, modified graphene, macroporous resin grafted with PEG (polyethylene glycol), mesoporous resin grafted with phosphate and microporous resin grafted with boric acid ester; and low-temperature forming: adding a sweetening agent, a forming agent, food-grade calcium carbonate, the enriched product and the dried and crushed pomace into the concentrated fruit vinegar liquid, uniformly stirring, and performing low-temperature forming to obtain the fruit vinegar chewable tablet. The fruit vinegar is introduced into the chewable tablet, the flavor of the chewable tablet is improved, meanwhile, the content of polyphenol, vitamin C and flavone is increased through adsorption and enrichment, and the chewable tablet is endowed with the functions of resisting oxidation, regulating metabolism and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of chewable tablet processing, and in particular relates to a method for preparing chewable tablet food. Background Art

[0002] Fruit vinegar has antioxidant properties, regulates sugar and lipid metabolism, and promotes digestion. Therefore, it is commonly used in a variety of food preparations, such as beverages, condiments, and jellies. However, its application in the preparation of chewable tablets is rare. This is because, without enrichment, the content of functional ingredients such as polyphenols, vitamin C, and flavonoids in fruit vinegar is low, making it difficult to meet the health benefits of chewable tablets. Furthermore, the acidic environment of fruit vinegar presents compatibility challenges with the chewable tablet molding process.

[0003] Current research on the enrichment of functional components in fruit vinegar lacks a broad-spectrum, universal adsorption and enrichment material. Existing technologies require different adsorption and enrichment materials for different fruit vinegars, such as apple, grape, and citrus, resulting in complex and costly processes. For example, polyamide resins are commonly used for the enrichment of apple polyphenols, macroporous adsorption resins are required for grape proanthocyanidins, and borate resins are commonly used for citrus flavonoids. These materials are not suitable for the universal enrichment of a wide range of fruit vinegar components.

[0004] In addition, most of the fruit residues produced in fruit vinegar production are directly discarded and not fully utilized, resulting in waste of resources.

[0005] Based on this, it is urgent to develop a technical solution that can enrich the functional components of various fruit vinegars, adapt to the preparation process of chewable tablets, and realize the resource utilization of fruit residues. Summary of the Invention

[0006] The object of the present invention is to provide a method for preparing a chewable tablet food, so as to effectively solve the technical problems existing in the prior art.

[0007] The purpose of the present invention is achieved through the following technical solutions: A method for preparing a chewable tablet food comprises the following steps: S1. Raw material pretreatment: Fruits are cored, peeled, and crushed at 0±3°C. The fruit is then filtered to obtain juice and pomace. S2. Enzymatic hydrolysis: The juice is subjected to enzymatic hydrolysis, followed by secondary filtration to obtain an enzymatic hydrolyzate; S3 fermentation: alcohol fermentation and acetic acid fermentation of the enzymatic hydrolysate, after which the pH of the system was adjusted to 6.5-7.5, followed by three-stage filtration to obtain a fermentation broth; S4 adsorption enrichment: The fermentation broth is passed through the adsorption enrichment material, and then the fermentation broth is not adsorbed and concentrated to obtain concentrated fruit vinegar liquid, the adsorbed components are desorbed and post-processed to obtain an enriched product; Among them, the adsorption and enrichment materials include modified resin, modified chitosan, and modified graphene; The modified resin includes a macroporous resin grafted with PEG, a mesoporous resin grafted with phosphate, and a microporous resin grafted with borate; The modified chitosan is first cross-linked with dialdehyde starch, then grafted with disulfide bonds, and finally grafted with polyethylene glycol; The modified graphene is obtained by first subjecting graphene to plasma etching, then grafting borate, then coating mesoporous silica, and then modifying with a silane coupling agent; S5. Low-temperature molding: Add sweetener, molding agent, food-grade calcium carbonate, enrichment product, and dried and crushed fruit pomace to the concentrated fruit vinegar liquid, stir evenly, and then mold at 45±5°C to obtain fruit vinegar chewable tablets.

[0008] As some possible implementation methods of the present application, in step S4, the pore size of the macroporous resin is 100-500 nm, the pore size of the mesoporous resin is 5-50 nm, and the pore size of the microporous resin is <2 nm.

[0009] As some possible implementation methods of the present application, in step S4, the mass ratio of macroporous resin:mesoporous resin:microporous resin is 2~3:2~3:1.

[0010] As some possible implementation methods of the present application, in step S4, the adsorption and enrichment material includes 50-70 parts by weight of modified resin, 10-20 parts by weight of modified chitosan, and 10-20 parts by weight of modified graphene.

