Bone-derived biological calcium and preparation method and application thereof

Abstract

The present application relates to the field of waste liquid treatment, and discloses a bone-derived biological calcium as well as a preparation method and application thereof.The bone-derived biological calcium contains a calcium source and water-soluble organic matter; wherein, the mass ratio of the calcium source and the water-soluble organic matter in the bone-derived biological calcium is 7-26:1-8 in terms of calcium element; wherein, the calcium source exists in the form of free calcium and chelated peptide calcium.The bone-derived biological calcium is prepared by using bone gelatin production waste liquid, which is a high-salt, high-chlorine and high-organic waste liquid discharged in the bone gelatin production process, as raw material, through coagulation and sedimentation, protein degradation, membrane separation to obtain a clear liquid, and then through evaporation and other processes to prepare liquid or solid bone-derived biological calcium.The method uses bone gelatin production waste liquid, which is a high-salt, high-chlorine and high-organic waste liquid discharged in the bone gelatin production process, as raw material, solves the problem of water and soil pollution caused by high-salt waste liquid, and solves the technical bottleneck of comprehensive utilization of gelatin industry waste liquid.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of waste liquid treatment, in particular to bone-derived biological calcium and a preparation method and application thereof. BACKGROUND

[0002] Bone gelatin production waste liquid is a kind of 'high-chlorine, high-salt, high-organic waste liquid' which is difficult to treat. This kind of waste liquid is complex in composition, difficult to treat, and complex in process. Due to the limitation of bone gelatin production waste liquid treatment technology, the current waste liquid treatment cost of gelatin enterprises at home and abroad is relatively high. In order to meet the waste liquid discharge standard and meet the environmental protection requirements, many enterprises have invested a lot of manpower, material resources and financial resources in waste liquid treatment, which has caused great burden to gelatin manufacturing enterprises. How to efficiently and economically treat bone gelatin production waste liquid is a worldwide problem.

[0003] For a long time, the research focus of bone gelatin manufacturing enterprises and research institutes studying this kind of waste liquid has been on the development of technology / process for removing organic matter. Generally, bone gelatin production waste liquid is discharged into a sewage treatment station and mixed with other low-salt waste liquid. After treatment, it is discharged. However, such treatment not only increases the cost and pressure of enterprises in environmental governance, but also wastes the economic value of bone gelatin production waste liquid. Few people study how to reuse this waste liquid for fertilizer application and turn waste into treasure. SUMMARY

[0004] The present application aims to overcome the problems of bone gelatin production waste liquid treatment and resource waste in the prior art, and provides a bone-derived biological calcium and a preparation method and application thereof. The bone-derived biological calcium of the present application is prepared by using high-salt, high-chlorine, high-organic waste liquid (i.e. bone gelatin production waste liquid) discharged in the bone gelatin production process as raw material, through coagulation sedimentation, protein degradation, membrane separation to obtain clear liquid, and then through evaporation process to prepare liquid or solid bone-derived biological calcium. This method treats bone gelatin production waste liquid through coagulation sedimentation, protein degradation, membrane separation and other processes to prepare bone-derived biological calcium rich in free calcium, chelated peptide calcium and water-soluble organic matter. The bone-derived biological calcium can be directly used as fertilizer or raw material for fertilizer application in agricultural production, and has the effect of increasing crop yield.

[0005] In order to achieve the above-mentioned purpose, the present application provides a bone-derived biological calcium, which contains a calcium source and water-soluble organic matter.

[0006] In the bone-derived biological calcium, the mass ratio of the calcium source and the water-soluble organic matter, calculated based on calcium element, is 7-26:1-8.

[0007] The calcium source exists in the form of free calcium and chelated peptide calcium.

[0008] The second aspect of the present application provides a method for preparing bone-derived bio-calcium, the method comprising: removing insoluble substances, degrading proteins and performing membrane separation on bone gel production waste liquid to obtain a liquid containing bone-derived bio-calcium.

[0009] In the method, the protein degradation is to degrade proteins with a molecular weight greater than or equal to 10000 Da into small molecular peptides with a molecular weight less than 10000 Da.

[0010] The membrane used in the membrane separation is a separation membrane with a molecular weight cut-off greater than or equal to 10000 Da.

[0011] The third aspect of the present application provides bone-derived bio-calcium prepared by the method as described above.

[0012] The fourth aspect of the present application provides application of the method as described above to treatment of bone gel production waste liquid.

[0013] The fifth aspect of the present application provides application of the bone-derived bio-calcium as described above in agriculture.

[0014] The above technical solutions achieve the following effects:

[0015] (1) solving pollution of high-salt waste liquid to water bodies and soil: the method of the present application realizes comprehensive utilization of bone gel production waste liquid, utilizes the potential economic value of the waste liquid, realizes waste-to-resource, and applies the obtained bone-derived bio-calcium to crops, while solving pollution of high-salt waste liquid to water bodies and soil.

[0016] (2) solving industry bottleneck: in the gelatin industry, bone gel production waste liquid is generally discharged into a sewage treatment station and discharged after treatment, and few people study how to recycle the waste liquid. The present application solves the technical bottleneck of comprehensive utilization of gelatin industry waste liquid.

[0017] (3) resource recycling and economic benefits: on the one hand, the method of the present application realizes recycling of gelatin production waste liquid, reducing the input of gelatin production cost; on the other hand, the bone-derived bio-calcium prepared by the method of the present application can be used as a fertilizer, has high application value, and the value can be 1500-3000 / ton, which is 2-4 times higher than the market price of industrial calcium chloride (300-700 yuan / ton), thus generating new economic benefits and improving the profitability of enterprises.

[0018] (4) compared with the process flow of the prior art, the method of the present application adds a protein degradation step, which processes proteins with a molecular weight of 10000 Da and above into small molecular peptides with a target molecular weight, improves the efficiency of subsequent evaporation, increases the content of chelating peptide calcium in the prepared bone-derived bio-calcium, and further improves the yield of crops when the bone-derived bio-calcium of the present application is used as a fertilizer or a fertilizer raw material.

[0019] (5) Compared with the process flow of the prior art, the method of the present application adds a membrane separation step, which uses a membrane with a specific molecular weight cut-off to ensure that the molecular weight of the small molecule peptides in the bone-derived biological calcium is controlled within the target range.

[0020] (6) The main nutrient elements in the bone-derived biological calcium of the present application are derived from livestock bones and are biogenic substances with biological activity. At the same time, the small molecule peptides with a target molecular weight obtained through the protein degradation process are contained, and the small molecule peptides form chelates with the biogenic calcium to generate more active biological calcium, which is more easily absorbed and utilized by crops, thereby further improving the yield and quality of crops. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 is a process flow chart of an embodiment of the present application;

[0022] Figure 2 is a process flow chart of another embodiment of the present application;

[0023] Figure 3 is a process flow chart of another embodiment of the present application;

[0024] Figure 4 is a fitting chart of the influence of the application of medium element water-soluble fertilizer A1 and amino acid-containing water-soluble fertilizer on the yield of tomatoes in Test Example 3. DETAILED DESCRIPTION

[0025] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and any values are understood to be approximate values. The exact numerical values should be considered to be an approximation within the range or value. For numerical ranges, the endpoints are included within the range, and the endpoints and individual points within the ranges are included within the range. The exact numerical values should be considered to be an approximation within the range or value.

[0026] The first aspect of the present application provides a bone-derived biological calcium, which contains a calcium source (Ca) and water-soluble organic matter;

[0027] wherein the mass ratio of the calcium source to the water-soluble organic matter in the bone-derived biological calcium is 7-26:1-8 (such as 0.875, 1, 1.25, 1.75, 2, 2.25, 2.75, 3, 3.25, 3.75, 4, 4.25, 4.75, 5, 7, 9, 11, 13, 15, 17, 19, 21, 23, 26 or any value between the above values) in terms of dry basis;

[0028] wherein the calcium source exists in the form of free calcium and chelated peptide calcium.

[0029] In some embodiments of the present application, the bone-derived biological calcium contains 7-26 wt% of calcium source based on dry basis, for example, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, or a value within a range consisting of any two of the above values.

[0030] In some embodiments of the present application, the bone-derived biological calcium contains 1-8 wt% of water-soluble organic matter based on dry basis, for example, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, or a value within a range consisting of any two of the above values.

[0031] In the present application, the bone-derived biological calcium refers to a product containing specific small molecular peptides and calcium source. The bone-derived biological calcium is a liquid or solid (granular or powdery) product prepared by taking the high-calcium, high-chlorine, and high-organic waste liquid discharged in the production process of bone gelatin as raw material, coagulating and precipitating, membrane separation, and protein degradation to obtain a bone-derived biological calcium solution, and then concentrating and granulating. The main nutrient elements in the product are derived from livestock bones and contain small molecular peptides, which are biological substances and have biological activity, and are more easily absorbed and utilized by crops. It should be understood that the bone-derived biological calcium described in the present application is a mixture containing calcium source, chlorine, water-soluble organic matter, and other components. Preferably, the bone-derived biological calcium described in the present application also contains a large amount of and trace elements required by plants in addition to Ca and Cl.

