Water-soluble fertilizer composition containing medium-quantity elements, preparation method of water-soluble fertilizer containing medium-quantity elements and its application

Abstract

This invention relates to the field of medium-element water-soluble fertilizers, and discloses a medium-element water-soluble fertilizer composition, a method for preparing the medium-element water-soluble fertilizer, and its applications. The medium-element water-soluble fertilizer composition contains bone-derived bio-calcium, a nutritional chelating agent, and optional nutrient adjuvants; wherein, on a dry basis, the mass ratio of the bone-derived bio-calcium:nutritive chelating agent:nutrient adjuvant is 25-50:10-40:0-25. The medium-element water-soluble fertilizer disclosed in this invention exhibits synergistic effects among its components, further improving crop yield and quality. Compared to other existing water-soluble fertilizers commonly used for calcium supplementation in crops, it can further increase fruit fresh weight, calcium accumulation, yield, and quality, and can also control various physiological diseases in crops.

Description

Technical Field

[0001] This invention relates to the field of water-soluble fertilizers containing medium-quantity elements, specifically to a water-soluble fertilizer composition containing medium-quantity elements, a method for preparing the water-soluble fertilizer containing medium-quantity elements, and its application. Background Technology

[0002] The production of gelatin from animal bones generates a large amount of wastewater, known as bone gelatin production waste liquid. If not properly utilized, this not only leads to a massive waste of social resources but also causes serious pollution to the social and ecological environment.

[0003] With the increase in crop multiple cropping index and yield in my country, coupled with the decrease in organic fertilizer use and the increase in phosphate fertilizer (phosphate ions) use, micronutrients in the soil have become a major obstacle to further improving crop yield and quality. Medium-element water-soluble fertilizers are a type of water-soluble fertilizer, referring to fertilizers with calcium and / or magnesium as the main components. Medium-element water-soluble fertilizers are classified into solid and liquid forms. With the development of facility agriculture and intensive land use in my country, fertigation technology has also developed rapidly, leading to an increasing demand for water-soluble fertilizers in agricultural production.

[0004] Currently, there is no existing technology for treating bone gelatin production wastewater to make it usable in fertilizers, nor is there any existing technology for preparing fertilizers using the treated products of bone gelatin production wastewater. Therefore, there is a huge market demand and broad application prospects for treating bone gelatin production wastewater to obtain raw materials that can be used to prepare water-soluble fertilizers containing medium-element components. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems existing in the prior art and provide a medium-element water-soluble fertilizer composition, a method for preparing the medium-element water-soluble fertilizer, and its applications. The medium-element water-soluble fertilizer of this invention has significant fertilizing effects on a variety of crops under different regions and environmental conditions; both rhizosphere application and foliar spraying can improve crop yield and quality.

[0006] To achieve the above objectives, the first aspect of the present invention provides a medium-element water-soluble fertilizer composition, the composition containing bone-derived bio-calcium, a nutritional chelating agent, and optional nutrient element adjuvants;

[0007] The mass ratio of bone-derived biological calcium, nutritional chelating agent, and nutritional element adjuvant, on a dry basis, is 25-50:10-40:0-25.

[0008] A second aspect of the present invention provides a method for preparing a water-soluble fertilizer containing medium-quantity elements, the method comprising: mixing bone-derived bio-calcium, a nutritional chelating agent, and optional nutrient element adjuvants under chelation conditions.

[0009] A third aspect of the present invention provides a water-soluble fertilizer containing medium-quantity elements prepared by the method described above.

[0010] The fourth aspect of this invention provides the application of bone gelatin production waste liquid in the preparation of water-soluble fertilizers containing medium-quantity elements.

[0011] The fifth aspect of this invention provides the application of the medium-element water-soluble fertilizer as described above in agricultural production.

[0012] Through the above technical solutions, the medium-element water-soluble fertilizer of the present invention, in addition to the medium elements specified in the prior art, also contains macro-elements, micro-elements, and water-soluble organic nutrients required for plant growth. A considerable portion of the micro-elements and organic nutrients are derived from animal sources. Compared with the existing traditional compound fertilizers using macro-elements, it can further improve the yield and quality of crops. The medium-element water-soluble fertilizer of the present invention contains chelates of micro-elements required for plant growth. With the synergistic effect among the components, compared with other water-soluble fertilizers commonly used for calcium supplementation in crops, it can further improve the fresh weight of fruits, calcium accumulation, yield, and quality of crops.

[0013] Furthermore, the inventors discovered that water-soluble fertilizers containing medium-element nutrients prepared using bone-derived bio-calcium as a raw material have high fertilizer efficiency and can increase crop yields. The water-soluble fertilizer of this invention combines bone-derived bio-calcium, a nutrient chelating agent, and optional nutrient adjuvants. The components have synergistic effects, which can further improve crop yields and quality in agricultural production applications and effectively control various physiological diseases of multiple crops. Attached Figure Description

[0014] Figure 1 This is a fitted graph showing the effect of applying medium-element water-soluble fertilizer A1 and amino acid-containing water-soluble fertilizer on tomato yield in Test Example 3. Detailed Implementation

[0015] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0016] The first aspect of the present invention provides a medium-element water-soluble fertilizer composition, the composition containing bone-derived bio-calcium, a nutritional chelating agent, and optional nutrient element adjuvants;

[0017] The mass ratio of bone-derived biological calcium, nutritional chelating agent, and nutritional element adjuvant, on a dry basis, is 25-50:10-40:0-25.

[0018] In some embodiments of the present invention, the bone-derived bio-calcium may be in the form of liquid bone-derived bio-calcium or solid bone-derived bio-calcium.

[0019] In this invention, the term "nutrient element" refers to elements essential for plant growth and / or beneficial elements that have a positive effect on plant growth. In some embodiments of this invention, the nutrient element is at least one selected from nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), iron (Fe), boron (B), manganese (Mn), zinc (Zn), copper (Cu), molybdenum (Mo), silicon (Si), cobalt (Co), vanadium (V), rare earth elements (RE), titanium (Ti), and nickel (Ni). Specifically, N, P, K, Ca, Mg, Fe, B, Mn, Zn, Cu, and Mo are elements among the 16 essential elements for plant growth, while Si, Co, V, RE, Ti, and Ni are beneficial elements that have a positive effect on plant growth.

[0020] In some embodiments of the present invention, the nutrient element in the nutrient element additive is at least one selected from nitrogen (N), phosphorus (P), potassium (K), iron (Fe), boron (B), manganese (Mn), zinc (Zn), copper (Cu), molybdenum (Mo), silicon (Si), cobalt (Co), vanadium (V), rare earth elements (RE), titanium (Ti), and nickel (Ni).

[0021] In some embodiments of the present invention, the nutrient element in the nutrient element adjuvant is at least one selected from nitrogen, potassium, zinc, and boron. That is, the nutrient element adjuvant is at least one selected from a nitrogen source, potassium source, zinc source, and boron source. In some embodiments of the present invention, the nitrogen source is urea. In some embodiments of the present invention, the potassium source is potassium nitrate and / or potassium chloride. In some embodiments of the present invention, the zinc source is zinc nitrate and / or zinc chloride. In some embodiments of the present invention, the boron source is borax. Preferably, the nutrient element adjuvant is at least one selected from urea, potassium nitrate, potassium chloride, zinc nitrate, zinc chloride, and borax.

[0022] In some embodiments of the present invention, those skilled in the art can make corresponding adjustments to the nutrient elements in the nutrient element adjuvant according to the actual growth needs of the crop. For example, the zinc or boron in the nutrient element adjuvant can be adjusted to other trace elements such as molybdenum, manganese, and iron, and / or beneficial elements such as silicon, cobalt, vanadium, rare earth elements, titanium, and nickel.

[0023] In this invention, there are no special requirements for the urea, potassium nitrate, zinc chloride, and borax, as long as they meet the national agricultural grade standards.

[0024] In some embodiments of the present invention, the mass ratio of the bone-derived bio-calcium to the nutritional chelating agent in the composition, on a dry basis, is 25-50:10-40 (e.g., 0.625, 0.7, 0.75, 1, 1.25, 1.5, 1.75, 2, 2.25, 2.5, 2.75, 3, 3.25, 3.5, 3.75, 4, 4.25, 4.5, 4.75, 5 or any value between the above values).

[0025] In some embodiments of the present invention, the mass ratio of the bone-derived bio-calcium to the nutrient element adjuvant in the composition, on a dry basis, is 25-50:0-25 (such as 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 7.5, 10, 12.5, 15, 17.5, 20, 25, 30, 35, 40, 45, 50 or any value between the above values).

[0026] In some embodiments of the present invention, the content of the optional nutrient element adjuvant is 0-25 wt% on a dry basis, based on the total weight of the composition. In some embodiments of the present invention, the content of the nitrogen source is 0-20 wt% on a dry basis, based on the total weight of the composition. The content of the potassium source is 0-20 wt% on a dry basis, based on the total weight of the composition. The content of the zinc source is 0-3 wt% on a dry basis, based on the total weight of the composition. The content of the boron source is 0-3 wt% on a dry basis, based on the total weight of the composition.

[0027] In some embodiments of the present invention, the content of the bone-derived bio-calcium is 50-70 wt% on a dry basis, based on the total weight of the composition. For example, it can be any one of 50 wt%, 52 wt%, 54 wt%, 56 wt%, 58 wt%, 60 wt%, 62 wt%, 64 wt%, 66 wt%, 68 wt%, 70 wt%, or a value within a range of any two of the above values.

[0028] In some embodiments of the present invention, the content of the nutritional chelating agent is 15-40 wt% on a dry basis, based on the total weight of the composition. For example, it can be any one of 15 wt%, 17 wt%, 19 wt%, 21 wt%, 23 wt%, 25 wt%, 27 wt%, 29 wt%, 31 wt%, 33 wt%, 35 wt%, 37 wt%, 39 wt%, 40 wt%, or a value within a range of any two of the above values.

[0029] In some embodiments of the present invention, to further enhance the fertilizer efficacy of the prepared medium-element water-soluble fertilizer, the nutrient chelating agent is an amino acid and / or fulvic acid. Preferably, the nutrient chelating agent is an amino acid; there are no special requirements for the amino acid, as long as it meets the national agricultural grade standard. Preferably, the amino acid is at least one of plant-derived amino acids and / or animal-derived amino acids. The amino acid can be commercially available; for example, solid amino acid raw materials from Xuzhou Weitian Technology Co., Ltd., with testing standard number NY1429-2010, can be used.