[0011] As some possible implementation methods of the present application, in step S4, the adsorption and enrichment material includes 55-68 parts by weight of modified resin, 12-18 parts by weight of modified chitosan, and 15-20 parts by weight of modified graphene.

[0012] As some possible implementation methods of the present application, in step S4, the adsorption and enrichment material includes 68 parts by weight of modified resin, 17 parts by weight of modified chitosan, and 15 parts by weight of modified graphene.

[0013] As some possible implementation methods of the present application, in step S1, the filter screen selected for the first-level filtration is a 100-300 mesh filter screen.

[0014] As some possible implementation methods of the present application, in step S2, 300-500 mesh diatomaceous earth filtration is selected for secondary filtration.

[0015] As some possible implementation methods of the present application, in step S3, the tertiary filtration material is a modified PES membrane, which is obtained by grafting sulfobetaine groups onto PES.

[0016] As some possible implementation methods of the present application, in step S5, the particle size of the dried and crushed pomace is 80-150 mesh.

[0017] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention introduces a fruit vinegar system into chewable tablets, enabling the chewable tablets to retain the flavor and physiological activity of the fruit vinegar. Through processes such as low-temperature crushing and low-temperature molding, while retaining the original flavor of the fruit vinegar, functional components such as polyphenols, vitamin C, and flavonoids are retained to the greatest extent. At the same time, the content of polyphenols, vitamin C, and flavonoids is increased through adsorption enrichment, giving the chewable tablets functions such as antioxidant and metabolic regulation.

[0018] The present invention dries and crushes the pomace obtained in the crushing stage and then adds it to the chewable tablets as a dietary fiber additive, thereby realizing waste utilization and effectively saving resources, while increasing the dietary fiber content of the chewable tablets and improving the taste and nutritional value.

[0019] Adjusting the pH of the fermentation broth to 6.5-7.5 not only avoids excessive breakage of disulfide bonds, but also allows the phosphate groups of the modified resin to fully dissociate, while ensuring normal gelatinization of the starch adhesive. This solves the compatibility problem between the acidity of fruit vinegar and the formation of chewable tablets, and achieves a smooth connection of the entire process from fruit vinegar to chewable tablets.

[0020] The present invention provides a universal adsorption resin material capable of efficiently enriching functional components such as polyphenols, vitamin C, and flavonoids from apples, grapes, and citrus fruits. The modified resin's hierarchical pore structure and functional groups adapt to molecules of varying sizes and properties. The dynamic response and hydrophilicity of the modified chitosan enhance adsorption efficiency and anti-pollution capabilities. The high specific surface area and specific adsorption of the modified graphene enhance the capture of flavonoids. The three components work together to efficiently enrich functional components such as polyphenols, vitamin C, and flavonoids. The resulting enriched product can be added to chewable tablets as needed, providing a rich source of natural functional ingredients for fruit vinegar chewable tablets. DETAILED DESCRIPTION

[0021] A method for preparing a chewable tablet food comprises the following steps: S1. Raw Material Pretreatment: Fruits (such as apples, grapes, and citrus fruits) are cored, peeled, and crushed at 0±3°C to minimize the loss of vitamin C and polyphenols. The fruit is then filtered to obtain juice and pomace. This primary filtration separates the pomace from the juice, preventing crude fiber from interfering with enzymatic hydrolysis. The pomace is then dried and crushed, and then added to the chewable tablets along with a dietary fiber additive.

[0022] S2. Enzymatic Hydrolysis: The juice is enzymatically hydrolyzed, followed by secondary filtration to obtain the hydrolyzate. This secondary filtration removes impurities such as colloids and proteins from the hydrolyzate, ensuring clarity and preventing clogging of subsequent fermentation equipment.

[0023] S3. Fermentation: The enzymatic hydrolysate undergoes alcoholic and acetic fermentation, after which the system pH is adjusted to 6.5-7.5. A tertiary filtration is then performed to obtain the fermentation broth. Tertiary filtration removes impurities from the fermentation broth, preventing them from clogging the adsorption and enrichment materials and reducing the enrichment efficiency. Adjusting the fermentation broth pH to 6.5-7.5 not only optimizes the adsorption performance of the adsorption and enrichment materials but also effectively addresses the compatibility issue between the acidity of fruit vinegar and the chewable tablet forming process. Specifically, this pH range prevents excessive disulfide bond breakage, maintaining a dense network structure of the modified chitosan during the adsorption phase and ensuring full exposure of adsorption sites, thereby enhancing the adsorption efficiency of functional ingredients from apples, grapes, and citrus fruits. Furthermore, this pH range allows the phosphate groups of the modified resin to fully dissociate, allowing for the specific adsorption of vitamin C through electrostatic interactions. The borate groups then form stable coordination bonds with the vicinal diol structures of citrus flavonoids, resulting in efficient adsorption of a variety of functional ingredients. In addition, in solving the compatibility problem of the molding process, starch adhesives can be gelatinized normally within this pH range, ensuring the smooth molding of chewable tablets.