[0032] In the present application, unless otherwise specified, the content of calcium source refers to the total content of free calcium and chelated calcium peptides calculated based on calcium element (Ca). The detection method of the content of calcium source (calculated based on calcium element) is GB / T 6436-2018 ethylenediamine tetraacetic acid disodium complexometric titration method.

[0033] In the present application, the water-soluble organic matter refers to the total organic matter in the bone-derived biological calcium that can be completely dissolved in water. The detection method of the content of water-soluble organic matter is NY / T1976-2010.

[0034] In some embodiments of the present application, the free calcium content in the bone-derived biological calcium is 7-25 wt%, and the chelated peptide calcium content is 0.5-4 wt% on a dry basis.

[0035] In some embodiments of the present application, the chelation rate is 2-50%. The inventors have found that the chelation rate of the chelated peptide calcium in the bone-derived biological calcium of the present application is significantly better than that of other products. The chelated peptide calcium can promote the absorption of calcium by plants and increase the yield of crops.

[0036] In the present application, the detection method of the free calcium content (calculated as calcium element) is as follows: referring to the fourth chapter 2.2 of the master's degree thesis of Shanxi Agricultural University entitled "Enzymatic preparation of sheep bone collagen peptide and research on peptide calcium chelation", after preparing the free calcium solution, the free calcium content is detected by GB / T 6436-2018 ethylenediamine tetraacetic acid disodium complexometric titration method.

[0037] In the present application, the calculation method of the chelation rate and the detection method of the chelated peptide calcium content (calculated as calcium element) are as follows: chelated peptide calcium content (calculated as calcium element) = calcium source content (calculated as calcium element) - free calcium content (calculated as calcium element); chelation rate = chelated peptide calcium content (calculated as calcium element) / calcium source content (calculated as calcium element) x 100%.

[0038] In some embodiments of the present application, the bone-derived biological calcium further contains Cl, and the Cl content in the bone-derived biological calcium is 11-45 wt% on a dry basis. In the bone-derived biological calcium, the detection method of the Cl content is GB / T 24890-2010.

[0039] In some embodiments of the present application, the bone-derived biological calcium further contains a large amount and medium and trace elements other than Ca and Cl, and the bone-derived biological calcium contains 0-3 wt% of the large amount and medium and trace elements other than Ca and Cl on a dry basis. The large amount and medium and trace elements other than Ca and Cl are at least one of phosphorus (P), potassium (K), magnesium (Mg), sulfur (S), copper (Cu), iron (Fe), manganese (Mn), zinc (Zn), boron (B), and molybdenum (Mo). In the bone-derived biological calcium, the magnesium content is calculated as Mg, the sulfur content is calculated as S, and the detection method of the magnesium and sulfur content is NY / T 1117-2010; the copper content is calculated as Cu, the iron content is calculated as Fe, the manganese content is calculated as Mn, the zinc content is calculated as Zn, and the molybdenum content is calculated as Mo, and the detection method of the copper, iron, manganese, zinc, and molybdenum content is NY / T 1974-2010; the phosphorus content is calculated as P2O5, and the detection method of the phosphorus content is NY / T 1977-2010; and the potassium content is calculated as K2O, and the detection method of the potassium content is GB / T 17767.3-2010.

[0040] In the present application, the large and medium trace elements in addition to Ca and Cl are also essential elements for plant growth. Therefore, when the bone-derived biological calcium is used as a fertilizer or a fertilizer raw material, the nutritional elements of crops can be further supplemented, and the growth of crops can be promoted.

[0041] In some embodiments of the present application, the water-soluble organic matter contains small molecule peptides, and the bone-derived biological calcium contains 0-4wt% of small molecule peptides on a dry basis.

[0042] In some embodiments of the present application, the molecular weight of the small molecule peptides is <10000 Da, preferably 500-5000 Da, further preferably 500-3000 Da, further preferably 700-2000 Da, and further preferably 700-1500 Da. The inventors have found that when the bone-derived biological calcium contains small molecule peptides with the above-mentioned molecular weight, the chelation rate of Ca and peptides during the production of bone-derived biological calcium products is improved, the content of chelated peptide calcium in bone-derived biological calcium is increased, and the effect of peptides on crop yield increase can be maintained.

[0043] In the present application, the detection method of the content and molecular weight of the small molecule peptides is to detect the molecular weight of the small molecule peptides by Appendix A (high-performance size exclusion chromatography method) of GB 31645-2018, and to detect the content of the small molecule peptides by the method for measuring protein content in GB / T 6432-2018.

[0044] In the present application, the bone-derived biological calcium also contains unavoidable impurities and crystal water.

[0045] In the present application, the form of the bone-derived biological calcium can be liquid and / or solid, i.e., liquid bone-derived biological calcium and / or solid bone-derived biological calcium.

[0046] In the present application, the dosage form of the solid bone-derived biological calcium can be routinely selected in the art, for example, can be at least one of granules, powders, and tablets.

[0047] In the present application, the dry basis of the bone-derived biological calcium refers to the amount of the bone-derived biological calcium dried in a vacuum oven (vacuum drying oven purchased from Shanghai-Heng Science and Technology Instrument Co., Ltd., DZF series) at a temperature of 50℃ and a vacuum degree of 7x10 4 Pa until the mass does not change continuously for 120 min.

[0048] In some embodiments of the present application, when the bone-derived biological calcium is a solid bone-derived biological calcium, the dry basis refers to the amount of the solid bone-derived biological calcium dried in a vacuum oven (vacuum drying oven purchased from Shanghai-Heng Science and Technology Instrument Co., Ltd., DZF series) at a temperature of 50℃ and a vacuum degree of 7x10 4Pa, the amount of the solid bone-derived bio-calcium before drying that is dried in a vacuum oven until the mass does not change for 120 minutes. It should be understood that the solid bone-derived bio-calcium before drying is not absolutely dry, but also contains a small amount of free water, and the water content of the solid bone-derived bio-calcium before drying refers to the content of free water in the solid bone-derived bio-calcium before drying, and the water content of the solid bone-derived bio-calcium before drying = (the mass of the solid bone-derived bio-calcium before drying - the mass of the solid bone-derived bio-calcium after drying) / the mass of the solid bone-derived bio-calcium before drying. In the present application, the water content of the solid bone-derived bio-calcium before drying is preferably 1-10%, and the dry basis content of the solid bone-derived bio-calcium before drying is preferably (1-water content) x 100%.

[0049] The second aspect of the present application provides a method for preparing bone-derived bio-calcium, the method comprising: removing insoluble substances, degrading proteins, and performing membrane separation on bone gel production waste liquid to obtain a liquid containing bone-derived bio-calcium.

[0050] In the present application, the protein degradation is to degrade proteins with a molecular weight greater than or equal to 10,000 Da in the material after protein degradation into small molecular peptides with a molecular weight less than 10,000 Da.

[0051] In the present application, the membrane used in the membrane separation is a separation membrane, and the separation membrane has a molecular weight cut-off greater than or equal to 10,000 Da.

[0052] In some embodiments of the present application, the method further comprises: concentrating the liquid containing bone-derived bio-calcium to TDS = 8-80 wt% to obtain liquid bone-derived bio-calcium. In the present application, the TDS refers to the total amount of dissolved solids.

[0053] In the present application, the concentration of the liquid containing bone-derived bio-calcium to TDS is any one of 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt% or a range formed by any two of the above values. Preferably, the concentration is to concentrate the liquid containing bone-derived bio-calcium to TDS = 15-80 wt%.

[0054] In some embodiments of the present application, the concentration is membrane concentration and / or evaporation. Preferably, the membrane used in the membrane concentration is a concentration membrane, preferably a reverse osmosis membrane, and further preferably an RO reverse osmosis membrane. In the present application, the conditions and methods of evaporation can be selected by conventional techniques in the art, which will not be described here.

[0055] In some embodiments of the present application, the concentration is concentrating the liquid containing bone-derived bio-calcium to TDS = 8-15wt% by membrane concentration.

[0056] In some embodiments of the present application, the concentration is concentrating the liquid containing bone-derived bio-calcium to TDS = 15-80wt% by evaporation.

[0057] In some preferred embodiments of the present application, the concentration is: firstly, concentrating the liquid containing bone-derived bio-calcium by membrane concentration, and then, concentrating the concentrated material by evaporation.

[0058] In the present application, the protein degradation is degrading macromolecular proteins into small molecular peptides with a target molecular weight, so that the molecular weight of the macromolecular proteins in the material after protein degradation is degraded to less than 10000Da. In the present application, the target molecular weight is less than 10000Da. The inventors have found that the content of chelated peptide calcium in the bone-derived bio-calcium prepared by protein degradation can be further improved. Compared with the bone-derived bio-calcium prepared without protein degradation, the content of chelated peptide calcium (calculated as calcium element) in the bone-derived bio-calcium prepared by protein degradation is 2-9 times higher.

[0059] In some embodiments of the present application, the protein degradation is at least one of chemical method, physical method and biological method. Preferably, the protein degradation is chemical method, and more preferably, sodium hypochlorite decomposition method.

