Non-water-soluble medium element granulated fertilizer containing yellow phosphorus slag and preparation method of non-water-soluble medium element granulated fertilizer

Abstract

The invention discloses a non-water-soluble medium-element granular fertilizer containing yellow phosphorus slag, relates to the technical field of chemical waste resource utilization and fertilizer synergism, and solves the problems that the existing medium-element fertilizer cannot be completely absorbed by crops, soil acidification is aggravated after long-term use, soil hardening is caused, and the like. The fertilizer is prepared from the following raw materials in percentage by weight: 80-85% of yellow phosphorus slag; 5-8% of a disintegrating agent; 1-3% of a modifier; 2-5% of trace elements; 1-4% of a biostimulant; the balance is inevitable impurities, and the content of the impurities is controlled to be 0.01-0.2%. The fertilizer is high in disintegration speed, and can provide sufficient nutrient substances for crops during the growth period of the crops, so that the growth vigor of the crops is better, the occurrence rate of crop diseases and insect pests is reduced, the effect of increasing production and income is achieved, and silicon in the yellow phosphorus slag can be effectively dissolved out to be absorbed and utilized by the crops.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of chemical waste resource utilization and fertilizer synergistic effect, and particularly relates to a non-water-soluble medium element granular fertilizer containing yellow phosphorus slag and a preparation method thereof. BACKGROUND

[0002] Soil acidification is a major agricultural environmental problem faced by the world today, especially in the southern region of China, Jiaodong Peninsula and part of the Northeast region, the problem of soil acidification is particularly serious. In recent years, due to long-term unreasonable fertilization, atmospheric acid deposition and industrial pollutants, the process of soil acidification has accelerated, causing a series of chain agricultural problems. The medium elements of calcium, magnesium, silicon and sulfur elements in the cultivated land in China are missing to varying degrees, and this large-scale deficiency of medium and trace elements directly leads to the imbalance of soil nutrient elements, which seriously affects agricultural production.

[0003] The harm of soil acidification mainly manifests in the following aspects: first, it directly damages the root system of crops, inhibits the growth of crops, and leads to yield reduction; second, it activates toxic elements such as aluminum and manganese in the soil, increases their biological availability, and has toxic effects on crops; third, it leads to soil compaction, decline of soil fertility, and destruction of soil structure; fourth, it increases the risk of heavy metal pollution, such as cadmium and other heavy metals, which are more active under acidic conditions and are more easily absorbed by crops and enter the food chain; fifth, it causes nutrient loss, and a large amount of salt-based ions such as calcium, magnesium and potassium are leached, leading to soil barrenness.

[0004] The causes of soil acidification are complex and diverse, mainly including natural factors and human factors. The natural factors mainly include the leaching and loss of alkaline salt-based ions caused by the high-temperature and rainy climate in the south; and the human factors include long-term excessive application of chemical nitrogen fertilizer, acid deposition caused by industrial emissions (sulfur oxides and nitrogen oxides form acid rain) and pollutants caused by industrial production. These factors superimpose on each other, accelerate the process of soil acidification, and make the acidification area of cultivated land in China reach about 919 million mu (pH < 6.5), among which the area of strong acid soil (pH < 5.5) has increased from about 169 million mu in the 1980s to 226 million mu in the early 21st century, and has increased in the past 30 years.

[0005] Yellow phosphorus slag is a solid waste produced in the process of producing yellow phosphorus by electric furnace method, and its main components are CaSiO3, phosphorus silicate, etc. rich in silicon, calcium, medium and trace elements and a small amount of unreacted elemental phosphorus, iron and aluminum oxides, which can be used as soil conditioner or fertilizer raw material. According to statistics, about 8-10 tons of yellow phosphorus slag are produced for every ton of yellow phosphorus. As the largest yellow phosphorus producer in the world, more than 8 million tons of yellow phosphorus slag is disposed by stacking every year in China, but the comprehensive utilization rate of yellow phosphorus slag is low at present.

[0006] The main utilization ways of yellow phosphorus slag at present include: filling the mined-out area of mine, producing building materials, producing fertilizer, etc. In the application of fertilizer, some studies have attempted to use yellow phosphorus slag mixed with other auxiliary agents as coating material to prepare slow-release fertilizer, and to add yellow phosphorus slag in livestock and poultry manure to prepare phosphorus and silicon-rich compost products, etc. However, these utilization methods generally have problems such as low efficiency, high cost, unstable effect, etc., and have not effectively solved the large-scale resource utilization problem of yellow phosphorus slag.

[0007] The difficulties in the treatment of yellow phosphorus slag mainly lie in the following aspects: first, strong alkaline pollution: yellow phosphorus slag is strongly alkaline (pH value as high as 10-12), direct application can easily lead to soil compaction; second, physical performance defects: the true density of yellow phosphorus slag is 2.8-3.2 g / cm³, the natural angle of repose is >45°, the flowability is poor, direct use in fertilizer production has problems such as difficulty in granulation, low particle strength, etc., and the powdery characteristics of yellow phosphorus slag can easily cause dust pollution; third, the modification technology is not mature, the existing modification methods have high cost and poor effect, and are difficult to be applied on a large scale.

