Mineral nutrient-rich bio-coupled powder and preparation method thereof

Abstract

The present application relates to the technical field of fertilizer, and especially relates to a biological coupling powder rich in mineral nutrition and a preparation method thereof, which comprises the following steps: activating calcium magnesium potassium sulfate to obtain activated calcium magnesium potassium sulfate, and determining whether the activation is qualified; in response to the qualified activation, mixing the activated calcium magnesium potassium sulfate with organic raw materials, determining whether the affinity and dissociation of the activated calcium magnesium potassium sulfate and the organic raw materials meet the standard based on the increment of water-soluble calcium and the pH change rate; in response to the qualified affinity and dissociation, determining the balance treatment of the mixture, and obtaining fermentation substrate; spraying a compound microbial inoculum to the fermentation substrate in a preset stage for solid-state aerobic fermentation treatment, determining the addition of the compound microbial inoculum based on the change rate of water-soluble calcium content, and obtaining fermentation product; aging the fermentation product, determining whether to extend the aging time based on the humification coefficient, and drying the fermentation product to obtain the biological coupling powder. The present application improves the biological coupling property of mineral nutrition and organic raw materials.

Description

Technical Field

[0001] This invention relates to the field of fertilizer technology, and in particular to a biocoupled powder rich in mineral nutrients and its preparation method. Background Technology

[0002] With the increasing demands for functional fertilizers in modern agriculture, single inorganic fertilizers or traditional organic fertilizers are no longer sufficient to meet the needs of high-yield and high-quality crops. Potassium calcium magnesium sulfate, as a natural mineral fertilizer, is rich in four medium-quantity elements: potassium, calcium, magnesium, and sulfur, and features comprehensive nutrition and slow-release properties. However, under natural conditions, potassium calcium magnesium sulfate minerals release nutrients slowly, making it difficult to provide sufficient nutrition to crops during their critical nutrient-demanding periods when they are directly applied.

[0003] On the other hand, livestock and poultry farming and feed processing generate a large amount of organic waste, such as chicken manure, trough cleaning feed, fallen feed, and corn and wheat impurities. These materials are rich in organic matter, but improper treatment can cause environmental pollution. Utilizing mineral nutrients and organic waste to prepare novel fertilizers with synergistic effects has become a hot research topic in the industry.

[0004] However, existing technologies have the following technical shortcomings when dealing with mineral-organic composite systems: Typically, minerals such as potassium sulfate, calcium sulfate, and magnesium sulfate are simply crushed and mixed directly with organic materials, or added as fillers to organic fertilizers. Because of the stable crystal structure of these minerals, the potassium, calcium, and magnesium ions are firmly bound, making it difficult for them to be released for use by microorganisms and crops in the short term. This simple physical mixing fails to achieve the chemical activation of mineral nutrients, resulting in the minerals merely serving as "fillers" in organic fertilizers, and their nutritional potential is not fully realized.

[0005] The mixing of minerals and organic matter typically achieves macroscopic homogeneity only through mechanical stirring, but this lacks chemical bonding between the two. During fermentation or storage, due to density differences, mineral particles easily separate and settle with organic matter, leading to uneven product properties and unstable application effects. Furthermore, the lack of microscopically cohesive mineral-organic complexes prevents the formation of the necessary "organic-inorganic interface" for subsequent microbial activity, thus limiting further microbial activation of the minerals.

[0006] Organic fertilizer fermentation processes often employ single inoculation or simple time control, with the succession of microbial communities during fermentation relying on natural processes. However, for special systems containing activated minerals, different functional microbial communities are required to dominate at different fermentation stages. A single inoculation cannot meet these staged functional needs, resulting in insufficient mineral activation and incomplete organic matter conversion.

[0007] Chinese Patent Publication No. CN118063250A discloses a micro / nano fertilizer rich in organic-inorganic coupled states and its preparation method. This invention utilizes a top-down technique for nanocrystals combined with steam explosion technology and microbial biomass conversion technology to prepare relatively large-particle natural base materials and mineral raw materials into micro / nano particles under the action of mechanical energy. Furthermore, under specific temperature and microbial conditions, a micro / nano fertilizer with an organic-inorganic coupled state is prepared.

[0008] However, the aforementioned micro / nano fertilizer rich in organic-inorganic coupled states and its preparation method have the following problems: 1. The mineral lattice structure was not destroyed at the chemical bond level, and the calcium and magnesium ions in the mineral still exist in a sparingly soluble state, unable to form a stable chemical coupling with organic matter.

[0009] 2. The lack of quantitative diagnosis and feedback control of the degree of chemical coupling between minerals and organic matter makes it impossible to ensure the formation of a stable organic-inorganic composite interface. Summary of the Invention

[0010] Therefore, the present invention provides a mineral-rich biocoupled powder and its preparation method to overcome the problems in the prior art where minerals and organic matter are difficult to form chemical coupling and the process lacks quantitative diagnosis and control.