[0060] It should be noted that, in the present application, unless otherwise specified, the molecular weight of the "protein" is greater than or equal to 10000Da, and the molecular weight of the "polypeptide", "oligopeptide" and "small molecular peptide" is less than 10000Da.

[0061] The inventors have found that the sodium hypochlorite decomposition method can effectively degrade the macromolecular proteins in the material to be degraded into small molecular peptides with a target molecular weight, thereby improving the content of chelated peptide calcium in the bone-derived bio-calcium prepared.

[0062] In some embodiments of the present application, the sodium hypochlorite decomposition method is: mixing sodium hypochlorite with the material to be degraded at 10-50℃ for 10-60min.

[0063] In some embodiments of the present application, the amount of sodium hypochlorite used is 0.1-1g, preferably 0.25-1g, relative to 1L of the material to be degraded. When the amount of sodium hypochlorite used is within the preferred range, the content of chelated peptide calcium and small molecular peptides in the bone-derived bio-calcium prepared can be further improved.

[0064] In the present application, the sodium hypochlorite can be used in the form of a solution. In some embodiments of the present application, the mass concentration of the sodium hypochlorite solution is 5-13%, and the volume ratio of the material to be subjected to protein degradation to the sodium hypochlorite solution is 1000:2-7. The inventors have found that when the mass concentration of the sodium hypochlorite solution is 10-13% and the volume ratio of the material to be subjected to protein degradation to the sodium hypochlorite solution is 1000:5-7, the content of chelated peptide calcium and the content of small molecule peptides in the bone-derived biological calcium prepared can be further increased.

[0065] In the present application, the membrane separation is such that the small molecule peptides in the material after the membrane separation (the clear liquid) have a molecular weight within the target molecular weight range.

[0066] In the present application, unless otherwise specified, the "concentrated liquid" and the "concentrated solution" refer to the liquid retained by the membrane, the "clear liquid" and the "permeate" refer to the liquid passing through the membrane, i.e. the liquid not retained by the membrane, and the "target molecular weight" refers to <10000 Da.

[0067] In the present application, the "concentration membrane" refers to a membrane for separating the solvent from the material to be subjected to membrane separation. It should be understood that in some cases, for the sake of clear expression, the "concentrated liquid of the concentration membrane" and the "concentrated solution of the concentration membrane" refer to the liquid on one side of the concentration membrane from which the solvent has been separated, and the "clear liquid of the concentration membrane" and the "permeate of the concentration membrane" refer to the liquid on the other side of the concentration membrane, i.e. the solvent.

[0068] In the present application, the "separation membrane" refers to a membrane that retains the molecules with a molecular weight greater than the target molecular weight. It should be understood that in some cases, for the sake of clear expression, the "concentrated liquid of the separation membrane" and the "concentrated solution of the separation membrane" refer to the liquid retained by the separation membrane, and the "clear liquid of the separation membrane" and the "permeate of the separation membrane" refer to the liquid not retained by the separation membrane.

[0069] In the present application, the membrane separation uses a separation membrane, and when the material to be subjected to membrane separation passes through the separation membrane, the small molecule peptides with the target molecular weight in the material to be subjected to membrane separation are separated into the clear liquid, and the obtained clear liquid is the material after the membrane separation.

[0070] In some embodiments of the present application, the method further comprises subjecting the concentrated liquid of the separation membrane to protein degradation, and the material after the protein degradation (i.e. the protein-degraded material) is subjected to membrane separation using the separation membrane.

[0071] In some embodiments of the present application, the water quality index of the clear liquid of the concentration membrane can reach the industrial recycled water standard, and can be used as reclaimed water for other processes in the production of gelatin.

[0072] In some preferred embodiments of the present application, in order to reduce the cost of protein degradation, the order of membrane separation and protein degradation is: first, the material to be separated by the membrane is subjected to membrane separation to obtain a concentrated solution of the separation membrane and a clear solution of the separation membrane. The concentrated solution of the separation membrane is subjected to protein degradation, and the material after protein degradation is subjected to the separation membrane again. In some embodiments of the present application, the separation membrane can be a single-stage separation membrane, and the molecular weight cut-off of the single-stage separation membrane is 500 Da-10000 Da.

[0073] In some embodiments of the present application, in order to improve the feasibility of large-scale production and reduce the cost and efficiency of bone-derived calcium production, the separation membrane can be a two-stage separation membrane comprising a first-stage separation membrane and a second-stage separation membrane, the molecular weight cut-off of the first-stage separation membrane is 5000 Da-10000 Da, and the molecular weight cut-off of the second-stage separation membrane is 500 Da-3000 Da.

[0074] In some embodiments of the present application, in order to improve the feasibility of large-scale production and reduce the cost and efficiency of bone-derived calcium production, the separation membrane can be a multi-stage separation membrane, which can comprise a first-stage separation membrane, a second-stage separation membrane, and a third-stage separation membrane, the molecular weight cut-off of the first-stage separation membrane is 5000 Da-10000 Da, the molecular weight cut-off of the second-stage separation membrane is 500 Da-3000 Da, and the molecular weight cut-off of the third-stage separation membrane is 700 Da-1500 Da.

[0075] In some embodiments of the present application, the insoluble substance removal is at least one of coagulation sedimentation, air flotation, grating, and filtration, and is preferably coagulation sedimentation.

[0076] In some embodiments of the present application, the target molecular weight is 500 Da

[0077] In some embodiments of the present application, the coagulation sedimentation comprises adjusting the pH value of the material to be coagulation sedimentated, mixing a coagulant and a flocculant with the material to be coagulation sedimentated to obtain a material after coagulation sedimentation and a sediment. The first liquid is used for subsequent treatment. Preferably, the pH value is 6-11, preferably 7-10. In the present application, because the bone gelatin production waste liquid contains colloidal impurities and inorganic salt ions, and the pH value is low, the water quality is acidic, and the chloride ion concentration is high, which is not conducive to the coagulation sedimentation of insoluble substances. Therefore, the present application adjusts the pH value of the water quality before the coagulation process, solving the problem that high-chlorine and acidic waste liquid cannot be coagulation sedimentated.

[0078] In some embodiments of the present application, the method further comprises: performing solid-liquid separation on the coagulation sedimentation product to obtain separated liquid and separated solid, wherein the separated liquid is returned to the coagulation sedimentation, and the separated solid is used to produce solid fertilizer, such as bio-organic fertilizer, organic-inorganic compound fertilizer, or compound microbial fertilizer.

[0079] In some embodiments of the present application, the coagulant is an inorganic coagulant, and is further preferably at least one of aluminum sulfate, polyaluminum chloride, polyferric sulfate, ferric chloride, or ferrous sulfate.

[0080] In some embodiments of the present application, the flocculant is polyacrylamide, and is further preferably at least one of anionic polyacrylamide, cationic polyacrylamide, or non-ionic polyacrylamide. In the present application, the molecular weight of the polyacrylamide can be a conventional molecular weight in the art, such as 6-25 million.

[0081] In the present application, the pH adjustment can use a conventional reagent in the art, such as at least one of calcium hydroxide or sodium hydroxide, and is preferably calcium hydroxide.

[0082] In some embodiments of the present application, the amount of the coagulant is 0.15-0.6 g, and the amount of the flocculant is 0.5-4.5 mg, relative to 1 L of the material to be coagulation co-precipitated.

[0083] In some embodiments of the present application, the coagulant and the flocculant are used in the form of a solution. In some embodiments of the present application, the mass concentration of the coagulant solution is 10-20%, and the mass concentration of the flocculant solution is 0.5-1.5 ‰. In this case, the amount of the coagulant solution added is 1.5-3 wt ‰, based on the total weight of the material to be coagulation precipitated. In some embodiments of the present application, the amount of the flocculant solution added is 1-3 wt ‰, based on the total weight of the material to be coagulation precipitated.

[0084] In some embodiments of the present application, the method further comprises: drying and granulating the liquid bone-derived biological calcium to obtain solid bone-derived biological calcium. In the present application, the drying is a conventional technique in the art, such as at least one of sheet drying, spray drying, infrared drying, hot air drying, or microwave drying, and the method and conditions are conventional choices in the art. In the present application, the granulation can be a conventional technical choice in the art, which is not described herein.

[0085] In the present application, the bone gelatin production waste liquid refers to high-calcium, high-chlorine, and high-organic waste liquid discharged in the bone gelatin production process.

[0086] In some embodiments of the present application, the pH of the bone gelatin production waste liquid is 3.5-7. The detection method of the pH is NY / T 1973-2021.

[0087] In some embodiments of the present application, the content of Ca in the bone gelatin production waste liquid is 15000-25000 mg / L. In some embodiments of the present application, the content of Cl in the bone gelatin production waste liquid is 28000-50000 mg / L. In some embodiments of the present application, the content of CODcr (chemical oxygen demand) in the bone gelatin production waste liquid is 2000-10000 mg / L. In some embodiments of the present application, the content of crude protein in the bone gelatin production waste liquid is 500-7000 mg / L. The detection method of the content of Ca in the bone gelatin production waste liquid is GB / T 6436-2018, the detection method of the content of Cl is GB11896-1989, the detection method of the content of CODcr is HJ 828-2017, and the detection method of the content of crude protein is GB / T 6432-2018. In some embodiments of the present application, the bone gelatin production waste liquid further contains oil and fat, and the content of oil and fat in the bone gelatin production waste liquid is 0-90 mg / L. The detection method of the content of oil and fat in the bone gelatin production waste liquid is HJ 637-2018.