[0030] In some embodiments of the present invention, the bone-derived bio-calcium contains a calcium source (Ca) and water-soluble organic matter;

[0031] Wherein, on a dry basis, the mass ratio of calcium source to water-soluble organic matter in the bone-derived bio-calcium (calculated as elemental calcium) is 7-26:1-8 (e.g., 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).

[0032] The calcium source exists in the form of free calcium and chelated peptide calcium.

[0033] In some embodiments of the present invention, the bone-derived bio-calcium contains 7-26 wt% calcium source on a dry basis, for example, any one of the following values ​​or a range of any two of the above: 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%, and 26 wt%.

[0034] In some embodiments of the present invention, the bone-derived bio-calcium contains 1-8 wt% water-soluble organic matter on a dry basis. For example, it can be any one of 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 of any two of the above values.

[0035] In this invention, the bone-derived bio-calcium refers to a product containing specific small-molecule peptides and a calcium source. This bone-derived bio-calcium is produced from high-calcium, high-chlorine, and high-organic wastewater discharged during bone gelatin production. The process involves coagulation and sedimentation, membrane separation, and protein degradation to obtain a bone-derived bio-calcium solution, followed by concentration and granulation to prepare a liquid or solid (granular or powdered) product. The main nutrients in this product are derived from animal bones, and it contains small-molecule peptides, making it a bio-based substance with biological activity, which is more easily absorbed and utilized by crops. It should be understood that the bone-derived bio-calcium of this invention is a mixture, containing not only a calcium source but also chlorine, water-soluble organic matter, and other components. Preferably, the bone-derived bio-calcium of this invention also contains macro- and micronutrients required by plants, in addition to Ca and Cl.

[0036] In this invention, unless otherwise specified, the content of the calcium source refers to the total content of free calcium and chelated peptide calcium, calculated as elemental calcium (Ca). The method for detecting the content of the calcium source (calculated as elemental calcium) is GB / T 6436-2018, ethylenediaminetetraacetic acid disodium complexometric titration method.

[0037] In this invention, the water-soluble organic matter refers to the total organic matter in bone-derived biological calcium that can be completely dissolved in water, and the detection method for the content of the water-soluble organic matter is NY / T1976-2010.

[0038] In some embodiments of the present invention, the content of free calcium in the bone-derived bio-calcium is 7-25 wt% and the content of chelated peptide calcium is 0.5-4 wt%, calculated on a dry basis, based on elemental calcium.

[0039] In this invention, the method for detecting the free calcium content (calculated as elemental calcium) is as follows: After preparing a free calcium solution according to Chapter 4, Section 2.2, Determination of Chelation Rate, of the master's thesis "Enzymatic Preparation and Peptide-Calcium Chelation Study of Sheep Bone Collagen Peptide" published by Shanxi Agricultural University, the free calcium content is detected by the disodium ethylenediaminetetraacetate complexometric titration method (GB / T 6436-2018).

[0040] In this invention, the method for detecting the calcium content (calculated as elemental calcium) of the chelated peptide is as follows: calcium content (calculated as elemental calcium) = calcium source content (calculated as elemental calcium) - free calcium content (calculated as elemental calcium).

[0041] In some embodiments of the present invention, the bone-derived bio-calcium further contains Cl, and the Cl content in the bone-derived bio-calcium is 11-45 wt% on a dry basis. The method for detecting the Cl content in the bone-derived bio-calcium is GB / T 24890-2010.

[0042] In some embodiments of the present invention, the bone-derived bio-calcium also contains macro- and micro-elements other than Ca and Cl. On a dry basis, the bone-derived bio-calcium contains 0-3 wt% of macro- and micro-elements other than Ca and Cl; 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 content of magnesium in the bone-derived bio-calcium is expressed as Mg, and the content of sulfur is expressed as S. The detection methods for magnesium and sulfur content are NY / T1117-2010. The content of copper is expressed as Cu, the content of iron is expressed as Fe, the content of manganese is expressed as Mn, the content of zinc is expressed as Zn, and the content of molybdenum is expressed as Mo. The detection methods for copper, iron, manganese, zinc, and molybdenum content are NY / T 1974-2010. The content of phosphorus is expressed as P2O5, and the detection method for phosphorus content is NY / T1977-2010. The content of potassium is expressed as K2O, and the detection method for potassium content is GB / T 17767.3-2010.

[0043] In some preferred embodiments of the present invention, the Mg content in the bone-derived bio-calcium is ≥0.55wt% on a dry basis.

[0044] In this invention, the macro- and micro-elements other than Ca and Cl are also essential for plant growth. Therefore, when the bone-derived bio-calcium is used as a fertilizer or fertilizer raw material, it can further supplement the nutrients of crops and promote crop growth.

[0045] In some embodiments of the present invention, the water-soluble organic matter contains small molecule peptides, and the bone-derived bio-calcium contains 0-4 wt% small molecule peptides on a dry basis.

[0046] In some embodiments of the present invention, the molecular weight of the small molecule peptide is <10000 Da, preferably 500-5000 Da, more preferably 500-3000 Da, more preferably 700-2000 Da, and even more preferably 700-1500 Da. The inventors have found that when the bone-derived bio-calcium contains small molecule peptides with the above-mentioned molecular weights, the proportion of chelated peptide calcium in the bone-derived bio-calcium increases, while maintaining the peptide's effect on increasing plant yield.

[0047] In this invention, the method for detecting the content and molecular weight of small molecule peptides is as follows: the molecular weight of small molecule peptides is detected by Appendix A (high performance size exclusion chromatography) of GB 31645-2018, and the content of small molecule peptides is detected by the method for determining protein content of GB / T 6432-2018.

[0048] In this invention, the bone-derived bio-calcium also contains unavoidable impurities and water of crystallization.

[0049] In this invention, the bone-derived bio-calcium can be in the form of liquid and / or solid, that is, it can be liquid bone-derived bio-calcium and / or solid bone-derived bio-calcium.

[0050] In this invention, the dosage form of the solid bone-derived bio-calcium can be conventionally selected in the art, for example, it can be at least one of granules, powder, and tablets.

[0051] In some embodiments of the present invention, the pH value of the bone-derived bio-calcium is 5.5-6.5. The method for detecting the pH value of the bone-derived bio-calcium is as follows: the bone-derived bio-calcium is diluted with water at a mass ratio of 1:250, and the pH value is detected according to NY / T 1973-2021.

[0052] In this invention, the dry basis of the bone-derived bio-calcium refers to the process of preparing the bone-derived bio-calcium at a temperature of 50°C and a vacuum degree of 7×10⁻⁶. 4 Pa is the amount of water dried in a vacuum oven (the vacuum drying oven was purchased from Shanghai-Heng Scientific Instruments Co., Ltd., DZF series) for 120 minutes without any change in mass.

[0053] In some embodiments of the present invention, when the bone-derived bio-calcium is solid bone-derived bio-calcium, the dry basis refers to the solid bone-derived bio-calcium being heated at 50°C and under a vacuum of 7×10⁻⁶. 4 Pa refers to the amount of solid bone-derived calcium that remains unchanged in mass after being dried in a vacuum oven for 120 minutes. It should be understood that the solid bone-derived calcium before drying is not completely dry and still contains a small amount of free water. The moisture content of the solid bone-derived calcium before drying refers to the content of free water in the solid bone-derived calcium before drying. The moisture content of the solid bone-derived calcium before drying = (mass of solid bone-derived calcium before drying - mass of solid bone-derived calcium after drying) / mass of solid bone-derived calcium before drying. Preferably, the moisture content of the solid bone-derived calcium before drying is 1-10%, and the dry basis content of the solid bone-derived calcium before drying is preferably (1 - moisture content) × 100%.

[0054] The inventors of this invention have discovered that when using the above-mentioned bone-derived bio-calcium, the components in the medium-element water-soluble fertilizer composition have a synergistic effect, and the resulting medium-element water-soluble fertilizer can further improve the yield and quality of crops, and can effectively prevent and control a variety of physiological diseases.

[0055] In some embodiments of the present invention, the bone-derived bio-calcium is prepared by the following method: removing insoluble matter, degrading proteins and separating membranes from bone gelatin production waste liquid to obtain a liquid containing bone-derived bio-calcium;

[0056] The protein degradation process 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.

[0057] The membrane used in the membrane separation is a separation membrane, and the molecular weight cutoff of the separation membrane is greater than or equal to 10,000 Da.

[0058] In some embodiments of the present invention, the method further includes: concentrating the liquid containing bone-derived bio-calcium to a TDS of 8-80 wt% to obtain liquid bone-derived bio-calcium. Herein, TDS refers to the total dissolved solids.

[0059] In this invention, the concentration of the liquid containing bone-derived bio-calcium to a TDS value within the range of any one of 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 22wt%, 25wt%, 28wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, and 80wt%, or any combination of two of the above values. Preferably, the concentration involves concentrating the liquid containing bone-derived bio-calcium to a TDS of 15-80wt%.

[0060] In some embodiments of the present invention, the concentration is membrane concentration and / or evaporation. Preferably, the membrane used for membrane concentration is a concentration membrane, preferably a reverse osmosis membrane, and more preferably an RO reverse osmosis membrane. In the present invention, the conditions and methods of evaporation can be selected using conventional techniques in the art, and will not be elaborated here.

[0061] In some embodiments of the present invention, the concentration is to concentrate the liquid containing bone-derived biogenic calcium to a TDS of 8-15 wt% by membrane concentration.

[0062] In some embodiments of the present invention, the concentration is achieved by evaporation of a liquid containing bone-derived biogenic calcium to a TDS of 15-80 wt%.

[0063] In some preferred embodiments of the present invention, the concentration is performed by first performing membrane concentration, and then evaporating the concentrated material.

[0064] In this invention, the protein degradation process involves converting large protein molecules into small peptides with a target molecular weight. Specifically, the material after protein degradation contains large protein molecules with a molecular weight greater than or equal to 10,000 Da, which are then converted into small peptides with a molecular weight less than 10,000 Da. The target molecular weight is <10,000 Da. The inventors have discovered that protein degradation can further increase the content of chelated peptide calcium in the obtained bone-derived calcium. Compared to bone-derived calcium obtained without protein degradation, the content of chelated peptide calcium (based on elemental calcium) in the bone-derived calcium obtained using protein degradation is 2-9 times higher.

[0065] In some embodiments of the present invention, the protein is degraded by at least one of chemical, physical, and biological methods. Preferably, the protein is degraded by a chemical method, and more preferably by sodium hypochlorite decomposition.

