Vinasse regenerated material as well as preparation method and application thereof

Abstract

The invention discloses a vinasse regenerated material as well as a preparation method and application thereof, and belongs to the technical field of degradable materials. The vinasse regenerated material is prepared from the following raw materials in parts by mass: 30 to 60 parts of vinasse protein, 3 to 10 parts of xanthan gum, 15 to 40 parts of polysaccharide, 40 to 80 parts of starch, 0.5 to 1 part of cross-linking agent, 10 to 65 parts of water and 0.5 to 1.5 parts of water repellent agent. According to the invention, vinasse protein in abandoned vinasse is taken as a raw material and is combined with degradable raw materials such as polysaccharide and starch to prepare the naturally degradable packaging material, and the naturally degradable packaging material has excellent biodegradability, can be rapidly degraded in a natural environment and has excellent mechanical properties, the elongation at break reaches 156.89%, the tensile strength reaches 18.92 MPa, and the packaging material is suitable for industrial production. The problem that the packaging material needs to be degraded by industrial compost is solved, and the problem of environmental pollution caused by waste vinasse is also avoided.

Description

Technical Field

[0001] The invention belongs to the technical field of degradable materials, and specifically relates to a wine lees regeneration material and a preparation method and application thereof. Background Art

[0002] Wine lees waste mainly refers to the residues produced in the winemaking process, namely, wine lees. Wine lees belong to solid waste (solid waste), which are solid and semi-solid waste materials produced by humans in production, consumption, life and other activities. Wine lees usually contain a large amount of organic matter and nutrients, such as crude protein, crude fat, crude fiber, etc., but also have the characteristics of high water content and high acid content, which are very easy to rot and deteriorate, breed toxins such as aflatoxin, and cause secondary environmental pollution.

[0003] However, wine lees waste is not without value. On the contrary, it has a variety of resource utilization possibilities. Wine lees, especially brewer's lees and white wine lees, are rich in protein. These proteins mainly come from the raw materials used in the winemaking process, such as barley, corn, etc. Taking brewer's lees as an example, its protein content can reach 24%-28%, fat content is 8%-11%, and sugar content is 1%-3%. Among these proteins, the content of essential amino acids is also quite high, accounting for 36.60% of the total amino acid content, which is much higher than the nutritional content of corn. These proteins are not only high in content, but also have good extractability. Through some extraction methods, such as alkaline extraction, salt or alcohol solution extraction, and even biotechnology such as fungal fermentation, the extractability and biological activity of proteins can be further improved.

[0004] At present, the fully degradable packaging products used on a large scale in the market are basically based on polylactic acid, dibasic acid diol copolyester series (polybutylene adipate / terephthalate, polybutylene succinate, polybutylene succinate-adipate, etc.), starch-based series, cellulose series and their composite materials. Although they meet the performance requirements of the packaging products and the biodegradable properties required for environmental protection, there are still many problems. For example, polylactic acid has large energy loss during the polymerization process and has a high preparation cost; and most of the products made of polylactic acid are compostable and degradable plastics, which cannot meet the requirements of rapid degradation under natural conditions and cannot achieve effective circulation.

[0005] Biomass materials are green, renewable, and biocompatible, and can be completely degraded in the natural environment after being abandoned. However, packaging materials made from a single biomass material have problems such as insufficient mechanical properties and poor ductility, and cannot meet the needs of daily use. Therefore, there is an urgent need for a green, renewable packaging material with excellent mechanical and ductility properties. Summary of the invention

[0006] In order to solve the problem that packaging materials in the prior art need to be degraded by industrial composting and have poor mechanical properties and ductility, the present invention uses wine lees protein in abandoned wine lees as raw material, combined with degradable raw materials such as polysaccharides and starch, to prepare naturally degradable packaging materials. It also solves the environmental pollution problem caused by wine lees waste and realizes the reuse of wine lees waste.

[0007] The present invention first provides a wine lees regeneration material, the raw materials of which include the following components in parts by weight: 30-60 parts of wine lees protein, 15-40 parts of polysaccharides, 40-80 parts of starch, 0.5-1 part of a cross-linking agent, 10-65 parts of water and 0.5-1.5 parts of a hydrophobic agent.

[0008] Among them, in the above-mentioned wine lees regeneration material, the wine lees protein is at least one of beer wine lees protein, white wine wine lees protein, red wine wine lees protein or yellow wine wine lees protein.

[0009] Among them, in the above-mentioned wine lees regeneration material, the polysaccharide is at least one of sodium alginate or xanthan gum.

[0010] Among them, in the above-mentioned wine lees regeneration material, the starch is at least one of oxidized high-amylose corn starch or carboxymethyl high-amylose corn starch.

[0011] Wherein, in the above-mentioned wine lees regeneration material, the cross-linking agent is at least one of citric acid, boric acid or calcium chloride.