[0011] To achieve the above objectives, the present invention provides a mineral-rich biocoupled powder and its preparation method, comprising: Potassium calcium magnesium sulfate is activated to obtain activated potassium calcium magnesium sulfate, and the activation process is deemed qualified based on the complexation rate of the activated potassium calcium magnesium sulfate. In response to the successful activation treatment, potassium calcium magnesium sulfate is mixed with organic raw materials to obtain a mixture. The water-soluble calcium increment and pH change rate of the mixture are obtained and compared with the preset water-soluble calcium increment and preset pH change rate to determine whether the affinity dissociation between activated potassium calcium magnesium sulfate and organic raw materials in the mixture meets the standard. In response to the achievement of affinity dissociation between activated potassium calcium magnesium sulfate and organic raw materials, the water-soluble calcium-to-magnesium ratio is determined based on the water-soluble calcium content, water-soluble magnesium content, and pH value of the mixture. The equilibrium treatment of the mixture is determined according to the water-soluble calcium-to-magnesium ratio and pH value to obtain the fermentation substrate. The compound microbial agent is sprayed into the fermentation substrate in several preset stages to carry out solid-state aerobic fermentation treatment, obtain fermentation products, obtain the water-soluble calcium content of the fermentation material in a single stage, and calculate the rate of change of water-soluble calcium content in adjacent stages to determine the need for additional compound microbial agent. The fermentation products are aged to obtain a humification coefficient, which determines whether to extend the aging time. The products are then dried to obtain a biocoupled powder.

[0012] Furthermore, based on the fact that the complexation rate of activated potassium calcium magnesium sulfate is greater than or equal to the preset complexation rate, the activation treatment is deemed qualified. The activation treatment conditions are as follows: potassium calcium magnesium sulfate is pulverized to below 325 mesh and added to the reaction vessel with organic active liquid at a mass ratio of 1:3 to 1:5. The pH is adjusted to 5.0 to 6.5, the temperature is controlled at 50℃ to 70℃, the stirring speed is 200 to 400 r / min, the reaction time is 2 to 4 hours, and the solid phase is dried to obtain activated potassium calcium magnesium sulfate. The complexation rate is a percentage of the ratio of organically complexed calcium content to total calcium content.

[0013] Furthermore, the mixing process includes: The organic raw materials are crushed to a particle size of ≤2cm to obtain pretreated organic raw materials; The activated potassium calcium magnesium sulfate and corn sucrose residue were added to a premixer at a mass ratio of 1:5 to 1:10 using a stepwise mixing method and mixed at a stirring speed of 60 to 100 r / min for 5 to 10 minutes to obtain premixed powder. The premixed powder and the organic raw materials are added into a twin-shaft paddle mixer at a mass ratio of 1:3 to 1:5 and mixed at a stirring speed of 60 to 120 r / min for 10 to 20 minutes to obtain a mixture.

[0014] Furthermore, based on the fact that the increase in water-soluble calcium in the mixture is greater than or equal to a preset increase in water-soluble calcium, and the pH change rate is greater than or equal to a preset pH change rate, it is determined that the affinity dissociation between activated potassium calcium magnesium sulfate and the organic raw materials in the mixture meets the standard. The increase in water-soluble calcium is the difference between the actual water-soluble calcium content and the theoretical weighted water-soluble calcium content. The theoretical weighted water-soluble calcium content is the sum of the product of the water-soluble calcium content of activated potassium calcium magnesium sulfate and the mass fraction of activated potassium calcium magnesium sulfate in the mixture, and the product of the water-soluble calcium content of the organic raw material and the mass fraction of the organic raw material in the mixture.

[0015] Furthermore, based on the fact that the water-soluble magnesium-calcium ratio is less than the minimum threshold of the preset water-soluble magnesium-calcium ratio, the mixture is determined to undergo the first equilibrium treatment; Based on the fact that the water-soluble magnesium-calcium ratio is greater than or equal to the minimum threshold of the preset water-soluble magnesium-calcium ratio and less than the maximum threshold of the preset water-soluble magnesium-calcium ratio, and the pH value is less than the preset first pH value or greater than the preset second pH value, the mixture is determined to undergo a second equilibrium treatment. Wherein, the water-soluble magnesium-calcium ratio is the molar ratio of the water-soluble magnesium content to the water-soluble calcium content; The first balancing treatment involves adding a water-soluble magnesium salt, which is magnesium sulfate heptahydrate or magnesium chloride hexahydrate, to the mixture. The amount added is 0.5% to 2.0% of the dry weight of the mixture. The stirring speed is 60 to 120 r / min, the stirring time is 15 to 30 min, and the settling time is 30 to 60 min. The second balancing process involves adding an acidic or alkaline regulator to the mixture. The alkaline regulator is one or more of calcium hydroxide, calcium carbonate, or wood ash, and the amount added is 0.5% to 2.0% of the dry weight of the mixture. The acidic regulator is one or more of citric acid, malic acid, or humic acid solution, and the amount added is 0.3% to 1.0% of the dry weight of the mixture.

[0016] Furthermore, based on the fact that the change rate of the first water-soluble calcium content is less than the preset change rate of the first water-soluble calcium content, 0.1% to 0.2% of the first compound bacterial agent is added, wherein, The first rate of change of water-soluble calcium content is a percentage of the ratio of the difference between the first water-soluble calcium content and the water-soluble calcium content of the fermentation substrate to the water-soluble calcium content of the fermentation substrate.

[0017] Furthermore, based on the fact that the change rate of the second water-soluble calcium content is less than the preset change rate of the second water-soluble calcium content, 0.1% to 0.2% of the second compound bacterial agent is added, wherein... The change rate of the second water-soluble calcium content is the percentage of the difference between the second water-soluble calcium content and the first water-soluble calcium content to the ratio of the first water-soluble calcium content.

[0018] Furthermore, based on the fact that the change rate of the third water-soluble calcium content is less than the preset change rate of the third water-soluble calcium content, 0.1% to 0.2% of the third compound bacterial agent is added, wherein, The rate of change of the third water-soluble calcium content is the percentage of the difference between the third water-soluble calcium content and the second water-soluble calcium content to the ratio of the second water-soluble calcium content.