[0066] It should be noted that, unless otherwise specified, in this invention, the molecular weight of the "protein" is greater than or equal to 10,000 Da, and the molecular weight of the "polypeptide", "oligopeptide", and "small molecule peptide" is less than 10,000 Da.

[0067] The inventors discovered in their research that using sodium hypochlorite decomposition can effectively process large protein molecules in the material to be degraded into small peptide molecules of the target molecular weight, thereby increasing the content of chelated peptide calcium in the final bone-derived bio-calcium.

[0068] In some embodiments of the present invention, the sodium hypochlorite decomposition method is as follows: at 10-50°C, sodium hypochlorite is mixed with the material to be degraded for 10-60 minutes.

[0069] In some embodiments of the present invention, the amount of sodium hypochlorite used is 0.1-1g, preferably 0.25-1g, relative to 1L of material to be degraded for protein. When the amount of sodium hypochlorite is within the preferred range, the content of chelated peptide calcium and small molecule peptides in the obtained bone-derived bio-calcium can be further increased.

[0070] In this invention, the sodium hypochlorite can be used in solution form. In some embodiments of this invention, the mass concentration of the sodium hypochlorite solution is 5-13%, and the volume ratio of the material to be degraded 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 degraded to the sodium hypochlorite solution is 1000:5-7, the content of chelated peptide calcium and small molecule peptides in the obtained bone-derived bio-calcium can be further increased.

[0071] In this invention, the membrane separation ensures that the molecular weight of small peptides in the separated material (clarified liquid) is within the target molecular weight range.

[0072] In this invention, unless otherwise specified, "concentrated liquid" or "concentrated liquid" refers to the liquid retained by the membrane, "clear liquid" or "permeate" refers to the liquid that passes through the membrane, that is, the liquid that is not retained by the membrane, and "target molecular weight" refers to <10000 Da.

[0073] In this invention, the term "concentrated membrane" refers to a membrane that separates solvent from the material to be separated. It should be understood that, in some cases, for clarity of expression, "concentrated liquid of the concentrated membrane" or "concentrated liquid of the concentrated membrane" refers to the liquid on one side of the concentrated membrane where the solvent has been separated, while "clear liquid of the concentrated membrane" or "permeate of the concentrated membrane" refers to the liquid on the other side of the concentrated membrane, i.e., the solvent.

[0074] In this invention, the term "separation membrane" refers to a membrane that retains a molecular weight greater than the target molecular weight. It should be understood that, in some cases, for clarity of expression, the terms "concentrate of the separation membrane" and "solidified liquid of the separation membrane" refer to the liquid retained by the separation membrane, while "clarified liquid of the separation membrane" and "permeate of the separation membrane" refer to the liquid not retained by the separation membrane.

[0075] In this invention, the membrane separation uses a separation membrane. When the material to be separated passes through the separation membrane, small molecule peptides with the target molecular weight in the material to be separated are separated into the clear liquid, and the clear liquid obtained is the material after membrane separation.

[0076] In some embodiments of the present invention, the method further includes protein degradation of the concentrate in the separation membrane, and the protein-degraded material (i.e., protein-degraded material) is then separated by the separation membrane.

[0077] In some embodiments of the present invention, the water quality indicators of the clarified liquid from the concentrated membrane can meet the industrial recycled water standards and can be reused as greywater in other processes of gelatin production.

[0078] In some preferred embodiments of the present invention, to reduce the cost of protein degradation, the sequence of membrane separation and protein degradation is as follows: first, the material to be separated is separated using a separation membrane to obtain a concentrate and a supernatant. The concentrate is then used for protein degradation, and the degraded material is then passed through the separation membrane again. In some embodiments of the present invention, the separation membrane can be a single-stage separation membrane with a molecular weight cutoff of 500 Da-10000 Da.

[0079] In some embodiments of the present invention, in order to improve the feasibility of large-scale production and reduce the production cost and efficiency of bone calcium, the separation membrane can be a two-stage separation membrane containing a primary separation membrane and a secondary separation membrane. The molecular weight cutoff of the primary separation membrane is 5000Da-10000Da, and the molecular weight cutoff of the secondary separation membrane is 500Da-3000Da.

[0080] In some embodiments of the present invention, in order to improve the feasibility of large-scale production and reduce the production cost and efficiency of bone calcium, the separation membrane can be a multi-stage separation membrane, which may contain a primary separation membrane, a secondary separation membrane, and a tertiary separation membrane. The molecular weight cutoff of the primary separation membrane is 5000 Da-10000 Da, the molecular weight cutoff of the secondary separation membrane is 500 Da-3000 Da, and the molecular weight cutoff of the tertiary separation membrane is 700 Da-1500 Da.

[0081] In some embodiments of the present invention, the removal of insoluble matter is at least one of coagulation sedimentation, flotation, grating, and filtration, preferably coagulation sedimentation.

[0082] In some embodiments of the present invention, 500 Da ≤ target molecular weight < 10000 Da. Preferably, the target molecular weight is 500 Da-3000 Da. Alternatively, the target molecular weight is 700 Da-2000 Da. Or, the target molecular weight is 700 Da-1500 Da. In the present invention, the range of the target molecular weight can be achieved by the molecular weight cutoff of the membrane and the number of separation membranes (i.e., single-stage separation membrane, two-stage separation membrane, multi-stage separation membrane).

[0083] In some embodiments of the present invention, the coagulation and sedimentation includes: adjusting the pH value of the material to be coagulated and precipitated, mixing the coagulant and flocculant with the material to be coagulated and precipitated, and obtaining the coagulated and precipitated material and sediment. The first liquid is used for subsequent treatment. Preferably, the pH value is 6-11, more preferably 7-10. In this invention, because the bone gelatin production wastewater contains colloidal impurities and inorganic salt ions, and has a low pH, is acidic, and has a high chloride ion concentration, which is unfavorable for coagulating and settling insoluble matter, the present invention adjusts the pH of the water before the coagulation process, solving the problem that high-chlorine, acidic wastewater cannot be coagulated and precipitated.

[0084] In some embodiments of the present invention, the method further includes: performing solid-liquid separation on the precipitate obtained by coagulation and sedimentation to obtain a separated liquid and a separated solid, wherein the separated liquid is returned to the coagulation and sedimentation, and the separated solid is used to produce solid fertilizer, such as bio-organic fertilizer, organic-inorganic compound fertilizer, or compound microbial fertilizer.

[0085] In some embodiments of the present invention, the coagulant is an inorganic coagulant, and is more preferably at least one of aluminum sulfate, polyaluminum chloride, polyferric sulfate, ferric chloride, and ferrous sulfate.

[0086] In some embodiments of the present invention, the flocculant is polyacrylamide, more preferably at least one selected from anionic polyacrylamide, cationic polyacrylamide, and nonionic polyacrylamide. In the present invention, the molecular weight of the polyacrylamide can be a conventional molecular weight in the art, for example, 6-25 million.

[0087] In this invention, the pH adjustment can use conventional reagents in the art, such as at least one of calcium hydroxide and sodium hydroxide, preferably calcium hydroxide.

[0088] In some embodiments of the present invention, the amount of the coagulant is 0.15-0.6g relative to 1L of material to be co-precipitated, and the amount of the flocculant is 0.5-4.5mg.

[0089] In some embodiments of the present invention, the coagulant and flocculant are used in solution form. In some embodiments of the present invention, the mass concentration of the coagulant solution is 10-20%, and the mass concentration of the flocculant solution is 0.5-1.5‰. Specifically, based on the total weight of the material to be coagulated and settled, the amount of coagulant solution added is 1.5-3 wt‰. In some embodiments of the present invention, based on the total weight of the material to be coagulated and settled, the amount of flocculant solution added is 1-3 wt‰.

[0090] In some embodiments of the present invention, the method further includes: drying and granulating the liquid bone-derived bio-calcium to obtain solid bone-derived bio-calcium. In this invention, the drying is a conventional technique in the art, such as at least one of flake drying, spray drying, infrared drying, hot air drying, and microwave drying; the method and conditions are conventionally selected in the art. In this invention, the granulation can be a conventional technique in the art, and will not be elaborated further here.

[0091] In this invention, the bone gelatin production waste liquid refers to the high-calcium, high-chlorine, and high-organic waste liquid discharged during the bone gelatin production process.

[0092] In some embodiments of the present invention, the pH of the bone gelatin production waste liquid is 3.5-7. The pH detection method is NY / T 1973-2021.

[0093] In some embodiments of the present invention, the Ca content in the bone gelatin production waste liquid is 15000-25000 mg / L. In some embodiments of the present invention, the Cl content in the bone gelatin production waste liquid is 28000-50000 mg / L. In some embodiments of the present invention, the CODcr (chemical oxygen demand) content in the bone gelatin production waste liquid is 2000-10000 mg / L. In some embodiments of the present invention, the crude protein content in the bone gelatin production waste liquid is 500-7000 mg / L. The detection methods for Ca content, Cl content, CODcr content, and crude protein content in the bone gelatin production waste liquid are GB / T 6436-2018, GB11896-1989, HJ 828-2017, and GB / T 6432-2018, respectively. In some embodiments of the present invention, the bone gelatin production waste liquid also contains oil, and the oil content in the bone gelatin production waste liquid is 0-90 mg / L. The method for detecting the oil content in the bone gelatin production waste liquid is HJ 637-2018.

[0094] In some embodiments of the present invention, the crude protein is at least one of protein, polypeptide, and oligopeptide.

[0095] In some embodiments of the present invention, the bone gelatin production waste liquid also contains macro- and micro-elements other than Ca and Cl, and the content of macro- and micro-elements other than Ca and Cl in the bone gelatin production waste liquid is 0-3000 mg / L; 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 waste liquid from bone gelatin production contains magnesium (Mg), sulfur (S), and the detection methods for magnesium and sulfur content are NY / T 1117-2010; copper (Cu), iron (Fe), manganese (Mn), zinc (Zn), and molybdenum (Mo), and the detection methods for copper, iron, manganese, zinc, and molybdenum content are NY / T 1974-2010; phosphorus (P2O5), and the detection method for phosphorus content is NY / T1977-2010; and potassium (K2O), and the detection method for potassium content is GB / T 17767.3-2010.

[0096] According to the method of this invention, bone-derived bio-calcium is produced using bone gelatin production waste liquid. Based on a daily production of 24 hours, the waste liquid treatment capacity is 850-3000 tons / day, and the output of bone-derived bio-calcium is 50-200 tons / day.

[0097] In some embodiments of the present invention, the method includes:

[0098] (a-1) Protein degradation was performed on the waste liquid from bone gelatin production to obtain protein degradation liquid a;

[0099] (a-2) Remove insoluble matter from the protein degradation solution to obtain first solid a and first liquid a;

[0100] (a-3) The first liquid a is separated by membrane separation to obtain clear liquid a and concentrated liquid a.