[0012] Among them, in the above-mentioned wine lees regeneration material, the hydrophobic agent is at least one of oleic acid, stearic acid or beeswax.

[0013] Wherein, in the above-mentioned distiller's grains regeneration material, the mass proportion of the distiller's grains protein is 35 to 55 parts.

[0014] Wherein, in the above-mentioned wine lees regeneration material, the mass proportion of the polysaccharide is 20 to 35 parts.

[0015] Wherein, in the above-mentioned distiller's grains regeneration material, the mass proportion of the starch is 45 to 75 parts.

[0016] Wherein, in the above-mentioned wine lees regeneration material, the mass fraction of the cross-linking agent is 0.6 to 0.9 parts.

[0017] Wherein, in the above-mentioned distiller's grains regeneration material, the mass proportion of water is 20 to 55 parts.

[0018] Among them, in the above-mentioned wine lees regeneration material, the mass proportion of the hydrophobic agent is 0.6 to 1.3 parts.

[0019] The present invention also provides a method for preparing the above-mentioned wine lees regeneration material, which comprises the following steps:

[0020] A. Mixing distiller's grains protein, polysaccharide, starch, a cross-linking agent, water and a hydrophobic agent according to parts by mass to obtain a mixture;

[0021] B. Extruding and granulating the mixture to obtain the wine lees recycled material.

[0022] Wherein, in the preparation method of the above-mentioned wine lees recycled material, in step B, the temperature of the extrusion granulation is 100-120°C.

[0023] The present invention also provides application of the above-mentioned wine lees recycled material in preparing packaging materials.

[0024] In the present invention, the vinasse protein can be a homemade product or a commercial product; when homemade, the vinasse protein is obtained by separation and purification from wine slurry waste, and the separation and purification method can adopt a conventional extraction method well known to those skilled in the art, and a common extraction method is an enzymatic extraction method; the enzymatic extraction method is also a method well known to those skilled in the art, such as the enzymatic extraction method used in the embodiments of the present invention.

[0025] In the present invention, the oxidized high-amylose corn starch and carboxymethyl high-amylose corn starch can be homemade or commercially available. When homemade, the commercially available high-amylose corn starch can be modified by conventional oxidation modification or carboxymethyl modification methods in the art, such as the preparation methods of oxidized high-amylose corn starch and carboxymethyl high-amylose corn starch used in the embodiments of the present invention.

[0026] Beneficial effects of the present invention:

[0027] The present invention uses the lees protein in the abandoned wine trough as raw material, and combines sodium alginate / xanthan gum and modified high-amylose corn starch to prepare a naturally degradable packaging material. After the modified high-amylose corn starch is mixed with the lees protein and polysaccharide, the lees protein matrix, the rigid molecular chain of high-amylose corn starch, and the flexible molecular chain of sodium alginate form a three-dimensional mesh network by the interaction of hydrogen bonds, which gives the lees recycled material better mechanical strength and toughness; after the polysaccharide is combined with the lees protein, the lees recycled material is given excellent ductility, which meets the needs of packaging use.

[0028] The wine lees recycled material of the present invention has good mechanical strength and mechanical properties, and also has excellent ductility and natural degradability, and has lower raw material cost. It can be quickly degraded in the natural environment, which solves the problem that packaging materials need to be degraded by industrial composting, and also effectively utilizes wine lees protein, avoiding environmental pollution caused by waste wine lees, and conforms to the green development strategy. The preparation method provided by the present invention has a simple process, low preparation cost, and can be applied to large-scale production. DETAILED DESCRIPTION

[0029] Specifically, a distiller's grains regeneration material, whose raw materials contain the following components in parts by weight: 30-60 parts of distiller's grains protein, 15-40 parts of polysaccharides, 40-80 parts of starch, 0.5-1 part of a cross-linking agent, 10-65 parts of water and 0.5-1.5 parts of a hydrophobic agent.

[0030] In the wine lees regeneration material of the present invention, the wine lees protein is at least one of beer wine lees protein, white wine wine lees protein, red wine wine lees protein or yellow wine wine lees protein, which can be obtained by separation and purification from wine lees waste, and the separation and purification method can adopt conventional extraction methods well known to those skilled in the art, such as conventional enzymatic extraction methods.

[0031] In the wine lees regeneration material of the present invention, the polysaccharide is at least one of sodium alginate or xanthan gum. The polysaccharide used in the present invention is sodium alginate / xanthan gum, which, after being mixed with wine lees protein, gives the wine lees regeneration material excellent ductility, meeting the requirements of packaging use.

[0032] The starch used in the present invention is modified high-amylose corn starch, specifically oxidized high-amylose corn starch and / or carboxymethyl high-amylose corn starch. After being mixed with distiller's grains protein and sodium alginate, the distiller's grains protein matrix, the rigid molecular chains of the high-amylose corn starch, and the flexible molecular chains of the sodium alginate form a meshed three-dimensional grid network through the interaction of hydrogen bonds, thereby giving the distiller's grains recycled material better mechanical strength and toughness.