[0088] In some embodiments of the present application, the crude protein is at least one of protein, polypeptide and oligopeptide.

[0089] In some embodiments of the present application, the bone gelatin production waste liquid further contains a large amount and a medium and trace amount of elements other than Ca and Cl, and the content of the large amount and the medium and trace amount of elements other than Ca and Cl in the bone gelatin production waste liquid is 0-3000 mg / L. The large amount and the medium and trace amount of elements other than Ca and Cl are at least one of phosphorus (P), potassium (K), magnesium (Mg), sulfur (S), copper (Cu), iron (Fe), manganese (Mn), zinc (Zn), boron (B) and molybdenum (Mo). In the bone gelatin production waste liquid, the content of magnesium is calculated as Mg, the content of sulfur is calculated as S, and the detection method of the content of magnesium and sulfur is NY / T 1117-2010; the content of copper is calculated as Cu, the content of iron is calculated as Fe, the content of manganese is calculated as Mn, the content of zinc is calculated as Zn, and the content of molybdenum is calculated as Mo, and the detection method of the content of copper, iron, manganese, zinc and molybdenum is NY / T 1974-2010; the content of phosphorus is calculated as P2O5, and the detection method of the content of phosphorus is NY / T1977-2010; the content of potassium is calculated as K2O, and the detection method of the content of potassium is GB / T 17767.3-2010.

[0090] The bone gelatin production waste liquid is used to produce the bone source biological calcium according to the method, the bone gelatin production waste liquid treatment capacity is 850-3000 tons / day, and the bone source biological calcium production capacity is 50-200 tons / day according to 24 hours of production per day.

[0091] In some embodiments of the present application, the method comprises:

[0092] (a-1) protein degradation of the bone gelatin production waste liquid to obtain a protein degradation liquid a;

[0093] (a-2) insoluble removal of the protein degradation liquid to obtain a first solid a and a first liquid a;

[0094] (a-3) membrane separation of the first liquid a to obtain a clear liquid a and a concentrated liquid a.

[0095] In some embodiments of the present application, the insoluble removal is coagulation sedimentation, and the coagulation sedimentation comprises: adjusting the pH value of the pretreatment liquid to 6-11, and mixing a coagulant and a flocculant with the protein degradation liquid a.

[0096] In some embodiments of the present application, the method further comprises: solid-liquid separation of the first solid a to obtain a permeate liquid a and sludge a, and the permeate liquid a is returned to the insoluble removal. The sludge a can be used to produce a solid fertilizer, for example, a bio-organic fertilizer, an organic-inorganic compound fertilizer, and a compound microbial fertilizer.

[0097] In the present application, the solid-liquid separation can be a conventional operation in the field, for example, at least one of plate and frame filter pressing, stacking, screw pressing, centrifugation, and belt filtration.

[0098] In some embodiments of the present application, the membrane separation comprises: the first liquid a passing through a separation membrane to obtain the clear liquid a (i.e. a liquid containing a bone source biological calcium solution) and the concentrated liquid a. Preferably, the concentrated liquid a is returned to the protein degradation.

[0099] In some embodiments of the present application, the indexes of the bone gelatin production waste liquid are shown in Table 1. Preferably, the components and contents of the bone source biological calcium are shown in Table 2 on a dry basis. The bone source biological calcium also inevitably contains impurities and crystal water.

[0100] Table 1

[0101]

[0102]

[0103] Table 2

[0104]

[0105] In some embodiments of the present application, the method comprises:

[0106] (b-1) insoluble matter removal is performed on the bone gelatin production waste liquid to obtain a first solid b and a first liquid b;

[0107] (b-2) protein degradation is performed on the first liquid b to obtain a protein degradation liquid b;

[0108] (b-3) membrane separation is performed on the protein degradation liquid b to obtain a clear liquid b and a concentrated liquid b.

[0109] In some embodiments of the present application, the insoluble matter removal is coagulation sedimentation, and the coagulation sedimentation comprises: adjusting the pH value to 7-10, and mixing a coagulant and a flocculant with the bone gelatin production waste liquid.

[0110] In some embodiments of the present application, the method further comprises: subjecting the first solid b to solid-liquid separation to obtain a permeate b and sludge b, and the permeate b is returned to the coagulation sedimentation. The sludge b can be used to produce a solid fertilizer, for example, a bio-organic fertilizer, an organic-inorganic compound fertilizer, or a compound microbial fertilizer.

[0111] In the present application, the solid-liquid separation can be a conventional operation in the art, for example, at least one of plate-and-frame filter pressing, stacker, screw press, centrifugation, and belt filtration.

[0112] In some embodiments of the present application, the membrane separation comprises: subjecting the protein degradation liquid b to a separation membrane to obtain the clear liquid b (i.e., a liquid containing bone-derived biological calcium) and the concentrated liquid b. Preferably, the concentrated liquid b is returned to the protein degradation.

[0113] In some embodiments of the present application, the indexes of the bone gelatin production waste liquid are shown in Table 3. Preferably, the components and contents of the bone-derived biological calcium are shown in Table 4 on a dry basis. The bone-derived biological calcium also contains impurities and crystal water inevitably.

[0114] Table 3

[0115]

[0116]

[0117] Table 4

[0118]

[0119] In some embodiments of the present application, the method comprises:

[0120] (c-1) insoluble matter removal is performed on the bone gelatin production waste liquid to obtain a first solid c and a first liquid c;

[0121] (c-2) performing membrane separation on the first liquid c to obtain a supernatant c and a concentrated liquid c;

[0122] (c-3) performing protein degradation on the concentrated liquid c to obtain a protein degradation liquid c, and returning the protein degradation liquid c to the membrane separation to obtain the supernatant c.

[0123] In some embodiments of the present application, the insoluble substance removal is coagulation sedimentation, which comprises adjusting the pH value to 7-10, and mixing a coagulant and a flocculant with the bone gelatin production waste liquid.

[0124] In some embodiments of the present application, the method further comprises: obtaining a permeate c and a sludge c by solid-liquid separation of the first solid c, and returning the permeate c to the coagulation sedimentation. The sludge c can be used for producing a solid fertilizer.

[0125] In the present application, the solid-liquid separation can be a conventional operation in the art, for example, can be at least one of plate-and-frame filter pressing, stack, screw press, centrifugation, and belt filtration.

[0126] In some embodiments of the present application, the indexes of the bone gelatin production waste liquid are shown in Table 5. In a preferred case, the components and contents of the bone-derived biological calcium are shown in Table 6 on a dry basis. The bone-derived biological calcium also contains impurities and crystal water inevitably.

[0127] Table 5

[0128]

[0129] Table 6

[0130]

[0131] The third aspect of the present application provides a bone-derived biological calcium prepared by the method as described above.

[0132] In some embodiments of the present application, the bone-derived biological calcium contains a calcium source and water-soluble organic matter, and the mass ratio of the calcium source and the water-soluble organic matter in the bone-derived biological calcium on a dry basis is 7-26:1-8 in terms of calcium element.

[0133] In some embodiments of the present application, the bone-derived biological calcium contains 7-26 wt% of the calcium source on a dry basis.

[0134] In some embodiments of the present application, the bone-derived biological calcium contains 1-8 wt% of the water-soluble organic matter on a dry basis.

[0135] In some embodiments of the present application, the calcium source exists in the form of free calcium and chelated peptide calcium.

[0136] In some embodiments of the present application, the content of the free calcium in the bone-derived biological calcium is 7-25 wt% in terms of calcium element and on a dry basis.

[0137] In some embodiments of the present application, the content of the chelated peptide calcium in the bone-derived biological calcium is 0.5-4 wt% in terms of calcium element and on a dry basis.

[0138] In some embodiments of the present application, the chelation rate is 2-50%.

[0139] In some embodiments of the present application, the bone-derived biological calcium further contains 0-3 wt% of macro-and micro-elements other than Ca and Cl on a dry basis; wherein the macro-and micro-elements other than Ca and Cl are at least one of phosphorus (P), potassium (K), magnesium (Mg), sulfur (S), copper (Cu), iron (Fe), manganese (Mn), zinc (Zn), boron (B), and molybdenum (Mo). The measurement method and detection method of the macro-and micro-elements are as described above, and will not be repeated here.

[0140] In some embodiments of the present application, the water-soluble organic matter contains small molecule peptides, and the bone-derived biological calcium contains 0-4 wt% of small molecule peptides on a dry basis.

[0141] In some embodiments of the present application, the small molecule peptides have a molecular weight of <10000 Da, preferably 500-5000 Da, further preferably 500-3000 Da, further preferably 700-2000 Da, and further preferably 700-1500 Da.

[0142] In the present application, the bone-derived biological calcium further contains unavoidable impurities and crystal water. The form, dosage form, dry basis, and water content of the bone-derived biological calcium are as described above, and will not be repeated here.

[0143] The fourth aspect of the present application provides the use of the method as described above in the treatment of bone gelatin production waste liquid.