[0019] Furthermore, based on the fact that the humification coefficient is less than the preset humification coefficient, it was determined that the aging time would be extended by 3–5 days, wherein… The aging process is as follows: the fermentation product is piled up and aged for 7 to 15 days, and the pile is turned over every 2 to 3 days. The humification coefficient is the ratio of the humic acid content of the aged material to the humic acid content of the fermentation product.

[0020] On the other hand, the present invention also provides a bio-coupling powder, which is prepared by mixing the following raw materials, including: activated potassium calcium magnesium sulfate, organic raw materials, and a compound microbial agent, wherein, The organic raw materials are a mixture of livestock waste and feed processing waste. The livestock waste includes one or more of chicken manure, trough feed, and fallen feed, accounting for 50% to 70% of the total organic raw materials. The feed processing waste includes one or more of corn impurities, wheat impurities, mushroom residue, and corn stalk residue, accounting for 30% to 50% of the total organic raw materials. The compound microbial agent is composed of Bacillus subtilis, Bacillus licheniformis, Bacillus mucilaginosus, Streptomyces and Saccharomyces cerevisiae in a mass ratio of 2:1:1:0.5:0.5.

[0021] Compared with existing technologies, the beneficial effects of this invention are as follows: This invention transforms inert mineral elements in potassium calcium magnesium sulfate into activated states with potential biological activity through activation treatment, ensuring that the activated potassium calcium magnesium sulfate entering subsequent processes possesses reactivity. Furthermore, it achieves quantitative diagnosis of the affinity dissociation degree between activated potassium calcium magnesium sulfate and organic raw materials through the increase in water-soluble calcium and pH change rate, avoiding the problem of mineral particles and organic matter stratification and sedimentation caused by insufficient chemical coupling, thus ensuring the uniformity and stability of the organic-inorganic composite system. Through balancing treatment, the magnesium-calcium element ratio and acid-base environment are controlled to a suitable range for microbial metabolism, avoiding microbial activity inhibition and nutrient fixation caused by ion competition or pH deviation, thus constructing an ideal micro-ecological environment for solid-state aerobic fermentation. By inoculating functional microbial communities in stages and using the change rate of water-soluble calcium content as the supplementation criterion, the succession of the microbial community and the fermentation temperature stage are matched, avoiding the problems of functional microbial community decline and insufficient mineral activation caused by single inoculation, ensuring the continuous release of minerals and the transformation of organic matter during fermentation, and realizing the synergistic resource utilization of mineral nutrients and organic waste.

[0022] Furthermore, this invention activates potassium calcium magnesium sulfate under weakly acidic and heated conditions using an organic active liquid. The active functional groups disrupt the mineral lattice structure and undergo coordination complexation reactions with calcium and magnesium ions, forming an organic-inorganic composite film on the surface of the potassium calcium magnesium sulfate. This transforms inert mineral elements into activated states with potential biological activity. The complexation rate is used as a quantitative criterion for the degree of activation, avoiding insufficient activation leading to low mineral bioavailability or resource waste caused by over-processing. This ensures that the activated potassium calcium magnesium sulfate entering subsequent processes possesses sufficient reactivity, laying the foundation for the coupling of potassium calcium magnesium sulfate with organic raw materials.

[0023] Furthermore, by measuring the increase in water-soluble calcium and the pH change rate of the mixture, this invention achieves a quantitative diagnosis of the degree of affinity dissociation between activated potassium sulfate calcium magnesium and organic raw materials, avoiding the problem of mineral particles and organic matter stratification and sedimentation caused by insufficient chemical coupling, ensuring the formation of an organic-inorganic composite interface, guaranteeing the stability of the organic-inorganic interface required for microbial action, and laying a structural foundation for the continuous release of mineral elements and the directional transformation of organic matter.

[0024] Furthermore, this invention achieves the construction of a fermentation substrate microenvironment by dual regulation of the water-soluble magnesium-calcium ratio and pH value in the mixed materials. The first balancing treatment, by adding water-soluble magnesium salts, avoids nutrient fixation and microbial metabolic inhibition caused by ion competition, ensuring the release of both magnesium and calcium elements during fermentation. The second balancing treatment prevents excessive dissolution and loss of calcium and magnesium elements under strongly acidic conditions or the formation of insoluble precipitates under strongly alkaline conditions, ensuring the stability of the mineral surface complexes and providing a common growth basis for the staged inoculation of the compound microbial agent. For cases where affinity dissociation is insufficient, pre-complexation treatment is performed by adding low-molecular-weight organic acids such as citric acid or malic acid. The chelation effect of carboxyl groups with calcium and magnesium ions on the mineral surface disrupts the residual crystal lattice structure, compensating for insufficient initial coupling and ensuring that the material can enter fermentation with appropriate reactivity. This avoids process fluctuations caused by batch differences and guarantees the stability and controllability of the process.

