Preparation method of micro-nano fishbone dust particle-based Pickering emulsion and product

Abstract

The invention discloses a preparation method of micro-nano fishbone dust particle-based Pickering emulsion and a product, and belongs to the technical field of food processing, fishbone is sequentially subjected to enzymolysis, degreasing, high-pressure cooking and drying, and fishbone coarse particles are obtained; carrying out micro-nano processing on the fishbone coarse particles to obtain micro-nano fishbone particles; mixing the micro-nano fishbone particles with water, and performing mechanical homogenization and ultrasonic treatment in an ice bath to obtain a micro-nano fishbone particle dispersion liquid; and mixing the micro-nano fish bone particle dispersion liquid with liquid oil, and carrying out homogeneous emulsification in an ice bath to obtain the micro-nano fish bone powder particle-based Pickering emulsion. The invention provides the Pickering emulsion prepared by taking the food-grade micro-nano fishbone particles as the solid stabilizer, the Pickering emulsion has wide application potential and prospect, sustainable full utilization of aquatic product processing by-product fishbone is realized, resources are saved, and environmental pollution is reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of food processing, and in particular relates to a preparation method of a micro-nano fish bone powder particle-based Pickering emulsion and a product thereof. Background Art

[0002] Aquatic products are an important source of high-quality protein, providing nearly one-third of the total animal protein intake. The processing of aquatic raw materials into aquatic products produces a significant amount of by-products, which can account for 40% to 60% of the total aquatic product volume. In fish processing, these by-products, including fish heads, bones, and skin, account for approximately 40% to 55% of the raw fish mass, with bones comprising a whopping 10% to 15% of the total mass. Fish bones are rich in collagen and other proteins, as well as trace elements such as calcium, phosphorus, iron, and selenium. Optimizing the utilization of fish bones has always been a challenge in the sustainable development of aquatic product processing. Currently, fish bones are being processed into ready-to-eat crispy fish bones and fish bone biscuits, while enzymatic hydrolysis and other methods are being used to extract active substances such as collagen peptides and chondroitin sulfate. Both have achieved some success. However, achieving high-value, full utilization of fish bones through simple processing remains a challenge.

[0003] In recent years, Pickering emulsions stabilized by solid particles have been widely used in many fields such as food, medicine and cosmetics due to their simple preparation methods and unique stability. At present, silica, plant proteins (such as zein, soy protein, etc.), animal proteins (such as whey protein, fish myofibrillar protein), etc. have been used to construct Pickering emulsions. Further exploration and creation of food-grade particles and their stable Pickering emulsions are of great significance for expanding their application and meeting the multiple needs of consumers. As mentioned above, fish bones contain a large amount of nutrients, but the current means of utilizing fish bones are still relatively limited. If fish bone particles can be used to prepare Pickering emulsions, it will not only be conducive to the high-value green utilization of fish bones, but also help to expand the types and application range of Pickering emulsions. Summary of the Invention

[0004] In response to the above problems, the present invention provides a method and product for preparing a Pickering emulsion based on micro-nano fish bone powder particles. The micro-nano fish bone powder particle-based Pickering emulsion is a green, edible fish bone particle-based high-stability Pickering emulsion with extremely broad application prospects. It broadens the application field of waste fish bones and provides a strong guarantee for promoting the sustainable development of the fishery and aquatic product industries. The process involved in the present invention is extremely simple, short in time, low in cost, and has strong industrial productivity. Moreover, when preparing the Pickering emulsion based on fish bone particles, no chemical surfactants are added, which is green and healthy. In short, by virtue of its simple operation, efficient production, economical cost and green concept, the present invention is very suitable for large-scale industrial production and has excellent industrialization prospects.

[0005] One of the technical solutions provided by the present invention:

[0006] A method for preparing a micro-nano fish bone powder particle-based Pickering emulsion comprises the following steps: subjecting fish bones to enzymatic hydrolysis, fat removal, high-pressure steaming, and drying in sequence to obtain coarse fish bone particles; subjecting the coarse fish bone particles to micro-nano processing to obtain micro-nano fish bone particles; mixing the micro-nano fish bone particles with water, and subjecting the mixture to mechanical homogenization and ultrasonic treatment in an ice bath to obtain a micro-nano fish bone particle dispersion; and mixing the micro-nano fish bone particle dispersion with liquid oil, and subjecting the mixture to homogenized and emulsified treatment in an ice bath to obtain the micro-nano fish bone powder particle-based Pickering emulsion.