[0024] S4. Adsorption enrichment: The fermentation broth is passed through an adsorption enrichment material, and the unadsorbed fermentation broth is concentrated to obtain concentrated fruit vinegar liquid. The adsorbed components are desorbed and post-processed to obtain an enriched product.

[0025] The adsorption and enrichment material provided by the present invention is a universal enrichment material capable of targeted adsorption and enrichment of polyphenols, vitamin C, and flavonoids in fruits such as apples, grapes, and citrus fruits. It can be added to chewable tablets based on their actual health needs to impart antioxidant and other functions. The adsorption and enrichment material comprises modified resins, modified chitosan, and modified graphene. The modified resins include macroporous resins grafted with PEG, mesoporous resins grafted with phosphate, and microporous resins grafted with borate. The modified chitosan is first cross-linked with dialdehyde starch, then grafted with disulfide bonds, and finally grafted with polyethylene glycol. The modified graphene is obtained by plasma etching graphene, grafting borate, coating with mesoporous silica, and then modifying with a silane coupling agent.

[0026] S5. Low-temperature molding: Add sweetener, molding agent, food-grade calcium carbonate, enrichment product, and dried and crushed fruit pomace to the concentrated fruit vinegar liquid, stir evenly, and then mold at 45±5°C to obtain fruit vinegar chewable tablets.

[0027] The functions of the components in the above-mentioned adsorption and enrichment materials are as follows: Modified resin: The resin skeleton with a macroporous-mesoporous-microporous hierarchical structure has a certain physical adsorption capacity and has a certain adsorption effect on grape proanthocyanidins, vitamin C, and citrus flavonoids, but its selectivity and adsorption efficiency are low. At the same time, due to the lack of specific functional groups, the adsorption capacity is small and it is easily interfered by other components in fruit vinegar.

[0028] Macroporous resin grafted with PEG: The hydrophilicity of PEG guides grape proanthocyanidins into the pores, significantly improving the adsorption efficiency of grape proanthocyanidins, reducing diffusion resistance, and increasing both adsorption capacity and rate. Mesoporous resin grafted with phosphate: The phosphate group dissociates at neutral pH and specifically adsorbs vitamin C through electrostatic interaction, effectively counteracting the competition from organic acids in apple and citrus vinegar, and significantly improving the adsorption selectivity and adsorption capacity of vitamin C. Microporous resin grafted with borate: borate forms a stable coordination bond with the vicinal diol structure of citrus flavonoids, achieving efficient and specific capture of citrus flavonoids, and significantly improving the adsorption rate.

[0029] Modified chitosan: Chitosan itself contains amino groups, which partially dissociate and become positively charged at neutral pH. It can adsorb negatively charged apple polyphenols, vitamin C, etc. through electrostatic effects, and also has a certain hydrogen bonding effect on citrus flavonoids. However, the mechanical strength of the chitosan itself is insufficient, the adsorption sites are easily exposed but not fully, the adsorption kinetics are lagged, and it is easily affected by impurities.

[0030] Dialdehyde starch crosslinking enhances chitosan's mechanical strength, preventing structural collapse during adsorption while providing a stable framework for subsequent modification. Grafted disulfide bonds maintain the density of the chitosan network at neutral pH, ensuring full exposure of adsorption sites. These bonds only break during subsequent acidic desorption, resolving the adsorption kinetic hysteresis associated with static crosslinking and effectively shortening the adsorption half-equilibrium time of apple polyphenols. Grafted polyethylene glycol enhances hydrophilicity, reduces impurity adsorption, and optimizes the diffusion pathways of polar molecules like vitamin C, enhancing vitamin C adsorption. It also exhibits a synergistic adsorption effect on apple polyphenols.

[0031] Modified graphene: Graphene itself has an ultra-high specific surface area and a π-π conjugated structure. It has strong physical adsorption and π-π interaction adsorption for polyphenols such as grape proanthocyanidins, and also has a certain adsorption capacity for citrus flavonoids. However, its adsorption for vitamin C is weak, and it is prone to sheet stacking, which affects the exposure of adsorption sites.

[0032] Plasma etching repairs the conjugated structure, increasing active sites on the graphene surface and enhancing the adsorption of grape proanthocyanidins. It also introduces active sites such as hydroxyl groups, creating conditions for the grafting of borate esters, indirectly enhancing the coordinated adsorption of citrus flavonoids. The grafted borate esters can form stable coordination bonds with citrus flavonoids in a neutral environment, improving the adsorption selectivity of citrus flavonoids.

