Double gel capable of being used for 3D printing and based on food processing byproduct particle stability and preparation and application of double gel

Abstract

The invention belongs to the technical field of food processing, and discloses a Pickering-based food processing by-product particle stable double gel capable of being used for 3D printing as well as preparation and application of the Pickering-based food processing by-product particle stable double gel. The preparation method of the double gel comprises the following steps: dispersing a food processing byproduct in water to obtain a dispersion liquid, and grinding to obtain a nano / submicron grinding particle dispersion liquid; adding the hydrogel into the grinding particle dispersion liquid, and stirring and mixing to obtain grinding particle hydrogel; adding the oil gel into edible vegetable oil, and stirring and mixing to obtain oil gel; and uniformly mixing the ground particle hydrogel and the oil gel, shearing at a high speed, and then cooling and solidifying to obtain the Pickering-based food processing by-product particle-stable double gel for 3D printing. By utilizing the interaction of the grinding particles, the hydrogel and the oleogel, the dual stability of an oil-water interface and a bulk phase is realized, and the 3D printing performance of the dual gel is effectively improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of food processing, and in particular relates to a double gel based on Pickering food processing byproduct particles that can be used for 3D printing, as well as preparation and application thereof. Background Art

[0002] As an emerging food processing technology, 3D food printing integrates multiple technologies, including digitalization and food processing, offering advantages such as personalization, nutrition, safety, and diverse shapes. In recent years, 3D printing has been widely used in the food industry, becoming a key driver of personalized precision nutrition.

[0003] Food processing byproducts, such as corn silk, soybean residue, mushroom stalks, celery leaves, radish leaves, beet stems and leaves, and sugarcane bagasse, are rich in nutrients such as cellulose, starch, protein, and various active substances (including polyphenols and flavonoids). However, resource utilization of these processing byproducts is low, high-value-added applications are rarely developed, and related products remain relatively scarce in the market. Exploring the deep processing and application of food processing byproducts and developing innovative functional foods will help improve economic and social benefits.

[0004] Bigels are semisolid mixtures composed of an oleogel and a hydrogel. Combining the characteristics of both oleogels and hydrogels, bigels offer enhanced thermodynamic stability, mechanical properties, and controllable delivery of nutrient-active substances compared to either oleogel or hydrogel alone. In recent years, bigels have garnered significant attention in the development of 3D-printed foods for personalized nutrition, offering a new approach to meeting consumer demands for health and nutrition.

[0005] Pickering particles irreversibly adsorb at the oil-water interface, forming a physical barrier that enhances the stability of the oil-water two-phase system. Media milling is a highly efficient processing technique that can transform food ingredients into nano / submicron Pickering particles, enhancing their emulsification properties while retaining their inherent health benefits. Applying media-milled Pickering particles to stabilize dual gels may be a novel strategy for achieving both interfacial and bulk stabilization, demonstrating significant potential for improving the printing accuracy, structural uniformity, and nutritional functionality of 3D-printed dual gels. Summary of the Invention

[0006] To overcome the shortcomings of the existing dual-gel system, such as easy oil-water separation and low printing precision, the primary purpose of the present invention is to provide a preparation method for a dual-gel based on Pickering food processing byproduct particle stabilization. By utilizing the interaction between abrasive particles, hydrogelator, and oleogelator, dual stability of the oil-water interface and bulk phase is achieved, effectively improving the 3D printing performance of the dual-gel.

[0007] Another object of the present invention is to provide a stable bigel based on Pickering food processing byproduct particles prepared by the above method.

[0008] Another object of the present invention is to provide the application of the above-mentioned dual gel based on Pickering food processing by-product particle stabilization in 3D printed food, especially in 3D printed functional food, 3D printed low-fat food, etc.