[0007] Furthermore, the high-pressure cooking temperature is 121° C., the pressure is 0.1 MPa, the processing time is 20 min, the solid-liquid ratio is 1:1.5 (w / w), and the drying is processed at 85° C. for 4 h.

[0008] Furthermore, the micro-nano processing is to place the coarse fish bone particles in a planetary ball mill for crushing, and the crushing speed is 1000r / min and the time is 2.5-30min.

[0009] Furthermore, the mass ratio of the micro-nano fishbone particles to water is 3:100.

[0010] Furthermore, the rotation speed of the mechanical homogenization is 10000 r / min, and the time is 1 minute; the power of the ultrasound is 400 W, the ultrasound mode is on for 5 seconds and off for 6 seconds, and the total ultrasound time is 4 minutes.

[0011] Furthermore, the volume ratio of the micro-nano fishbone particle dispersion to the liquid oil is 5:10.

[0012] Furthermore, the liquid oil includes one or more of soybean oil, rapeseed oil, fish oil, peanut oil, olive oil, corn oil, walnut oil, linseed oil and sunflower oil.

[0013] Furthermore, the homogenization and emulsification speed is 15000 r / min, the homogenization time is 1 minute each time, and the homogenization and emulsification are performed 3 times in total.

[0014] Furthermore, the fish bones include one or more of cod bones, salmon bones, silver carp bones, black carp bones, grass carp bones, bighead carp, crucian carp, and tilapia bones.

[0015] The second technical solution provided by the present invention is:

[0016] The above preparation method can prepare a Pickering emulsion based on micro-nano fish bone powder particles.

[0017] Compared with the prior art, the present invention has the following advantages and technical effects:

[0018] (1) The present invention provides a method for preparing a Pickering emulsion based on micro-nano fish bone particles. First, the fish bones are micronized from top to bottom through thawing, enzymatic hydrolysis, fat removal, high-pressure steaming, hot air drying and ball milling processing steps. Then, during the homogenization emulsification process, the micro-nano fish bone particles achieve long-term stability of the emulsion through effective adsorption at the water-oil interface. The particle size of the Pickering emulsion remains in the range of 25-50 μm during storage at 4°C, and the stability index of the emulsion after 28 days is greater than 85%.

[0019] (2) The present invention provides a Pickering emulsion created by using food-grade micro-nano fish bone particles as a solid stabilizer, which has broad application potential and prospects. It not only realizes the sustainable full utilization of fish bones, a by-product of aquatic product processing, but also saves resources and reduces environmental pollution.

[0020] (3) The process involved in the present invention is simple and controllable, and the equipment used is common, low-cost, and suitable for industrial-scale production; and no chemical surfactants, adjuvants, additives, etc. are added during the preparation of the micro-nano fishbone particle-based Pickering emulsion, meeting consumers' demand for clean labels. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0022] Figure 1 These are the appearances of the fishbone particle-based Pickering emulsions prepared in Examples 1-9 and Comparative Example 1 after 0 days, 14 days, and 28 days;

[0023] Figure 2 The particle size distribution of the fishbone particle-based Pickering emulsions prepared in Examples 1-9 and Comparative Example 1 at 0 days, 14 days, and 28 days;

[0024] Figure 3 The microstructures of the fishbone particle-based Pickering emulsions prepared in Examples 1-9 and Comparative Example 1 at 0 days, 14 days, and 28 days. DETAILED DESCRIPTION

[0025] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0026] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any intermediate value within a stated value or stated range and any other stated value or intermediate value within the stated range is also encompassed by the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0027] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0028] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be exemplary only.

[0029] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0030] The present invention discloses a method for preparing a micro-nano fish bone particle-based Pickering emulsion, which specifically includes: using fish bone steaks, a by-product of aquatic product processing, as raw materials, firstly preparing micro-nano fish bone particles by means of high-efficiency enzymatic hydrolysis, edible alkali degreasing, high temperature and high pressure softening and ball milling; further obtaining a uniform aqueous dispersion of micro-nano fish bone particles by means of high-speed homogenization and high-intensity ultrasonic dispersion; finally, adding the aqueous dispersion of micro-nano fish bone particles to an oil phase, and preparing a highly stable micro-nano fish bone particle-based Pickering emulsion by high-speed shear emulsification. The present invention creatively uses fish bone particles as a solid stabilizer to prepare an edible Pickering emulsion by micro-nano processing of fish bones, a by-product of aquatic products, and does not add any non-edible substances such as chemical surfactants, adjuvants and additives during the emulsion preparation stage. The prepared emulsion has high stability and is simple to operate, realizing a new high-value green utilization of fish bones, a by-product of aquatic products, while also greatly expanding the types and application range of Pickering emulsions.