[0008] At present, some documents also disclose the use of yellow phosphorus slag to prepare calcium-silicon-magnesium fertilizer, such as patent application CN119263920A, which discloses a method for preparing polymeric calcium-magnesium fertilizer from yellow phosphorus slag. The product obtained by the reaction of yellow phosphorus slag with raffinate acid is used as raw material, and the phosphorus, calcium and magnesium elements in phosphoric acid slag and yellow phosphorus slag are fully utilized to form polymeric phosphorus, calcium and magnesium elements. The technical problems of high pH value of yellow phosphorus slag as fertilizer raw material and the difficulty in utilizing the effective calcium, magnesium and silicon elements of yellow phosphorus slag are solved. The phosphorus in the prepared product has slow-release property, and the phosphorus in the product will not be quickly fixed when applied to soil, but slowly releases orthophosphate to meet the needs of crops. Due to the action of polyphosphoric acid, magnesium and calcium are not easily leached by water, and the product is particularly suitable for crops with high demand for calcium and magnesium. For example, patent application CN113582780A discloses a phosphorus and silicon-rich compost product prepared by adding yellow phosphorus slag and a production method thereof, which comprises the following steps: adding 5-20% (w:w) of yellow phosphorus slag to livestock and poultry manure, uniformly mixing with compost conditioner, and carrying out high-temperature aerobic composting to obtain compost product after the temperature rising period, high-temperature period, temperature decreasing period and composting period. The total phosphorus content of the compost product produced by this method is higher than 2%, the total silicon content is higher than 10%, the citric acid-soluble phosphorus content is not less than 0.5%, and the citric acid-soluble silicon content is not less than 0.9%. The use of yellow phosphorus slag to produce organic fertilizer can significantly increase the phosphorus and silicon content of organic fertilizer, and the product is nutrient-rich, has great market potential and broad prospects, and solves the environmental problems caused by the large-scale storage of yellow phosphorus slag. However, the above methods cannot effectively dissolve the silicon in yellow phosphorus slag, which makes it difficult for crops to absorb and utilize it.

[0009] Medium elements are essential nutrients for crop growth, although the demand is not as much as nitrogen, phosphorus and potassium, but play a key role in crop physiological metabolism. Silicon can enhance the strength of the stem, improve the ability to resist lodging; calcium promotes the formation of cell wall, improve fruit quality; potassium regulates water metabolism, enhances resistance; magnesium is the core component of chlorophyll, directly involved in the process of photosynthesis. In addition, these elements also participate in enzyme activation, nutrient transport, energy conversion and other important physiological processes to ensure the healthy growth of crops.

[0010] The medium element fertilizer on the market at present is dominated by water-soluble fertilizer, such as calcium magnesium nitrate, calcium ammonium nitrate, calcium chloride, etc. Although it can be completely and rapidly dissolved in water and easily absorbed by crops, it contains acid ions, which can aggravate the problem of soil acidification if used for a long time. Moreover, not all raw materials used can be completely absorbed by crops, causing problems such as soil compaction.

[0011] Although yellow phosphorus slag is rich in medium elements such as calcium, magnesium and silicon, its strong alkalinity (pH 10-12) can lead to problems such as degradation of water-soluble phosphorus and ammonia volatilization if used directly as fertilizer. In addition, the physical properties (particle size, solubility, etc.) of yellow phosphorus slag are not suitable for direct application as fertilizer. It is particularly important to develop a method for producing non-water-soluble medium element granular fertilizer using yellow phosphorus slag. SUMMARY

[0012] In view of the above shortcomings, the present application provides a non-water-soluble medium element granular fertilizer containing yellow phosphorus slag and a preparation method thereof. The fertilizer has a fast disintegration rate and can provide sufficient nutrients for crops during their growth, resulting in better growth and reduced incidence of crop diseases and pests, thereby achieving the effect of increasing yield and income. Silicon in the yellow phosphorus slag can be effectively dissolved and absorbed by crops. The specific technical solutions are as follows: A non-water-soluble medium element granular fertilizer containing yellow phosphorus slag is made from the following raw materials by weight percentage: Yellow phosphorus slag 80-85%; Disintegrating agent 5-8%; Modifier 1-3%; Trace elements 2-5%; Biostimulants 1-4%; The balance is unavoidable impurities, and the impurity content is controlled at 0.01-0.2%.

[0013] Preferably, the disintegrating agent is biochemical fulvic acid powder or attapulgite powder.

[0014] Preferably, the modifier includes a hydrophilic silica modifier, a hydrophilic calcium carbonate modifier, a hydrophilic magnesium carbonate modifier. The hydrophilic silica modifier is hexamethyldisilazane (HMDS) and / or dimethyldichlorosilane (DDS); the hydrophilic calcium carbonate modifier is sodium stearate; and the hydrophilic magnesium carbonate modifier is a titanate coupling agent.

[0015] Preferably, the trace elements are boric acid, ferrous sulfate, and zinc sulfate, and the mass ratio of boric acid, ferrous sulfate, and zinc sulfate is (2.8-3.2):1:1.

[0016] Preferably, the biological stimulant is one or more of biochemical fulvic acid fermentation broth, fish peptide enzymatic hydrolysate, shrimp peptide enzymatic hydrolysate, seaweed enzymatic hydrolysate, fruit oligosaccharide-containing molasses fermentation broth, chitosan, and GeDong-like Bacillus.

[0017] The preparation method of the biochemical fulvic acid fermentation broth is: biochemical fulvic acid is fermented by using Saccharomyces cerevisiae, Aspergillus oryzae, and / or Aspergillus niger; and the inoculation amount of the Saccharomyces cerevisiae, Aspergillus oryzae, and / or Aspergillus niger is 1.1%, 0.2%, and 0.3% of the weight of the biochemical fulvic acid, respectively.

[0018] The preparation method of the fish peptide enzymatic hydrolysate is: fish offal is crushed into fish paste, mixed according to a water-to-fish paste weight ratio of 1-2:1, heated to above 90℃ for 10-15 min for sterilization, cooled to 50-55℃ for incubation, the pH value of the enzymatic hydrolysis reaction system is controlled to be 6.5-7.5, 0.1%-0.3% of the weight of the fish paste of protease solution at a temperature of 50℃ is added, intermittent slow stirring is performed for 2.5-3.5 h, the enzyme is inactivated, and cooling and filtration are performed to obtain the fish peptide enzymatic hydrolysate.