[0025] Furthermore, this invention divides the fermentation process into three stages by varying the fermentation temperature, and sprays compound microbial agents at each stage. This achieves dynamic matching between microbial community succession and fermentation stages. When the temperature is below 50°C, Bacillus subtilis and Saccharomyces cerevisiae are sprayed, utilizing the mesophilic, highly biodegradable organic matter for proliferation and metabolism, producing organic acids and enzymes to destroy the fibrous structure of the organic raw materials. The change rate of water-soluble calcium content is used as a quantitative criterion for activation efficiency, avoiding activation lag caused by insufficient initial microbial activity. When the temperature rises above 50°C, Bacillus licheniformis and Bacillus mucilaginosus are sprayed, utilizing... The thermophilic properties accelerate the degradation of organic matter and continuously disrupt the residual crystal structure of minerals. The release rate of minerals is monitored by the change rate of water-soluble calcium content, avoiding the interruption of mineral dissolution caused by the decline of bacterial activity at high temperatures. When the temperature drops below 45°C, spraying Streptomyces promotes the decomposition of recalcitrant organic matter and the formation of humic precursors. The humification process is judged by the change rate of water-soluble calcium content, avoiding incomplete organic matter transformation caused by the decline of microbial function. Furthermore, by supplementing with appropriate bacterial agents, the problem of functional bacterial decline caused by single inoculation is avoided, thus achieving the synergistic promotion of mineral activation and organic humification.

[0026] Furthermore, this invention quantifies the degree of aging through the humification coefficient, thereby determining the maturity state of the fermentation product. This avoids instability of organic matter in the biocoupled powder due to insufficient aging time, avoids extended production cycles and resource waste caused by excessive aging, and ensures the stability of the biocoupled powder during storage and application. Attached Figure Description

[0027] Figure 1 This is a flowchart illustrating the steps of a method for preparing a mineral-rich biocoupled powder according to an embodiment of the present invention. Figure 2 This is a logic diagram for determining whether the activation process is qualified in an embodiment of the present invention; Figure 3 This is a logic diagram for determining the balance treatment of the mixture in an embodiment of the present invention; Figure 4 This is a flowchart illustrating the steps involved in adjusting process parameters during fermentation, as described in an embodiment of the present invention. Detailed Implementation

[0028] To make the objectives and advantages of the present invention clearer, the present invention will be further described below with reference to embodiments; it should be understood that the specific embodiments described herein are merely for explaining the present invention and are not intended to limit the present invention.

[0029] Preferred embodiments of the present invention will now be described with reference to the accompanying drawings. Those skilled in the art should understand that these embodiments are merely illustrative of the technical principles of the present invention and are not intended to limit the scope of protection of the present invention.

[0030] It should be noted that in the description of this invention, the terms "upper", "lower", "left", "right", "inner", "outer", etc., which indicate directions or positional relationships, are based on the directions or positional relationships shown in the accompanying drawings. This is only for the convenience of description and is not intended to indicate or imply that the device or element must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, it should not be construed as a limitation of this invention.

[0031] Please see Figure 1 The diagram shown is a flowchart illustrating the steps of preparing a mineral-rich biocoupled powder according to an embodiment of the present invention.

[0032] The method for preparing a mineral-rich biocoupled powder according to embodiments of the present invention includes: Step S1: Activate potassium calcium magnesium sulfate to obtain activated potassium calcium magnesium sulfate, and determine whether the activation treatment is qualified based on the complexation rate of activated potassium calcium magnesium sulfate. Step S2: In response to the activation treatment being qualified, potassium calcium magnesium sulfate is mixed with organic raw materials to obtain a mixture. The water-soluble calcium increment and pH change rate of the mixture are obtained and compared with the preset water-soluble calcium increment and preset pH change rate to determine whether the affinity dissociation between activated potassium calcium magnesium sulfate and organic raw materials in the mixture meets the standard. Step S3: In response to the activation of the affinity dissociation of potassium calcium magnesium sulfate with the organic raw material, the water-soluble calcium ratio is determined based on the water-soluble calcium content, water-soluble magnesium content and pH value of the mixture. The equilibrium treatment of the mixture is determined according to the water-soluble magnesium calcium ratio and pH value to obtain the fermentation substrate. Step S4: Spray the compound microbial agent into the fermentation substrate in several preset stages to carry out solid-state aerobic fermentation treatment, obtain fermentation products, obtain the water-soluble calcium content of the fermentation material in a single stage, calculate the rate of change of water-soluble calcium content in adjacent stages, and determine the need to add compound microbial agent. Step S5: Based on the fermentation product, perform aging treatment to obtain the humification coefficient, in order to determine whether to extend the aging time, and perform drying treatment to obtain biocoupled powder.

[0033] In this embodiment of the invention, the organic raw materials are livestock waste and feed processing waste. The livestock waste includes one or more of chicken manure, trough cleaning feed, and fallen feed. The feed processing waste includes one or more of corn impurities, wheat impurities, mushroom residue, and corn sucrose residue.

[0034] In this embodiment of the invention, the compound microbial agent is prepared in the following mass ratio: Bacillus subtilis: Bacillus licheniformis: Bacillus mucilaginosus: Streptomyces: Saccharomyces cerevisiae = 2:1:1:0.5:0.5.

[0035] Specifically, this invention transforms inert mineral elements in potassium calcium magnesium sulfate into potentially bioactive activated states through activation treatment, ensuring that the activated potassium calcium magnesium sulfate entering subsequent processes possesses reactivity. Furthermore, it quantifies the degree of affinity dissociation between the activated potassium calcium magnesium sulfate and organic raw materials by measuring the increase in water-soluble calcium and pH change rate, avoiding the problem of mineral particle and organic matter stratification and sedimentation caused by insufficient chemical coupling, thus ensuring the uniformity and stability of the organic-inorganic composite system. Through balancing treatment, the magnesium-calcium element ratio and acid-base environment are controlled to a suitable range for microbial metabolism, avoiding microbial activity inhibition and nutrient fixation caused by ion competition or pH deviation, thus constructing an ideal micro-ecological environment for solid-state aerobic fermentation. By inoculating functional microbial communities in stages and using the change rate of water-soluble calcium content as a supplementation criterion, the succession of the microbial community and the fermentation temperature stages are matched, avoiding the problems of functional community decline and insufficient mineral activation caused by single inoculation, ensuring the continuous release of minerals and the transformation of organic matter during fermentation, and achieving the synergistic resource utilization of mineral nutrients and organic waste.