[0031] The neutral protease used in the present invention is an endoprotease purchased from Beijing Solebow Technology Co., Ltd.

[0032] The temperature range of the ice bath in the embodiment of the present invention is 0-10°C.

[0033] The fish bones in the embodiment of the present invention are cod fish bones.

[0034] Example 1 Preparation method of a micro-nano fish bone powder particle-based Pickering emulsion

[0035] (1) Preparation of micro-nano fish bone particles: 1000 g of frozen fish bone chops were thawed and added to 2.5 L of an aqueous solution containing a neutral protease, the mass of which was 3% of the mass of the frozen fish bone. The fish bone chops were enzymatically hydrolyzed at 50°C for 3 h to separate the excess minced meat. Next, the enzymatically hydrolyzed fish bone was soaked in an edible alkali solution (0.25 wt%) for 5 h to remove fat. After the degreasing process, the fish bone was soaked and rinsed with drinking water to remove excess edible alkali. An appropriate amount of water (solid-liquid ratio of 1:1.5, w / w) was added to the obtained fish bone. The fish bone was further treated at 121°C and 0.1 MPa for 20 min to soften the fish bone. The fish bone was then hot-air dried in an oven at 85°C for 4 h. Finally, the dried fish bone was placed in a planetary ball mill and crushed at a speed of 1000 r / min for 2.5 min to obtain micro-nano fish bone particles.

[0036] (2) Preparation of micro-nano fishbone particle dispersion: The micro-nano fishbone particles were mixed with water in an ice bath to prepare a 3 wt% aqueous solution of micro-nano fishbone particles. The mixture was homogenized at 10,000 rpm for 1 min. Ultrasonic dispersion was then performed at a power of 400 W in an ultrasonic mode of on for 5 s and off for 6 s for a total of 4 min to obtain a micro-nano fishbone particle dispersion.

[0037] (3) Preparation of a micro-nano fishbone particle-based Pickering emulsion: The micro-nano fishbone particle dispersion prepared in step (2) was mixed with soybean oil at a volume ratio of 1:2, and homogenized and emulsified at 15,000 rpm for 3 minutes under an ice bath to obtain a micro-nano fishbone particle-based Pickering emulsion, which was recorded as Pickering emulsion 1.

[0038] Example 2 Preparation Method of a Micro-Nano Fish Bone Powder Particle-Based Pickering Emulsion

[0039] (1) Preparation of micro-nano fish bone particles: 1000 g of frozen fish bone chops were thawed and added to 2.5 L of an aqueous solution containing a neutral protease, the mass of which was 3% of the mass of the frozen fish bone. The fish bone chops were enzymatically hydrolyzed at 50°C for 3 h to separate the excess minced meat. The enzymatically hydrolyzed fish bone chops were then soaked in an edible alkali solution (0.25 wt%) for 5 h to remove fat. After the degreasing process, the fish bone chops were soaked and rinsed in drinking water to remove excess edible alkali. An appropriate amount of water (solid-liquid ratio of 1:1.5, w / w) was added to the obtained fish bone chops. The fish bone chops were further treated at 121°C and 0.1 MPa for 20 min to soften the fish bone chops. The fish bone chops were then hot-air dried in an oven at 85°C for 4 h. The dried fish bone chops were then placed in a planetary ball mill and crushed at 1000 r / min for 5 min to obtain micro-nano fish bone particles.

[0040] (2) Preparation of micro-nano fishbone particle dispersion: The micro-nano fishbone particles were mixed with water in an ice bath to prepare a 3 wt% aqueous solution of micro-nano fishbone particles. The mixture was homogenized at 10,000 rpm for 1 min. Ultrasonic dispersion was then performed at a power of 400 W in an ultrasonic mode of on for 5 s and off for 6 s for a total of 4 min to obtain a micro-nano fishbone particle dispersion.

