Ocean shell nano biological calcium and preparation method thereof
The preparation of marine shell nanobiocalcium through cleaning, calcining, aging, digestion, carbonization and other steps has solved the problem of low utilization efficiency of marine shell calcium resources, achieved efficient and environmentally friendly calcium resource conversion, and provided high-value food Biocalcium resources.
Patent Information
- Application Number
- CN202411420830.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-12
- Publication Date
- 2024-12-10
AI Technical Summary
The prior art is difficult to effectively utilize the calcium resources in marine shells, resulting in waste of resources and low added value, and lack of low-cost, high-efficiency and high-value utilization methods.
The preparation of marine shell nanobiocalcium through cleaning, calcining, aging, digestion, carbonization and other steps is achieved, and the resource utilization of calcium resources is provided, and a simple and environmentally friendly high-value calcium product production method is provided.
It has achieved efficient utilization of marine shell calcium resources, produced high-quality food biological calcium resources, and has industrial value, and is simple in methods, few operating steps, and has no pollution to the environment.
Smart Images
Figure CN119100433A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the fields of environmental protection, new material technology and food bio-calcium, and specifically relates to marine shell nano bio-calcium and a preparation method thereof. Background Art
[0002] Marine shells are the outer shells of mollusks living in the ocean, a type of calcified substance secreted by special glandular cells. The main components of marine shells are about 95% calcium carbonate and a small amount of chitin. The consumption of shells in fisheries, aquaculture in coastal areas of my country and inland areas alone exceeds 7 million tons per year, involving scallop shells, clam shells, oyster shells, etc. At present, these marine shells are mostly used in landfills and poultry feeds, with low added value and causing serious waste of calcium resources. Therefore, how to rationally use marine shells to prepare high-value calcium products has gradually become an important technical development direction.
[0003] At present, the main ways to utilize marine shells are road landfill and poultry feed. There are also patent reports on mechanically crushing marine shells to prepare heavy calcium carbonate powder (ZL202011444399.4), light calcium carbonate (ZL201310127210.2) and nano calcium carbonate (ZL201410705021.3). Among them, marine shells can be used to prepare nano calcium carbonate (ZL201711381061.7) by hydrochloric acid acidification and Na2CO3 precipitation, or by grinding to prepare calcium carbonate powder and combining it with subcritical hydrolysis to prepare nano calcium carbonate (ZL201910496467.2). However, how to use the calcium resources in marine shells at low cost, high efficiency and high value is still a major challenge, and it is also the frontier direction of the utilization of marine shell calcium resources.
[0004] To this end, the patent washes and calcines the marine shells to obtain the marine shell calcined material, obtains the marine shell nano bio-calcium through aging, digestion, carbonization and other processes, and then obtains the marine shell nano bio-calcium finished product through filtration, washing and drying, which can provide high-quality food bio-calcium resources for humans. The process method is simple, has few operating steps and is pollution-free to the environment, realizes the resource utilization of marine shell calcium, and is in line with the development direction of modern industry. Summary of the invention
[0005] The present invention aims to provide a method for controllably preparing nano biocalcium using marine shells as raw materials. The present invention prepares a nano biocalcium through simple steps of marine shell calcination, aging, digestion, carbonization, etc., which provides a new idea for the utilization of marine shell resources and has potential industrial value in terms of environmental protection and economic benefits. The marine shell nano biocalcium preparation method provided by the present invention is simple, and the crystal form and size of the biocalcium are controllable and the yield is high.
[0006] The marine shell nano biocalcium and its preparation method can use marine shells as raw materials to prepare nano biocalcium with controllable crystal form and size, and the specific steps are as follows:
[0007] 1) Cleaning the collected marine shells and calcining them at 850-1000° C. for 6-12 hours to obtain calcined materials;
[0008] 2) grinding the marine shell calcined material in step 1), adding it to hot water at 60-85° C., aging it for 24-48 hours, passing it through a 200-mesh sieve, and adjusting the slurry concentration to 8-11 degrees Baume to obtain a slurry;
[0009] 3) Control the temperature of the slurry in step 2) to below 25°C, add Sodium polyacrylate is carbonized to pH=7-8 and stirred for 30 minutes. After the reaction is completed, it is filtered and washed 3 times. The filter cake is dried, ground and sieved to obtain marine shell nano-biocalcium. BRIEF DESCRIPTION OF THE DRAWINGS
[0010] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.