[0019] The preparation method of the shrimp peptide enzymatic hydrolysate is: shrimp heads, shells, or small miscellaneous shrimps are crushed into shrimp paste, mixed according to a water-to-shrimp paste weight ratio of 1-1.5:1, heated to above 90℃ for 10-15 min for sterilization, cooled to 50-55℃ for incubation, the pH value of the enzymatic hydrolysis reaction system is controlled to be 7.0-8.0, 0.1%-0.3% of the weight of the shrimp paste of protease solution at a temperature of 50℃ is added, intermittent slow stirring is performed for 2.5-3.5 h, the enzyme is inactivated, and cooling and filtration are performed to obtain the shrimp peptide enzymatic hydrolysate.

[0020] The preparation method of the fruit oligosaccharide-containing molasses fermentation broth is: sugarcane molasses is fermented by using Aspergillus oryzae and / or Aspergillus niger. The specific steps are disclosed in the prior patent application (patent application number: CN202411889591.2, patent name: A method for preparing an agricultural biological stimulant containing fruit oligosaccharides from molasses and its application) of the applicant.

[0021] Preferably, the non-water-soluble secondary element granular fertilizer has a pH value of 9.8-10.2, a moisture content of 0.7-1.0%, a particle size of 1.00-4.75 mm, a non-water-soluble secondary element content of 34-39%, wherein the calcium content is 33-34% and the magnesium content is 1-3%.

[0022] Preferably, the preparation method of the non-water-soluble secondary element granular fertilizer comprises the following steps: (1) the yellow phosphorus slag is sent into a pulverizer for pulverization, a modifier is added for modification, a disintegrating agent and trace elements are added for mixing, and a mixture is obtained; (2) the mixture of step (1) is transferred into a high-efficiency round-pot granulator, a biological stimulant aqueous solution is sprayed, and the non-water-soluble secondary element granular fertilizer is obtained.

[0023] Preferably, in step (1), the pulverization is to a particle size of 200-300 mesh.

[0024] Preferably, in step (1), the stirring speed of the modification is 2000-2500 r / min, and the time is 20-40 min.

[0025] Preferably, in step (2), the rotation speed of the high-efficiency round-pot granulator is 15-20 r / min.

[0026] Since there is a small amount of hydrophobic substances in the yellow phosphorus slag, such as gunnellite (3CaO·SiO2·CaF2), the hydrophobic substances are not easy to be absorbed and utilized by crops, the yellow phosphorus slag is modified by adding a modifier, so that the hydrophobic substances in the yellow phosphorus slag are dissolved, thereby being more easily absorbed and utilized by crops.

[0027] Chitosan is a naturally occurring component in fungi, nematodes, insects and crustaceans, which regulates the plant defense mechanism related to plant toxin biosynthesis, active oxygen and pathogenicity-related proteins, so that the plant has stronger resistance to biological and non-biological stress.

[0028] Bacillus jingdonensis is a silicate bacterium, which can promote the absorption of silicon elements by plants.

[0029] Compared with the prior art, the present application has the following advantages: 1. In the prior art, many fertilizer disintegrating agents are chemical disintegrating agents, and pure chemical disintegrating agents cannot be utilized by crops. The biochemical fulvic acid in the present application is plant nutrition itself, can dissolve silicon in the yellow phosphorus slag (so that the silicon is more easily absorbed by crops), has a disintegrating effect, contains nutrients that can be absorbed by crops after degradation, and can improve the soil. The biochemical fulvic acid is like a "prebiotic" for the soil, which can provide nutrients for soil microorganisms.

[0030] 2. The invention modifies yellow phosphorus slag, which makes the hydrophobic substances in the yellow phosphorus slag dissolve and release in ionic form, which is not only more easily absorbed and utilized by crops, but also fully mobilizes the sulfate, phosphate, borate and other anions in the soil, adjusts the balance between soil anions and cations; at the same time, the calcium, magnesium, iron, copper and other cations contained in the yellow phosphorus slag and other raw materials can also make the soil elements more balanced; after the granular fertilizer is applied to the soil, the insoluble hydrophobic substances are slowly released and dissolved under the action of the modifier, and are absorbed by the crop root system, achieving slow-release effect, thereby greatly improving the immunity of plants and enhancing the disease resistance of crops.

[0031] 3. The biochemical fulvic acid and the biochemical fulvic acid fermentation liquor used in the invention are excellent natural chelating agents, which can wrap around the calcium ions (Ca²⁺), magnesium ions (Mg²⁺) and the like dissolved from the fertilizer, forming stable, small-molecular-weight fulvic acid-metal complexes, effectively preventing these elements from being fixed in the soil (such as calcium forming insoluble substances with phosphate), greatly improving the effectiveness and mobility of secondary elements; they can also stimulate plant root growth, making the root system more developed, thereby expanding the nutrient absorption area and allowing crops to more effectively contact and absorb the activated fertilizer; in addition, they can also provide carbon sources and energy for beneficial microorganisms, promote microbial reproduction, and further promote fertilizer dissolution. The biochemical fulvic acid fermentation liquor, fish peptide enzymatic hydrolysate, shrimp peptide enzymatic hydrolysate and other substances in the biological stimulant are rich in small-molecule peptides, amino acids and plant hormone precursors such as cytokinins and auxins (IAA), which can be directly absorbed by the root system, transmitting the "growth-promoting" signal to the plant, directly stimulating cell division and elongation; moreover, these amino acids and peptide segments themselves are also excellent organic chelating agents, which can assist the biochemical fulvic acid and the biochemical fulvic acid fermentation liquor in activating the granular fertilizer.