[0041] (3) Preparation of a micro-nano fishbone particle-based Pickering emulsion: The micro-nano fishbone particle dispersion prepared in step (2) was mixed with soybean oil at a volume ratio of 1:2, and homogenized and emulsified at 15,000 rpm for 3 minutes in an ice bath to prepare a micro-nano fishbone particle-based Pickering emulsion, which was recorded as Pickering emulsion 2.

[0042] Example 3 Preparation method of a micro-nano fish bone powder particle-based Pickering emulsion

[0043] (1) Preparation of micro-nano fish bone particles: 1000 g of frozen fish bone chops were thawed and added to 2.5 L of an aqueous solution containing a neutral protease, the mass of which was 3% of the mass of the frozen fish bone. The fish bone chops were enzymatically hydrolyzed at 50°C for 3 h to separate the excess minced meat. The enzymatically hydrolyzed fish bone was then soaked in an edible alkali solution (0.25 wt%) for 5 h to remove fat. After the degreasing process, the fish bone was soaked and rinsed with drinking water to remove excess edible alkali. An appropriate amount of water (solid-liquid ratio of 1:1.5, w / w) was added to the obtained fish bone. The fish bone was further treated at 121°C and 0.1 MPa for 20 min to soften the fish bone. The fish bone was then hot-air dried in an oven at 85°C for 4 h. The dried fish bone was then placed in a planetary ball mill and pulverized at a speed of 1000 r / min for 7.5 min to obtain micro-nano fish bone particles.

[0044] (2) Preparation of micro-nano fishbone particle dispersion: The micro-nano fishbone particles were mixed with water in an ice bath to prepare a 3 wt% aqueous solution of micro-nano fishbone particles. The mixture was homogenized at 10,000 rpm for 1 min. Ultrasonic dispersion was then performed at a power of 400 W in an ultrasonic mode of on for 5 s and off for 6 s for a total of 4 min to obtain a micro-nano fishbone particle dispersion.

[0045] (3) Preparation of a micro-nano fishbone particle-based Pickering emulsion: The micro-nano fishbone particle dispersion prepared in step (2) was mixed with soybean oil at a volume ratio of 1:2, and homogenized and emulsified at a high speed of 15,000 r / min for 3 minutes under an ice bath to prepare a micro-nano fishbone particle-based Pickering emulsion, which was recorded as Pickering emulsion 3.

[0046] Example 4 Preparation Method of a Micro-Nano Fish Bone Powder Particle-Based Pickering Emulsion

[0047] (1) Preparation of micro-nano fish bone particles: 1000 g of frozen fish bone chops were thawed and added to 2.5 L of an aqueous solution containing a neutral protease, the mass of which was 3% of the mass of the frozen fish bone. The fish bone chops were enzymatically hydrolyzed at 50°C for 3 h to separate the excess minced meat. Next, the enzymatically hydrolyzed fish bone was soaked in an edible alkali solution (0.25 wt%) for 5 h to remove fat. After the degreasing, the fish bone was soaked and rinsed with drinking water to remove excess edible alkali. An appropriate amount of water (solid-liquid ratio of 1:1.5, w / w) was added to the obtained fish bone. The fish bone was further treated at 121°C and 0.1 MPa for 20 min to soften the fish bone. The fish bone was then hot-air dried in an oven at 85°C for 4 h. Finally, the dried fish bone was placed in a planetary ball mill and crushed at a speed of 1000 r / min for 10 min to obtain micro-nano fish bone particles.

[0048] (2) Preparation of micro-nano fishbone particle dispersion: The micro-nano fishbone particles were mixed with water in an ice bath to prepare a 3 wt% aqueous solution of micro-nano fishbone particles. The mixture was homogenized at 10,000 rpm for 1 min. Ultrasonic dispersion was then performed at a power of 400 W in an ultrasonic mode of on for 5 s and off for 6 s for a total of 4 min to obtain a micro-nano fishbone particle dispersion.

[0049] (3) Preparation of a Pickering emulsion based on micro-nano fishbone particles: The micro-nano fishbone particle dispersion prepared in step (2) was mixed with soybean oil at a volume ratio of 1:2, and homogenized and emulsified at 15,000 rpm for 3 minutes in an ice bath to prepare a micro-nano fishbone particle-based Pickering emulsion, which was recorded as Pickering emulsion 4.