[0033] Coating with mesoporous silica can solve the problem of graphene sheet stacking, maintain the stability of the mesoporous structure under neutral conditions, shorten the diffusion path of citrus flavonoids, and increase the adsorption rate. At the same time, it protects graphene and borate, reduces the degree of oxidation, and maintains stable adsorption performance.

[0034] Silane coupling agent modification enhances the interfacial bonding between graphene and other adsorption materials, maintains the stability of the adsorption system, and improves the overall adsorption effect. The synergistic effect of these components forms a highly efficient enrichment network for functional ingredients (polyphenols, vitamin C, and flavonoids) found in apples, grapes, and citrus fruits. The modified resin's hierarchical pore structure and functional groups adapt to molecules of varying sizes and properties. The dynamic response and hydrophilicity of the modified chitosan enhance adsorption efficiency and anti-fouling capabilities. The high surface area and specific adsorption of the modified graphene enhance the capture of functional molecules. These three components work together to efficiently enrich a broad spectrum of functional ingredients, including polyphenols, vitamin C, and flavonoids, providing a rich source of natural functional ingredients for fruit vinegar chewable tablets.

[0035] The molecular sizes of functional ingredients in different fruits vary significantly. For example, grape proanthocyanidins have a molecular weight of >2000Da, vitamin C is 176Da, and citrus flavonoids are approximately 600Da. To better accommodate the adsorption needs of molecules of varying sizes, the pore sizes of the three resins have been further limited: the macroporous resin has a pore size of 100-500nm, the mesoporous resin has a pore size of 5-50nm, and the microporous resin has a pore size of <2nm. The macropores optimize the diffusion of grape proanthocyanidins, the mesopores optimize the electrostatic adsorption of vitamin C, and the micropores specifically capture citrus flavonoids, effectively improving overall enrichment efficiency.

[0036] To further enhance the adsorption of polyphenols, vitamin C, and flavonoids by the adsorption and enrichment material, some embodiments of the present application further limit the amounts of the components used in the adsorption and enrichment material. Specifically, the adsorption and enrichment material comprises 50-70 parts by weight of modified resin, 10-20 parts by weight of modified chitosan, and 10-20 parts by weight of modified graphene. In the modified resin, the mass ratio of macroporous resin: mesoporous resin: microporous resin is 2-3:2-3:1.

[0037] In order to ensure the smooth progress of the enzymatic hydrolysis process, as some feasible implementation methods of the present application, in step S1, the filter screen selected for the first-level filtration is a 100-300 mesh filter screen. The filter screen with this particle size can effectively separate the pomace and the juice, and prevent the crude fiber from affecting the enzymatic hydrolysis.

[0038] In order to ensure the smooth progress of the fermentation process, as some possible implementation methods of the present application, in step S2, 300-500 mesh diatomaceous earth filtration is selected for secondary filtration.

[0039] To prevent clogging of the adsorption and enrichment material by impurities in the fermentation broth and to effectively reduce filtration losses of polyphenols, vitamin C, and flavonoids, some possible embodiments of this application further define the tertiary filtration material. Specifically, in step S3, the tertiary filtration material is a modified PES membrane obtained by grafting sulfobetaine groups onto PES; the pore size of the modified PES membrane is 50-200 microns. PES (polyethersulfone) membranes possess excellent mechanical strength and chemical stability, effectively intercepting bacterial fragments, colloidal particles, and incompletely enzymatically hydrolyzed polysaccharide impurities in the fermentation broth. The grafting of sulfobetaine forms a zwitterionic layer on the PES membrane surface, dissipating surface static electricity and preventing electrostatic attraction with negatively charged polyphenols and vitamin C. Simultaneously, a continuous hydration layer forms on the membrane surface, hindering direct contact between solutes and the membrane surface, reducing hydrogen bonding and adsorption, and thus, the adsorption of polyphenols and vitamin C.

[0040] In order to further improve the taste of the chewable tablet, as some possible embodiments of the present application, the particle size of the pomace is further limited, that is, in step S5, the particle size of the dried and crushed pomace is 80-150 mesh. This particle size can ensure the hardness of the chewable tablet and provide a suitable chewing feeling.

[0041] Next, the preparation method of the chewable tablet will be described in detail.

[0042] Example 1 S1. Core and peel the apples, then crush them at 0±3°C. Filter through a 200-mesh filter to obtain juice and pomace.