[0011] Figure 1 This is a scanning electron microscope image of nano calcium carbonate particles prepared from scallop shells in Example 1;
[0012] Figure 2 This is a scanning electron microscope image of nano calcium carbonate particles prepared using clam shells in Example 2.
[0013] Figure 3 This is a scanning electron microscope image of nano calcium carbonate particles prepared using oyster shells in Example 3. DETAILED DESCRIPTION
[0014] The present invention is further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto. The specific implementation methods are as follows:
[0015] Embodiment 1:
[0016] 1) 500 g of scallop shells were washed and calcined at 950° C. for 8 h to obtain a calcined material;
[0017] 2) Grind the calcined scallop shell material, add it into 70°C hot water, age it for 36 hours, pass it through a 200-mesh sieve, and adjust the slurry concentration to 10 degrees Baume;
[0018] 3) Keep the slurry liquid at a constant temperature of 20°C, add 5‰ sodium polyacrylate to carbonize until the pH value reaches 7.0, and stir for 30 minutes;
[0019] 4) The slurry obtained in 3) was filtered and washed three times, and the filter cake was dried, ground and sieved to obtain scallop shell nano-shell marine biological calcium with a yield of 98.5%, a content of 97.79%, a whiteness of 96.1%, and a specific surface area of 22.1 m 2 / g, particle size 45-75nm. Sample SEM as attached Figure 1 shown.
[0020] Embodiment 2:
[0021] 1) 500 g of clam shells were washed and calcined at 1000° C. for 8 h to obtain a calcined material;
[0022] 2) grinding the calcined clam shell material, adding it to 80°C hot water, aging it for 48 hours, passing it through a 200-mesh sieve, and adjusting the slurry concentration to 9 degrees Baume;
[0023] 3) Keep the slurry at a constant temperature of 21°C, add 5‰ sodium polyacrylate to carbonize until the pH value reaches 7.0, and stir for 30 minutes;
[0024] 4) The slurry obtained in 3) was filtered and washed three times, and the filter cake was dried, ground and sieved to obtain clam shell nano-shell marine biological calcium with a yield of 97.8%, a content of 95.24%, a whiteness of 95.1%, and a specific surface area of 21.02 m 2 / g, particle size 18-26nm. Sample SEM as attached Figure 2 shown.
[0025] Embodiment 3:
[0026] 1) 500 g of oyster shells were washed and calcined at 900° C. for 10 h to obtain a calcined material;
[0027] 2) Grind the calcined oyster shell material, add it into 60°C hot water, age it for 24 hours, pass it through a 200-mesh sieve, and adjust the slurry concentration to 11 degrees Baume;
[0028] 3) Keep the slurry at a constant temperature of 23°C, add 2‰ sodium polyacrylate to carbonize until the pH value reaches 7.0, and stir for 30 minutes;
[0029] 4) The slurry obtained in 3) was filtered and washed three times, and the filter cake was dried, ground and sieved to obtain oyster shell nano shell marine biological calcium with a yield of 98.0%, a content of 97.88%, a whiteness of 95.3%, and a specific surface area of 25.41 m 2 / g, particle size 40-60nm. Sample SEM as attached Figure 3 shown.
Claims
1. A marine shell nano biocalcium and a preparation method thereof, characterized in that: The marine shell nano biocalcium is prepared from marine shells as raw materials, the weight percentage of calcium carbonate is greater than 95%, and its microscopic morphology is a nanostructure.
2. According to claim 1, a marine shell nano bio-calcium and a preparation method thereof, characterized in that: 1) Cleaning the collected marine shells and calcining them at 850-1000° C. for 6-12 hours to obtain calcined materials; 2) grinding the marine shell calcined material in step 1), adding it to hot water at 60-85° C., aging it for 24-48 hours, passing it through a 200-mesh sieve, and adjusting the slurry concentration to 8-11 degrees Baume to obtain a slurry; 3) Cool the slurry in step 2) to below 25°C and add Sodium polyacrylate is carbonized to pH=7-8 and stirred for 30 minutes. After the reaction is completed, it is filtered and washed 3 times. The filter cake is dried, ground and sieved to obtain marine shell nano-biocalcium.
3. A marine shell nano biocalcium and a preparation method thereof according to claim 2, characterized in that: In step 1), the marine shells are preferably scallop shells, clam shells, oyster shells, etc., which are easily available and have high edible and medicinal value.