[0009] The purpose of the present invention is achieved through the following solutions:

[0010] A method for preparing a double gel based on Pickering food processing byproduct particles that can be used for 3D printing comprises the following steps:

[0011] (1) Physically modifying food processing byproducts into nano / submicron particles using media milling technology: dispersing food processing byproducts in water to obtain a dispersion, and milling to obtain a nano / submicron abrasive particle dispersion;

[0012] (2) forming an abrasive particle hydrogel through abrasive particle-hydrogelling agent interaction: adding the hydrogelling agent to the abrasive particle dispersion obtained in step (1), stirring and mixing to obtain an abrasive particle hydrogel;

[0013] (3) the oleogel and the edible vegetable oil form a stable oleogel: the oleogel is added to the edible vegetable oil and stirred to obtain the oleogel;

[0014] (4) Based on the Pickering stabilization mechanism, the abrasive particles, hydrogel and oleogel interact to form a stable double gel: the abrasive particle hydrogel and oleogel are evenly mixed, sheared at high speed, and then cooled and solidified to obtain a double gel based on Pickering food processing byproduct particles that can be used for 3D printing.

[0015] The food processing by-product described in step (1) is at least one of corn silk, soybean residue, mushroom stalks, celery leaves, radish leaves, beet stems and leaves, and sugarcane bagasse.

[0016] The step (1) of dispersing the food processing by-products into water refers to crushing the freeze-dried food processing by-products and passing them through a 36-60 mesh sieve before dispersing them into water.

[0017] The dispersing in water to form a dispersion in step (1) means that the crushed food processing by-products are dispersed in water at a ratio of 1 to 5% (w / w), that is, the mass ratio of the food processing by-products to water is 1 to 5%.

[0018] The grinding described in step (1) is performed using a medium grinding machine at a grinding speed of 2500 to 9000 rpm and a grinding bead filling rate of 55% to 70% (v / v). The resulting dispersion is circulated and ground for 15 to 60 minutes, and the temperature is controlled not to exceed 40°C during the grinding process to obtain a nano / submicron abrasive particle dispersion. The grinding beads are preferably 0.3 to 0.7 mm zirconium oxide beads.

[0019] The hydrogel described in step (2) is at least one of carrageenan, xanthan gum, gelatin, konjac gum and guar gum.

[0020] The stirring in step (2) refers to stirring at 100-500 rpm and 40-90° C. for 10-30 min.

[0021] The amount of the hydrogel in step (2) satisfies the mass ratio of the hydrogel to the abrasive particle dispersion being 0.5% to 1%.

[0022] The oil gel described in step (3) is at least one of candelilla wax, beeswax, rice bran wax and sunflower seed wax.

[0023] The edible vegetable oil described in step (3) is at least one of linseed oil, soybean oil, rapeseed oil, corn oil and peanut oil.

[0024] The amount of the oil gel in step (3) satisfies the following conditions: the mass ratio of the oil gel to the edible vegetable oil is 3% to 5%.

[0025] The stirring in step (3) refers to stirring at 100-500 rpm and 60-80° C. for 10-30 min.

[0026] The volume ratio of the abrasive particle hydrogel to the oil gel in step (4) is 3:7 to 7:3.

[0027] The high-speed shearing described in step (4) refers to high-speed shearing at 10,000 to 13,000 rpm for 2 to 5 minutes.

[0028] The cooling and solidification in step (4) refers to cooling to 0-10°C to solidify the gel.

[0029] This method uses media milling to physically modify food processing byproducts to produce nano- / submicron-sized abrasive particles. These particles are then used in conjunction with a hydrogel to create a hydrogel-structured aqueous phase. An oleogel and vegetable oil are then used to create an oleogel-structured oil phase. Based on the Pickering stabilization mechanism, the abrasive particles, hydrogel, and oleogel interact at the interface to form a stable dual-gel system, thereby achieving both improved interfacial and bulk stability.

[0030] A double gel based on Pickering food processing byproduct particles that can be used for 3D printing is prepared by the above method.

[0031] Functional active substances can also be added to the Pickering food processing by-product particle-stabilized dual gel that can be used for 3D printing to prepare functional foods. The functional active substances can be selectively added to the oil gel or hydrogel during the preparation process according to the properties of the functional active substances.

[0032] The above-mentioned double gel based on Pickering food processing byproduct particle stabilization that can be used for 3D printing is used in the preparation of 3D printed food.