[0043] S2. Mix juice and water in a ratio of 1:2. Add 0.1% cellulase and 0.1% pectinase (based on the weight of the juice). Ultrasonicate at 200W and 40°C for 35 minutes. Filter through 300-mesh diatomaceous earth. Adjust the pH of the filtrate to 4.5-5.0 and inactivate the enzymes at 60°C for 10 minutes to obtain an enzymatic hydrolyzate.

[0044] S3. Add 0.8 wt% activated Saccharomyces cerevisiae to the enzymatic hydrolysate and ferment at 26-28°C until the alcohol content reaches 7% (v / v). Then, add 3 wt% acetic acid bacteria and continue fermenting at 28-30°C with a ventilation rate of 0.8 ± 0.2 vvm until the acetic acid content reaches 5.5% (w / v). Add edible calcium carbonate and adjust the pH to 6-7.5. Finally, filter the fermentation broth through a modified PES membrane with a pore size of 150 μm to obtain the fermentation broth. S4. Wet-pack the adsorption enrichment material (composed of a mixture of 70 parts by weight of modified resin, 12 parts by weight of modified chitosan, and 18 parts by weight of modified graphene, with the mass ratio of PEG-grafted macroporous resin, phosphate-grafted mesoporous resin, and borate-grafted microporous resin in the modified resin being 2:2:1) into a stainless steel adsorption column (20 cm diameter, aspect ratio 3:1) at a packing density of 0.7 g / mL. Backwash the column with deionized water until the effluent is clear to remove fine particles and impurities. The fermentation broth was passed through the adsorption column from top to bottom at a flow rate of 3 BV / h (BV = column volume). The operating temperature was 25-28°C, and the pH was maintained at 6.5-7.5. The concentrations of polyphenols (calculated as gallic acid), vitamin C, and flavonoids (calculated as rutin) in the effluent were monitored online. When the concentration of the target component in the effluent reached 10% of the feed concentration, adsorption was considered saturated, and sample loading was stopped.

[0045] The desorption liquid (aqueous citric acid solution with a pH of 3.0-4.0) was then passed through the adsorption column from bottom to top at a flow rate of 2.5 BV / h, with an operating temperature of 30°C. The desorption liquid was collected until the concentration of the target component was less than 5 mg / L.

[0046] The collected desorption liquid is concentrated to 1 / 3 of the original volume under the conditions of a vacuum degree of -0.08 MPa and a temperature of 30°C, and then sterilized by ultraviolet light to obtain an enriched concentrated liquid. The enriched concentrated liquid can be directly added to step S5, or the enriched concentrated liquid can be freeze-dried to obtain enriched powder and added to step S5. The enriched powder is easy to store when it is not used up, so that it can be added at any time later.

[0047] In the adsorption enrichment stage, the fermentation liquid that has passed through the adsorption enrichment material is collected and concentrated to 1 / 3 of the original volume under the conditions of a vacuum degree of -0.08 MPa and a temperature of 45°C to obtain concentrated fruit vinegar liquid, which is then sterilized.

[0048] S5. Low-temperature molding: 350 parts by weight of concentrated fruit vinegar liquid are added with 100 parts by weight of a sweetener, 180 parts by weight of pregelatinized corn starch, 6 parts by weight of food-grade calcium carbonate, 75 parts by weight of a functional component (the functional component here is any one of the enriched concentrates of Examples 1, 3, and 4, or a mixture of any two or more of the concentrates, depending on actual needs; an enrichment powder of a corresponding weight may also be added), 70 parts by weight of dried and crushed pomace (100 mesh), and 3 parts by weight of magnesium stearate. The mixture is stirred uniformly at 25-30°C, and then tableted using a rotary tablet press at 45°C to obtain fruit vinegar chewable tablets.