[0033] In the wine lees regeneration material of the present invention, the cross-linking agent is at least one of citric acid, boric acid or calcium chloride. The present invention uses citric acid, boric acid and calcium chloride as cross-linking agents to effectively achieve cross-linking between wine lees proteins, thereby improving the mechanical properties and mechanical strength of the wine lees regeneration material.

[0034] In the wine lees regeneration material of the present invention, the hydrophobic agent is at least one of oleic acid, stearic acid or beeswax.

[0035] In order to further improve the performance of the wine lees regeneration material of the present invention, the present invention optimizes and adjusts the dosage of each component as follows:

[0036] The weight percentage of the distiller's grains protein is 35 to 55 parts;

[0037] The mass proportion of the polysaccharide is 20 to 35 parts;

[0038] The mass parts of the starch are 45 to 75 parts;

[0039] The mass fraction of the cross-linking agent is 0.6 to 0.9 parts;

[0040] The mass parts of the water are 20 to 55 parts;

[0041] The mass fraction of the hydrophobic agent is 0.6 to 1.3 parts.

[0042] The present invention also provides a method for preparing the above-mentioned wine lees regeneration material, which comprises the following steps:

[0043] A. Mixing distiller's grains protein, polysaccharide, starch, a cross-linking agent, water and a hydrophobic agent according to parts by mass to obtain a mixture;

[0044] B. Extruding and granulating the mixture to obtain the wine lees recycled material.

[0045] Wherein, in the preparation method of the above-mentioned wine lees recycled material, in step B, the temperature of the extrusion granulation is 100-120°C.

[0046] The invention also provides application of the wine lees recycled material in packaging materials.

[0047] The present invention is further described in detail below by way of examples, but the protection scope of the present invention is not limited to the scope of the examples.

[0048] In the following examples, the wine trough protein was obtained by enzymatic extraction, and the specific method was as follows:

[0049] Materials and Reagents:

[0050] Wine lees: choose white wine lees, beer lees, red wine lees or yellow wine lees, with an initial humidity of about 60%-70%.

[0051] Enzyme preparations:

[0052] Alcalase: Suitable for alkaline environment, the action temperature is 50℃-60℃, and the optimal pH is 8.0-9.0.

[0053] Trypsin: The action temperature is 37°C and the optimal pH is 7.5-8.5.

[0054] Neutrase: The action temperature is 40℃-50℃, and the optimum pH is 6.5-7.5.

[0055] Buffer:

[0056] Phosphate buffer (PBS): used to maintain the pH stability of the reaction system, generally at a concentration of 0.05M.

[0057] Tris-HCl buffer: used for trypsin reaction, the concentration is 0.1M.

[0058] Distilled water: used for dilution, washing and purification after protein precipitation.

[0059] Equipment and instruments:

[0060] Constant temperature water bath: used to control the temperature of enzymatic hydrolysis reaction.

[0061] High-speed centrifuge: used for solid-liquid separation, with a rotation speed of 8000rpm.

[0062] pH meter: Accurately measure the pH value of the reaction solution.

[0063] Freeze dryer or spray dryer: used to obtain distillers grains protein powder.

[0064] Extraction steps:

[0065] 1. Preprocessing

[0066] Washing and drying of lees: Wash the fresh lees repeatedly with distilled water to remove attached impurities and sugar; use a centrifuge (3000rpm, 15 minutes) or vacuum filtration equipment to remove excess water from the lees; use a freeze dryer to dry the lees, control the drying temperature to -40°C, and continue for 24 hours to obtain dry lees with a moisture content of less than 10%; grind the dried lees to obtain lees powder with a particle size of about 80-100 mesh, and set it aside.

[0067] 2. Enzymatic reaction

[0068] Prepare enzymatic hydrolysate: suspend the vinasse powder in buffer at a solid-liquid ratio of 1:10 (i.e., add 100g vinasse powder to 1000mL buffer), stir thoroughly, and adjust the pH to a range suitable for enzyme action; when alkaline protease is used, adjust the pH to 8.5 and maintain the temperature at 55°C; when trypsin is used, adjust the pH to 8.0 and maintain the temperature at 37°C.

[0069] Enzyme addition: Add enzyme preparation according to enzyme activity, usually at a ratio of 1:100 (i.e., add 1g enzyme preparation to 100g of vinasse powder) and continue stirring to ensure full contact between the enzyme and vinasse powder.

[0070] Enzyme hydrolysis time: The reaction time is controlled to 4 hours. During this period, samples can be collected every 30 minutes to detect the protein content to determine the optimal enzymolysis time.