[0036] Specifically, the activation process includes: Potassium calcium magnesium sulfate minerals are crushed to below 325 mesh to obtain fine mineral powder; The mineral powder and organic active liquid are added to a reaction vessel at a mass ratio of 1:3 to 1:5. The pH is adjusted to 5.0 to 6.5, the temperature is 50℃ to 70℃, the stirring speed is 200 to 400 r / min, and the reaction time is 2 to 4 hours to obtain an activated slurry. The activated slurry is subjected to solid-liquid separation, and the solid phase is dried to obtain activated potassium calcium magnesium sulfate.

[0037] In this embodiment of the invention, the organic active liquid contains one or more of humic acid, amino acids or sugar alcohols, with a mass concentration of 5% to 15%.

[0038] Understandably, calcium and magnesium elements in potassium sulfate calcium magnesium minerals usually exist in the form of aluminosilicates or sulfates, which have low bioavailability. Humic acids, amino acids, or sugar alcohols contain active functional groups such as carboxyl groups (-COOH) and hydroxyl groups (-OH). Under weakly acidic and heating conditions, these functional groups can disrupt the crystal structure of the mineral surface and undergo coordination or complexation reactions with exposed calcium and magnesium ions, forming an organic-inorganic composite film on the mineral surface. This transforms the inert mineral elements into an "activated state" with potential biological activity.

[0039] Please see Figure 2 As shown, it is a logic judgment diagram for determining whether the activation process is qualified in an embodiment of the present invention.

[0040] Specifically, potassium calcium magnesium sulfate is activated to obtain activated potassium calcium magnesium sulfate, and the activation treatment is deemed qualified based on the complexation rate of the activated potassium calcium magnesium sulfate. If the complexation rate of activated potassium calcium magnesium sulfate is greater than or equal to the preset complexation rate, the activation treatment is deemed qualified. If the complexation rate of activated potassium calcium magnesium sulfate is less than the preset complexation rate, the activation treatment is deemed unqualified.

[0041] In this embodiment of the invention, the activation complexation rate of potassium calcium magnesium sulfate is the percentage of the ratio of organic complexed calcium content to total calcium content. The process of obtaining the organic complexed calcium content is as follows: after activation treatment, a sample is randomly taken from the activation reaction vessel to obtain the sample to be tested. The sample is extracted with deionized water at a solid-to-water ratio of 1:10 at 25°C for 30 minutes by shaking. After filtration, the filtrate is passed through a 0.45μm filter membrane, and the free calcium ion content is determined by inductively coupled plasma optical emission spectrometry (ICP-OES). Organic complexed calcium content = total calcium content - free calcium ion content.

[0042] In this embodiment of the invention, the preset complexation rate ranges from 70% to 85%, preferably set to 75%, but the above value is not limited to this, and those skilled in the art can adjust the value according to actual needs.

[0043] Specifically, in response to the failure of the activation process, the activated potassium calcium magnesium sulfate is re-added to the reactor for a secondary activation process.

[0044] In this embodiment of the invention, the secondary activation treatment is as follows: the activated potassium calcium magnesium sulfate that failed the activation treatment is added to a reaction vessel at a mass ratio of 1:4, the pH is adjusted to 5.0-6.0, the temperature is 65℃-75℃, the stirring speed is 200-400 r / min, and the reaction time is 4-6 hours to obtain an activated slurry. The activated slurry is then subjected to solid-liquid separation, and the solid phase is dried to obtain secondary activated potassium calcium magnesium sulfate.

[0045] In this embodiment of the invention, the complexation rate of the secondary activated potassium calcium magnesium sulfate is resampled and measured. If the complexation rate of the secondary activated potassium calcium magnesium sulfate is less than the preset complexation rate, the secondary activated potassium calcium magnesium sulfate is determined to be discarded.

[0046] Specifically, this invention activates potassium calcium magnesium sulfate under weakly acidic and heated conditions using an organic active liquid. The active functional groups disrupt the mineral lattice structure and undergo coordination complexation reactions with calcium and magnesium ions, forming an organic-inorganic composite film on the surface of the potassium calcium magnesium sulfate. This transforms inert mineral elements into an activated state with potential biological activity. The complexation rate is used as a quantitative criterion for the degree of activation, avoiding insufficient activation leading to low mineral bioavailability or resource waste caused by over-processing. This ensures that the activated potassium calcium magnesium sulfate entering subsequent processes possesses sufficient reactivity, laying the foundation for the coupling of potassium calcium magnesium sulfate with organic raw materials.

[0047] Specifically, the mixing process includes: The organic raw materials are crushed to a particle size of ≤2cm to obtain pretreated organic raw materials; The activated potassium calcium magnesium sulfate and corn sucrose residue were added to a premixer at a mass ratio of 1:5 to 1:10 using a stepwise mixing method. The stirring speed was 60 to 100 r / min and the mixing time was 5 to 10 minutes to obtain premixed powder. The premixed powder and the organic raw materials are added to a twin-shaft paddle mixer at a mass ratio of 1:3 to 1:5. The stirring speed is 60 to 120 r / min and the mixing time is 10 to 20 minutes to obtain a mixture.