[0144] The inventors have found that the use of the method as described above in the treatment of bone gelatin production waste liquid can solve the problem of high-salt waste liquid discharge, and at the same time improve the utilization value of bone gelatin production waste liquid.

[0145] The fifth aspect of the present application provides the use of the bone-derived biological calcium as described above in agriculture.

[0146] In some embodiments of the present application, the use is the use of the bone-derived biological calcium in fertilizers.

[0147] In some embodiments of the present application, the bone-derived biological calcium can be directly used as a fertilizer, or can be used as a fertilizer raw material.

[0148] In some embodiments of the present application, the bone-derived biological calcium is used as a fertilizer or a raw material of a fertilizer, which can increase the yield of crops, improve the survival rate of seedlings, and improve the quality of crops.

[0149] The present application will be described in detail below by way of examples. In the following examples, unless otherwise specified, the reagents, raw materials, and instruments used can be obtained commercially, and the methods used are conventional methods in the art.

[0150] 1. The detection methods of various indicators in gelatin production waste liquid are shown in Table 7.

[0151] Table 7

[0152]

[0153] 2. In the bone-derived biological calcium:

[0154] The detection method of calcium source content (calculated based on calcium element) is GB / T 6436-2018 ethylenediamine tetraacetic acid disodium complex titration method.

[0155] The detection method of Cl content is GB / T 24890-2010.

[0156] The detection method of free calcium content (calculated based on calcium element) is as follows: after preparing the free calcium solution according to the fourth chapter 2.2 determination of chelation rate of the master's degree thesis of Shanxi Agricultural University, Enzymatic Preparation of Sheep Bone Collagen Peptide and Research on Chelation of Peptide Calcium, the free calcium content is detected by GB / T6436-2018 ethylenediamine tetraacetic acid disodium complex titration method.

[0157] The detection method of chelated peptide calcium content (calculated based on calcium element) and chelation rate is as follows: chelated peptide calcium content (calculated based on calcium element) is calcium source content-free calcium content (calculated based on calcium element); chelation rate of calcium = chelated peptide calcium content (calculated based on calcium element) / calcium source content x 100%.

[0158] The detection method of small molecule peptide content and molecular weight is as follows: the molecular weight is detected by GB 31645-2018 Appendix A (high-performance size exclusion chromatography method), and the small molecule peptide content is detected by the method of GB / T 6432-2018 for detecting protein content.

[0159] The detection method of water-soluble organic matter content is NY / T1976-2010;

[0160] The detection method of Mg and S content is NY / T 1117-2010;

[0161] The detection method of Cu, Fe, Mn, Zn, B, and Mo content is NY / T 1974-2010;

[0162] The detection method of P content is NY / T1977-2010;

[0163] The detection method of K content is GB / T 17767.3-2010.

[0164] Example 1

[0165] The indicators of the bone gelatin production waste liquid used in this example are shown in Table 8, and the process flow is carried out according to the process shown in Figure 1

[0166] Table 8

[0167]

[0168] (1) Protein degradation: chemical method is used to degrade protein by using sodium hypochlorite. At 25℃, add a 13wt% first-grade industrial sodium hypochlorite solution to the gelatin waste liquid to be treated, the volume ratio of gelatin waste liquid to sodium hypochlorite solution is 1000:6, and stir for 30min to mix the gelatin waste liquid and sodium hypochlorite solution well, so that the macromolecular protein in the waste liquid is converted into small molecular peptides, and protein degradation liquid a is obtained.

[0169] (2) Coagulation and sedimentation (i.e. insoluble matter removal): place the protein degradation liquid a in a coagulation reactor, adjust the pH value to 9 by using a calcium hydroxide solution; add a 10wt% PAC (polyaluminum chloride) solution and a 1‰ PAM (anionic polyacrylamide, molecular weight 150 million) solution respectively for coagulation and sedimentation (based on the total weight of the protein degradation liquid, the addition amount of the PCA solution and the PAM solution is 1.5wt‰ and 1wt‰ respectively), to obtain the first solid a and the first liquid a.

[0170] (3) After the first solid a obtained by coagulation and sedimentation is dewatered by a plate and frame filter press, sludge a and permeate a are obtained, the sludge a can be used for producing solid fertilizer, and the permeate a is returned to the coagulation reactor for further coagulation and sedimentation.

[0171] (4) Membrane separation: the first liquid a obtained by coagulation and sedimentation is introduced into a membrane separation system, and membrane separation is carried out by using a separation membrane with a molecular weight cut-off of 10000Da (purchased from Tianjin Membrane Science and Technology Co., Ltd., model TUIE4230), to obtain clear liquid a and concentrated liquid a. The concentrated liquid a is returned to the protein degradation.

[0172] (5) Concentration: the clear liquid a obtained by membrane separation is subjected to membrane concentration by using a RO reverse osmosis membrane (purchased from Tianjin Membrane Science and Technology Co., Ltd., brand UOT), and the concentrated liquid obtained is introduced into an evaporation system for evaporation, and concentrated to TDS of 55wt%, to obtain liquid bone source biological calcium. The permeate of the RO reverse osmosis membrane and the condensate water in the evaporation process can be used as reclaimed water for other processes in gelatin production. ​

[0173] (6) The liquid bone-derived bio-calcium is cooled and flaked (i.e. flake drying) by a cooling flaker, and then granulated by a granulator to obtain granular bone-derived bio-calcium (i.e. solid bone-derived bio-calcium A), and 63 g of solid bone-derived bio-calcium A can be produced from 1 L of gelatin production waste liquid.

[0174] The solid bone-derived bio-calcium A is dried at a temperature of 50°C, a vacuum degree of 7 x 10 4 Pa for 120 min until its mass does not change, and the components and contents thereof are detected, and the results are shown in Table 9. The water content of the solid bone-derived bio-calcium A before drying is 7%.

[0175] Table 9

[0176]

[0177] According to the above method, the bone-derived bio-calcium is produced using the gelatin production waste liquid, and the gelatin production waste liquid treatment amount is 1500 tons / day, and the bone-derived bio-calcium production amount is 94.5 tons / day, calculated according to 24 h of production per day.

[0178] Example 2

[0179] The indicators of the gelatin production waste liquid used in this example are shown in Table 10, and the process flow is carried out according to Figure 2 .

[0180] Table 10

[0181]

[0182]

[0183] (1) Coagulation sedimentation (i.e. insoluble matter removal): the gelatin production waste liquid is placed in a coagulation reactor, and the pH value is adjusted to 8 by using a calcium hydroxide solution; a mass fraction of 15% PAC (polyaluminum chloride) solution and 1‰ PAM (anionic polyacrylamide, molecular weight of 15 million) solution are added for coagulation sedimentation (based on the total weight of the gelatin production waste liquid, the addition amount of the PCA solution and the PAM solution is 1.5 wt‰ and 1 wt‰, respectively), to obtain a first solid b and a first liquid b.

[0184] (2) The first solid b obtained by coagulation sedimentation is dewatered by a plate and frame filter press to obtain a sludge b and a permeate b, and the sludge b can be used for producing a solid fertilizer, and the permeate b is returned to the coagulation reactor for continuous coagulation sedimentation.

[0185] (3) Protein degradation: the first liquid b obtained by coagulation and sedimentation is added with 13% by mass concentration of primary industrial sodium hypochlorite at 20℃, and the gelatin waste liquid: sodium hypochlorite (volume ratio) is 1000:6, and stirred for 30 min, so that the macromolecular proteins in the waste liquid are changed into small molecular peptides, to obtain the protein degradation liquid b.

[0186] (4) Membrane separation: the protein degradation liquid b is fed into a membrane separation system, and through a separation membrane with a molecular weight cut-off of 10000 Da (purchased from Tianjin Membrane Technology Co., Ltd., model TUIE4230), a clear liquid b and a concentrated liquid b are obtained, and the concentrated liquid b is returned to the protein degradation process for protein degradation.

[0187] (5) Concentration: the clear liquid b obtained by membrane separation is fed into an RO reverse osmosis membrane, and the concentrated liquid of the RO reverse osmosis membrane is evaporated in an evaporation system to a TDS of 35wt%, to obtain a liquid bone source biological calcium. The water quality indicators of the permeate of the RO reverse osmosis membrane and the condensate water in the evaporation process can reach the industrial reuse water standard, and can be used as reclaimed water for other processes in the gelatin production.

[0188] (6) The liquid bone source biological calcium is cooled and flaked by a cooling flaking machine (i.e. flaking drying), and then granulated by a granulator to obtain granular bone source biological calcium (i.e. solid bone source biological calcium B), and 70g of solid bone source biological calcium B can be produced from 1L of bone gelatin production waste liquid.

[0189] The solid bone source biological calcium B is dried at a temperature of 50℃ and a vacuum degree of 7x10 4 Pa for 120 min, and the mass does not change, and the components and contents are detected, and the results are shown in Table 11. The water content of the solid bone source biological calcium B before drying is 6%.