[0071] 3. Stop enzymatic hydrolysis

[0072] Temperature termination: After the enzymatic hydrolysis is completed, the enzyme activity is terminated by rapidly heating the reaction system to 90°C and maintaining it for 10 minutes.

[0073] 4. Solid-liquid separation

[0074] Centrifugation: Separate the liquid phase from the solid residue using a high-speed centrifuge at 8000 rpm for 20 minutes; collect the supernatant and the solid residue can be further processed or discarded.

[0075] 5. Protein precipitation

[0076] Isoelectric precipitation: Adjust the pH of the supernatant to the isoelectric point of the protein. Generally, use 1M hydrochloric acid to adjust the pH to 4.5 and keep stirring for 30 minutes. The protein will gradually precipitate.

[0077] Centrifugal collection: Use high-speed centrifugation at 8000 rpm again for 15 minutes to collect the protein precipitate.

[0078] 6. Protein purification

[0079] Washing: Use a small amount of distilled water to wash the protein precipitate to remove impurities, repeat 2-3 times.

[0080] Drying: Freeze-dry the washed protein precipitate (-40°C, 24 hours), or use spray drying method, controlling the inlet temperature at 150°C and the outlet temperature at 80°C.

[0081] 7. Product processing

[0082] The final distiller's grains protein is a white or light yellow powder with a moisture content of less than 5% and a protein content usually between 60% and 70%.

[0083] In the following examples, oxidized high-amylose corn starch is prepared by the following method: first, high-amylose corn starch is mixed with distilled water at a solid-liquid ratio of 1g:10mL to form a starch suspension. After adjusting the pH to 8.0-9.5, slowly add a 1%-5% mass concentration of sodium hypochlorite aqueous solution or a 30% mass concentration of hydrogen peroxide aqueous solution, and the amount of effective oxidant is 3%-8% of the mass of starch. Stir the reaction at 35°C-45°C for 1-3 hours, keeping the pH stable during the reaction. After the reaction is completed, adjust the pH to 6.0-7.0 with dilute acid to terminate the reaction. The starch is separated by high-speed centrifugation, washed with distilled water, and finally dried at 60°C to obtain oxidized high-amylose corn starch powder.

[0084] Carboxymethyl high-amylose corn starch is prepared by the following method: First, high-amylose corn starch is mixed with water in a ratio of 1g:4mL to form a starch suspension, and then sodium hydroxide aqueous solution is added to adjust the pH of the system to 10-12, and stirred for 30 minutes for alkalization. Next, sodium chloroacetate (0.5%-2% of the mass of starch) is slowly added and reacted at 60°C for 2-4 hours to cause carboxymethylation of the starch molecules. After the reaction is completed, the pH is adjusted to neutral by adding dilute hydrochloric acid or acetic acid solution to terminate the reaction. Subsequently, the product is centrifuged to remove by-products, washed with distilled water to neutrality, and finally dried and ground at 50°C-60°C to obtain carboxymethyl high-amylose corn starch powder.

[0085] Example 1

[0086] 30 parts of beer grain protein, 15 parts of sodium alginate, 40 parts of oxidized high-amylose corn starch, 0.5 parts of citric acid, 10 parts of water, and 0.5 parts of oleic acid.

[0087] Mix 30 parts of beer grain protein, 15 parts of sodium alginate, 40 parts of oxidized high-amylose corn starch, 0.5 parts of citric acid, 10 parts of water and 0.5 parts of oleic acid to obtain a mixture;

[0088] The mixed material is extruded and granulated at 108 degrees Celsius to obtain the wine lees recycled material.

[0089] Example 2

[0090] 40 parts of liquor lees protein, 20 parts of sodium alginate, 50 parts of oxidized high-amylose corn starch, 1 part of citric acid, 20 parts of water, and 1 part of oleic acid.

[0091] Mix 40 parts of liquor lees protein, 20 parts of sodium alginate, 50 parts of oxidized high-amylose corn starch, 1 part of citric acid, 20 parts of water and 1 part of oleic acid to obtain a mixture;

[0092] The mixed material is extruded and granulated at 102 degrees Celsius to obtain the wine lees recycled material.

[0093] Example 3

[0094] 45 parts of beer grain protein, 20 parts of xanthan gum, 70 parts of oxidized high-amylose corn starch, 0.5 parts of boric acid, 35 parts of water, and 0.5 parts of stearic acid.

[0095] Mix 45 parts of beer grain protein, 20 parts of xanthan gum, 70 parts of oxidized high-amylose corn starch, 0.5 parts of boric acid, 35 parts of water and 0.5 parts of stearic acid to obtain a mixture;

[0096] The mixed material is extruded and granulated at 100 degrees Celsius to obtain the wine lees recycled material.