[0032] 4. The effective substances of the non-water-soluble secondary element granular fertilizer of the invention can be dissolved and absorbed and utilized by crops, and each raw material used can be degraded after being applied to the soil, easily absorbed by crops, and completely absorbed and utilized by crops after degradation, without aggravating soil acidification and causing soil compaction and other problems in the long term. Moreover, since the non-water-soluble secondary element granular fertilizer is alkaline, it can also neutralize the pH value of acidic soil when applied to acidic soil, thereby effectively improving the pH value of acidic soil and improving the soil. The non-water-soluble secondary element granular fertilizer can provide sufficient nutrients for crops during their growth, making the crops grow better and reducing the incidence of crop diseases and pests, thereby achieving the effect of increasing yield and income.

[0033] 5. The non-water-soluble micronutrient granular fertilizer of the present application adds disintegrating agent biochemical fulvic acid in the non-water-soluble micronutrient granular fertilizer, the fertilizer can quickly disintegrate in the soil to provide the fertilizer for crops, and the fertilizer is slowly released and dissolved under the action of the modifier, the nutrient release period matches the crop fertilizer requirement law, effectively avoiding the problem of affecting crop growth caused by "early stage starvation and late stage enrichment"; and in the preparation process, the biological stimulant aqueous solution is added by spraying, the granular fertilizer forms a core structure of yellow phosphorus slag and modifier as the core and the biological stimulant aqueous solution as the shell. BRIEF DESCRIPTION OF DRAWINGS

[0034] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiment description. Obviously, the drawings in the following description are some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creating labor on the premise that the drawings are not limited.

[0035] Figure 1 The finished product of the non-water-soluble micronutrient granular fertilizer containing yellow phosphorus slag prepared by the method of the present application; Figure 2 The non-water-soluble micronutrient granular fertilizer containing yellow phosphorus slag prepared by the method of the present application disintegrates when meeting water. DETAILED DESCRIPTION

[0036] The specific embodiments of the present application will be described in detail below, but it should be understood that the protection scope of the present application is not limited by the specific embodiments. Unless otherwise defined, all professional terms used in the following are the same as those commonly understood by those skilled in the art. The professional terms used in this paper are only for the purpose of describing the specific embodiments and are not intended to limit the protection scope of the present application. Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present application can be purchased from the market or can be prepared by existing methods.

[0037] Example 1 A non-water-soluble micronutrient granular fertilizer containing yellow phosphorus slag is made of the following raw materials by weight percentage: yellow phosphorus slag 80%, disintegrating agent 8%; modifier 3%, trace elements 5%, biological stimulant 4%, and unavoidable impurities.

[0038] Among them, the disintegrating agent is biochemical fulvic acid powder; the modifier is hexamethyldisilazane (HMDS), sodium stearate and titanate coupling agent; the trace elements are boric acid, ferrous sulfate and zinc sulfate, and the mass ratio of boric acid, ferrous sulfate and zinc sulfate is 2.8:1:1; the biological stimulant is biochemical fulvic acid fermentation broth, fish peptide enzymatic hydrolysate and shrimp peptide enzymatic hydrolysate with a mass ratio of 1:1:1.

[0039] The pH value of the non-water-soluble micronutrient granular fertilizer is 9.8, the moisture content is 0.7%, the particle size is 1.00 mm, the non-water-soluble micronutrient content is 34%, and the calcium content is 33% and the magnesium content is 2%.

[0040] A preparation method of the non-water-soluble micronutrient granular fertilizer comprises the following steps: (1) The yellow phosphorus slag is sent into a pulverizer to be crushed to a mesh particle size of 200 mesh, a modifier is added and uniformly mixed, stirring modification is performed at a speed of 2000 r / min for 20 min, then a disintegrating agent and trace elements are added and uniformly mixed to obtain a mixture; (2) The mixture of step (1) is transferred into a high-efficiency round pot granulator at a speed of 15 r / min, a biological stimulant aqueous solution is sprayed on one side, and granulation is performed on the other side to obtain the non-water-soluble micronutrient granular fertilizer.

[0041] Example 2 A non-water-soluble micronutrient granular fertilizer containing yellow phosphorus slag is prepared from the following raw materials by weight percentage: yellow phosphorus slag 85%, disintegrating agent 5%; modifier 3%, trace elements 5%, biological stimulant 2%, and unavoidable impurities.

[0042] The disintegrating agent is attapulgite powder; the modifier includes a hydrophilic silicon dioxide modifier, a hydrophilic calcium carbonate modifier, and a hydrophilic magnesium carbonate modifier; the trace elements are boric acid, ferrous sulfate, and zinc sulfate, and the mass ratio of boric acid, ferrous sulfate, and zinc sulfate is 3.2:1:1; the biological stimulant is biochemical fulvic acid fermentation liquor, seaweed enzymatic hydrolysate, fruit oligosaccharide-containing molasses fermentation liquor, and Jiaodong-like Bacillus sp.

[0043] The pH value of the non-water-soluble micronutrient granular fertilizer is 10.2, the moisture content is 1.0%, the particle size is 4.75 mm, the non-water-soluble micronutrient content is 39%, the calcium content is 34%, and the magnesium content is 2%.

[0044] A preparation method of the non-water-soluble micronutrient granular fertilizer comprises the following steps: (1) The yellow phosphorus slag is sent into a pulverizer to be crushed to a mesh particle size of 300 mesh, a modifier is added and uniformly mixed, stirring modification is performed at a speed of 2500 r / min for 40 min, then a disintegrating agent and trace elements are added and uniformly mixed to obtain a mixture; (2) The mixture of step (1) is transferred into a high-efficiency round pot granulator at a speed of 20 r / min, a biological stimulant aqueous solution is sprayed on one side, and granulation is performed on the other side to obtain the non-water-soluble micronutrient granular fertilizer.

[0045] Example 3 A non-water-soluble secondary element granular fertilizer containing yellow phosphorus slag is made from the following raw materials by weight percentage: yellow phosphorus slag 82%, disintegrating agent 6%; modifier 3%, trace elements 5%, biological stimulant 4%, and unavoidable impurities.