[0190] Table 11

[0191]

[0192]

[0193] According to the above method, the bone source biological calcium is produced using the bone gelatin production waste liquid, and according to the calculation of 24h per day, the bone gelatin production waste liquid treatment capacity is 1500 tons / day, and the yield of bone source biological calcium is 105 tons / day.

[0194] Example 3

[0195] The indicators of the bone gelatin production waste liquid used in this example are shown in Table 12, and the process flow is carried out according to Figure 3 .

[0196] Table 12

[0197]

[0198] (1) Coagulation sedimentation (i.e. insoluble matter removal): The bone gelatin production waste liquid is placed in a coagulation reactor, and the pH value is adjusted to 10 using a calcium hydroxide solution; a 20wt% PAC (polyaluminum chloride) solution and a 1wt% PAM (anionic polyacrylamide, molecular weight 15 million) solution are added for coagulation sedimentation (based on the total weight of the gelatin production waste liquid, the addition amount of the PCA solution and the PAM solution is 1.5wt% and 1wt%, respectively), to obtain a first solid c and a first liquid c.

[0199] (2) The first solid c obtained by coagulation sedimentation is dewatered by a plate and frame filter press to obtain a sludge c and a permeate c, and the sludge c can be used for producing a solid fertilizer, and the permeate c is returned to the coagulation reactor for further coagulation.

[0200] (3) Membrane separation: the first liquid c obtained by coagulation sedimentation is introduced into a membrane separation system, and membrane separation is performed by using a separation membrane with a molecular weight cut-off of 10,000 Da (purchased from Tianjin Membrane Technology Co., Ltd., model TUIE4230), to obtain a clear liquid c and a concentrated liquid c.

[0201] (4) Protein degradation: at 25°C, a first concentrated liquid c is mixed with sodium hypochlorite by adding a 13wt% first industrial sodium hypochlorite solution to the concentrated liquid c, and the volume ratio of the first concentrated liquid c to sodium hypochlorite is 1,000:6, and stirring for 30 min, so that the macromolecular proteins in the waste liquid are converted into small molecular peptides, to obtain a protein degradation liquid c, and the protein degradation liquid c is introduced into a membrane separation system for membrane separation by using a separation membrane with a molecular weight cut-off of 2,000 Da.

[0202] (5) Concentration: the clear liquid c obtained by membrane separation is introduced into a RO reverse osmosis membrane, and the concentrated liquid of the RO reverse osmosis membrane is introduced into an evaporation system for evaporation, and the TDS is concentrated to 45wt%, to obtain a liquid bone source biological calcium. The water quality indicators of the permeate of the RO reverse osmosis membrane and the condensate water in the evaporation process can reach the industrial recycled water standard, and can be used as reclaimed water for other processes in the gelatin production.

[0203] (6) The liquid bone source biological calcium is cooled and flaked by a cooling flaking machine (i.e. flaking drying), and then granulated by a granulator to obtain granular bone source biological calcium waste liquid (i.e. solid bone source biological calcium C), and 63g of solid bone source biological calcium C can be produced from 1L of bone gelatin production waste liquid.

[0204] The solid bone source biological calcium C is dried at a temperature of 50°C and a vacuum degree of 7x10 4Pa, dried until the mass does not change for 120 min, and the components and contents were detected, and the results are shown in Table 13. The water content of the solid bone-derived bio-calcium C before drying was 8%.

[0205] Table 13

[0206]

[0207] According to the above method, the bone-derived bio-calcium was produced using the bone gelatin production waste liquid. According to the calculation of 24 h of treatment per day, the bone gelatin production waste liquid treatment amount was about 1500 tons / day, and the bone-derived bio-calcium production amount was about 120 tons / day.

[0208] Example 4

[0209] The solid bone-derived bio-calcium D was prepared according to the method of Example 1, except that in the protein degradation step, the first grade industrial sodium hypochlorite with a mass concentration of 13% was added to the bone gelatin production waste liquid at 25°C, the gelatin waste liquid:sodium hypochlorite (volume ratio) was 1000:3, and the gelatin waste liquid was fully mixed with the sodium hypochlorite for 30 min to change the macromolecular proteins in the waste liquid into small molecular peptides.

[0210] Each 1 L of bone gelatin production waste liquid can produce 45 g of solid bone-derived bio-calcium D.

[0211] The solid bone-derived bio-calcium D was dried at a temperature of 50°C and a vacuum degree of 7x10 4 Pa until the mass did not change for 120 min, and the components and contents were detected, and the results are shown in Table 14. The water content of the solid bone-derived bio-calcium D before drying was 7.2%.

[0212] Table 14

[0213]

[0214] According to the above method, the bone-derived bio-calcium was produced using the bone gelatin production waste liquid. According to the calculation of 24 h of treatment per day, the bone gelatin production waste liquid treatment amount was about 1500 tons / day, and the bone-derived bio-calcium production amount was about 67.5 tons / day.

[0215] Comparative Example 1

[0216] The solid bone-derived bio-calcium E was prepared according to the method of Example 1, except that the bone gelatin production waste liquid was not subjected to protein degradation and was directly subjected to coagulation and sedimentation.

[0217] Each 1 L of bone gelatin production waste liquid can produce 18 g of solid bone-derived bio-calcium E.

[0218] The solid bone-derived bio-calcium E was dried at a temperature of 50°C and a vacuum degree of 7x10 4Pa, dried until the mass does not change for 120 min, and the components and contents were detected, and the results are shown in Table 15. Among them, the water content of solid bone-derived bio-calcium E before drying was 7.3%.

[0219] Table 15

[0220]

[0221] Test Example 1

[0222] This test example is used to illustrate the use effect of bone-derived bio-calcium on crops sunflower.

[0223] 1 Materials and Methods

[0224] 1.1 Exemplary Materials

[0225] 1.1.1 Exemplary Crops and Varieties: Sunflower, Variety: Gual 316

[0226] 1.1.2 Exemplary Materials: Solid bone-derived bio-calcium prepared in Example 3 (solid bone-derived bio-calcium C), industrial calcium chloride dihydrate (Weifang Haizhiyuan Chemical Co., Ltd.).

[0227] 1.1.3 Exemplary Location, Time, and Soil Nutrient Conditions

[0228] From May 20 to October 25, 2020, this test example was demonstrated in the public village project area of the autonomous region saline-alkali land improvement demonstration project in the Linhe District Baonao Town, and the soil nutrient conditions are shown in Table 16.

[0229] Table 16 Soil Nutrient Content Status Table of Test Demonstration Field

[0230]

[0231] 1.2 Demonstration Design

[0232] A total of three treatments were set up: treatment group 1 (i.e. control group) did not apply any calcium source; treatment group 2 applied bone-derived bio-calcium; treatment group 3 applied industrial calcium chloride (industrial calcium chloride dihydrate). The total area was 30 mu, and the area of each treatment plot was 10 mu. The test did not set up repetitions,

[0233] 1.3 Application Method

[0234] Treatment group 1 (control group): directly after the rotary land, harrow, ridge, and sow. The demonstration field cultivation management measures and water and fertilizer management measures were synchronized and consistent with the local field. Sunflower was sown on May 25, and the sowing plant number was 1800 plants / mu.

[0235] Treatment group 2 (application of bone source biological calcium): Bone source biological calcium is applied to the soil by large-scale spraying machine before spring ploughing, 50 kg per mu, followed by rotary ploughing, harrowing, ridging and sowing. The demonstration field cultivation management measures and water and fertilizer management measures are synchronized and consistent with local fields. Sunflower is sown on May 25, with 1800 plants per mu.

[0236] Treatment group 3 (application of industrial calcium chloride dihydrate): Industrial calcium chloride dihydrate is applied to the soil by large-scale spraying machine before spring ploughing, 50 kg per mu, followed by rotary ploughing, harrowing, ridging and sowing. The demonstration field cultivation management measures and water and fertilizer management measures are synchronized and consistent with local fields. Sunflower is sown on May 25, with 1800 plants per mu.

[0237] 2 Demonstration results and analysis

[0238] 2.1 Demonstration results

[0239] 2.1.1 Effect of application of bone source biological calcium on relevant observation indicators of sunflower at each growth stage

[0240] During the growth period of sunflower, the application effect of each treatment was studied through field sampling investigation and fixed-point observation, and the specific content is shown in Table 17.

[0241] Table 17 Determination of various indicators of sunflower at each growth stage

[0242]

[0243]

[0244] Note: The data in the table are the average values of each treatment, and the end of each column data with the same letter indicates that there is no significant difference (DMRT method, p=0.05).

[0245] [1] The determination method of seedling survival rate is: when the average height of sunflower reaches 13-15 cm, 5 test points are randomly selected for each treatment group, the test area of each point is 3 m 2 , the existing plant number is determined, and the existing plant number per mu of each treatment group is calculated. The seedling survival rate calculation formula is: seedling survival rate (%) = existing plant number per mu ÷ sown plant number per mu.

[0246] [2] The determination method of soil bulk density is: soil bulk density is determined at each treatment group at the present budding stage, and the detection method is NY / T 1121.4-2006.

[0247] [3] The determination method of chlorophyll content is: at the full flowering stage, 3 test points are randomly selected for each treatment group, 5 plants are selected for each test point, and the chlorophyll content (SPAD value) of the upper 3 functional leaves of each plant is determined. The instrument used is TYS-4N chlorophyll meter.