[0049] In the above preparation method, the preparation methods of some components are as follows: A. The preparation method of modified PES membrane is as follows: A1. A PES membrane (molecular weight cutoff 100 kDa, 1 m²) was immersed in 1 L of 5 wt% NaOH solution and sonicated at 40°C for 1 h (power 300 W). The membrane was then rinsed with water until neutral and vacuum dried at 50°C for 8 h to obtain a pretreated PES membrane. A2. Prepare a 1 L water-ethanol mixed solution (water:ethanol ratio:3:1, volume ratio) containing 200 g of 3-[(methacryloyloxy)propyl]dimethylaminopropanesulfonate (SBMA) and 2 g of camphorquinone-ethanolamine photoinitiator (mass ratio:1). Immerse the pretreated PES membrane in this solution and irradiate it with 365 nm UV light (500 W) for 4 h. After the reaction, wash with deionized water and vacuum dry at 60°C for 24 h to obtain the modified PES membrane. A3. Dissolve 150 g of modified PES in 850 g of a 30 wt% N-methylpyrrolidone (NMP)-water mixture to prepare a membrane solution. Scrape a film (200 μm thickness) onto a glass plate, then immerse the film in a 30°C water coagulation bath and heat-treat it at 40°C for 2 h using infrared radiation (1000 W). This produces a modified PES membrane with a pore size of 50-200 μm. B. The preparation method of PEG-grafted macroporous resin is as follows: B1. In supercritical CO ２ In the reactor, 500 g of styrene and 100 g of divinylbenzene were added and the supercritical CO ２ (pressure 10 MPa, temperature 60℃) as the medium, suspension polymerization for 6 h to prepare macroporous resin with pore size of 100-500 nm. B2. Add 500 g of macroporous resin, 100 g of PEG-2000, and 20 g of potassium carbonate to 500 mL of an ethanol-water mixture (ethanol to water volume ratio of 1:4) and react under 300 W microwave irradiation (temperature 60°C) for 1 h to prepare a PEG-grafted macroporous resin. C. The preparation method of the mesoporous resin grafted with phosphate ester is as follows: C1. Mix 400 g of styrene, 100 g of triethyl citrate, and 10 g of initiator (AIBN) and polymerize at 50°C for 8 h to produce a mesoporous resin with a pore size of 5-50 nm. C2. Add 500 g of mesoporous resin and 200 g of sodium dihydrogen phosphate to 1 L of deionized water and react at 250 W ultrasonic power for 2 h (temperature 48°C) to prepare the mesoporous resin grafted with phosphate ester. D. The preparation method of microporous resin grafted with borate is as follows: D1. Add 250 g of styrene, 50 g of divinylbenzene, and 1000 g of deionized water into a reactor and react at 120°C for 12 h to obtain a microporous resin with a pore size of <2 nm. D2. Add 250 g of microporous resin, 50 g of tributyl borate, and 10 g of immobilized lipase (Novozym 435) to 500 mL of an isopropanol-water mixture (volume ratio 1:1) and react at 40°C for 6 h to prepare a microporous resin grafted with borate. E. The environmentally friendly preparation method of modified chitosan is as follows: E1. Add 5 L of water, 50 g of hydrogen peroxide solution (30% by mass), and 0.5 g of FeSO ４ , and oxidized at 50℃ for 2 h to obtain dialdehyde starch. 100 g of chitosan (deacetylation degree > 90%) was dissolved in 2 L of 2 wt% acetic acid solution, followed by the addition of 80 g of dialdehyde starch and stirring at 25 °C for 4 h to prepare cross-linked chitosan. E2. Add 100 g of cross-linked chitosan to 1 L of deionized water and 20 g of ethyl 2-imidodithiocarbamate hydrochloride. React at 40°C for 3 h and then at room temperature in an oxygen atmosphere for 2 h to obtain thiolated chitosan. E3. Add 100 g of thiolated chitosan, 150 g of PEG-4000, and 10 g of sodium carbonate to 500 mL of deionized water and microwave for 1 h at 400 W and 60°C to obtain modified chitosan. F. The preparation method of modified graphene is as follows: F1. Place 100 g of graphene in a plasma reactor and introduce an Ar / O2 mixed gas (volume ratio 4:1). Etch the graphene at a pressure of 10 Pa and a power of 100 W for 3 min to produce etched graphene. F2. Add all the etched graphene, 50 g of boric acid, and 50 g of 3-aminophenylboronic acid to 1 L of 0.1 M sodium hydroxide aqueous solution. Ultrasonicate the mixture at 60°C and 300 W for 2 h to prepare borate-bonded graphene. F3. Disperse 100 g of borate-grafted graphene in 1 L of an ethanol-water mixture (ethanol:water = 1:3), add 20 g of ammonia water, stir evenly, and then add 100 mL of tetraethyl orthosilicate (TEOS) dropwise. React at 40°C for 24 h, and then calcine at 550°C for 6 h to obtain mesoporous silica-coated graphene. F4. Mix 100 g of mesoporous silica-coated graphene with 10 g of KH-570 coupling agent and melt-react them at 80°C for 2 h to obtain modified graphene. It is worth noting that the steps for regeneration after each adsorption saturation are as follows: ① Water washing and acid removal: Use deionized water to rinse the adsorption column from top to bottom at a flow rate of 8BV / h until the pH of the effluent stabilizes at 6.0-7.0.