[0048] In this embodiment of the invention, the organic raw material is a mixture of livestock waste and feed processing waste. The livestock waste includes one or more of chicken manure, trough cleaning feed, and fallen feed, accounting for 50% to 70% of the total organic raw material. The feed processing waste includes one or more of corn impurities, wheat impurities, mushroom residue, and corn sucrose residue, accounting for 30% to 50% of the total organic raw material.

[0049] Specifically, in response to the activation treatment being qualified, potassium calcium magnesium sulfate is mixed with organic raw materials to obtain a mixture. The water-soluble calcium increment and pH change rate of the mixture are obtained and compared with preset water-soluble calcium increment and preset pH change rate, respectively, to determine whether the affinity dissociation between activated potassium calcium magnesium sulfate and organic raw materials in the mixture meets the standard. If the increase in water-soluble calcium in the mixture is greater than or equal to the preset increase in water-soluble calcium, and the pH change rate is greater than or equal to the preset pH change rate, then it is determined that the affinity dissociation between activated potassium calcium magnesium sulfate and organic raw materials in the mixture meets the standard. If the increase in water-soluble calcium in the mixture is less than the preset increase in water-soluble calcium, or the pH change rate is less than the preset pH change rate, then it is determined that the affinity dissociation between activated potassium calcium magnesium sulfate and organic raw materials in the mixture does not meet the standard.

[0050] In this embodiment of the invention, the preset water-soluble calcium increment ranges from 250 to 350 mg / kg, and the preset pH change rate ranges from +0.4 to +0.8. However, the above values ​​are not limited to these values, and those skilled in the art can adjust the values ​​according to actual needs.

[0051] In this embodiment of the invention, the process of obtaining the water-soluble calcium increment of the mixture is as follows: the water-soluble calcium content of activated potassium calcium magnesium sulfate and the water-soluble calcium content of organic raw materials are measured respectively, the theoretical weighted water-soluble calcium content is calculated, a premixed material sample is taken and deionized water is added at a solid-to-water ratio of 1:10 and shaken for 30 minutes, filtered, and the actual water-soluble calcium content is measured using a calcium ion selective electrode. The water-soluble calcium increment is the difference between the actual water-soluble calcium content and the theoretical weighted water-soluble calcium content.

[0052] In this embodiment of the invention, the theoretical weighted water-soluble calcium content is the sum of the product of the water-soluble calcium content of activated potassium calcium magnesium sulfate and the mass fraction of activated potassium calcium magnesium sulfate in the mixture, and the product of the water-soluble calcium content of the organic raw material and the mass fraction of the organic raw material in the mixture.

[0053] In this embodiment of the invention, the process of obtaining the pH change rate is as follows: 10g of premixed material is added to 100mL of deionized water and stirred for 5 minutes. The pH value of the premixed material is then measured using a pH meter. At the same time, the pH value of the organic raw material without the addition of activated potassium calcium magnesium sulfate is also measured. The pH change rate is the difference between the pH value of the premixed material and the pH value of the organic raw material without the addition of activated potassium calcium magnesium sulfate.

[0054] It is understandable that after activated potassium calcium magnesium sulfate is mixed with organic raw materials, the organic functional groups complexed on the surface of the activated potassium calcium magnesium sulfate interact with the acidic groups in the organic raw materials, causing more calcium elements in the activated potassium calcium magnesium sulfate to dissolve in ionic form. This results in a higher water-soluble calcium content than the weighted average water-soluble calcium content. Furthermore, activated potassium calcium magnesium sulfate itself has a certain acid-base buffering capacity. When mixed with organic raw materials, it neutralizes some of the acidic groups of organic acids in the organic raw materials, causing a change in the pH value of the system. Under normal circumstances, organic raw materials are mostly weakly acidic, while the organic complex layer enriched on the surface of activated potassium calcium magnesium sulfate is weakly alkaline or slightly alkaline. Therefore, the pH value of the mixture often shows an upward trend, with a positive pH change rate. If the pH change rate is negative after mixing, it indicates that an effective chemical coupling has not been formed between the activated potassium calcium magnesium sulfate and the organic raw materials. The mineral particles still exist in an inert state and have failed to perform acid-base buffering and ion exchange functions, resulting in substandard affinity dissociation.

[0055] Specifically, this invention achieves a quantitative diagnosis of the affinity dissociation degree between activated potassium sulfate calcium magnesium and organic raw materials by measuring the increase in water-soluble calcium and pH change rate of the mixture. This avoids the problem of mineral particles and organic matter stratification and sedimentation caused by insufficient chemical coupling, ensures the formation of an organic-inorganic composite interface, guarantees the stability of the organic-inorganic interface required for microbial action, and lays a structural foundation for the continuous release of mineral elements and the directional transformation of organic matter.

[0056] Please see Figure 3 As shown, it is a logic diagram for determining the balance treatment of the mixture in an embodiment of the present invention.