[0050] Example 5

[0051] Preparation of micro-nano fish bone particles: 1000g of frozen fish bone chops were thawed and added to 2.5L of an aqueous solution containing a neutral protease (3% by weight of the frozen fish bone). The fish bone chops were enzymatically hydrolyzed at 50°C for 3 hours to separate the excess minced meat. The enzymatically hydrolyzed fish bone chops were then soaked in a 0.25wt% edible alkali solution for 5 hours to remove fat. After the degreasing process, the fish bone chops were soaked and rinsed with drinking water to remove excess edible alkali. An appropriate amount of water (solid-to-liquid ratio of 1:1.5, w / w) was added to the resulting fish bone chops. The chops were further treated at 121°C and 0.1MPa for 20 minutes to soften the fish bone chops. The chops were then hot-air dried in an 85°C oven for 4 hours. The dried fish bone chops were then placed in a planetary ball mill and pulverized at 1000 rpm for 12.5 minutes to obtain micro-nano fish bone particles.

[0052] (2) Preparation of micro-nano fishbone particle dispersion: The micro-nano fishbone particles were mixed with water in an ice bath to prepare a 3 wt% aqueous solution of micro-nano fishbone particles. The mixture was homogenized at 10,000 rpm for 1 min. Ultrasonic dispersion was then performed at a power of 400 W in an ultrasonic mode of on for 5 s and off for 6 s for a total of 4 min to obtain a micro-nano fishbone particle dispersion.

[0053] (3) Preparation of a micro-nano fishbone particle-based Pickering emulsion: The micro-nano fishbone particle dispersion prepared in step (2) was mixed with soybean oil at a volume ratio of 1:2, and homogenized and emulsified at 15,000 rpm for 1 min in an ice bath. The homogenization and emulsification were repeated three times to prepare a micro-nano fishbone particle-based Pickering emulsion, which was recorded as Pickering emulsion 5.

[0054] Example 6

[0055] (1) Preparation of micro-nano fish bone particles: 1000 g of frozen fish bone chops were thawed and added to 2.5 L of an aqueous solution containing a neutral protease, the mass of which was 3% of the mass of the frozen fish bone. The fish bone chops were enzymatically hydrolyzed at 50°C for 3 h to separate the excess minced meat. The enzymatically hydrolyzed fish bone was then soaked in an edible alkali solution (0.25 wt%) for 5 h to remove fat. After the degreasing process, the fish bone was soaked and rinsed in drinking water to remove excess edible alkali. An appropriate amount of water (solid-liquid ratio of 1:1.5, w / w) was added to the obtained fish bone. The fish bone was further treated at 121°C and 0.1 MPa for 20 min to soften the fish bone. The fish bone was then hot-air dried in an oven at 85°C for 4 h. The dried fish bone was then placed in a planetary ball mill and pulverized at a speed of 1000 r / min for 15 min to obtain micro-nano fish bone particles.

[0056] (2) Preparation of micro-nano fishbone particle dispersion: The micro-nano fishbone particles were mixed with water in an ice bath to prepare a 3 wt% aqueous solution of micro-nano fishbone particles. The mixture was homogenized at 10,000 rpm for 1 min. Ultrasonic dispersion was then performed at a power of 400 W in an ultrasonic mode of on for 5 s and off for 6 s for a total of 4 min to obtain a micro-nano fishbone particle dispersion.

[0057] (3) Preparation of a micro-nano fishbone particle-based Pickering emulsion: The micro-nano fishbone particle dispersion prepared in step (2) was mixed with soybean oil at a volume ratio of 1:2, and homogenized and emulsified at 15,000 rpm for 3 minutes in an ice bath to prepare a micro-nano fishbone particle-based Pickering emulsion, which was recorded as Pickering emulsion 6.

[0058] Example 7

[0059] (1) Preparation of micro-nano fish bone particles: 1000 g of frozen fish bone chops were thawed and added to 2.5 L of an aqueous solution containing a neutral protease, the mass of which was 3% of the mass of the frozen fish bone. The fish bone chops were enzymatically hydrolyzed at 50°C for 3 h to separate the excess minced meat. The enzymatically hydrolyzed fish bone was then soaked in an edible alkali solution (0.25 wt%) for 5 h to remove fat. After the degreasing process, the fish bone was soaked and rinsed with drinking water to remove excess edible alkali. An appropriate amount of water (solid-liquid ratio of 1:1.5, w / w) was added to the obtained fish bone. The fish bone was further treated at 121°C and 0.1 MPa for 20 min to soften the fish bone. The fish bone was then hot-air dried in an oven at 85°C for 4 h. The dried fish bone was then placed in a planetary ball mill and pulverized at a speed of 1000 r / min for 20 min to obtain micro-nano fish bone particles.