[0046] The disintegrating agent is biochemical fulvic acid powder; the modifier is dimethyldichlorosilane (DDS), sodium stearate, and titanate coupling agent; the trace elements are boric acid, ferrous sulfate, and zinc sulfate, and the mass ratio of boric acid, ferrous sulfate, and zinc sulfate is 2.9:1:1; the biological stimulant is biochemical fulvic acid fermentation liquor, shrimp peptide enzymatic hydrolysate, seaweed enzymatic hydrolysate, chitosan, and GaoDong-like Bacillus sp. in a mass ratio of 1:1:1:1:1.

[0047] The pH value of the non-water-soluble secondary element granular fertilizer is 9.9, the water content is 0.8%, the particle size is 2.00 mm, the non-water-soluble secondary element content is 35%, the calcium content is 33%, and the magnesium content is 3%.

[0048] A preparation method of the non-water-soluble secondary element granular fertilizer comprises the following steps: (1) The yellow phosphorus slag is sent into a pulverizer to be pulverized to a mesh particle size of 220 mesh, the modifier is added and uniformly mixed, stirred at a speed of 2100 r / min for 25 min, then the disintegrating agent and the trace elements are added and uniformly mixed to obtain a mixture; (2) The mixture of step (1) is transferred into a high-efficiency round-pot granulator at a speed of 16 r / min, the biological stimulant aqueous solution is sprayed, and granulation is performed to obtain the non-water-soluble secondary element granular fertilizer.

[0049] Example 4 A non-water-soluble secondary element granular fertilizer containing yellow phosphorus slag is made from the following raw materials by weight percentage: yellow phosphorus slag 84%, disintegrating agent 8%; modifier 1%, trace elements 5%, biological stimulant 2%, and unavoidable impurities.

[0050] The disintegrating agent is biochemical fulvic acid powder and attapulgite powder in a mass ratio of 1:1; the modifier is hexamethyldisilazane (HMDS), sodium stearate, and titanate coupling agent; the trace elements are boric acid, ferrous sulfate, and zinc sulfate, and the mass ratio of boric acid, ferrous sulfate, and zinc sulfate is 3.1:1:1; the biological stimulant is biochemical fulvic acid fermentation liquor, fish peptide enzymatic hydrolysate, shrimp peptide enzymatic hydrolysate, seaweed enzymatic hydrolysate, chitosan, and GaoDong-like Bacillus sp. in a mass ratio of 1:1:1:1:1:1.

[0051] The pH value of the non-water-soluble secondary element granular fertilizer is 10.1, the water content is 0.9%, the particle size is 4.00 mm, the non-water-soluble secondary element content is 38%, the calcium content is 34%, and the magnesium content is 2%.

[0052] A preparation method of the non-water-soluble secondary element granular fertilizer as described above, comprising the following steps: (1) The yellow phosphorus slag is sent into a pulverizer to be pulverized to a mesh particle size of 280 meshes, a modifier is added and uniformly mixed, stirring modification is performed at a rotating speed of 2400 r / min for 35 min, then a disintegrating agent and trace elements are added and uniformly mixed to obtain a mixture; (2) The mixture of step (1) is transferred into a high-efficiency round pot granulator with a rotating speed of 19 r / min, a biological stimulant aqueous solution is sprayed on one side, and granulation is performed on the other side to obtain the non-water-soluble secondary element granular fertilizer.

[0053] Example 5 A non-water-soluble secondary element granular fertilizer containing yellow phosphorus slag is prepared from the following raw materials by weight percentage: yellow phosphorus slag 83%, disintegrating agent 7%; modifier 3%, trace elements 4%, biological stimulant 3%, and unavoidable impurities.

[0054] The disintegrating agent is biochemical fulvic acid powder and attapulgite powder with a mass ratio of 1:1; the modifier is a hydrophilic silicon dioxide modifier, sodium stearate and a titanate coupling agent; the modifier of the hydrophilic silicon dioxide is hexamethyldisilazane (HMDS) and dimethyldichlorosilane (DDS) with a mass ratio of 1:1; the trace elements are boric acid, ferrous sulfate and zinc sulfate, and the mass ratio of boric acid, ferrous sulfate and zinc sulfate is 3:1:1; the biological stimulant is biochemical fulvic acid fermentation liquor, fish peptide enzymatic hydrolysate, shrimp peptide enzymatic hydrolysate, seaweed enzymatic hydrolysate, molasses fermentation liquor containing fructo-oligosaccharides and Gengdong-like Bacillus sp. with a mass ratio of 1:1:1:1:1:1.

[0055] The pH value of the non-water-soluble secondary element granular fertilizer is 10, the moisture content is 0.8%, the particle size is 3.00 mm, the non-water-soluble secondary element content is 36%, of which the calcium content is 34% and the magnesium content is 2%.

[0056] A preparation method of the non-water-soluble secondary element granular fertilizer as described above, comprising the following steps: (1) The yellow phosphorus slag is sent into a pulverizer to be pulverized to a mesh particle size of 250 meshes, a modifier is added and uniformly mixed, stirring modification is performed at a rotating speed of 2300 r / min for 30 min, then a disintegrating agent and trace elements are added and uniformly mixed to obtain a mixture; (2) The mixture of step (1) is transferred into a high-efficiency round pot granulator with a rotating speed of 17 r / min, a biological stimulant aqueous solution is sprayed on one side, and granulation is performed on the other side to obtain the non-water-soluble secondary element granular fertilizer.

[0057] Comparative Example 1 The difference from Example 1 is that the disintegrating agent is replaced by polyvinylpyrrolidone, and other conditions remain unchanged.

[0058] Comparative Example 2 The difference from Example 1 is that the modifier is replaced by phosphogypsum, and other conditions remain unchanged.