[0097] Example 4

[0098] 60 parts of red wine lees protein, 35 parts of xanthan gum, 80 parts of carboxymethyl high-amylose corn starch, 1 part of calcium chloride, 55 parts of water, and 1 part of beeswax.

[0099] Mix 60 parts of red wine lees protein, 35 parts of xanthan gum, 80 parts of carboxymethyl high-amylose corn starch, 1 part of calcium chloride, 55 parts of water and 1 part of beeswax to obtain a mixture;

[0100] The mixed material is extruded and granulated at 120 degrees Celsius to obtain the wine lees recycled material.

[0101] Example 5

[0102] 55 parts of red wine lees protein, 40 parts of sodium alginate, 68 parts of carboxymethyl high-amylose corn starch, 0.7 parts of boric acid, 40 parts of water, and 0.9 parts of stearic acid.

[0103] Mix 55 parts of red wine lees protein, 40 parts of sodium alginate, 68 parts of carboxymethyl high-amylose corn starch, 0.7 parts of boric acid, 40 parts of water and 0.9 parts of stearic acid to obtain a mixture;

[0104] The mixed material is extruded and granulated at 112 degrees Celsius to obtain the wine lees recycled material.

[0105] Example 6

[0106] 50 parts of rice wine lees protein, 25 parts of sodium alginate, 78 parts of oxidized high-amylose corn starch, 0.7 parts of calcium chloride, 50 parts of water, and 1 part of beeswax.

[0107] Mix 50 parts of rice wine lees protein, 25 parts of sodium alginate, 78 parts of oxidized high-amylose corn starch, 0.7 parts of calcium chloride, 50 parts of water and 1 part of beeswax to obtain a mixture;

[0108] The mixed material is extruded and granulated at 120 degrees Celsius to obtain the wine lees recycled material.

[0109] Example 7

[0110] 45 parts of rice wine lees protein, 35 parts of xanthan gum, 65 parts of carboxymethyl high-amylose corn starch, 0.8 parts of citric acid, 72 parts of water, and 0.5 parts of oleic acid.

[0111] Mix 45 parts of rice wine lees protein, 35 parts of xanthan gum, 65 parts of carboxymethyl high-amylose corn starch, 0.8 parts of citric acid, 72 parts of water and 0.5 parts of oleic acid to obtain a mixture;

[0112] The mixed material is extruded and granulated at 114 degrees Celsius to obtain the wine lees recycled material.

[0113] Example 8

[0114] 55 parts of beer grain protein, 40 parts of xanthan gum, 80 parts of oxidized high-amylose corn starch, 1.5 parts of boric acid, 65 parts of water, and 1.5 parts of beeswax.

[0115] Mix 55 parts of beer grain protein, 40 parts of xanthan gum, 80 parts of oxidized high-amylose corn starch, 1.5 parts of boric acid, 65 parts of water and 1.5 parts of beeswax to obtain a mixture;

[0116] The mixed material is extruded and granulated at 118 degrees Celsius to obtain the wine lees recycled material.

[0117] Example 9

[0118] 50 parts of liquor lees protein, 40 parts of sodium alginate, 48 parts of oxidized high-amylose corn starch, 1 part of calcium chloride, 66 parts of water, and 1.2 parts of stearic acid.

[0119] Mix 50 parts of liquor lees protein, 40 parts of sodium alginate, 48 parts of oxidized high-amylose corn starch, 1 part of calcium chloride, 66 parts of water and 1.2 parts of stearic acid to obtain a mixture;

[0120] The mixed material is extruded and granulated at 120 degrees Celsius to obtain the wine lees recycled material.

[0121] Example 10

[0122] 35 parts of rice wine lees protein, 15 parts of sodium alginate, 40 parts of oxidized high-amylose corn starch, 0.8 parts of boric acid, 45 parts of water, and 1.2 parts of beeswax.

[0123] Mix 35 parts of rice wine lees protein, 15 parts of sodium alginate, 40 parts of oxidized high-amylose corn starch, 0.8 parts of boric acid, 45 parts of water and 1.2 parts of beeswax to obtain a mixture;

[0124] The mixed material is extruded and granulated at 1121 degrees Celsius to obtain the wine lees recycled material.

[0125] Embodiment 11

[0126] 44 parts of liquor lees protein, 32 parts of xanthan gum, 56 parts of oxidized high-amylose corn starch, 0.6 parts of calcium chloride, 48 parts of water, and 0.6 parts of oleic acid.

[0127] Mix 44 parts of liquor lees protein, 32 parts of xanthan gum, 56 parts of oxidized high-amylose corn starch, 0.6 parts of calcium chloride, 48 parts of water and 0.6 parts of oleic acid to obtain a mixture;

[0128] The mixed material is extruded and granulated at 105 degrees Celsius to obtain the wine lees recycled material.