[0050] ② Functional group restoration: A 0.15 M dithiothreitol (DTT) aqueous solution was passed into the adsorption column from bottom to top at a flow rate of 1.5 BV / h for 45 min at room temperature; it was then flushed with deionized water at a flow rate of 8 BV / h until the DTT concentration in the effluent was <0.1 mM. Then, use ethanol-water (volume ratio 1:1) solution (dosage 2BV) at a flow rate of 3BV / h through the adsorption column to remove residual organic matter on the surface (such as pigments and peptides in vinegar), and then rinse with deionized water until there is no ethanol smell.

[0051] Example 2 Compared with Example 1, the amount of each component in the adsorption and enrichment material was adjusted, and the other parameters and steps were the same as Example 1.

[0052] The amounts of the components after adjustment are: 65 parts by weight of modified resin, 15 parts by weight of modified chitosan, and 13 parts by weight of modified graphene, and the mass ratio of the three pore size resins in the modified resin remains unchanged.

[0053] Example 3 Compared with Example 1, apples were replaced with grapes, and the other parameters and steps remained unchanged.

[0054] Example 4 Compared with Example 1, apples were replaced with citrus fruits, and the other parameters and steps remained unchanged.

[0055] Comparative Example 1 Compared with Example 1, the three resins were not modified, and the remaining parameters and steps were the same as Example 1.

[0056] Comparative Example 2 Compared with Example 1, the adsorption and enrichment material only contains modified resin, without modified chitosan and modified graphene, and the other parameters and steps are the same as Example 1.

[0057] Comparative Example 3 Compared with Example 1, no disulfide bond was introduced into the modified chitosan, and the remaining parameters and steps were the same as Example 1.

[0058] Comparative Example 4 Compared with Example 1, the modified graphene is not coated with mesoporous silica and is not modified with KH-570 coupling agent. The remaining parameters and steps are the same as Example 1.

[0059] Experimental example 1. Chewable tablet quality comparison experiment.

[0060] The relevant properties of the chewable tablets prepared in Examples 1-4 were measured, and the test results are shown in Table 1.

[0061] Table 1: As shown in Table 1, the chewable tablets prepared in the four examples had a hardness range of 248-257 N, meeting the chewing hardness requirements for chewable tablets; the moisture content was all <5%, meeting the moisture limit for candies in GB 17399-2016; the total colony count was <100 CFU / g and the coliform group was <30 MPN / 100g, and the microbial indicators all met the standards, indicating that different ratios of fruit raw materials and adsorption materials had no significant effect on the basic quality of the chewable tablets, and the process stability was strong.

[0062] 2. Comparison of adsorption and enrichment material performance.

[0063] The adsorption capacity recovery rate (%) refers to the adsorption capacity recovery rate after 30 cycles of adsorption and desorption. The comparison results are shown in Table 2.

[0064] Table 2: From Table 2 we can see that: Example 1-2: ① The synergistic effect of modified resin, modified chitosan and modified graphene is relatively stable, and can maintain efficient adsorption and desorption of polyphenols, vitamin C and flavonoids.

[0065] ② The synergistic effect of modified resin, chitosan and graphene is stable. After 30 adsorption and desorption cycles, the adsorption capacity recovery rates of polyphenols, vitamin C and flavonoids are all ≥92.6%.

[0066] Example 3: ① After apples were replaced with grapes, the difference in raw material composition caused the binding force between the adsorption and enrichment material and polyphenols, vitamin C, and flavonoids to change. Certain components in grapes may have affected the interaction between the functional groups in the adsorption and enrichment material and the target components, resulting in a certain degree of decrease in the adsorption and desorption rates.

[0067] ② Because the tartaric acid in grapes competes with the phosphate groups for binding sites, after 30 adsorption and desorption cycles, a large amount of vitamin C adsorption sites are lost.

[0068] Example 4: After replacing apples with citrus, the components in citrus are better compatible with the adsorption enrichment material. The macroporous resin grafted with PEG, the mesoporous resin grafted with phosphate, and the microporous resin grafted with borate in the adsorption enrichment material form a more effective adsorption-desorption equilibrium with the polyphenols, vitamin C, and flavonoids in citrus, thereby improving the adsorption and desorption performance.

[0069] Comparative Example 1: ① The unmodified resin lacks specific functional groups and cannot form strong interactions with polyphenols, vitamin C, and flavonoids, making it difficult to achieve efficient adsorption and desorption of the target components. Therefore, the adsorption and desorption rates are much lower than those in the examples.

[0070] ② Because the unmodified resin lacks specific functional groups, adsorption is mainly physical adsorption. After 30 cycles, the pore blockage rate is serious, resulting in a serious loss of adsorption sites for polyphenols, vitamin C, and flavonoids.