[0060] (2) Preparation of micro-nano fishbone particle dispersion: The micro-nano fishbone particles were mixed with water in an ice bath to prepare a 3 wt% aqueous solution of micro-nano fishbone particles. The mixture was homogenized at 10,000 rpm for 1 min. Ultrasonic dispersion was then performed at a power of 400 W in an ultrasonic mode of on for 5 s and off for 6 s for a total of 4 min to obtain a micro-nano fishbone particle dispersion.

[0061] (3) Preparation of a micro-nano fishbone particle-based Pickering emulsion: The micro-nano fishbone particle dispersion prepared in step (2) was mixed with soybean oil at a volume ratio of 1:2, and homogenized and emulsified at 15,000 rpm for 1 min in an ice bath. The homogenization and emulsification were repeated three times to prepare a micro-nano fishbone particle-based Pickering emulsion, which was recorded as Pickering emulsion 7.

[0062] Example 8

[0063] (1) Preparation of micro-nano fish bone particles: 1000 g of frozen fish bone chops were thawed and added to 2.5 L of an aqueous solution containing a neutral protease, the mass of which was 3% of the mass of the frozen fish bone. The fish bone chops were enzymatically hydrolyzed at 50°C for 3 h to separate the excess minced meat. The enzymatically hydrolyzed fish bone was then soaked in an edible alkali solution (0.25 wt%) for 5 h to remove fat. After the degreasing process, the fish bone was soaked and rinsed with drinking water to remove excess edible alkali. An appropriate amount of water (solid-liquid ratio of 1:1.5, w / w) was added to the obtained fish bone. The fish bone was further treated at 121°C and 0.1 MPa for 20 min to soften the fish bone. The fish bone was then hot-air dried in an oven at 85°C for 4 h. The dried fish bone was then placed in a planetary ball mill and pulverized at a speed of 1000 r / min for 25 min to obtain micro-nano fish bone particles.

[0064] (2) Preparation of micro-nano fishbone particle dispersion: The micro-nano fishbone particles were mixed with water in an ice bath to prepare a 3 wt% aqueous solution of micro-nano fishbone particles. The mixture was homogenized at 10,000 rpm for 1 min. Ultrasonic dispersion was then performed at a power of 400 W in an ultrasonic mode of on for 5 s and off for 6 s for a total of 4 min to obtain a micro-nano fishbone particle dispersion.

[0065] (3) Preparation of a Pickering emulsion based on micro-nano fishbone particles: The micro-nano fishbone particle dispersion prepared in step (2) was mixed with soybean oil at a volume ratio of 1:2, and homogenized and emulsified at 15,000 rpm for 3 min in an ice bath to prepare a micro-nano fishbone particle-based Pickering emulsion, which was recorded as Pickering emulsion 8.

[0066] Example 9

[0067] (1) Preparation of micro-nano fish bone particles: 1000 g of frozen fish bone chops were thawed and added to 2.5 L of an aqueous solution containing a neutral protease, the mass of which was 3% of the mass of the frozen fish bone. The fish bone chops were enzymatically hydrolyzed at 50°C for 3 h to separate the excess minced meat. The enzymatically hydrolyzed fish bone chops were then soaked in an edible alkali solution (0.25 wt%) for 5 h to remove fat. After the degreasing process, the fish bone chops were soaked and rinsed with drinking water to remove excess edible alkali. An appropriate amount of water (solid-liquid ratio of 1:1.5, w / w) was added to the obtained fish bone chops. The fish bone chops were further treated at 121°C and 0.1 MPa for 20 min to soften the fish bone chops. The fish bone chops were then hot-air dried in an oven at 85°C for 4 h. The dried fish bone chops were then placed in a planetary ball mill and crushed at 1000 r / min for 30 min to obtain micro-nano fish bone particles.

[0068] (2) Preparation of micro-nano fishbone particle dispersion: The micro-nano fishbone particles were mixed with water in an ice bath to prepare a 3 wt% aqueous solution of micro-nano fishbone particles. The mixture was homogenized at 10,000 rpm for 1 min. Ultrasonic dispersion was then performed at a power of 400 W in an ultrasonic mode of on for 5 s and off for 6 s for a total of 4 min to obtain a micro-nano fishbone particle dispersion.