[0101] In some embodiments of the present invention, the removal of insoluble matter is a coagulation and precipitation process, which includes: adjusting the pH of the pretreatment solution to 6-11, and mixing the coagulant and flocculant with the protein degradation solution a.

[0102] In some embodiments of the present invention, the method further includes: separating the first solid a into permeate a and sludge a through solid-liquid separation, wherein the permeate a is returned to the insoluble matter removal process. The sludge a can be used to produce solid fertilizer, such as bio-organic fertilizer, organic-inorganic compound fertilizer, or compound microbial fertilizer.

[0103] In this invention, the solid-liquid separation can be a conventional operation in the art, such as at least one of plate and frame filter press, stacked filter press, screw press, centrifugation, and belt filter.

[0104] In some embodiments of the present invention, the membrane separation includes: passing a first liquid a through a separation membrane to obtain a clear liquid a (i.e., a liquid containing bone-derived bio-calcium solution) and a concentrated liquid a. Preferably, the concentrated liquid a is returned to protein degradation.

[0105] In some embodiments of the present invention, the parameters of the bone gelatin production waste liquid are shown in Table 1. Preferably, the composition and content of the bone-derived bio-calcium, on a dry basis, are shown in Table 2. The bone-derived bio-calcium inevitably contains impurities and water of crystallization.

[0106] Table 1

[0107]

[0108] Table 2

[0109]

[0110] In some embodiments of the present invention, the method includes:

[0111] (b-1) Remove insoluble substances from the bone gelatin production waste liquid to obtain a first solid b and a first liquid b;

[0112] (b-2) The first liquid b is subjected to protein degradation to obtain protein degradation solution b;

[0113] (b-3) The protein degradation solution b is separated by membrane separation to obtain clear solution b and concentrated solution b.

[0114] In some embodiments of the present invention, the removal of insoluble matter is a coagulation and precipitation process, which includes: adjusting the pH value to 7-10 and mixing the coagulant and flocculant with the bone gelatin production waste liquid.

[0115] In some embodiments of the present invention, the method further includes: separating the first solid b into permeate b and sludge b through solid-liquid separation, wherein the permeate b is returned to coagulation sedimentation. The sludge b can be used to produce solid fertilizer, such as bio-organic fertilizer, organic-inorganic compound fertilizer, or compound microbial fertilizer.

[0116] In this invention, the solid-liquid separation can be a conventional operation in the art, such as at least one of plate and frame filter press, stacked filter press, screw press, centrifugation, and belt filter.

[0117] In some embodiments of the present invention, the membrane separation includes: passing the protein degradation solution b through a separation membrane to obtain a clear solution b (i.e., a liquid containing bone-derived biogenic calcium) and a concentrated solution b. Preferably, the concentrated solution b is returned to the protein degradation solution.

[0118] In some embodiments of the present invention, the parameters of the bone gelatin production waste liquid are shown in Table 3. Preferably, the composition and content of the bone-derived bio-calcium, on a dry basis, are shown in Table 4. The bone-derived bio-calcium inevitably contains impurities and water of crystallization.

[0119] Table 3

[0120]

[0121] Table 4

[0122]

[0123]

[0124] In some embodiments of the present invention, the method includes:

[0125] (c-1) Remove insoluble substances from the bone gelatin production waste liquid to obtain a first solid c and a first liquid c;

[0126] (c-2) The first liquid c is subjected to membrane separation to obtain clear liquid c and concentrated liquid c;

[0127] (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.

[0128] In some embodiments of the present invention, the removal of insoluble matter is a coagulation and precipitation process, which includes: adjusting the pH value to 7-10 and mixing the coagulant and flocculant with the bone gelatin production waste liquid.

[0129] In some embodiments of the present invention, the method further includes: separating the first solid c into permeate c and sludge c through solid-liquid separation, wherein the permeate c is returned to coagulation sedimentation. The sludge c can be used to produce solid fertilizer.

[0130] In this invention, the solid-liquid separation can be a conventional operation in the art, such as at least one of plate and frame filter press, stacked filter press, screw press, centrifugation, and belt filter.

[0131] In some embodiments of the present invention, the parameters of the bone gelatin production waste liquid are shown in Table 5. Preferably, the composition and content of the bone-derived bio-calcium, on a dry basis, are shown in Table 6. The bone-derived bio-calcium inevitably contains impurities and water of crystallization.

[0132] Table 5

[0133]

[0134] Table 6

[0135]

[0136]

[0137] In some embodiments of the present invention, the Ca content is 10-13 wt% based on the total weight of the composition on a dry basis.

[0138] In some embodiments of the present invention, the content of N is 2-15 wt% based on the total weight of the composition on a dry basis.

[0139] In some embodiments of the present invention, the amino acid content is 6-20 wt% based on the total weight of the composition on a dry basis.

[0140] In some embodiments of the present invention, the content of K (calculated as K2O) is 0.03-10 wt% based on the total weight of the composition on a dry basis.

[0141] In some embodiments of the present invention, the Zn content is 0.0012-1.5 wt% based on the total weight of the composition on a dry basis.

[0142] In some embodiments of the present invention, the content of B is 0.00025-0.5 wt% based on the total weight of the composition on a dry basis.

[0143] A second aspect of the present invention provides a method for preparing a water-soluble fertilizer containing medium-quantity elements, the method comprising: mixing the bone-derived bio-calcium, a nutritional chelating agent, and an optional nutrient element adjuvant under chelation conditions.

[0144] In this invention, the types and contents of the bone-derived bio-calcium, nutritional chelating agent, and nutritional element adjuvant are as described above and will not be repeated here.

[0145] In some embodiments of the present invention, the method includes: mixing the bone-derived bio-calcium, the nutritional chelating agent, and optional nutritional element adjuvants in the presence of a solvent and under chelation conditions.

[0146] In some embodiments of the present invention, there are no special requirements for the amount of solvent, as long as it is sufficient to dissolve the mixed materials.

[0147] In some embodiments of the present invention, the solvent is water.

[0148] In this invention, the chelation method can be selected using conventional techniques in the art, such as stirring, heating, or heat preservation; the chelation temperature can be selected using conventional techniques in the art, such as 93-95℃; and the chelation time can be selected using conventional techniques in the art, such as 38-45 min.

[0149] In this invention, the medium-element water-soluble fertilizer obtained by the preparation method can be a liquid product or a solid product of medium-element water-soluble fertilizer.

[0150] In some embodiments of the present invention, when the water-soluble fertilizer containing medium-quantity elements is a liquid product of water-soluble fertilizer containing medium-quantity elements, the method includes:

[0151] The bone-derived bio-calcium, nutritional chelating agent, optional nutrient element adjuvants, and water are added to a reaction vessel, stirred, heated to 93-95℃, and kept at that temperature for 38-45 minutes to obtain a medium-element water-soluble fertilizer liquid product.

[0152] In some embodiments of the present invention, when the medium-element water-soluble fertilizer is a solid product of medium-element water-soluble fertilizer, the method further includes:

[0153] (1) Add the bone-derived biological calcium, nutritional chelating agent, optional nutrient element adjuvant and water to the reaction vessel, stir and heat to 93-95℃, keep warm for 38-45min, and obtain a medium-element water-soluble fertilizer liquid product.

[0154] (2) The liquid product of medium element water-soluble fertilizer is dehydrated and dried to obtain the solid product of medium element water-soluble fertilizer.

[0155] In this invention, the dehydration and drying are conventional techniques in the art, such as spray drying and / or freeze drying.

[0156] In some embodiments of the present invention, the dehydration and drying is a conventional technical operation in the art, as long as the moisture content in the solid product of the medium-element water-soluble fertilizer is ≤3wt%.

[0157] The third aspect of the present invention provides a medium-element water-soluble fertilizer prepared by the preparation method described above.

[0158] In this invention, both the liquid and solid water-soluble fertilizer products containing medium-element elements comply with the relevant provisions and requirements of the standard “NY2266—2012”.

[0159] It should be understood that the components in the medium-element water-soluble fertilizer have a synergistic effect, with priority given to their impact on crop growth. Therefore, in some embodiments, not all micronutrients in the medium-element water-soluble fertilizer are chelated.

[0160] In some embodiments of the present invention, the content of nutrient elements in the medium-element water-soluble fertilizer is 2-15 wt% on a dry basis.

[0161] In some embodiments of the present invention, the nutrient elements in the medium-element water-soluble fertilizer are at least one selected from nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), iron (Fe), boron (B), manganese (Mn), zinc (Zn), copper (Cu), molybdenum (Mo), silicon (Si), cobalt (Co), vanadium (V), rare earth elements (RE), titanium (Ti), and nickel (Ni).

[0162] In this invention, when the nutrient elements in the medium-element water-soluble fertilizer are calcium, magnesium, zinc, and boron, the content of the nutrient elements in the medium-element water-soluble fertilizer is determined according to the requirements specified in NY2266-2012, and the detection method refers to the method specified in NY2266-2012; when the nutrient element in the medium-element water-soluble fertilizer is nitrogen, the content of the nutrient element in the medium-element water-soluble fertilizer is calculated as N, and the detection method is NY / T1977-2010; when the nutrient element in the medium-element water-soluble fertilizer is phosphorus, the content of the nutrient element in the medium-element water-soluble fertilizer is calculated as P2O5, and the detection method is the distillation titration method in NY / T1977-2010; when the nutrient element in the medium-element water-soluble fertilizer is potassium, the content of the nutrient element in the medium-element water-soluble fertilizer is calculated as K2O, and the detection method is NY / T1977-2010. In some embodiments of the present invention, the fertilizer is a liquid product or a solid product of a water-soluble fertilizer containing medium-element components. When the fertilizer is a liquid product of a water-soluble fertilizer containing medium-element components, the fertilizer also contains a solvent and / or a surfactant, the content of which can be conventionally selected in the art. Preferably, the solvent is water.

[0163] The fourth aspect of this invention provides the application of bone gelatin production waste liquid in the preparation of water-soluble fertilizers containing medium-quantity elements.

[0164] In some embodiments of the present invention, the application is the use of bone-derived bio-calcium in water-soluble fertilizers containing medium-quantity elements.

[0165] In this invention, the application can be to common crops in the field, such as grains, oilseeds, melons, fruits, and vegetables. Preferably, the crop is a melon, fruit, vegetable, or oilseed crop. More preferably, the crop is at least one of tomato, pepper, leek, lettuce, and cucumber.