[0033] The mechanism of the present invention is:

[0034] The emulsification properties of the ground particles, a by-product of food processing, are enhanced by physical modification using media grinding technology. The ground particles can be adsorbed at the oil-water interface of the dual gel to form a physical barrier based on the Pickering stabilization mechanism. The synergistic network structure formed by the ground particles and the hydrogel gives the dual gel better elasticity and shear recovery properties. The oil gel enhances the supporting capacity of the system by increasing hardness and viscosity. The hydrogel and ground particles are co-adsorbed at the oil-water interface to form a dense interface layer, which hinders the migration of the oil gel to the oil-water interface. The indispensable joint action of the three significantly improves the interfacial and bulk stability of the dual gel.

[0035] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0036] (1) The present invention utilizes media milling technology to modify food processing byproducts, thereby improving the emulsification properties of the ground particles and retaining the active ingredients of the food processing byproducts. The preparation process is simple, environmentally friendly, pollution-free, and free of reagent residues. The raw materials are widely available and low-cost, making full use of the processing byproducts.

[0037] (2) The dual-gel system prepared using abrasive particles achieves dual stability at the interface and in the bulk phase through the unique interaction between the abrasive particles and the hydrogel / oleogel based on the Pickering stabilization mechanism. The resulting dual-gel exhibits high-precision 3D printing performance, characterized by a uniform structure, no oil-water separation, and a smooth surface with sharp lines.

[0038] (3) The double gel system prepared by the present invention is based on the Pickering particle stabilization mechanism of natural origin, avoiding the use of traditional small molecule emulsifiers, thereby effectively circumventing the toxic risks that small molecule emulsifiers may cause to the human body. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1This is the 3D printing effect diagram of Example 1.

[0040] Figure 2 This is the 3D printing effect diagram of Example 2.

[0041] Figure 3 This is the 3D printing effect diagram of Example 3.

[0042] Figure 4 This is the 3D printing effect diagram of comparative example 1.

[0043] Figure 5 This is the 3D printing effect diagram of comparative example 2.

[0044] Figure 6 This is the 3D printing effect diagram of comparative example 3.

[0045] Figure 7 This is the appearance diagram of Comparative Example 4. DETAILED DESCRIPTION

[0046] The present invention will be described in further detail below with reference to the Examples and accompanying drawings, but the embodiments of the present invention are not limited thereto. Where specific conditions are not specified in the Examples, conventional conditions or conditions recommended by the manufacturer were followed. Reagents or instruments used, where the manufacturer is not specified, are commercially available conventional products.

[0047] Example 1

[0048] (1) Mushroom stalk powder was added to water at a concentration of 3% (w / w) to obtain a mushroom stalk dispersion. The obtained mushroom stalk dispersion was circulated and ground for 30 min using a medium grinding machine at a grinding speed of 3500 rpm and a 0.3 mm zirconia bead filling rate of 55% (v / v). The temperature was controlled not to exceed 40°C during the grinding process to obtain a mushroom stalk particle dispersion.

[0049] (2) Guar gum was added to the mushroom pedicle particle dispersion at a concentration of 1% (w / w), and stirred at 300 rpm and 60° C. for 30 min to obtain a mushroom pedicle particle hydrogel.

[0050] (3) Rice bran wax was added to peanut oil at a concentration of 4% (w / w), and the mixture was stirred at 500 rpm and 80° C. for 30 min to obtain an oil gel.

[0051] (4) The mushroom pedicle particle hydrogel and oil gel obtained in step (2) and step (3) were subjected to high-speed shearing at 12,000 rpm for 3 minutes at an oil-water ratio of 7:3 (v / v), and after cooling and solidification, a stable double gel based on Pickering mushroom pedicle particles that can be used for 3D printing was obtained.

[0052] (5) The double gel obtained in step (4) was loaded into the barrel of a food 3D printer and printed at a printing speed of 90 mm / s, an extrusion speed of 110 mm / s, and room temperature.

[0053] Figure 1 This is the 3D printing effect of the dual-gel based on Pickering mushroom pedicle particles obtained in Example 1. The dual-gel molding effect is excellent, with a clear printed structure, a smooth and uniform surface, no delamination, and no oil-water separation.

[0054] Example 2

[0055] (1) Corn silk powder was added to water at a concentration of 5% (w / w) to obtain a corn silk dispersion. The corn silk dispersion was circulated and ground for 60 min using a medium grinding machine at a grinding speed of 3500 rpm and a 0.3 mm zirconium oxide bead filling rate of 70% (v / v). The temperature was controlled not to exceed 40° C. during the grinding process to obtain a corn silk particle dispersion.