[0071] Comparative Example 2: ① When only modified resin is present, the synergistic effect of modified chitosan and modified graphene is lacking, and the overall performance of the material is limited. Modified chitosan and modified graphene play an important role in enhancing the material's adsorption capacity for target components and improving desorption performance.

[0072] ② When only modified resin is used, the dynamic cross-linking of chitosan and the high specific surface area of graphene are lacking, and the recovery rate of polyphenol adsorption capacity is reduced.

[0073] Comparative Example 3: ① The lack of disulfide bonds affects its structural stability and ability to bind to target components. Disulfide bonds help maintain the chitosan network structure and enhance the adsorption effect on polyphenols.

[0074] ② Because the chitosan network without disulfide bonds is easy to expand during acidic desorption, the exposure rate of polyphenol adsorption sites is seriously reduced after 30 cycles.

[0075] Comparative Example 4: ① Uncoated mesoporous silica reduces the adsorption sites. Mesoporous silica coating can increase the specific surface area and active sites of the material, and enhance the adsorption capacity of flavonoids and other components.

[0076] ② The borate groups on the graphene surface not coated with mesoporous silica were easily oxidized within 30 cycles, and the flavonoid coordination bond breakage rate increased.

Claims

1. A method for preparing a chewable tablet food, characterized in that: The steps include: S1. Raw material pretreatment: Fruits are cored, peeled, and crushed at 0±3°C. The fruit is then filtered to obtain juice and pomace. S2. Enzymatic hydrolysis: The juice is subjected to enzymatic hydrolysis, followed by secondary filtration to obtain an enzymatic hydrolyzate; S3 fermentation: alcohol fermentation and acetic acid fermentation of the enzymatic hydrolysate, after which the pH of the system was adjusted to 6.5-7.5, followed by three-stage filtration to obtain a fermentation broth; S4 adsorption enrichment: The fermentation broth is passed through the adsorption enrichment material, and then the fermentation broth is not adsorbed and concentrated to obtain concentrated fruit vinegar liquid, the adsorbed components are desorbed and post-processed to obtain an enriched product; Among them, the adsorption and enrichment materials include modified resin, modified chitosan, and modified graphene; The modified resin includes a macroporous resin grafted with PEG, a mesoporous resin grafted with phosphate, and a microporous resin grafted with borate; The modified chitosan is first cross-linked with dialdehyde starch, then grafted with disulfide bonds, and finally grafted with polyethylene glycol; The modified graphene is obtained by first subjecting graphene to plasma etching, then grafting borate, then coating mesoporous silica, and then modifying with a silane coupling agent; S5. Low-temperature molding: Add sweetener, molding agent, food-grade calcium carbonate, enrichment product, and dried and crushed fruit pomace to the concentrated fruit vinegar liquid, stir evenly, and then mold at 45±5°C to obtain fruit vinegar chewable tablets.

2. The method for preparing a chewable tablet food according to claim 1, wherein: In step S4, the pore size of the macroporous resin is 100-500 nm, the pore size of the mesoporous resin is 5-50 nm, and the pore size of the microporous resin is less than 2 nm.

3. The method for preparing a chewable tablet food according to claim 1, wherein: In step S4, the mass ratio of macroporous resin:mesoporous resin:microporous resin is 2-3:2-3:

1.

4. The method for preparing a chewable tablet food according to claim 3, wherein: In step S4, the adsorption and enrichment material includes 50-70 parts by weight of modified resin, 10-20 parts by weight of modified chitosan, and 10-20 parts by weight of modified graphene.

5. The method for preparing a chewable tablet food according to claim 3, wherein: In step S4, the adsorption and enrichment material includes 55-68 parts by weight of modified resin, 12-18 parts by weight of modified chitosan, and 15-20 parts by weight of modified graphene.

6. The method for preparing a chewable tablet food according to claim 3, wherein: In step S4, the adsorption and enrichment material includes 68 parts by weight of modified resin, 17 parts by weight of modified chitosan, and 15 parts by weight of modified graphene.

7. The method for preparing a chewable tablet food according to claim 1, wherein: In step S1, the filter screen selected for the first-level filtration is a 100-300 mesh filter screen.

8. The method for preparing a chewable tablet food according to claim 1, wherein: In step S2, the secondary filtration is performed using 300-500 mesh diatomaceous earth filtration.

9. The method for preparing a chewable tablet food according to claim 1, wherein: In step S3, the tertiary filtration material is a modified PES membrane obtained by grafting sulfobetaine groups onto PES; the pore size of the modified PES membrane is 50-200 microns.

10. The method for preparing a chewable tablet food according to claim 1, wherein: In step S5, the particle size of the dried and crushed pomace is 80-150 mesh.

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