[0166] In some embodiments of the present invention, the application is in the preparation of a medium-element water-soluble fertilizer that increases the fresh weight of crop fruits. Preferably, the fruit is a chili pepper and / or a tomato.

[0167] In some embodiments of the present invention, the application is in the preparation of water-soluble fertilizers containing medium-quantity elements to increase crop yield.

[0168] In some embodiments of the present invention, the application is in the preparation of water-soluble fertilizers containing medium-quantity elements that increase the calcium content of crops. Preferably, the calcium content is the calcium content of crop fruits and / or the calcium content of crop leaves.

[0169] In some embodiments of the present invention, the application is in the preparation of water-soluble fertilizers containing medium-quantity elements to improve the quality of crops.

[0170] In some embodiments of the present invention, the application is in the preparation of medium-element water-soluble fertilizers that improve the storage time of crops.

[0171] In some embodiments of the present invention, the application is in the preparation of water-soluble fertilizers containing medium-element components that reduce crop disease incidence. Preferably, the application is in the preparation of water-soluble fertilizers containing medium-element components that reduce the incidence of yellow tip disease in leeks and blossom-end rot in tomatoes. Preferably, the application is in the preparation of water-soluble fertilizers containing medium-element components that reduce blossom-end rot in tomatoes.

[0172] The fifth aspect of this invention provides the application of water-soluble fertilizers containing medium-quantity elements in agricultural production.

[0173] The inventors have discovered that using the medium-element water-soluble fertilizer of this invention in agricultural production, especially on melons, fruits, and vegetables, can quickly replenish the various nutrients needed for crop growth, effectively prevent and control various physiological diseases of crops, and improve the yield and quality of crops.

[0174] In this invention, the application can be to common crops in the field, such as grains, oilseeds, melons, fruits, and vegetables. Preferably, the crop is a melon, fruit, vegetable, or oilseed crop. More preferably, the crop is at least one of tomato, pepper, leek, lettuce, and cucumber.

[0175] In some embodiments of the present invention, the application is to increase the fresh weight of crop fruits.

[0176] In some embodiments of the present invention, the application is to increase crop yield.

[0177] In some embodiments of the present invention, the application is to increase the calcium content of crops. Preferably, the calcium content is the calcium content of crop fruits and / or the calcium content of crop leaves.

[0178] In some embodiments of the present invention, the application is to improve the quality of crops.

[0179] In some embodiments of the present invention, the application is to improve the storage time of crops.

[0180] In some embodiments of the present invention, the application is to reduce the incidence of crop diseases. Preferably, the application is to reduce the incidence of yellow tip disease in chives. Preferably, the application is to reduce blossom-end rot in tomatoes.

[0181] The present invention will be described in detail below through embodiments.

[0182] In the following embodiments, unless otherwise specified, all raw materials used are commercially available, and all methods used are conventional methods in the art.

[0183] In the following examples, unless otherwise specified, all raw materials used were commercially available. Urea, potassium nitrate, zinc chloride, and borax all met national agricultural grade standards. The solid amino acid raw material was purchased from Xuzhou Weitian Technology Co., Ltd., and its testing standard number is NY1429-2010.

[0184] In the following embodiments, the solid bone-derived bio-calcium is obtained from bone gelatin production wastewater through a filtration and dehydration process. Wherein:

[0185] 1. The various indicators and detection methods in gelatin production waste liquid are shown in Table 7:

[0186] Table 7

[0187]

[0188]

[0189] 2. In bone-derived bio-calcium:

[0190] The method for detecting calcium source content (calculated as elemental calcium) is GB / T 6436-2018 disodium ethylenediaminetetraacetate complexometric titration method.

[0191] The method for detecting Cl content is GB / T 24890-2010.

[0192] The method for detecting free calcium content (calculated as elemental calcium) is as follows: After preparing a free calcium solution, referring to Chapter 4, Section 2.2, "Enzymatic Preparation and Peptide-Calcium Chelation Study of Sheep Bone Collagen Peptide" in the Master's Thesis of Shanxi Agricultural University, "Determination of Chelation Rate", the free calcium content was detected by the disodium ethylenediaminetetraacetate complexometric titration method in GB / T6436-2018.

[0193] The detection methods for chelated peptide calcium content and chelation rate (calculated as elemental calcium) are as follows: chelated peptide calcium content (calculated as elemental calcium) is the calcium source content minus the free calcium content (calculated as elemental calcium); calcium chelation rate = chelated peptide calcium content (calculated as elemental calcium) / calcium source content × 100%.

[0194] The methods for detecting the content and molecular weight of small molecule peptides are as follows: the molecular weight is detected by Appendix A of GB 31645-2018 (high performance size exclusion chromatography), and the content of small molecule peptides is detected by the method for determining protein content in GB / T 6432-2018.

[0195] The method for detecting water-soluble organic matter content is NY / T1976-2010;

[0196] The detection method for Mg and S content is NY / T 1117-2010;

[0197] The detection methods for Cu, Fe, Mn, Zn, B, and Mo content are NY / T 1974-2010;

[0198] The detection method for P content is NY / T1977-2010;

[0199] The method for detecting potassium (K) content is GB / T 17767.3-2010.

[0200] The wastewater parameters from bone gelatin production used in the preparation of solid bone-derived bio-calcium in the following examples are shown in Table 8, and the specific process flow is as follows:

[0201] Table 8

[0202]

[0203] (1) Coagulation and sedimentation (i.e. removal of insoluble matter): The bone gelatin production waste liquid is placed in a coagulation reactor and the pH value is adjusted to 10 using calcium hydroxide solution; a 20% PAC (polyaluminum chloride) solution and a 1‰ PAM (anionic polyacrylamide with a molecular weight of 15 million) solution are added for coagulation and sedimentation (based on the total weight of the gelatin production waste liquid, the amount of PCA solution and PAM solution added is 1.5wt‰ and 1wt‰, respectively), to obtain the first solid c and the first liquid c.

[0204] (2) The first solid c obtained by coagulation sedimentation is dewatered by plate and frame filter press to obtain sludge c and permeate c. Sludge c can be used to produce solid fertilizer, and permeate c is returned to the coagulation reactor for coagulation.

[0205] (3) Membrane separation: The first liquid c obtained by coagulation and sedimentation is introduced into the membrane separation system and separated by a separation membrane with a molecular weight cutoff of 10000 Da (purchased from Tianjin Membrane Technology Co., Ltd., model TUIE4230) to obtain clear liquid c and concentrated liquid c.

[0206] (4) Protein degradation: At 25°C, add 13% industrial sodium hypochlorite of first grade to concentrate c. The volume ratio of first concentrate c to sodium hypochlorite is 1000:6. Stir for 30 minutes to fully mix the first concentrate c with sodium hypochlorite, and convert the large molecular protein in the waste liquid into small molecular peptides to obtain protein degradation liquid c. Then, enter the membrane separation system and perform membrane separation through a separation membrane with a molecular weight cutoff of 2000 Da.

[0207] (5) Concentration: The clear liquid c obtained from membrane separation is fed into the RO reverse osmosis membrane, and the concentrate from the RO reverse osmosis membrane is fed into the evaporation system for evaporation and concentration until the TDS is 45wt%, thus obtaining liquid bone-derived bio-calcium. The water quality indicators of the permeate from the RO reverse osmosis membrane and the condensate from the evaporation process meet the industrial recycled water standards and can be reused as greywater in other processes of gelatin production.

[0208] (6) The liquid bone-derived bio-calcium is cooled and precipitated by a cooling precipitator (i.e., precipitated drying), and then granulated by a granulator to obtain granular bone-derived bio-calcium waste liquid (i.e., solid bone-derived bio-calcium). 63g of solid bone-derived bio-calcium can be produced from every 1L of bone gelatin production waste liquid.

[0209] Solid bone-derived bio-calcium was subjected to a temperature of 50℃ and a vacuum degree of 7×10⁻⁶. 4 The calcium was dried at 1000 Pa for 120 minutes without any change in mass. The components and their contents were then analyzed, and the results are shown in Table 9. The moisture content of the solid bone-derived bio-calcium before drying was 8%.

[0210] Table 9

[0211]

[0212] Of which, on a dry basis, the magnesium content is 0.8 wt%.

[0213] The pH of solid bone-derived bio-calcium is 6.1 (the pH test method for bone-derived bio-calcium is: dilute the bone-derived bio-calcium with water at a mass ratio of 1:250, and then test the pH value).

[0214] Example 1

[0215] This embodiment illustrates the preparation of medium-element water-soluble fertilizer A1 according to the method of the present invention.

[0216] (1) Components: Weigh 500 kg of solid bone-derived bio-calcium and 300 kg of solid amino acid raw materials by weight;

[0217] (2) Add the components from step (1) to the reactor, then add water to 1000 liters, stir and heat to 95°C, keep warm for 40 minutes to obtain medium element water-soluble fertilizer A1 (medium element water-soluble fertilizer liquid product).

[0218] Example 2

[0219] This embodiment illustrates the preparation of medium-element water-soluble fertilizer A2 according to the method of the present invention.

[0220] Medium-element water-soluble fertilizer liquid product A1 was prepared according to the method of Example 1. A1 was spray-dried to dehydrate it so that the moisture content (H2O) was ≤3.0wt%, and medium-element water-soluble fertilizer A2 (medium-element water-soluble fertilizer liquid product) was obtained.

[0221] Example 3

[0222] This embodiment illustrates the preparation of a medium-element water-soluble fertilizer B1 containing nutrient element adjuvants according to the method of the present invention.

[0223] (1) Components: Weigh out 500 kg of solid bone-derived biological calcium, 200 kg of solid amino acid raw materials, and 200 kg of urea by weight.

[0224] (2) Add the components from step (1) to the reactor, add water to 1000 liters, stir and heat to 95°C, keep warm for 40 minutes to obtain medium element water-soluble fertilizer B1 (medium element water-soluble fertilizer liquid product).

[0225] Example 4

[0226] This embodiment illustrates the preparation of a medium-element water-soluble fertilizer B2 containing nutrient element adjuvants according to the method of the present invention.

[0227] Medium element water-soluble fertilizer liquid product B1 was prepared according to the method of Example 3. B1 was spray dried to remove water so that the moisture content (H2O) was ≤3.0wt%, and medium element water-soluble fertilizer B2 (medium element water-soluble fertilizer solid product) was obtained.

[0228] Example 5

[0229] This embodiment illustrates the preparation of a medium-element water-soluble fertilizer C1 containing nutrient element adjuvants according to the method of the present invention.