[0069] (3) Preparation of a Pickering emulsion based on micro-nano fishbone particles: The micro-nano fishbone particle dispersion prepared in step (2) was mixed with soybean oil at a volume ratio of 1:2, and homogenized and emulsified at 15,000 rpm for 3 min in an ice bath to prepare a micro-nano fishbone particle-based Pickering emulsion, which was recorded as Pickering emulsion 9.

[0070] Comparative Example 1

[0071] (1) Preparation of coarse fish bone particles: After thawing 1000g of frozen fish bone chops, add them to 2.5L of an aqueous solution containing a neutral protease, the mass of which is 3% of the mass of the frozen fish bones, and perform enzymatic hydrolysis at 50°C for 3h to separate the excess minced meat; then soak the enzymatically hydrolyzed fish bones in a food alkali solution (0.25wt%) for 5h to remove fat, and after degreasing, soak and rinse the fish bones in drinking water to remove excess edible alkali. Add an appropriate amount of water to the obtained fish bones (solid-liquid ratio 1:1.5, w / w), continue to treat at 121°C and 0.1MPa for 20min to soften the fish bones, and then dry them in an 85°C oven with hot air for 4h. Finally, place the dried fish bones in a mortar and grind them for 30min to obtain coarse fish bone particles;

[0072] (2) Preparation of a coarse fishbone particle dispersion: The coarse fishbone particles were mixed with water in an ice bath to prepare a 3 wt% aqueous solution of coarse fishbone particles. The mixture was homogenized at 10,000 rpm for 1 min. Ultrasonic dispersion was then performed at a power of 400 W in an ultrasonic mode of 5 s on and 6 s off for a total of 4 min to obtain a coarse fishbone particle dispersion.

[0073] (3) Preparation of coarse fishbone particle-based Pickering emulsion: The coarse fishbone particle dispersion prepared in step (2) was mixed with soybean oil at a volume ratio of 1:2, and homogenized and emulsified at a high speed of 15,000 r / min for 3 minutes under an ice bath to obtain Pickering emulsion comparative example 1.

[0074] Performance test 1

[0075] The Pickering emulsions prepared in Examples 1-9 and Comparative Example 1 were placed in sample bottles, respectively, and allowed to stand at 4°C for 0, 14, and 28 days. The total height of the emulsion (Ht) and the total height of the emulsified phase (He) in the sample bottles at different storage periods were observed and measured. The appearance of the fishbone particle-based Pickering emulsions prepared in Examples 1-9 and Comparative Example 1 after 0, 14, and 28 days is shown in the following figures. Figure 1 As shown in Table 1, the volume fraction of the emulsified phase and the stability index of the Pickering emulsions prepared in Examples 1-9 and Comparative Example 1 are measured.

[0076] Emulsion phase volume fraction (%) = (He / Ht) × 100% Formula (1)

[0077] Stability index (%) = (28-day emulsified phase volume fraction / 0-day emulsified phase volume fraction) × 100%

[0078] Formula (2)

[0079] Table 1

[0080]

[0081] like Figure 1As shown in Table 1, fish bone particles can be used as solid particles to stabilize Pickering emulsions, which provides an opportunity for the development of new edible solid particles and opens up a new way to solve the sustainable utilization of fish bone waste. When the storage time is 0 days, compared with Comparative Example 1, it is found that the micro-nano fish bone particle Pickering emulsions prepared based on different ball milling times have a higher emulsion phase volume fraction (>86.5%), which means that the ball milling treatment further enhances the ability of fish bone particles to stabilize Pickering emulsions as solid particles. After 14 days and 28 days of storage, the emulsion phase volume fraction of each group of samples decreased slightly, but the emulsion phase volume fraction of Examples 1-9 was still significantly higher than that of Comparative Example 1; in addition, the stability index of all emulsions after 28 days of storage was higher than 86.1%, further indicating that fish bone particles can stabilize Pickering emulsions, and the stability of the emulsions prepared after the fish bone particles were ball milled was also significantly improved.

[0082] Performance test 2

[0083] The droplet size of the fishbone particle-based Pickering emulsions prepared in Examples 1-9 and Comparative Example 1 was measured using a laser particle size analyzer. The pump speed was set to 2500 r / min, the shading rate was within the range of 5%-10%, and the volume-weighted average diameter (D) of the emulsion droplets during different storage periods was recorded. [4,3] The microstructure of fishbone particle-based Pickering emulsions at different storage periods was observed using an optical microscope.