[0059] Comparative Example 3 The difference from Example 1 is that no biological stimulant is added, and other conditions remain unchanged.

[0060] Comparative Example 4 The difference from Example 1 is that the preparation method of the non-water-soluble micronutrient element granular fertilizer comprises the following steps: uniformly stirring yellow phosphorus slag, a disintegrating agent, a modifier, trace elements and a biological stimulant, placing them in an extrusion granulator, performing extrusion granulation, screening fertilizer particles meeting the particle size requirement, and sending them into a drying device for drying, and other conditions remain unchanged.

[0061] 1. Disintegration speed test The same amount of granular fertilizer prepared by the method of Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4 is respectively placed in normal temperature pure water, and the solid-liquid ratio of each experiment is 1:50. The structure disappearance (fragments not greater than 2mm) of the granular fertilizer is observed by visual method, and the time required for complete disintegration of the granular fertilizer is recorded. Each group is repeated 10 times, and the average value is taken as the result. The experimental results are shown in Table 1 below.

[0062] Table 1 Disintegration performance comparison From the above experiments, it can be seen that the disintegration time of the granular fertilizer of the present application is more reasonable.

[0063] 2. Field experiment In order to test the application effect of the non-water-soluble micronutrient element granular fertilizer produced by the present application on citrus, the applicant carried out citrus fertilizer application effect test in two places in Lingchuan County, Guangxi in 2023 according to the requirements of the Ministry of Agriculture and Rural Affairs "Fertilizer Registration Management Method", "Fertilizer Registration Guide" and "Fertilizer Effect Test and Evaluation General Requirements" (NY / T2544-2014). The specific test conditions are as follows: Test Example 1 In July-December 2023, a plot test of citrus fertilizer application effect was carried out in Youjiang Village, Sanjie Town, Lingchuan County. The specific test method and test results are as follows: 1. Materials and methods 1.1 Test soil The test was carried out in July 2023 in Li Xinrong's contracted field in Lujiang Village, Sanjie Town, Lingchuan County (East longitude: 110.382572, North latitude: 25.501713). The soil for the test is water and soil, the soil name is Yuchao mud field, the soil texture is sandy loam, the terrain is flat, the fertility is medium and uniform, the drainage is convenient, and no fertilizer test has been done in recent years. The soil nutrients in the plough layer are: organic matter 26.4 g / kg, total nitrogen 1.83 g / kg, available phosphorus (P0) 24.7 mg / kg, available potassium (K0) 66.0 mg / kg, and pH value 5.5. The test crop is citrus, the variety is: sand sugar orange, the tree age is 6 years, the planting specification is 2.5*3.0m, and 89 are planted per mu. The non-water-soluble medium element granular fertilizer (Ca+Mg≥20.0%; particle size (1.00mm-4.75mm)≥90%; dosage form: granules) prepared by the present application Example 1 is used for the test.

[0064] 1.2 Test method The test has three treatments, three repetitions, and random block arrangement. The plot area is 67.5m (9 fruit trees), and the test treatments are as follows: Treatment 1: conventional fertilization + application of non-water-soluble medium element granular fertilizer prepared by Example 1. In the fruit swelling period, non-water-soluble medium element granular fertilizer prepared by Example 1 is applied once, and 30kg / mu of the product is used as topdressing.

[0065] Treatment 2: blank control.

[0066] Treatment 3: conventional fertilization.

[0067] Conventional fertilization: 45% compound fertilizer 95 kg, potassium sulfate 20 kg per mu.

[0068] 1.3 Test process Topdressing time: according to the test requirements, non-water-soluble medium element granular fertilizer prepared by Example 1 is applied once on July 20, treatment 2 does not apply anything, and treatment 3 is conventionally fertilized.

[0069] Conventional fertilization: base fertilizer is applied on February 21: compound fertilizer 45 kg; first topdressing is applied on May 18: each treatment applies compound fertilizer 25 kg per mu; second topdressing is applied on July 20: each treatment applies compound fertilizer 25 kg per mu; third topdressing is applied on September 28: each treatment applies potassium sulfate 20 kg per mu. Except for different test fertilization, other fertilization, pest control and other agricultural operation factors are consistent for each treatment in the test.

[0070] On December 22, 2023, the plots were harvested, and each treatment plot was harvested separately and the yield was calculated. Before harvesting, 5 plants were randomly selected for each treatment to investigate the biological characteristics of sand sugar orange.

[0071] 2 Test results and analysis 2.1 Effects of different treatments on biological characteristics of sugar orange Table 2 Effects of different treatments on biological characteristics of sugar orange As shown in Table 2, compared with conventional fertilization (treatment 3), the average number of fruits per plant of the sugar orange treated with the non-water-soluble medium element granular fertilizer prepared in Example 1 (treatment 1) increased by 8.5, the average weight of single fruit increased by 2.7 g, the yield per plant increased by 2.3 kg, the soluble solids increased by 0.8%, the leaf color was darker, and the incidence of diseases and pests was lower.

[0072] 2.2 Effects of different treatments on yield of sugar orange Table 3 Yield statistics of sugar orange in different treatment plots The test results showed that the yield per mu of treatment 1 was increased by 206.1 kg, and the yield was increased by 6.9% compared with treatment 3.

[0073] 2.3 Variance analysis Table 4 Results of variance analysis table The results of variance analysis showed that the F value between treatments was 4116.40, which was greater than F0.01, and the difference between treatments reached a very significant level. The F value between blocks was 1.80 < (F) 6.94, indicating that the fertility of the test field was uniform, and the test was reliable.

[0074] 2.4 New complex difference comparison and significance test Table 5 Results of new complex difference comparison and significance test From the results of new complex difference comparison, the yield per mu of treatment 1 was increased by 206.1 kg, and the yield was increased by 6.9% compared with treatment 3, and the difference was extremely significant.