[0248] From the main indicators of sunflower growth period, compared with the control group, the application of bone source biological calcium can improve the seedling survival rate of sunflower, and the difference is significant; the soil bulk density decreases significantly at the present budding stage; the chlorophyll content of sunflower leaves increases significantly at the full flowering stage. Compared with the application of industrial calcium chloride dihydrate, the seedling survival rate and the reduction range of soil bulk density are significantly different at the same period after the application of bone source biological calcium, and the chlorophyll content also increases significantly.

[0249] 2.1.2 Effect of bone source biological calcium on sunflower yield

[0250] Before the sunflower is harvested, the yield of each treatment is measured, and the "Z" type five-point random sampling is used to measure the number of plants per mu (the same as the method of measuring seedling survival rate), 5 plants are taken from each point, and the number of seeds per plate and the hundred seed weight are measured, and the theoretical yield of each treatment is calculated according to the measurement results.

[0251] Calculation formula: yield per mu = number of seeds per plate x hundred seed weight x number of plants per mu x 10 -5 x 0.8

[0252] The analysis of sunflower yield is shown in Table 18.

[0253] Table 18 Sunflower yield results

[0254]

[0255] Note: The data in the table is the average value of each treatment, and the end of the yield per mu data with the same letter indicates that there is no significant difference (DMRT method, p=0.05).

[0256] As shown in Table 18, the yield of sunflower is significantly increased after the application of bone source biological calcium. Compared with the control group, the hundred seed weight and yield of sunflower are increased by 2.56g and 89.88kg respectively, and the yield increase is 13.35% and 50.52% respectively; compared with the application of industrial calcium chloride dihydrate, the hundred seed weight and yield of sunflower are increased by 1.94g and 69.2g respectively, and the yield increase is 9.8% and 34.8% respectively.

[0257] 2.2 Benefit analysis

[0258] The economic benefit (only considering the fertilizer input) and the comparison results between treatments are shown in Table 19.

[0259] Table 19 Economic benefit analysis

[0260]

[0261] Note: The price of sunflower in 2020 is calculated according to the quality of fur and hair, and the income per mu does not include the cost (including labor cost, water and electricity cost, fertilizer, seed, pesticide cost, etc.), which is a relative value.

[0262] As can be seen from Table 19, the application of bone source biological calcium can increase yield and income, with a yield of 267.79 kg per mu, a price increase of 1.2 yuan / kg, an increase of 496.6 yuan per mu compared with the control, and a significant increase in income.

[0263] Similar yield-increasing effects were also obtained using the solid bone source biological calcium prepared in Examples 1 and 2.

[0264] Test Example 2

[0265] 1. Basic situation of test site

[0266] 1.1 Test site: Chankeng Village, Xiaoxi Town, Pinghe County, Fujian Province

[0267] 1.2 Landform type: mountainous

[0268] 1.3 Soil type and soil texture: lateritic red soil, medium soil

[0269] 1.4 Test conditions: open-air planting

[0270] 1.5 Implementing unit: Pinghe Maye Fruit Co., Ltd.

[0271] 1.6 Test time: April 2, 2022 to May 3, 2022

[0272] 2. Test materials

[0273] 1.1 Test crop: pomelo, variety Sanhongmiyu, tree age 12 years.

[0274] 1.2 Test fertilizer: solid bone source biological calcium of Example 1 (solid bone source biological calcium A).

[0275] 3. Test design

[0276] 3.1 Test treatment: a total of two treatments, treatment 1 is the control group without application of bone source biological calcium; treatment 2 is the application of bone source biological calcium 0.25 kg / plant.

[0277] 3.2 Field design: a total area of 12 mu, two plots are set up, the area of plot 1 of treatment 1 is 2 mu; the area of plot 2 of treatment 2 is 10 mu; the application of fertilizer and the amount of fertilizer of each plot are shown in Table 20.

[0278] Table 20

[0279]

[0280]

[0281] 4. Fertilization method and time

[0282] 4.1 Fertilization method: treatment 2 uses 0.25 kg per tree, and is diluted 150-200 times for irrigation; treatment 1 (control group) is irrigated with the same amount of water.

[0283] 4.2 Fertilization time: April 5, 2022

[0284] 5 Test results

[0285] 5.1 Effect on leaf thickness and chlorophyll

[0286] Measurement method: randomly select 3 test points in each plot, select 3 trees in each test point, and measure the leaf thickness and chlorophyll content (SPAD value) of 30 functional leaves in the same part of each tree. The instrument used is LS-4 leaf thickness detector and TYS-4N chlorophyll meter. The measurement results are shown in Table 21.

[0287] 5.2 Effect on fruit setting rate

[0288] Measurement method: randomly select 3 test points in each plot, select 3 trees in each test point, and measure the number of fruits of each tree. The measurement results are shown in Table 21.

[0289] Table 21

[0290]

[0291] Note: The data in the table are the average values of 3 test points. The end of each column of data with the same letter indicates that there is no significant difference (DMRT method, p = 0.05).

[0292] The test results show that compared with the control group, after using bone-derived biological calcium, the leaf thickness, chlorophyll content and fruit number of pomelo are significantly improved, the leaf thickness is increased by 11.1%, the chlorophyll content is increased by 9.9%, and the fruit setting rate is increased by 32.3%.

[0293] The solid bone-derived biological calcium prepared in Examples 2 and 3 also has similar yield-increasing effects.

[0294] Test Example 3

[0295] This test example is used to illustrate the effect of the fertilizer prepared by the present application using solid bone-derived biological calcium as raw material.

[0296] Medium-element water-soluble fertilizer A1 preparation: (1) Components: 500 kg of solid bone-derived biological calcium (solid bone-derived biological calcium C) of Example 3 and 300 kg of amino acid solid raw material (purchased from Xuzhou Futian Technology Co., Ltd., detection standard No. NY1429-2010) by weight;

[0297] (2) The components in step (1) are added to a reaction kettle, then water is added to 1000 liters, stirred and heated to 95°C, and kept for 40 minutes to obtain the medium element water-soluble fertilizer A1.

[0298] The prepared medium element water-soluble fertilizer A1 is detected, and the results are shown in Table 22. Among them, the calcium content, magnesium content, zinc content, boron content, water-insoluble content, and pH value are detected according to the technical indicators of liquid products of medium element water-soluble fertilizer in the Agricultural Industry Standard of the People's Republic of China NY2266-2012; the nitrogen content is detected according to the distillation titration method in NY / T 1977-2010; and the potassium content is detected according to the method specified in NY / T 1977-2010.

[0299] Table 22

[0300] Water soluble fertilizer with medium amount of elements A1 Standard Calcium (Ca), g / L 102 ≥100 Nitrogen (N), g / L 23.4 - Potassium (K2O), g / L 0.3 - Zinc (Zn), g / L 0.01 - Boron (B), g / L 0.002 - Water insoluble content, g / L ≤50 ≤50 pH (1 :250 dilution) 4.6 3.0-9.0

[0301] The content of amino acid in the medium element water-soluble fertilizer is detected according to the method specified in NY / T 1975, and the results show that the content of amino acid in the medium element water-soluble fertilizer A1 is 129 g / L.

[0302] 1 Test materials and methods

[0303] 1.1 Test fertilizers

[0304] Medium element water-soluble fertilizer A1

[0305] Amino acid-containing water-soluble fertilizer (produced by Sinofert Holdings Limited, Ca≥140 g / L, amino acid≥100 g / L)

[0306] Compound fertilizer (produced by Haifa Chemicals Ltd. (China) Chemical Group Co., Ltd., N, P2O5, K2O content is 12-6-42)

[0307] 1.2 Test crops: tomatoes.

[0308] 1.3 Test conditions: greenhouse cultivation.

[0309] 1.4 Test site: Inner Mongolia Green Energy Agricultural Science and Technology Demonstration Park in Baheaotian Town, Xincheng District, Hohhot City.

[0310] 1.5 Implementing unit: College of Grassland and Resource Environment, Inner Mongolia Agricultural University.

[0311] 1.6 Test time: June 1, 2021-November 17, 2021.

[0312] 2 Test design

[0313] 2.1 Plot design

[0314] The experiment adopts single factor complete random design, the experiment has 7 treatments, each treatment sets 3 times repeats random distribution, namely sets 21 test plots. The test plot area is 23.4m 2 (9m long 2.6m wide), each plot plants 2 rows of tomatoes, the transplanting density is 1140 plants / mu, the row spacing is 130cm, and the plant spacing is 45cm. The planting row starts trapezoidal ridge (0.4m high, 0.3m wide at the top, 0.8m wide at the bottom) to prevent the fertilizer and water from flowing horizontally between the test plots.

[0315] 2.2 Fertilization treatment

[0316] The fertilization amount of each time of the middle element water-soluble fertilizer A1 and the water-soluble fertilizer containing amino acid is set to 3 gradient treatments, that is, the conventional fertilization amount 5kg / (time·mu), 2 times fertilization amount 10kg / (time·mu), and 3 times fertilization amount 15kg / (time·mu). A control (CK) treatment is set, and the control fertilization amount is 0kg / (time·mu). No base fertilizer is applied in each treatment, and compound fertilizer (12-6-42) is applied twice from 3cm to the top fruit discoloration, and the amount of each treatment is 15kg / (time·mu). Other production management measures adopt the local conventional management method.