[0084] Figure 2 The particle size distribution diagrams of the fishbone particle-based Pickering emulsions prepared in Examples 1-9 and Comparative Example 1 at 0 days, 14 days and 28 days.

[0085] Figure 3 The microstructures of the fishbone particle-based Pickering emulsions prepared in Examples 1-9 and Comparative Example 1 at 0 days, 14 days, and 28 days.

[0086] Combine Figure 2 and Figure 3 All emulsions exhibited a particle size distribution between 20 μm and 50 μm, exhibiting a regular spherical shape with an intact interface. The particle size of the emulsions in Examples 1-9 was significantly lower than that in Comparative Example 1, indicating that the ball-milled fishbone particles were more adsorbed at the water-oil interface, reducing surface tension and stabilizing the emulsions. This result is consistent with the volume change of the emulsion phase. After 14 and 28 days of storage, the particle size, shape, and microstructure of the emulsion droplets remained virtually unchanged in both the Comparative Examples and the Examples, further demonstrating the feasibility of fishbone particles for stabilizing Pickering emulsions.

[0087] Based on the confirmation that coarse fishbone particles can stabilize Pickering emulsions, the present invention further realizes micronization of fishbone particles through ball milling, promotes the adsorption of fishbone particles at the water-oil two-phase interface, reduces the particle size of emulsion droplets, and effectively improves the stability of the emulsion.

[0088] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A method for preparing a Pickering emulsion based on micro-nano fish bone powder particles, characterized in that: The following steps are involved: The fish bones are sequentially subjected to enzymatic hydrolysis, fat removal, high-pressure steaming, and drying to obtain coarse fish bone particles; the coarse fish bone particles are subjected to micro-nano processing to obtain micro-nano fish bone particles; the micro-nano fish bone particles are mixed with water, and mechanical homogenization and ultrasound are performed in an ice bath to obtain a micro-nano fish bone particle dispersion; the micro-nano fish bone particle dispersion is mixed with liquid oil, and homogenization and emulsification are performed in an ice bath to obtain the micro-nano fish bone powder particle-based Pickering emulsion.

2. The method for preparing the micro-nano fish bone powder particle-based Pickering emulsion according to claim 1, characterized in that: The high-pressure cooking temperature is 121° C., the pressure is 0.1 MPa, the processing time is 20 min, the solid-liquid ratio is 1:1.5 (w / w), and the drying is carried out at 85° C. for 4 h.

3. The method for preparing the micro-nano fish bone powder particle-based Pickering emulsion according to claim 1, characterized in that: The micro-nano processing is to place the coarse fish bone particles in a planetary ball mill for crushing, and the crushing speed is 1000 r / min and the time is 2.5-30 min.

4. The method for preparing the micro-nano fish bone powder particle-based Pickering emulsion according to claim 1, characterized in that: The mass ratio of the micro-nano fishbone particles to water is 3:

100.

5. The method for preparing the micro-nano fish bone powder particle-based Pickering emulsion according to claim 1, characterized in that: The speed of the mechanical homogenization was 10,000 r / min, and the time was 1 min. The power of the ultrasound was 400 W, and the ultrasound mode was on for 5 s and off for 6 s, and the total ultrasound time was 4 min.

6. The method for preparing the micro-nano fish bone powder particle-based Pickering emulsion according to claim 1, characterized in that: The volume ratio of the micro-nano fishbone particle dispersion to the liquid oil is 5:

10.

7. The method for preparing the micro-nano fish bone powder particle-based Pickering emulsion according to claim 6, characterized in that: The liquid oil includes one or more of soybean oil, rapeseed oil, fish oil, peanut oil, olive oil, corn oil, walnut oil, linseed oil and sunflower oil.

8. The method for preparing the micro-nano fish bone powder particle-based Pickering emulsion according to claim 1, characterized in that: The speed of the homogenization and emulsification was 15000 r / min, the homogenization time was 1 min each time, and the homogenization and emulsification were performed 3 times in total.

9. The method for preparing the micro-nano fish bone powder particle-based Pickering emulsion according to claim 1, characterized in that: The fish bones include one or more of cod bones, salmon bones, silver carp bones, black carp bones, grass carp bones, bighead carp, crucian carp, and tilapia bones.

10. A Pickering emulsion based on micro-nano fish bone powder particles prepared by the preparation method according to any one of claims 1 to 9.

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