[0129] Example 12

[0130] 54 parts of red wine lees protein, 36 parts of sodium alginate, 65 parts of carboxymethyl high-amylose corn starch, 0.8 parts of citric acid, and 0.7 parts of oleic acid.

[0131] Mix 54 parts of red wine lees protein, 36 parts of sodium alginate, 65 parts of carboxymethyl high-amylose corn starch, 0.8 parts of citric acid and 0.7 parts of oleic acid to obtain a mixture;

[0132] The mixed material is extruded and granulated at 108 degrees Celsius to obtain the wine lees recycled material.

[0133] Embodiment 13

[0134] 62 parts of rice wine lees protein, 25 parts of sodium alginate, 60 parts of carboxymethyl high-amylose corn starch, 0.8 parts of boric acid, 46 parts of water, and 1.2 parts of oleic acid.

[0135] Mix 62 parts of rice wine lees protein, 25 parts of sodium alginate, 60 parts of carboxymethyl high-amylose corn starch, 0.8 parts of boric acid, 46 parts of water and 1.2 parts of oleic acid to obtain a mixture;

[0136] The mixed material is extruded and granulated at 112 degrees Celsius to obtain the wine lees recycled material.

[0137] Embodiment 14

[0138] 55 parts of red wine lees protein, 32 parts of sodium alginate, 62 parts of oxidized high-amylose corn starch, 0.9 parts of calcium chloride, 60 parts of water, and 1.4 parts of stearic acid.

[0139] Mix 55 parts of red wine lees protein, 32 parts of sodium alginate, 62 parts of oxidized high-amylose corn starch, 0.9 parts of calcium chloride, 60 parts of water and 1.4 parts of stearic acid to obtain a mixture;

[0140] The mixed material is extruded and granulated at 105 degrees Celsius to obtain the wine lees recycled material.

[0141] Embodiment 15

[0142] 38 parts of liquor lees protein, 40 parts of xanthan gum, 66 parts of oxidized high-amylose corn starch, 0.7 parts of citric acid, 62 parts of water, and 1.5 parts of oleic acid.

[0143] Mix 38 parts of liquor lees protein, 40 parts of xanthan gum, 66 parts of oxidized high-amylose corn starch, 0.7 parts of citric acid, 62 parts of water and 1.5 parts of oleic acid to obtain a mixture;

[0144] The mixed material is extruded and granulated at 110 degrees Celsius to obtain the wine lees recycled material.

[0145] Example 16

[0146] 38 parts of liquor lees protein, 40 parts of xanthan gum, 66 parts of oxidized high-amylose corn starch, 0.6 parts of boric acid, 36 parts of water and 1.5 parts of oleic acid.

[0147] Mix 38 parts of liquor lees protein, 40 parts of xanthan gum, 66 parts of oxidized high-amylose corn starch, 0.6 parts of boric acid, 36 parts of water and 1.5 parts of oleic acid to obtain a mixture;

[0148] The mixed material is extruded and granulated at 115 degrees Celsius to obtain the wine lees recycled material.

[0149] Embodiment 17

[0150] 32 parts of red wine lees protein, 15 parts of xanthan gum, 44 parts of carboxymethyl high-amylose corn starch, 0.9 parts of calcium chloride, 65 parts of water, and 1.5 parts of beeswax.

[0151] Mix 32 parts of red wine lees protein, 15 parts of xanthan gum, 44 parts of carboxymethyl high-amylose corn starch, 0.9 parts of calcium chloride, 65 parts of water and 1.5 parts of beeswax to obtain a mixture;

[0152] The mixed material is extruded and granulated at 118 degrees Celsius to obtain the wine lees recycled material.

[0153] Embodiment 18

[0154] 56 parts of beer grain protein, 35 parts of sodium alginate, 50 parts of oxidized high-amylose corn starch, 0.8 parts of calcium chloride, 42 parts of water, and 0.8 parts of stearic acid.

[0155] Mix 56 parts of beer grain protein, 35 parts of sodium alginate, 50 parts of oxidized high-amylose corn starch, 0.8 parts of calcium chloride, 42 parts of water and 0.8 parts of stearic acid to obtain a mixture;

[0156] The mixed material is extruded and granulated at 118 degrees Celsius to obtain the wine lees recycled material.

[0157] Embodiment 19

[0158] 52 parts of beer grain protein, 38 parts of xanthan gum, 69 parts of carboxymethyl high-amylose corn starch, 1 part of calcium chloride, 1.2 parts of beeswax, and 42 parts of water.

[0159] Mix 52 parts of beer grain protein, 38 parts of xanthan gum, 69 parts of carboxymethyl high-amylose corn starch, 1 part of calcium chloride and 1.2 parts of beeswax to obtain a mixture;

[0160] The mixed material is extruded and granulated at 115 degrees Celsius to obtain the wine lees recycled material.