[0230] (1) Components: By weight, weigh 500 kg of solid bone source calcium, 150 kg of solid amino acid raw materials, 200 kg of potassium nitrate, 20 kg of zinc chloride, and 30 kg of borax.

[0231] (2) Add the components from step (1) to the reactor, add water to 1000 liters, stir and heat to 95°C, keep warm for 40 minutes to obtain medium element water-soluble fertilizer C1 (medium element water-soluble fertilizer liquid product).

[0232] Example 6

[0233] Medium-element water-soluble fertilizer liquid product C1 was prepared according to the method of Example 3. C1 was spray-dried to dehydrate it so that the moisture content (H2O) was ≤3.0wt%, and medium-element water-soluble fertilizer C2 (medium-element water-soluble fertilizer liquid product) was obtained.

[0234] Test Example 1

[0235] The medium-element water-soluble fertilizers prepared in Examples 1-6 were tested, and the results are shown in Tables 10 and 11. The calcium, magnesium, zinc, boron, water-insoluble matter, and pH values ​​were tested according to the technical indicators for liquid and solid medium-element water-soluble fertilizers as specified in the Agricultural Industry Standard of the People's Republic of China NY2266-2012; the nitrogen content was tested according to the distillation titration method in NY / T 1977-2010; and the potassium content was tested according to the method specified in NY / T 1977-2010.

[0236] Table 10

[0237]

[0238]

[0239] The amino acid content in water-soluble fertilizers containing medium-element elements was tested according to the method specified in NY / T 1975-2010. The results showed that the amino acid content in water-soluble fertilizer A1 was 129 g / L, the amino acid content in water-soluble fertilizer B1 was 87 g / L, and the amino acid content in water-soluble fertilizer C1 was 62 g / L.

[0240] Table 11

[0241]

[0242] The amino acid content in water-soluble fertilizers containing medium-element elements was tested according to the method specified in NY / T 1975-2010. The results showed that the amino acid content in water-soluble fertilizer A2 was 15 wt%, the amino acid content in water-soluble fertilizer B2 was 9.5 wt%, and the amino acid content in water-soluble fertilizer C2 was 6.8 wt%.

[0243] Test Example 2

[0244] This test case is used to illustrate the fertilization effect between bone-derived bio-calcium and medium-element water-soluble fertilizer B1.

[0245] 1. Basic Information of the Experimental Site

[0246] 1.1 Test Location: Halinger Village, Jiuyuan District, Baotou City, Inner Mongolia

[0247] 1.2 Landform type: alluvial plain

[0248] 1.3 Soil type and texture: Chestnut calcareous soil; Medium loam

[0249] 1.4 Experimental conditions: Arched greenhouse cultivation

[0250] 1.5 Implementing Unit: Inner Mongolia Dongbao Datian Biotechnology Co., Ltd.

[0251] 1.6 Test period: June 10, 2021 – August 16, 2021

[0252] 2. Experimental Materials

[0253] 1.1 The crop tested: lettuce.

[0254] 1.2 Test fertilizers: Bone-derived bio-calcium, water-soluble fertilizer B1 (containing medium-quantity elements)

[0255] 3 Experimental Design

[0256] 3.1 Experimental treatments: Two treatments were set up: Treatment 1 was bone-derived bio-calcium (10 kg / mu); Treatment 2 was water-soluble fertilizer B1 (10 kg / mu).

[0257] 3.2 Field Design: The plot is 10.6m long and 6.3m wide, with a net area of ​​66.8㎡ (equivalent to 0.1 mu).

[0258] Repeat three times, setting up a protected row. A total of 6 cells were set up, with 3 cells undergoing treatment 1 and the other 3 cells undergoing treatment 2. The fertilizer applied and the amount of fertilizer applied to each cell are shown in Table 12.

[0259] Table 12

[0260] project crop Fertilization treatment Fertilizer application rate Community 1 lettuce Bone-derived bio-calcium 10kg / mu Community 2 lettuce Medium element water-soluble fertilizer B1 10kg / mu Community 3 lettuce Bone-derived bio-calcium 10kg / mu Community 4 lettuce Medium element water-soluble fertilizer B1 10kg / mu Community 5 lettuce Bone-derived bio-calcium 10kg / mu Community 6 lettuce Medium element water-soluble fertilizer B1 10kg / mu

[0261] 4. Fertilization methods and timing

[0262] 4.1 Fertilization method: Apply fertilizer with irrigation water.

[0263] 4.2 Fertilization time: June 28th

[0264] 4. Experimental Results

[0265] 4.1 Impact on yield

[0266] Production testing date: August 20th.

[0267] Yield measurement method: Before harvesting lettuce, three sampling points were randomly selected from each plot, with a sampling area of ​​1 square meter at each point, for harvesting and weighing. The yield measurement results are shown in Table 13.

[0268] Table 13

[0269]

[0270] Note: Data ending with the same letter in the table indicate no significant difference (DMRT method, p = 0.05).

[0271] The experimental results showed that there was a significant difference between treatments 1 and 2, with the average yield of treatment 2 being significantly higher than that of treatment 1 (p<0.05). In other words, compared with bone-derived bio-calcium, the use of water-soluble fertilizer B1 (a medium-element fertilizer) significantly increased lettuce yield, with an increase of 20.5%.

[0272] Test Example 3

[0273] This test case illustrates the fertilizer efficacy of liquid product A1, a water-soluble fertilizer containing medium-quantity elements.

[0274] 1. Experimental Materials and Methods

[0275] 1.1 Test Fertilizers

[0276] Medium-element water-soluble fertilizer liquid product A1 (density 1.3g / cm³) 3 )

[0277] Sugar alcohol calcium (manufactured by Brant Corporation, USA, with a calcium content of approximately 140 g / L and a density of 1.47 g / cm³). 3 )

[0278] Calcium chloride (chemical reagent, Ca content approximately 36 wt%)

[0279] 1.2 Test crops: tomatoes and peppers.

[0280] 1.3 Experimental conditions: Greenhouse potted plants

[0281] 1.4 Experimental site: Greenhouse No. 21, College of Resources and Environment, South China Agricultural University, Guangzhou, Guangdong Province.

[0282] 1.5 Implementing Unit: Crop Nutrition and Fertilization Research Laboratory, South China Agricultural University.

[0283] 2. Test Plan

[0284] The experiment included four treatment groups: a water-soluble fertilizer containing medium-quantity elements (A1), sugar alcohol calcium, calcium chloride, and a water control. Each treatment group had five replicates (i.e., for tomatoes, each treatment had five pots planted with one tomato plant per pot, for a total of 20 pots; for peppers, each treatment had five pots planted with one pepper plant per pot, for a total of 20 pots). Except for the water control group, the total amount of calcium sprayed was consistent across all treatments.

[0285] The names of each treatment group and the substances used are as follows:

[0286] Treatment 1 (Water Control): 2L of water;

[0287] Treatment 2 (calcium chloride): Take 2.24g of calcium chloride, dilute it with 2L of water, and then add 4mL of surfactant (Tween 20);

[0288] Treatment 3 (sugar alcohol calcium): Take 8g of sugar alcohol calcium and dilute it with water to 2L;

[0289] Treatment 4 (medium element water-soluble fertilizer A1): Take 10.4g of medium element water-soluble fertilizer A1, dilute it with 2L of water, and then add 4mL of surfactant (Tween 20).

[0290] Specific procedures: Spray for the first time 4 days after transplanting. After the first spray, spray once every 7 days for a total of 3 times. Spray both sides of the leaves until they are dripping wet.

[0291] 3 Survey Indicators

[0292] Twenty days after the third spraying, three replicates with uniform growth were selected from five replicates for each treatment. The SPAD value of functional leaves of peppers / tomatoes was measured. Leaves (20 functional leaves per replicate) and fruits (5 uniformly grown pepper fruits per replicate for peppers; 10 uniformly grown tomato fruits per replicate) were harvested as fruit and leaf samples, respectively, and the fresh weight of the fruits was weighed. The fruit and leaf samples were labeled, placed in paper bags, and dried at approximately 50-60 degrees Celsius. The dry weight of the leaves and fruits was recorded. The leaf and fruit samples were then pulverized, carbonized, and ashed, and the calcium content of the leaves and fruits was determined using an atomic absorption spectrophotometer.

[0293] 4. Experimental Results

[0294] 4.1 Effects of different forms of calcium on the fresh weight of single fruits from pepper-tomato plants

[0295] The fresh weight of fruits treated with water-soluble fertilizer A1 (treatment 1), sugar alcohol calcium (treatment 2), and calcium chloride (treatment) was compared with the fresh weight of fruits in the water control (treatment 1). The results are shown in Table 14.

[0296] Table 14

[0297]

[0298] Note: The data in the table are the averages of three replicates. Data with the same letter at the end of each column indicate no significant difference (DMRT method, p = 0.05).

[0299] Table 14 shows that: 1. Foliar application of three calcium fertilizers—calcium chloride, imported sugar alcohol calcium, and medium-element water-soluble fertilizer A1—all increased pepper yield. Among them, peppers sprayed with medium-element water-soluble fertilizer A1 showed a significant yield increase of 38.77%; 2. Foliar application of both calcium chloride and medium-element water-soluble fertilizer A1 increased tomato yield. Tomatoes sprayed with medium-element water-soluble fertilizer A1 showed a significant yield increase of 34.81%.

[0300] 4.2 Effects of different forms of calcium on calcium concentration in pepper and tomato leaves

[0301] The leaf calcium content of treatments 2, 3, and 4 was compared with that of treatment 1, and the results are shown in Table 15.

[0302] Table 15

[0303]

[0304] Note: The data in the table are the averages of three replicates. Data with the same letter at the end of each column indicate no significant difference (DMRT method, p = 0.05).

[0305] As shown in Table 15, foliar spraying of calcium chloride, imported sugar alcohol calcium, and water-soluble fertilizer A1 (a medium-element fertilizer) can significantly increase the calcium content in pepper leaves, with increases ranging from 11.95% to 34.53%. For tomatoes, spraying with all three calcium fertilizers can increase the calcium content in leaves, but water-soluble fertilizer A1 (a medium-element fertilizer) can significantly increase the calcium content in tomato leaves, with an increase of 22.74%.

[0306] 4.3 Effects of different forms of calcium on calcium accumulation in pepper and tomato fruits

[0307] The calcium content of fruits from treatments 2, 3, and 4 was compared with the calcium content of leaves from treatment 1, and the results are shown in Table 16.

[0308] Table 16

[0309]

[0310] Note: The data in the table are the averages of three replicates. Data with the same letter at the end of each column indicate no significant difference (DMRT method, p = 0.05).