[0056] (2) Xanthan gum was added to the corn silk particle dispersion at a concentration of 0.5% (w / w), and the mixture was stirred at 300 rpm and 40° C. for 30 min to obtain a corn silk particle hydrogel.

[0057] (3) Candelilla wax was added to soybean oil at a concentration of 5% (w / w), and the mixture was stirred at 500 rpm and 80° C. for 30 min to obtain an oil gel.

[0058] (4) The corn silk particle hydrogel and oil gel obtained in step (2) and step (3) were subjected to high-speed shearing at 10,000 rpm for 5 minutes at an oil-water ratio of 5:5 (v / v), and after cooling and solidification, a stable double gel based on Pickering corn silk particles that can be used for 3D printing was obtained.

[0059] (5) The double gel obtained in step (4) was loaded into the barrel of a food 3D printer and printed at a printing speed of 100 mm / s, an extrusion speed of 100 mm / s, and room temperature.

[0060] Figure 2 This is the 3D printing effect of the Pickering corn silk particle stabilization dual gel obtained in Example 2. It shows good molding ability, clear printed structure, distinct lines, no delamination, and no oil-water separation.

[0061] Example 3

[0062] (1) Bagasse powder was added to water at a concentration of 3% (w / w) to obtain a bagasse dispersion. The obtained bagasse dispersion was circulated and ground for 30 min using a medium grinding machine at a grinding speed of 3500 rpm and a 0.3 mm zirconia bead filling rate of 60% (v / v). The temperature was controlled not to exceed 40° C. during the grinding process to obtain a bagasse corn silk particle dispersion.

[0063] (2) Carrageenan was added to the sugarcane bagasse particle dispersion at a concentration of 1% (w / w), and the mixture was stirred at 300 rpm and 60° C. for 30 min to obtain a sugarcane bagasse particle hydrogel.

[0064] (3) Beeswax was added to linseed oil at a concentration of 3% (w / w), and stirred at 500 rpm and 80°C for 30 min to obtain an oil gel.

[0065] (4) The bagasse particle hydrogel and oil gel obtained in step (2) and step (3) were subjected to high-speed shearing at 13,000 rpm for 2 minutes at an oil-water ratio of 3:7 (v / v), and after cooling and solidification, a stable double gel based on Pickering bagasse particles that can be used for 3D printing was obtained.

[0066] (5) The double gel obtained in step (4) was loaded into the barrel of a food 3D printer and printed at a printing speed of 80 mm / s, an extrusion speed of 120 mm / s, and room temperature.

[0067] Figure 3 This is the result of the dual-gel 3D printing based on Pickering bagasse particles obtained in Example 3. It shows good molding ability, clear printed structure, distinct lines, no delamination, and no oil-water separation.

[0068] Comparative Example 1

[0069] Refer to the steps and conditions of Example 1, except that the ratio of oleogel to hydrogel in step (3) is 0:1.

[0070] Figure 4 This is the 3D printing result of Comparative Example 1. While the sample obtained under these conditions is capable of 3D printing, the printing quality is poor. Due to the lack of oil gel, the sample's hardness and viscosity are insufficient, resulting in poor printing quality, a rough surface, poor interlayer adhesion, and some structure collapse and distortion.

[0071] Comparative Example 2

[0072] Refer to the steps and conditions of Example 2, except that the corn silk particle dispersion in step (2) is replaced by an equal mass of pure water.

[0073] Figure 5This is the 3D printing result of Comparative Example 2. Under these conditions, the sample lacked corn silk particles, which easily caused oil-water separation during the printing process, resulting in a partially dotted structure on the printed image surface. The printed shape also collapsed and could not support its own weight.

[0074] Comparative Example 3

[0075] Refer to the steps and conditions of Example 3, except that the carrageenan concentration in step (2) is 0%.

[0076] Figure 6 This is the 3D printing effect diagram of Comparative Example 3. The sample obtained under this condition completely loses its 3D printing molding ability due to the lack of hydrogel and collapses immediately after printing.