[0161] Embodiment 20

[0162] 48 parts of rice wine lees protein, 40 parts of xanthan gum, 66 parts of oxidized high-amylose corn starch, 1 part of boric acid, 1.5 parts of oleic acid, and 42 parts of water.

[0163] Mix 48 parts of rice wine lees protein, 40 parts of xanthan gum, 66 parts of oxidized high-amylose corn starch, 1 part of boric acid and 1.5 parts of oleic acid to obtain a mixture;

[0164] The mixed material is extruded and granulated at 118 degrees Celsius to obtain the wine lees recycled material.

[0165] Comparative Example 1

[0166] The method is basically the same as Example 1, except that oxidized high-amylose corn starch is not added.

[0167] Comparative Example 2

[0168] It is basically the same as Example 1, the only difference being that the oxidized high-amylose starch is prepared from rice.

[0169] Performance Testing

[0170] The mechanical properties of the wine lees recycled materials obtained in Examples 1 to 20 and Comparative Examples 1 to 2 were tested, and the results are shown in Table 1.

[0171] Table 1 Mechanical properties test results of wine lees recycled materials obtained in Examples and Comparative Examples

[0172] Case Elongation at break % Tensile strength MPa Case Elongation at break % Tensile strength MPa Example 1 152.32 16.89 Embodiment 11 156.87 18.92 Example 2 154.26 17.24 Example 12 153.49 18.12 Example 3 149.13 17.65 Embodiment 13 156.23 17.92 Example 4 149.26 18.42 Embodiment 14 155.46 18.22 Example 5 152.42 18.23 Embodiment 15 155.21 18.56 Example 6 151.28 17.98 Example 16 155.19 18.71 Example 7 155.49 17.45 Embodiment 17 155.93 18.54 Example 8 155.32 18.21 Embodiment 18 155.42 18.29 Example 9 156.89 18.23 Embodiment 19 156.12 18.46 Example 10 152.43 18.42 Embodiment 20 156.22 18.29 Comparative Example 1 98.75 9.2 Comparative Example 2 102.52 10.26

[0173] It can be seen from Table 1 that the wine lees recycled material provided by the present invention has excellent mechanical strength and ductility. It can be seen from the test that the wine lees recycled material provided by the present invention has a maximum elongation at break of 156.89% and a maximum tensile strength of 18.92 MPa.

[0174] From the data of Comparative Example 2, the elongation at break and tensile strength of the distiller's grains regeneration material can be significantly improved by adding oxidized high-amylose corn starch in the present application, and when the oxidized high-amylose starch is prepared by rice, the improvement of mechanical properties is not obvious, because the effect of high-amylose starch on distiller's grains protein is mainly reflected in its interaction with protein. During the high-moisture extrusion process, amylose and protein are phase-separated in the die mouth area, which promotes the aggregation of protein molecules and forms a denser rigid structure. This interaction causes the amylose gel filled in the protein matrix in the molding area to form a steric hindrance to protein rearrangement and cross-linking, thereby forming a layered gel structure in the final extrudate. High temperature and drought stress can cause the amylose content of rice to decrease and the protein content to increase, which means that the relationship between amylose and protein in rice changes, and a dense rigid structure cannot be formed, resulting in the mechanical properties of the distiller's grains regeneration material not being significantly improved. The spatial structure of oxidized high-amylose starch in corn is mainly composed of two polysaccharides, amylose and amylopectin, forming a specific three-dimensional spatial structure. Starch is a natural high molecular weight polycrystalline polymer, which is formed by a specific three-dimensional structure of amylose and amylopectin molecules, forming the crystalline region and amorphous region of starch particles. It is a chain molecule formed by α-D-glucose connected by α-D-1,4-glycosidic bonds, with a right-handed helical structure. Every 6 glucose units form a pitch of the helix. The helix contains only lipophilic hydrogen atoms, and the hydroxyl groups are located on the outside of the helix. This special structure forms a stable network structure when combined with wine trough protein, thereby improving the elongation at break and tensile strength of wine trough recycled materials.

[0175] It can be seen from Comparative Example 1 and the examples that the mechanical strength is greatly reduced without adding high-amylose starch. This is because the molecular structures of vinasse protein, polysaccharides (such as sodium alginate and xanthan gum) and high-amylose starch are rich in polar groups such as hydroxyl (-OH) and carboxyl (-COOH), which can form close interactions with other molecules through hydrogen bonds. The formation of such hydrogen bonds helps to: enhance the overall strength and structural stability of the material and improve the tensile strength and toughness of the material. In addition, the use of cross-linking agents (such as citric acid, boric acid, and calcium chloride) can react with functional groups (such as carboxyl and hydroxyl) in vinasse protein, sodium alginate and high-amylose starch to form covalent cross-linked bonds. Through cross-linking, a more stable three-dimensional network structure can be constructed, thereby improving the mechanical strength, thermal stability and water resistance of the material. For example, citric acid can react with hydroxyl groups in protein and starch molecules to form ester bonds, thereby improving the mechanical strength of the material. Boric acid reacts with cis-dihydroxy groups (such as sodium alginate) in polysaccharide molecules to form a cross-linked structure, further enhancing the network structure of the material.