[0311] As shown in Table 16, in terms of calcium absorption (cumulative amount), foliar spraying of medium-element water-soluble fertilizer A1 significantly increased calcium absorption in pepper fruits by 37.86% and in tomato fruits by 11.29%. Sugar alcohol calcium and calcium chloride basically did not show any increase in absorption.

[0312] Test Example 3

[0313] This test case is used to further illustrate the fertilizer efficacy of medium-element water-soluble fertilizer A1.

[0314] 1. Experimental Materials and Methods

[0315] 1.1 Test Fertilizers

[0316] Medium element water-soluble fertilizer A1

[0317] Amino acid-containing water-soluble fertilizer (produced by Sinochem Fertilizer Holdings Co., Ltd., Ca≥140g / L, amino acids≥100g / L)

[0318] Compound fertilizer (produced by Haifa (China) Chemical Group Co., Ltd., Israel, with N, P2O5, and K2O content of 12-6-42).

[0319] 1.2 The crop tested: tomato.

[0320] 1.3 Experimental conditions: Greenhouse cultivation

[0321] 1.4 Test site: Inner Mongolia Green Energy Agricultural Science and Technology Demonstration Park, Baoheshao Town, Xincheng District, Hohhot City.

[0322] 1.5 Implementing Unit: College of Grassland and Resource Environment, Inner Mongolia Agricultural University.

[0323] 1.6 Test period: June 1, 2021 - November 17, 2021.

[0324] 2 Experimental Design

[0325] 2.1 Community Design

[0326] This experiment employed a single-factor completely randomized design, with a total of 7 treatments, each with 3 replicates of a randomized distribution, resulting in a total of 21 experimental plots. The area of ​​each experimental plot was 23.4 m². 2 (9m long and 2.6m wide), two rows of tomatoes are planted in each plot, with a transplanting density of 1140 plants / acre, a row spacing of 130cm, and a plant spacing of 45cm. Trapezoidal raised ridges (0.4m high, 0.3m wide at the top, and 0.8m wide at the bottom) are built between the planting rows to prevent fertilizer and water from flowing laterally between the experimental plots.

[0327] 2.2 Fertilization treatment

[0328] For the application of medium-element water-soluble fertilizer A1 and amino acid-containing water-soluble fertilizer, three gradations were set up for each application: conventional application rate of 5 kg / (application·acre); double application rate of 10 kg / (application·acre); and triple application rate of 15 kg / (application·acre). A control (CK) treatment was set up with an application rate of 0 kg / (application·acre). No basal fertilizer was applied to any treatment. Compound fertilizer (12-6-42) was applied twice from the time the bottom fruit reached 3 cm in height until the top fruit changed color, with each treatment applying 15 kg / (application·acre). Other production management measures followed local conventional management methods.

[0329] There were 7 treatments: ① Conventional application of water-soluble fertilizer A1 containing medium elements; ② 2 times the application of water-soluble fertilizer A1 containing medium elements; ③ 3 times the application of water-soluble fertilizer A1 containing medium elements; ④ Conventional application of water-soluble fertilizer containing amino acids; ⑤ 2 times the application of water-soluble fertilizer containing amino acids; ⑥ 3 times the application of water-soluble fertilizer containing amino acids; ⑦ Control (irrigation water).

[0330] 3. Fertilization methods and timing

[0331] 3.1 Fertilization Methods

[0332] The water was applied to the soil via drip irrigation, and the amount of water used for irrigation in each plot was kept consistent according to the water meter readings during the experiment.

[0333] 3.2 Fertilization time

[0334] The fertilizer application time for each treatment is shown in Table 17.

[0335] Table 17

[0336]

[0337] 4. Test data determination and sampling

[0338] Yield measurement: Ten tomato plants were randomly selected from each plot for calibration. At each yield measurement, all mature tomatoes from the calibrated plants were harvested, weighed, and the yield of each plant was recorded. A total of six yield measurements were conducted throughout the tomato's growth period: August 7, 2021 (first measurement), August 24, 2021 (second measurement), August 31, 2021 (third measurement), September 7, 2021 (fourth measurement), September 25, 2021 (fifth measurement), and October 16, 2021 (sixth measurement).

[0339] Sugar content determination: Sugar content determination involves randomly selecting 10 tomatoes from each plot after yield measurement and weighing for sugar content determination. The number and time of sugar content determination are consistent with the number and time of yield measurement. The method for sugar content determination is as follows: juice obtained from the same part of a ripe tomato fruit is dripped into a calibrated PAL-1 digital display saccharimeter (ATAGO, Japan; measurement accuracy: Brix: ±0.2%) to determine the sugar content of the tomato fruit.

[0340] 5 Results and Analysis

[0341] 5.1 Impact on tomato yield

[0342] The results of the six yield measurements are shown in Table 18 (Effects of each treatment on tomato yield). The experimental 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% to 49.6%. (2) compared with amino acid-containing water-soluble fertilizer, medium-element water-soluble fertilizer A1 has a more obvious effect on promoting the growth and increasing the yield of tomatoes. The yields of the treatments with 1x, 2x, and 3x amounts of medium-element water-soluble fertilizer A1 are 26.54%, 7.41%, and 1.15% higher than the corresponding treatments with amino acid-containing water-soluble fertilizer, respectively. (3) The yields of different fertilization treatments of medium-element water-soluble fertilizer A1 are 1566 kg / mu, 1862 kg / mu, and 2061 kg / mu higher than the control and no-fertilization treatment, respectively. Based on the average annual tomato purchase price of 3 yuan / kg in Hohhot greenhouse area, the increased output value per mu is 4698 yuan, 5586 yuan, and 6183 yuan, respectively.

[0343] Table 18

[0344]

[0345] Note: Data with the same letter at the end of each column indicates no significant difference (DMRT method, p = 0.05).

[0346] The fertilization effects of applying water-soluble fertilizer containing medium-quantity elements (A1) and water-soluble fertilizer containing amino acids were fitted using a linear plus plateau model, respectively. The fitting results are as follows: Figure 1 As shown in the figure. The fitting results indicate that the recommended application rates of water-soluble fertilizer A1 containing medium-element components and water-soluble fertilizer containing amino acids are 6.26 kg / (application·acre) and 14.61 kg / (application·acre), respectively, corresponding to yields of 53.67 kg / 10 plants and 53.92 kg / 10 plants, respectively. Compared with water-soluble fertilizer containing amino acids, water-soluble fertilizer A1 containing medium-element components can reduce the application rate of water-soluble fertilizer containing amino acids by 8.12 kg / (application·acre) to achieve the recommended yield (53.67 kg / 10 plants), a reduction of 56.5%.

[0347] 5.2 Effect on tomato sugar content

[0348] The results of six sugar content measurements are shown in Table 19 (Effects of different treatments on tomato sugar content (°Brix)). The experimental results showed that (1) compared with the control (treatment 7), the application of water-soluble fertilizer A1 (treatments 1, 2, and 3) and water-soluble fertilizer containing amino acids (treatments 4, 5, and 6) could significantly increase the sugar content of tomatoes. (2) compared with the control, the application of water-soluble fertilizer containing amino acids increased the sugar content of tomatoes by an average of 5.1% to 9.4%. (3) compared with water-soluble fertilizer containing amino acids, water-soluble fertilizer A1 containing medium elements could further increase the sugar content of tomatoes, with an increase of 1.1% to 5.3%.

[0349] Table 19

[0350]

[0351] Note: Data with the same letter at the end of each column indicates no significant difference (DMRT method, p = 0.05).

[0352] Test Example 4

[0353] This test case illustrates the fertilizer efficacy of water-soluble fertilizer B1 containing medium-quantity elements.

[0354] 1. Basic Information of the Experimental Site

[0355] 1.1 Test Location: Xiaobalagai Village, Sharqin Town, Donghe District, Baotou City, Inner Mongolia

[0356] 1.2 Landform type: alluvial plain

[0357] 1.3 Soil type and texture: Chestnut soil; Light loam

[0358] 1.4 Experimental conditions: Chives were grown outdoors, and lettuce was grown in arched tunnels.

[0359] 1.5 Implementing Unit: Hewang Agriculture and Animal Husbandry Company, Baotou City, Inner Mongolia

[0360] 1.6 Test period: May 5, 2021 – August 5, 2021

[0361] 2. Experimental Materials

[0362] 1.1 Test crops: chives and lettuce.

[0363] 1.2 Test fertilizers: Medium-element water-soluble fertilizer B1, compound fertilizer (purchased from agricultural input market, N, P2O5, K2O content is 15-15-15).

[0364] 3 Experimental Design

[0365] 3.1 Experimental treatments: Two treatments were set up. Treatment 1 was 10 kg / mu of medium-element water-soluble fertilizer B1; treatment 2 was 10 kg / mu of compound fertilizer (traditional fertilizer).

[0366] 3.2 Field design: The total area of ​​the leek experiment was 2.4 mu, with two plots (plot 1 and plot 2), each plot being 1.2 mu; the total area of ​​the lettuce experiment was 3.8 mu, with two plots (plot 3 and plot 4), each plot being 1.9 mu.

[0367] The fertilizers and amounts applied to each plot are shown in Table 20.

[0368] Table 20

[0369] project crop Fertilization treatment Fertilizer application rate Community 1 Chinese chives Compound fertilizer 10kg / mu Community 2 Chinese chives Medium element water-soluble fertilizer B1 10kg / mu Community 3 lettuce Compound fertilizer 10kg / mu Community 4 lettuce Medium element water-soluble fertilizer B1 10kg / mu

[0370] 4. Fertilization methods and timing

[0371] 4.1 Fertilization method: Apply fertilizer with irrigation water.

[0372] 4.2 Fertilization time: June 10 for chives (when chives are 9-12cm tall); July 5 for lettuce (9-10 days after transplanting).

[0373] 4. Experimental Results

[0374] 4.1 Impact on yield

[0375] Yield measurement dates: June 25 for chives; August 15 for lettuce.

[0376] Yield measurement method: Five sampling points were randomly selected from each plot, with a sampling area of ​​1 square meter per point. Chives or lettuce were harvested and weighed by plot. The yield of the plot treated with water-soluble fertilizer B1 was compared with that of the plot treated with compound fertilizer. The results are shown in Table 21.

[0377] Table 21

[0378] project crop Single-season yield (kg / mu / time) Increase / decrease (%) Community 1 Chinese chives 2863 —— Community 2 Chinese chives 3396 18.6 Community 3 lettuce 1468 —— Community 4 lettuce 1938 32.0

[0379] The experimental results show that, compared with traditional fertilization, the use of water-soluble fertilizer B1 with medium elements can increase the yield of both leeks and lettuce, with an increase of 18.6% for leeks and 32.0% for lettuce.