[0057] Specifically, in response to the activation of the affinity dissociation of potassium calcium magnesium sulfate with organic raw materials, the water-soluble calcium content, water-soluble magnesium content and pH value of the mixture are used to determine the water-soluble magnesium-calcium ratio, and the equilibrium treatment of the mixture is determined according to the water-soluble magnesium-calcium ratio and pH value to obtain the fermentation substrate. The water-soluble magnesium-calcium ratio is determined, and the water-soluble magnesium-calcium ratio is compared with the minimum threshold and the maximum threshold of the preset water-soluble magnesium-calcium ratio, respectively. The pH value is compared with the preset first pH value and the preset second pH value, respectively. If the water-soluble magnesium-calcium ratio is less than the preset minimum threshold for the water-soluble magnesium-calcium ratio, then the mixture is determined to undergo the first equilibrium treatment. If the water-soluble magnesium-calcium ratio is greater than or equal to the preset minimum threshold and less than the preset maximum threshold, and the pH value is less than the preset first pH value or greater than the preset second pH value, then the mixture is determined to undergo a second equilibrium treatment. If the water-soluble magnesium-calcium ratio is greater than or equal to the preset maximum threshold, or if the water-soluble magnesium-calcium ratio is greater than or equal to the preset minimum threshold and less than the preset maximum threshold, and the pH value is greater than or equal to the preset first pH value and less than or equal to the preset second pH value, then the mixture will not be balanced and will be used as the fermentation substrate.

[0058] In this embodiment of the invention, the water-soluble magnesium-calcium ratio is the molar ratio of the water-soluble magnesium content to the water-soluble calcium content.

[0059] In this embodiment of the invention, the minimum threshold value of the preset water-soluble magnesium-calcium ratio is 0.10, the maximum threshold value of the preset water-soluble magnesium-calcium ratio is 0.35, the preset first pH value is 6.5, and the preset second pH value is 7.8. However, the above values ​​are not limited to these, and those skilled in the art can adjust the values ​​according to actual needs.

[0060] In this embodiment of the invention, the first balancing treatment is to add a water-soluble magnesium salt to the mixture, wherein the water-soluble magnesium salt is magnesium sulfate heptahydrate or magnesium chloride hexahydrate, the amount added is 0.5% to 2.0% of the dry basis mass of the mixture, the stirring speed is 60 to 120 r / min, the stirring time is 15 to 30 min, and the standing time is 30 to 60 min.

[0061] In this embodiment of the invention, the second balancing process is as follows: if the pH value is less than or equal to 6.5, an alkaline regulator is added to the mixture, wherein the alkaline regulator is one or more of calcium hydroxide, calcium carbonate, or wood ash, and the amount added is 0.5% to 2.0% of the dry basis mass of the mixture. After adding, the mixture is turned over and mixed to increase the pH value to the range of 6.8 to 7.5. If the pH value is greater than or equal to 7.8, an acidic regulator is added to the mixture, wherein the acidic regulator is one or more of citric acid, malic acid, or humic acid solution, and the amount added is 0.3% to 1.0% of the dry basis mass of the mixture. After adding, the mixture is turned over and mixed to decrease the pH value to the range of 7.0 to 7.5.

[0062] It is understandable that magnesium and calcium have a dual relationship of synergy and antagonism in microbial metabolism and crop nutrient absorption. Excessive calcium ions will compete for magnesium ion binding sites on the microbial cell membrane, inhibiting the absorption and utilization of magnesium by microorganisms, thereby affecting metabolic processes such as ATP synthesis and enzyme activity activation in microorganisms. The first balance treatment ensures that magnesium and calcium are released synergistically under the action of microorganisms, avoiding nutrient fixation or metabolic inhibition caused by ion competition. In addition, the pH environment can promote the stability of mineral surface complexes, preventing excessive dissolution and loss of calcium and magnesium under strong acid conditions, or the formation of insoluble precipitates under strong alkaline conditions.

[0063] Specifically, in response to the failure of the activated potassium calcium magnesium sulfate to achieve the required affinity dissociation with the organic raw material, an organic acid solution is added to the mixture.

[0064] In this embodiment of the invention, the organic acid is citric acid or malic acid, and the amount added is 0.5% to 1.0% of the dry basis mass of the mixture. After stirring evenly, it is allowed to stand for 2 to 4 hours.

[0065] Specifically, this invention achieves the construction of a fermentation substrate microenvironment by dual regulation of the water-soluble magnesium-calcium ratio and pH value in the mixed materials. The first balancing treatment adds water-soluble magnesium salts, avoiding nutrient fixation and microbial metabolic inhibition caused by ion competition, ensuring the release of magnesium and calcium during fermentation. The second balancing treatment prevents excessive dissolution and loss of calcium and magnesium under strongly acidic conditions or the formation of insoluble precipitates under strongly alkaline conditions, ensuring the stability of the mineral surface complexes and providing a common growth basis for the staged inoculation of the compound microbial agent. For cases where affinity dissociation is insufficient, pre-complexation treatment is performed by adding low-molecular-weight organic acids such as citric acid or malic acid. The chelation effect of carboxyl groups with calcium and magnesium ions on the mineral surface disrupts the residual crystal lattice structure, compensating for insufficient initial coupling and ensuring that the material can enter fermentation with appropriate reactivity. This avoids process fluctuations caused by batch differences and ensures the stability and controllability of the process.

[0066] Please see Figure 4 As shown, it is a flowchart of the steps for adjusting process parameters during fermentation in an embodiment of the present invention.