[0317] 7 treatments are set: ① the conventional fertilization amount of the middle element water-soluble fertilizer A1; ② 2 times fertilization amount of the middle element water-soluble fertilizer A1; ③ 3 times fertilization amount of the middle element water-soluble fertilizer A1; ④ the conventional fertilization amount of the water-soluble fertilizer containing amino acid; ⑤ 2 times fertilization amount of the water-soluble fertilizer containing amino acid; ⑥ 3 times fertilization amount of the water-soluble fertilizer containing amino acid; and ⑦ control (irrigation water).

[0318] 3 Fertilization method and fertilization time

[0319] 3.1 Fertilization method

[0320] It is applied into the soil in the form of drip irrigation, and the irrigation water amount of each plot in each experiment is controlled to be consistent according to the water meter data.

[0321] 3.2 Fertilization time

[0322] The fertilization time of each treatment is shown in Table 23.

[0323] Table 23

[0324]

[0325] 4 Test data determination and sampling

[0326] Yield determination: 10 tomato plants were randomly selected for calibration in each plot. The mature tomatoes of the calibration tomato plants were all picked and weighed during each yield measurement. The yield of each plant was recorded. The yield was measured six times during the whole growth period of the tomato, on August 7, 2021 (first time), August 24, 2021 (second time), August 31, 2021 (third time), September 7, 2021 (fourth time), September 25, 2021 (fifth time), and October 16, 2021 (sixth time).

[0327] Sugar determination: 10 tomatoes were randomly selected for sugar determination after the yield measurement and weighing in each plot. The number of sugar determination and the time were consistent with the number of yield measurement and the time. The method of sugar determination was as follows: the juice obtained from the same part of the mature tomato fruits was dropped into the calibrated PAL-1 digital sugar meter (Japan ATAGO, measurement accuracy: sugar Brix: ±0.2%), and the sugar content of the tomato fruits was determined.

[0328] 5Results and analysis

[0329] 5.1Effect on tomato yield

[0330] The results of the six yield measurements are shown in Table 24 (effect of each treatment on tomato yield). The test results show that (1) compared with the control, the application of medium element water-soluble fertilizer A1 and amino acid-containing water-soluble fertilizer can increase the yield by 8.8%-49.6%.(2) Compared with the amino acid-containing water-soluble fertilizer, the medium element water-soluble fertilizer A1 has more obvious effect on promoting growth and increasing yield. The yield of the 1-fold, 2-fold and 3-fold amount of medium element water-soluble fertilizer A1 is increased by 26.54%, 7.41% and 1.15% respectively compared with the corresponding treatment of amino acid-containing water-soluble fertilizer.(3) The yield of different fertilizer treatments of medium element water-soluble fertilizer A1 is higher than that of the control without fertilizer by 1566 kg / mu, 1862 kg / mu and 2061 kg / mu respectively. According to the average tomato purchase price of 3 yuan / kg in Hohhot greenhouse area, the added value per mu is 4698 yuan, 5586 yuan and 6183 yuan respectively.

[0331] Table 24

[0332]

[0333]

[0334] Note: The end of each column data with the same letter indicates no significant difference (DMRT method, p=0.05).

[0335] The linear plus plateau model was used to fit the fertilizer effect of applying medium element water-soluble fertilizer A1 and applying amino acid-containing water-soluble fertilizer, and the fitting results are as follows:Figure 4 The fitting results show that the recommended application amounts of the medium element water-soluble fertilizer A1 and the water-soluble fertilizer containing amino acid are 6.26 kg / (time·mu) and 14.61 kg / (time·mu) respectively, and the corresponding yields are 53.67 kg / 10 plants and 53.92 kg / 10 plants respectively. Compared with the water-soluble fertilizer containing amino acid, the medium element water-soluble fertilizer A1 can reduce the application amount of the water-soluble fertilizer containing amino acid by 8.12 kg / (time·mu) when the yield (53.67 kg / 10 plants) is achieved at the recommended application amount, and the reduction is 56.5%.

[0336] As can be seen from Example 1 and Example 4, when the volume ratio of the material to be degraded to protein and sodium hypochlorite is within the preferred range, the bone-derived biological calcium prepared has the chelated peptide calcium content increased by 2.75 times and the small molecule peptide increased by 2.75 times. As can be seen from Example 1 and Comparative Example 1, the bone-derived biological calcium prepared by degrading the bone gelatin production waste liquid has the chelated peptide calcium content increased by 4.5 times and the small molecule peptide content increased by 5.5 times.

[0337] The above describes the preferred embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including various technical features combined in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and belong to the protection scope of the present application.

Claims

1. A method for preparing bone-derived bio-calcium, characterized in that, The method includes: The waste liquid from bone gelatin production is subjected to insoluble removal, protein degradation, and membrane separation to obtain a liquid containing bone-derived bio-calcium. The removal of insoluble matter is at least one of coagulation sedimentation, flotation, and filtration. The protein degradation is performed by at least one of chemical, physical, and biological methods, wherein the protein degradation causes proteins with a molecular weight greater than or equal to 10,000 Da in the degraded material to be degraded into small molecule peptides with a molecular weight less than 10,000 Da; the membrane used in the membrane separation is a separation membrane, and the separation membrane has a molecular weight cutoff greater than or equal to 10,000 Da. The waste liquid from the bone gelatin production has a pH of 3.5-7, a Ca content of 10000-28000 mg / L, a Cl content of 18000-50000 mg / L, a CODcr content of 2000-10000 mg / L, a crude protein content of 500-7000 mg / L, a fat content of 0-90 mg / L, and a content of macro- and micro-elements other than Ca and Cl of 0-3000 mg / L, wherein the macro- and micro-elements are at least one of P, K, Mg, S, Cu, Fe, Mn, Zn, B, and Mo.

2. The method according to claim 1, wherein, The method further includes: concentrating the liquid containing bone-derived bio-calcium to a total dissolved solids content of 8-80 wt%.

3. The method according to claim 2, wherein, The liquid containing bone-derived bio-calcium is concentrated to a total dissolved solids content of 15-80 wt%.

4. The method according to claim 2, wherein, The concentration is a membrane concentration and / or evaporation.

5. The method according to claim 4, wherein, The membrane used for membrane concentration is a concentration membrane.

6. The method according to claim 5, wherein, The concentration membrane is a reverse osmosis membrane.

7. The method according to claim 1, wherein, The coagulation and sedimentation process includes: adjusting the pH value of the material to be coagulated and sedimented, and mixing the coagulant and flocculant with the material to be coagulated and sedimented.

8. The method according to claim 7, wherein, The coagulant is an inorganic coagulant, and the flocculant is polyacrylamide.

9. The method according to claim 8, wherein, The inorganic coagulant is at least one of aluminum sulfate, polyaluminum chloride, polyferric sulfate, ferric chloride, and ferrous sulfate.

10. The method according to claim 8, wherein, Polyacrylamide includes at least one of anionic polyacrylamide, cationic polyacrylamide, and nonionic polyacrylamide.

11. The method according to claim 1, wherein, The chemical method is the sodium hypochlorite decomposition method: at 10-50℃, sodium hypochlorite is mixed with the material to be degraded for 10-60 minutes, the amount of sodium hypochlorite used is 0.1-1 g / L, and the mass concentration of the sodium hypochlorite solution is 5-13%.

12. The method according to any one of claims 1-11, wherein, The Ca content in the bone gelatin production waste liquid is 15000-25000 mg / L; And / or, the Cl content in the bone gelatin production waste liquid is 28000-50000 mg / L.

13. The method according to any one of claims 1-11, wherein, The method includes: (a-1) Protein degradation was carried out on the waste liquid from bone gelatin production to obtain protein degradation liquid a; (a-2) Remove insoluble matter from the protein degradation solution to obtain the first solid a and the first liquid a; (a-3) The first liquid a is subjected to membrane separation to obtain clear liquid a and concentrated liquid a; And / or, the method includes: (b-1) Remove insoluble substances from the bone gelatin production waste liquid to obtain a first solid b and a first liquid b; (b-2) The first liquid b is subjected to protein degradation to obtain protein degradation solution b; (b-3) The protein degradation solution b is separated by membrane separation to obtain clear solution b and concentrated solution b; And / or, the method includes: (c-1) Remove insoluble substances from the bone gelatin production waste liquid to obtain a first solid c and a first liquid c; (c-2) The first liquid c is subjected to membrane separation to obtain clear liquid c and concentrated liquid c; (c-3) The concentrated solution c is subjected to protein degradation to obtain protein degradation solution c. The protein degradation solution c is returned to the membrane separation to obtain clear solution c.

14. Bone-derived bio-calcium obtained by the method of any one of claims 1-13.

15. The application of the method according to any one of claims 1-13 in the treatment of bone gelatin production wastewater.

16. The use of the bone-derived bio-calcium of claim 14 in improving crop yield and / or quality.

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