[0380] 4.2 Impact on Commodity

[0381] 4.2.1 Storage time

[0382] The length of time vegetables are stored is one of the important indicators that vegetable farmers and consumers can directly judge the marketability of vegetables. After collection, vegetable samples are stored at room temperature (26-28℃) (record the start time), observed, and the relative humidity of the air is maintained at 50-60%. The vegetables are observed for rot every 12 hours.

[0383] When the percentage of rotten vegetables (i.e., the percentage of rotten vegetables out of all vegetables) reached 15%, the termination time was recorded, and the storage time (i.e., from the start time to the termination time) was also recorded. The storage time of the plot treated with water-soluble fertilizer B1 was compared with that of the plot treated with compound fertilizer. The effects of different treatments on the storage time of leeks and lettuce are shown in Table 22.

[0384] The criteria for judging vegetable rot are as follows: for chives, rot is defined as a single leaf of ≥0.5cm in length showing signs of decay on its surface; for lettuce, rot is defined as a single leaf of ≥1.0cm in length showing signs of decay on its surface. 2 The standard for determining whether a lettuce plant is rotten is based on the area of ​​rot.

[0385] Table 22

[0386] project crop Storage time (h) Increase / decrease time (h) Community 1 Chinese chives 120 —— Community 2 Chinese chives 168 48 Community 3 lettuce 72 —— Community 4 lettuce 96 24

[0387] The experimental results show that compared with traditional fertilization, the use of medium-element water-soluble fertilizer B1 can increase the storage time of chives and lettuce. The storage time of chives can be increased by 48 hours (2 days) and that of lettuce by 24 hours (1 day).

[0388] 4.2.2 Yellowing tips of chives

[0389] Yellowing tips on chives significantly impact their marketability, making it a pressing technical challenge for local farmers. On June 25th, while measuring chive yield, the yellowing tip phenomenon was also observed during chive growth. The results are shown in Table 23.

[0390] The criteria for judging yellow tips on chives are: if one leaf of a single chive plant is yellow for a length of ≥0.5cm, then the chive plant is considered to be a yellow tip diseased plant;

[0391] Yellow tip incidence of chives = Number of chives with yellow tip disease in the yield measurement area / Total number of chives in the yield measurement area × 100%.

[0392] Table 23

[0393] project crop Yellow tip incidence (%) Increase / decrease (%) Community 1 Chinese chives 0.6 —— Community 2 Chinese chives 33.9 -33.3

[0394] The experimental results show that, compared with traditional fertilization, the use of water-soluble fertilizer B1 with medium-quantity elements can significantly prevent the occurrence of yellow tips in leek production.

[0395] Test Example 5

[0396] This test example is used to illustrate the fertilizer efficacy of water-soluble fertilizer C1 containing medium-quantity elements.

[0397] 1. Basic Information of the Experimental Site

[0398] 1.1 Test sites: Xiawu Village, Qucun Town, and Jixu Village, Shicun Town, Quwo County, Shanxi Province

[0399] 1.2 Landform type: Lacustrine plain

[0400] 1.3 Soil type and texture: Calcareous brown soil, medium loam

[0401] 1.4 Experimental conditions: Greenhouse

[0402] 1.5 Implementing Unit: Quwo County Smart Vegetable Valley Development Service Center, Shanxi Province

[0403] Minye Fruit and Vegetable Planting Cooperative, Quwo County, Shanxi Province

[0404] 1.6 Test period: February 7, 2022 – March 15, 2022

[0405] 2. Experimental Materials

[0406] 1.1 Test crops: cucumber and tomato.

[0407] 1.2 Test fertilizers: Medium-element water-soluble fertilizer C1, compound fertilizer (purchased from agricultural input market, N, P2O5, K2O content is 15-15-15).

[0408] 3 Experimental Design

[0409] 3.1 Experimental treatments: Two treatments were set up. Treatment 1 was 10 kg / mu of medium-element water-soluble fertilizer C1; Treatment 2 was 10 kg / mu of compound fertilizer (traditional fertilizer).

[0410] 3.2 Field Design: The total area of ​​the cucumber experiment was 1.8 mu, with a plot area of ​​0.9 mu, numbered as plot 1 and plot 2; the total area of ​​the tomato experiment was 2.0 mu, with a plot area of ​​1.0 mu, numbered as plot 3 and plot 4. The fertilizer application and amount for each plot are shown in Table 24.

[0411] Table 24

[0412] project crop Fertilization treatment Fertilizer application rate Community 1 cucumber Compound fertilizer 10kg / mu Community 2 cucumber Medium element water-soluble fertilizer C1 10kg / mu Community 3 tomato Compound fertilizer 10kg / mu Community 4 tomato Medium element water-soluble fertilizer C1 10kg / mu

[0413] 4. Fertilization methods and timing

[0414] 4.1 Fertilization method: Apply fertilizer with irrigation water.

[0415] 4.2 Fertilization time: Cucumbers should be fertilized once on February 7th and once on February 17th; tomatoes should be fertilized once on February 8th and once on February 18th.

[0416] 4. Experimental Results

[0417] 4.1 Impact on yield

[0418] Yield measurement period: Cucumbers will be harvested every other day from February 9th to March 9th; tomatoes will be harvested daily from February 10th to March 9th.

[0419] Yield measurement method: The yield was measured and recorded in plots at harvest time to obtain the final cumulative yield. The cumulative yield of the plots treated with water-soluble fertilizer C1 (medium-element fertilizer) was compared with that of the plots treated with compound fertilizer. The results are shown in Table 25.

[0420] Table 25

[0421] project crop Cumulative yield (kg / mu) Increase / decrease (%) Community 1 cucumber 2625 —— Community 2 cucumber 3184 21.3 Community 3 tomato 3775 —— Community 4 tomato 4405 16.7

[0422] The experimental results show that, compared with traditional fertilization, the use of medium-element water-soluble fertilizer C1 can increase the yield of cucumbers and tomatoes, with the yield increase of 21.3% for cucumbers and 16.7% for tomatoes.

[0423] 4.2 Impact on blossom-end rot in tomatoes

[0424] Blossom-end rot in tomatoes is a physiological disorder and a common disease in tomato production, significantly impacting the marketability of tomatoes. After harvesting tomatoes from plots 3 and 4, the number of tomatoes with blossom-end rot was counted, and the incidence rate was calculated. The results are shown in Table 26. Blossom-end rot incidence rate = (Number of tomatoes with blossom-end rot / Total number of harvested tomatoes) * 100%.

[0425] Table 26

[0426]

[0427]

[0428] The experimental results show that, compared with traditional fertilization, the use of water-soluble fertilizer C1 with medium-quantity elements can effectively prevent the occurrence of blossom-end rot in tomatoes.

[0429] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A water-soluble fertilizer composition containing medium-quantity elements, characterized in that, The composition contains bone-derived bio-calcium, a nutritional chelating agent, and optional nutritional element additives; The mass ratio of bone-derived biological calcium, nutritional chelating agent, and nutritional element adjuvant, on a dry basis, is 25-50:10-40:0-25. The bone-derived bio-calcium is prepared by the following method: removing insoluble matter, degrading proteins, and separating the waste liquid from bone gelatin production to obtain a liquid containing bone-derived bio-calcium.

2. The composition according to claim 1, wherein, The nutrient element in the nutrient element additive is at least one of nitrogen, phosphorus, potassium, iron, boron, manganese, zinc, copper, molybdenum, silicon, cobalt, vanadium, rare earth elements, titanium, and nickel.

3. The composition according to claim 2, wherein, The nutrient element in the nutrient element additive is at least one of nitrogen, potassium, zinc and boron.

4. The composition according to claim 1, wherein, The nutrient element additive is at least one of urea, potassium nitrate, potassium chloride, zinc nitrate, zinc chloride, and borax.

5. The composition according to claim 1, wherein, The nutritional chelating agent is an amino acid and / or fulvic acid.

6. The composition according to claim 5, wherein, The nutritional chelating agent is an amino acid.

7. The composition according to any one of claims 1-6, wherein, The bone-derived bio-calcium contains a calcium source and water-soluble organic matter; On a dry basis, the mass ratio of calcium source to water-soluble organic matter in the bone-derived bio-calcium is 7-26:1-8 (calculated as elemental calcium). The calcium source exists in the form of free calcium and chelated peptide calcium.

8. The composition according to claim 7, wherein, The bone-derived bio-calcium also contains macro- and micro-elements other than Ca and Cl. On a dry basis, the bone-derived bio-calcium contains 0-3 wt% macro- and micro-elements other than Ca and Cl; wherein the macro- and micro-elements other than Ca and Cl are at least one of P, K, Mg, S, Cu, Fe, Mn, Zn, B, and Mo.

9. The composition according to claim 8, wherein, On a dry basis, the Mg content in the bone-derived bio-calcium is ≥0.55wt%.

10. The composition according to claim 7, wherein, The pH of the bone-derived bio-calcium is 5.5-6.

5.

11. A method for preparing a water-soluble fertilizer containing medium-quantity elements, characterized in that, The method includes: mixing bone-derived bio-calcium, a nutritional chelating agent, and optional nutritional element adjuvants under chelation conditions; The bone-derived bio-calcium is prepared by the following method: removing insoluble matter, degrading proteins, and separating the waste liquid from bone gelatin production to obtain a liquid containing bone-derived bio-calcium.

12. A water-soluble fertilizer containing medium-quantity elements, characterized in that, The medium-element water-soluble fertilizer is prepared by the method described in claim 11.

13. The medium-element water-soluble fertilizer according to claim 12, wherein, The medium-element water-soluble fertilizer is either a liquid product or a solid product.

14. The application of the medium-element water-soluble fertilizer composition according to any one of claims 1-10 or the medium-element water-soluble fertilizer according to claims 12-13 in agricultural production.

15. The application according to claim 14, wherein, The application is in the preparation of water-soluble fertilizers containing medium-quantity elements to increase the fresh weight of crop fruits.

16. The application according to claim 14, wherein, The application is in the preparation of water-soluble fertilizers containing medium-quantity elements to increase crop yield.

17. The application according to claim 14, wherein, The application is in the preparation of water-soluble fertilizers containing medium-quantity elements that increase the calcium content in crops.

18. The application according to claim 14, wherein, The application is in the preparation of water-soluble fertilizers containing medium-quantity elements to improve the quality of crops.

Images