[0176] In addition, it can be seen from Comparative Example 1 and the embodiment that the elongation at break is greatly reduced without the addition of high-amylose starch. This is due to the interaction of the molecular chains. The protein chain of distiller's grains protein has a certain rigidity and can provide basic mechanical support for the material. The molecular chain structure of high-amylose starch is more rigid, especially its high-amylose part has strong crystallinity. This rigid molecular chain can form a strong physical crosslink with distiller's grains protein. Polysaccharides, especially sodium alginate and xanthan gum, have long-chain flexible molecular structures. These flexible molecular chains can be filled between the rigid molecular chains of protein and starch, thereby improving the toughness and ductility of the material. The mutual complementation and synergy between the rigid and flexible molecular chains enable the material to have good ductility while maintaining strength.

[0177] In addition, the intermolecular compatibility and interaction can also link the wine grain protein and high-amylose starch as well as polysaccharides and wine grain protein. For example, there are a large number of amino acid residues (such as carboxyl, amino, hydroxyl, etc.) in wine grain protein. These polar groups can interact with the hydroxyl groups in the starch molecules through hydrogen bonds or van der Waals forces to form a tighter combination. Polysaccharides such as sodium alginate and wine grain protein can form a complex cross-linked network through electrostatic interaction or hydrogen bonds, so that the material has better film-forming and stability. Physical and chemical properties can also be enhanced. Oxidation and carboxymethylation modification introduce more polar groups such as carboxyl and hydroxyl groups into starch molecules. These polar groups can form stronger hydrogen bonds and ionic bonds with wine grain protein and polysaccharide molecules, further improving the adhesion and mechanical properties of the material. The molecules of sodium alginate can form a gel structure by chelating with calcium ions. The combination of this structure and wine grain protein can enhance the toughness and water resistance of the material. In addition, these components all have a certain hydrophilicity and can absorb moisture, thereby having good fluidity in material processing, which is convenient for mixing and molding. Under certain temperature and humidity conditions, a stable film structure can be formed through the interaction between molecules, making it suitable for use as a packaging material.

[0178] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in the relevant field should understand that the specific implementation methods of the present invention can still be modified or replaced by equivalents. Any modification or equivalent replacement that does not depart from the spirit and scope of the present invention should be covered within the scope of protection of the claims of the present invention.

Claims

1. Wine lees recycled material, characterized by: The raw materials include the following components in parts by weight: 30-60 parts of wine lees protein, 15-40 parts of polysaccharide, 40-80 parts of starch, 0.5-1 part of cross-linking agent, 10-65 parts of water and 0.5-1.5 parts of hydrophobic agent.

2. The wine lees regeneration material according to claim 1, characterized in that: The distiller's grains protein is at least one of beer distiller's grains protein, white wine distiller's grains protein, red wine distiller's grains protein or yellow wine distiller's grains protein.

3. The wine lees regeneration material according to claim 1, characterized in that: The polysaccharide is at least one of sodium alginate or xanthan gum.

4. The wine lees regeneration material according to claim 1, characterized in that: The starch is at least one of oxidized high-amylose corn starch and carboxymethyl high-amylose corn starch.

5. The wine lees regeneration material according to claim 1, characterized in that: The cross-linking agent is at least one of citric acid, boric acid or calcium chloride.

6. The wine lees regeneration material according to claim 1, characterized in that: The hydrophobic agent is at least one of oleic acid, stearic acid or beeswax.

7. The wine lees regeneration material according to any one of claims 1 to 6, characterized in that: At least one of the following is met: The weight percentage of the distiller's grains protein is 35 to 55 parts; The mass proportion of the polysaccharide is 20 to 35 parts; The mass parts of the starch are 45 to 75 parts; The mass fraction of the cross-linking agent is 0.6 to 0.9 parts; The mass parts of the water are 20 to 55 parts; The mass fraction of the hydrophobic agent is 0.6 to 1.3 parts.

8. The method for preparing the wine lees regeneration material according to any one of claims 1 to 7, characterized in that: The following steps are involved: A. Mixing distiller's grains protein, polysaccharide, starch, a cross-linking agent, water and a hydrophobic agent according to parts by mass to obtain a mixture; B. Extruding and granulating the mixture to obtain the wine lees recycled material.

9. The method for preparing wine lees recycled material according to claim 8, characterized in that: In step B, the temperature of the extrusion granulation is 100-120°C.

10. Use of the wine lees recycled material according to any one of claims 1 to 7 in preparing packaging materials.