[0075] 2.5 Input-output ratio benefit of different treatments Table 6 Economic benefit table of sugar orange in different treatments Note: Each kg of sugar orange is calculated at 4.2 yuan, the non-water-soluble medium element granular fertilizer (granules) prepared in Example 1 is calculated at 4000 yuan / t, the compound fertilizer is calculated at 6 yuan / kg, and the potassium sulfate is calculated at 8 yuan / kg. Other inputs include pesticide, field management labor cost and other expenses, and the difference is due to the increased cost of fertilization in treatment 1 and treatment 3.

[0076] As shown in Table 6, based on the actual production acceptance of input-output fertilizer efficiency, Treatment 1, which combined conventional fertilization with the application of the non-water-soluble granular fertilizer prepared in Example 1, increased income per mu by 865.62 yuan and 7254.09 yuan compared to conventional fertilization and the blank control, respectively. After deducting fertilizer and other investments, the increased income was 745.62 yuan and 6244.09 yuan, respectively. In summary, the application of the non-water-soluble granular fertilizer prepared in Example 1 can effectively increase the yield and income of tangerines.

[0077] The above experiments show that, on the basis of conventional fertilization, the application of the non-water-soluble granular fertilizer of medium-element fertilizer prepared in Example 1 of this application to tangerines increased the yield by 206.1 kg / mu (6.9%) compared with conventional fertilization, and the biostatistical test reached a highly significant level. The application of the non-water-soluble granular fertilizer of medium-element fertilizer prepared in Example 1 can effectively increase the yield and income of tangerines. Treatment 1, conventional fertilization + application of the non-water-soluble granular fertilizer of medium-element fertilizer prepared in Example 1, increased income by RMB 865.62 and RMB 7254.09 per mu compared with conventional fertilization and the blank control, respectively. After deducting fertilizer and other investments, the increased revenue was RMB 745.62 and RMB 6244.09, respectively.

[0078] Experimental Example 2 A small-plot experiment on the fertilizer application effect on citrus was conducted in Huangbai Village, Tanxia Town, Lingchuan County from July to December 2023. The specific experimental methods and results are as follows: 1. Materials and Methods 1.1 Test Soil The experiment was conducted in July 2023 on a contracted field of Li Huibao in Huangbai Village, Tanxia Town, Lingchuan County (110.285365 E, 25.467814 N). The test soil was paddy soil, named "fertile tidal sandy loam," with a sandy loam texture, flat terrain, moderate and uniform fertility, and convenient irrigation and drainage. No fertilizer trials had been conducted in recent years. The topsoil nutrients were: organic matter 27.8 g / kg, total nitrogen 1.96 g / kg, available phosphorus (P0) 24.9 mg / kg, available potassium (K0) 83.5 mg / kg, and pH 6.0. The test crop was citrus, variety: Satsuma mandarin orange, 6 years old, planted at a spacing of 2.3*3.5m, with 83 trees per mu (approximately 0.067 hectares). The non-water-soluble granular fertilizer containing medium-quantity elements prepared in Example 2 of this invention (Ca+Mg≥20.0%; particle size (1.00mm-4.75mm)≥90%; formulation: granules) was tested.

[0079] 1.2 Test Methods The experiment consisted of three treatments, with three replicates, arranged in a randomized block design. The plot size was 64.4 m² (8 fruit trees). The treatments were as follows: Treatment 1: Conventional fertilization + application of the non-water-soluble granular fertilizer of medium elements prepared in Example 2. Apply the non-water-soluble granular fertilizer of medium elements prepared in Example 2 once during the fruit enlargement period, using 30 kg / mu of this product as top dressing.

[0080] Treatment 2: blank control.

[0081] Treatment 3: conventional fertilization.

[0082] Conventional fertilization: 45% compound fertilizer 92 kg, potassium sulfate 25 kg per mu.

[0083] 1.3 Test process Time of application: according to the requirements of the test, on July 25, treatment 1 was applied with non-water-soluble medium element granular fertilizer prepared in example 2 once; treatment 2 was not applied with anything; treatment 3 was conventional fertilization.

[0084] Conventional fertilization: base fertilizer was applied on February 21: compound fertilizer 42 kg; first time of application of topdressing: each treatment was applied with compound fertilizer 25 kg per mu; second time of application of topdressing: each treatment was applied with compound fertilizer 25 kg per mu; third time of application of topdressing: each treatment was applied with potassium sulfate 25 kg per mu.

[0085] In the test, the different factors of fertilization, disease and pest control and other agricultural operations were consistent except for the different spraying of fertilizers.

[0086] On December 26, 2023, all plots were harvested, and each treatment plot was harvested separately, and the yield was calculated. Before harvesting, 5 plants were randomly and continuously taken for each treatment to investigate the biological characteristics of sugar orange.

[0087] 2 Test results and analysis 2.1 Effect of different treatments on the biological characteristics of sugar orange Table 7 Effect of different treatments on the biological characteristics of sugar orange As shown in Table 7, compared with conventional fertilization (treatment 3), the average number of fruits per plant of treatment 1 (non-water-soluble medium element granular fertilizer prepared in example 2) increased by 9.5, the average weight of single fruit increased by 3.7 g, the yield per plant increased by 2.9 kg, the soluble solids increased by 0.8%, the leaf color was darker, and the incidence of disease and pests was lower.

[0088] 2.2 Effect of different treatments on the yield of sugar orange Table 8 Yield statistics table of sugar orange in different treatment plots The test results showed that the average yield per mu of treatment 1 was increased by 236.7 kg, which was 8.4% higher than that of treatment 3.

[0089] 2.3 Variance analysis Table 9 Results of variance analysis table The results of variance analysis showed that the F value between treatments was 998.00, which was greater than F0.01, and the difference between treatments reached a very significant level. The F value between plots was 2.21<(F)6.94, indicating that the fertility of the test field was uniform and the test was reliable.