[0077] Comparative Example 4

[0078] Refer to the steps and conditions of Example 2, except that the concentration of xanthan gum in step (2) is 0%, and the concentration of candelilla wax in step (3) is 0%.

[0079] Figure 7 This is the appearance picture of Comparative Example 4. The sample obtained under this condition lacks oil gel and hydrogel, and flows after being inverted. It cannot support its own weight and cannot be used for 3D printing.

[0080] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A method for preparing a double gel based on Pickering food processing byproduct particles for 3D printing, characterized in that The following steps are involved: (1) dispersing food processing byproducts in water to obtain a dispersion, and grinding to obtain a nano / submicron abrasive particle dispersion; (2) adding a hydrogel to the abrasive particle dispersion obtained in step (1), stirring and mixing to obtain an abrasive particle hydrogel; (3) adding the oleogel to the edible vegetable oil and stirring to obtain the oleogel; (4) The ground particle hydrogel and oil gel were mixed evenly, sheared at high speed, and then cooled and solidified to obtain a stable double gel based on Pickering food processing byproduct particles that can be used for 3D printing.

2. The method for preparing a double gel based on Pickering food processing byproduct particles that can be used for 3D printing according to claim 1, characterized in that: The food processing by-product described in step (1) is at least one of corn silk, soybean residue, mushroom stalks, celery leaves, radish leaves, beet stems and leaves, and sugarcane bagasse.

3. The method for preparing a double gel stabilized by Pickering food processing byproduct particles for 3D printing according to claim 1, characterized in that: The dispersion in water to form a dispersion in step (1) means that the crushed food processing by-products are dispersed in water at a ratio of 1 to 5%, that is, the mass ratio of the food processing by-products to water is 1 to 5%; The grinding described in step (1) refers to circulating the obtained dispersion for 15min to 60min at a grinding speed of 2500 to 9000rpm and a grinding bead filling rate of 55% to 70%, and controlling the temperature not to exceed 40°C during the grinding process to obtain a nano / submicron grinding particle dispersion, wherein the grinding beads are 0.3 to 0.7mm zirconia beads.

4. The method for preparing a double gel based on Pickering food processing byproduct particles for 3D printing according to claim 1, characterized in that: The hydrogel described in step (2) is at least one of carrageenan, xanthan gum, gelatin, konjac gum, and guar gum; The stirring in step (2) refers to stirring at 100-500 rpm and 40-90° C. for 10-30 min; The amount of the hydrogel in step (2) satisfies the mass ratio of the hydrogel to the abrasive particle dispersion being 0.5% to 1%.

5. The method for preparing a double gel based on Pickering food processing byproduct particles that can be used for 3D printing according to claim 1, characterized in that: The oleogel described in step (3) is at least one of candelilla wax, beeswax, rice bran wax, and sunflower seed wax; The edible vegetable oil in step (3) is at least one of linseed oil, soybean oil, rapeseed oil, corn oil, and peanut oil; The amount of the oleogel in step (3) satisfies the following conditions: the mass ratio of the oleogel to the edible vegetable oil is 3% to 5%; The stirring in step (3) refers to stirring at 100-500 rpm and 60-80° C. for 10-30 min.

6. The method for preparing a double gel based on Pickering food processing byproduct particles for 3D printing according to claim 1, characterized in that: The volume ratio of the abrasive particle hydrogel to the oil gel in step (4) is 3:7 to 7:3; The high-speed shearing described in step (4) refers to high-speed shearing at 10,000 to 13,000 rpm for 2 to 5 minutes.

7. The method for preparing a double gel stabilized by Pickering food processing byproduct particles for 3D printing according to claim 1, characterized in that: The ground particle hydrogel of step (2) may also be embedded with water-soluble functional active substances; The oil gel of step (3) can also be embedded with oil-soluble functional active substances.

8. A stabilized bigel based on Pickering food processing byproduct particles for 3D printing, prepared according to the method of any one of claims 1 to 7.

9. Use of the Pickering food processing byproduct particle-stabilized dual gel for 3D printing according to claim 8 in the preparation of 3D printed food.

10. Use of the Pickering food processing by-product particle-stabilized dual gel for 3D printing according to claim 8 in 3D printing functional foods and 3D printing low-fat foods.

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