[0090] 2.4 New range comparison and significance test Table 10 New range comparison and significance test results table From the results of the new range comparison in Table 10, the yield per mu of treatment 1 was increased by 236.7 kg, an increase of 8.4%, compared with treatment 3, and the difference was extremely significant.

[0091] 2.5 Input-output ratio benefit of different treatments Table 11 Economic benefit table of different treatments of sand sugar orange Note: Each kg of sand sugar orange is calculated at 4.2 yuan, the non-water-soluble medium element granular fertilizer prepared in Example 2 is calculated at 4000 yuan / t, the compound fertilizer is calculated at 6 yuan / kg, and the potassium sulfate is calculated at 8 yuan / kg. Other inputs include pesticide, field management labor cost and other expenses, and the difference is that treatment 1 and treatment 3 increase the use of fertilizer.

[0092] Through the input-output efficiency of the actual production acceptance (see Table 11), the conventional fertilization + the non-water-soluble medium element granular fertilizer prepared in Example 2 per mu increased the income by 994.25 and 7507.62 yuan compared with the conventional fertilization and the blank control, respectively, and the net income was increased by 874.25 and 6435.62 yuan, respectively, after deducting the fertilizer and other investments. In summary, the use of the non-water-soluble medium element granular fertilizer prepared in Example 2 can effectively increase the yield and income of sand sugar orange.

[0093] From the above experiments, on the basis of conventional fertilization, the non-water-soluble medium element granular fertilizer prepared in Example 1 produced by Guangxi Tengyi Biological Products Co., Ltd. was applied to sand sugar orange, and the yield per mu was increased by 236.7 kg, an increase of 8.4%, and the biological statistical test reached a very significant level. The use of the non-water-soluble medium element granular fertilizer prepared in Example 2 can effectively increase the yield and income of sand sugar orange, and the conventional fertilization + the non-water-soluble medium element granular fertilizer prepared in Example 2 per mu increased the income by 994.25 and 7507.62 yuan compared with the conventional fertilization and the blank control, respectively, and the net income was increased by 874.25 and 6435.62, respectively, after deducting the fertilizer and other investments.

[0094] The foregoing description of specific exemplary embodiments of the application has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the application to the precise forms disclosed, and obviously many modifications and variations are possible in light of the above teaching. It is intended that the scope of the application be limited not with this detailed description, but rather by the claims appended hereto.

Claims

1. A non-aqueous secondary element granular fertilizer containing yellow phosphorus slag, characterized by, It is made of the following raw materials with the following weight percentages: Yellow phosphorus slag 80-85%; Disintegrant 5-8%; Modifier 1-3%; Trace elements 2-5%; Biostimulants 1-4%; The rest is inevitable impurities, and the impurity content is controlled at 0.01-0.2%.

2. The non-aqueous oligoelement particulate fertilizer according to claim 1, characterized in that, The disintegrant is biochemical fulvic acid powder or attapulgite powder.

3. The non-aqueous oligoelement particulate fertilizer according to claim 1, characterized in that, The modifier includes hydrophilic silica modifier, hydrophilic calcium carbonate modifier, and hydrophilic magnesium carbonate modifier; the hydrophilic silica modifier is hexamethyldisilazane and / or dimethyldichlorosilane; the hydrophilic calcium carbonate modifier is sodium stearate; and the hydrophilic magnesium carbonate modifier is a titanate coupling agent.

4. The non-aqueous oligoelement particulate fertilizer according to claim 1, characterized in that, The trace elements are boric acid, ferrous sulfate, and zinc sulfate, and the mass ratio of boric acid, ferrous sulfate, and zinc sulfate is (2.8-3.2):1:

1.

5. The non-aqueous oligoelement particulate fertilizer according to claim 1, characterized in that, The biostimulants are one or more than one of biochemical fulvic acid fermentation broth, fish peptide enzymatic hydrolysate, shrimp peptide enzymatic hydrolysate, seaweed enzymatic hydrolysate, honeycomb fermentation broth containing fructo-oligosaccharides, chitosan, and Bacillus ginseng.

6. The non-aqueous oligoelement particulate fertilizer according to claim 5, characterized in that, The preparation method of the fish peptide enzymatic hydrolysate is as follows: fish meal and water are added to a fermenter in a mass ratio of 1:9, heated to 90°C, cooled to 50-55°C, and then 1% of the fish meal weight of protease and lipase are added for enzymatic hydrolysis for 12 hours to obtain the fish peptide enzymatic hydrolysate.

7. The non-aqueous oligoelement particulate fertilizer according to claim 1, characterized in that, The pH value of the non-water-soluble micronutrient granular fertilizer is 9.8-10.2, the water content is 0.7-1.0%, the particle size is 1.00-4.75 mm, and the non-water-soluble micronutrient content is 34-39%, of which the calcium content is 33-34% and the magnesium content is 1-3%.

8. A process for the production of the non-aqueous particulate microelement fertilizer according to any one of claims 1 to 7, characterized in that, The method comprises the following steps: (1) The yellow phosphorus slag is sent into a pulverizer for pulverization, the modifier is added and uniformly mixed for modification, then the disintegrant and the trace elements are added and uniformly mixed to obtain a mixture; (2) The mixture of step (1) is transferred into a high-efficiency round-pot granulator, biostimulant aqueous solution is sprayed, and granulation is performed to obtain the non-water-soluble micronutrient granular fertilizer.

9. The production method according to claim 8, characterized by, In step (1), the pulverization is to a particle size of 100-200 mesh; the stirring speed of the modification is 2000-2500 r / min, and the time is 20-40 min.

10. The preparation method according to claim 8, characterized in that, In step (2), the rotation speed of the high-efficiency round-pot granulator is 15-20 r / min.

Images