[0067] Specifically, the compound microbial agent is sprayed into the fermentation substrate in a preset stage to carry out solid-state aerobic fermentation treatment, obtain fermentation products, obtain the water-soluble calcium content of the fermentation material in a single stage, and calculate the rate of change of water-soluble calcium content in adjacent stages to determine the need for additional compound microbial agent. Step S41: The fermentation substrate is loaded into a fermentation tank, and a first compound microbial agent composed of Bacillus subtilis and Saccharomyces cerevisiae is sprayed on. The inoculation amount is 0.3% to 0.6% of the fermentation substrate mass. The mixture is then turned over. After fermentation for 24 hours, multiple samples are taken from the fermentation tank and mixed to determine the first water-soluble calcium content of the fermented material. If the change rate of the first water-soluble calcium content is less than the preset change rate of the first water-soluble calcium content, 0.1% to 0.2% of the first compound microbial agent is added, and the mixture is turned over again. If the change rate of the first water-soluble calcium content is greater than or equal to the preset change rate of the first water-soluble calcium content, no additional first compound microbial agent is added. Step S42: Based on the temperature of the fermentation material being greater than or equal to 50°C, a second compound microbial agent composed of Bacillus licheniformis and Bacillus mucilaginosus is sprayed, with an inoculation amount of 0.2% to 0.5% of the fermentation substrate mass. The material is then turned over. After fermentation for 24 hours, multiple samples are taken from the fermentation tank and mixed to determine the second water-soluble calcium content of the fermentation material. If the change rate of the second water-soluble calcium content is less than the preset change rate, 0.1% to 0.2% of the second compound microbial agent is added, and the material is turned over again. If the change rate of the second water-soluble calcium content is greater than or equal to the preset change rate, no additional second compound microbial agent is added. Step S43: Based on the temperature of the fermentation material being less than or equal to 45°C, a third compound microbial agent composed of Streptomyces is sprayed, with an inoculation amount of 0.1% to 0.3% of the fermentation substrate mass. The material is then turned over. After 24 hours of fermentation, multiple samples are taken from the fermentation tank and mixed to determine the change rate of the third water-soluble calcium content in the fermentation material. If the change rate of the third water-soluble calcium content is less than the preset change rate, 0.1% to 0.2% of the third compound microbial agent is added, and the material is turned over again. If the change rate of the third water-soluble calcium content is greater than or equal to the preset change rate, no additional third compound microbial agent is added.

[0068] In this embodiment of the invention, after adding the corresponding compound microbial agent and turning the pile again in steps S41-S43, if the rate of change of water-soluble calcium content is still less than the preset value, the corresponding compound microbial agent is added again. If the same step is repeated twice and the standard is still not met, the material is determined to be unqualified and fermentation is terminated.

[0069] In this embodiment of the invention, the preset stage is three stages divided according to the fermentation process: the first stage is when the temperature of the fermentation material is less than 50°C, the second stage is when the temperature of the fermentation material is greater than or equal to 50°C, and the third stage is when the temperature of the fermentation material is less than or equal to 45°C. The single stage is any one of the preset stages.

[0070] In this embodiment of the invention, the process of obtaining the water-soluble calcium content in a single stage is as follows: fermentation material is taken and deionized water is added at a solid-to-water ratio of 1:10 and shaken for 30 minutes for extraction. After filtration, the water-soluble calcium content is determined using a calcium ion selective electrode.

[0071] In this embodiment of the invention, the preset first water-soluble calcium content change rate ranges from 15% to 25%, the preset second water-soluble calcium content change rate ranges from 20% to 35%, and the preset third water-soluble calcium content change rate ranges from 10% to 20%. However, the above values ​​are not limited to these values, and those skilled in the art can adjust the values ​​according to actual needs.

[0072] In this embodiment of the invention, the rate of change of water-soluble calcium is the percentage of the difference between the water-soluble calcium content in the current stage and the water-soluble calcium content in the previous stage, and the ratio of the water-soluble calcium content in the previous stage. The rate of change of water-soluble calcium content in the first stage is the percentage of the difference between the first water-soluble calcium content and the water-soluble calcium content of the fermentation substrate, and the ratio of the water-soluble calcium content of the fermentation substrate.

[0073] In this embodiment of the invention, the fermentation process conditions are: initial temperature 25℃~35℃, and ventilation rate 0.1~0.3m³. 3 / min˙m 3 The material should be turned over every 1 to 2 days to raise the temperature of the fermentation material to 55℃ to 65℃ within 2 to 4 days and maintain it for 5 to 7 days, then let it cool down naturally.

[0074] Specifically, this invention divides the fermentation process into three stages by varying the fermentation temperature, and sprays a compound microbial agent in each stage. This achieves dynamic matching between microbial community succession and the fermentation stages. When the temperature is below 50°C, Bacillus subtilis and Saccharomyces cerevisiae are sprayed, utilizing the mesophilic, highly biodegradable organic matter for proliferation and metabolism, producing organic acids and enzymes to destroy the fibrous structure of the organic raw materials. The change rate of water-soluble calcium content is used as a quantitative criterion for activation efficiency, avoiding activation lag caused by insufficient initial microbial activity. When the temperature rises above 50°C, Bacillus licheniformis and Bacillus mucilaginosus are sprayed, utilizing... The thermophilic properties accelerate the degradation of organic matter and continuously disrupt the residual crystal structure of minerals. The release rate of minerals is monitored by the change rate of water-soluble calcium content, avoiding the interruption of mineral dissolution caused by the decline of bacterial activity at high temperatures. When the temperature drops below 45°C, spraying Streptomyces promotes the decomposition of recalcitrant organic matter and the formation of humic precursors. The humification process is judged by the change rate of water-soluble calcium content, avoiding incomplete organic matter transformation caused by the decline of microbial function. Furthermore, by supplementing with appropriate bacterial agents, the problem of functional bacterial decline caused by single inoculation is avoided, thus achieving the synergistic promotion of mineral activation and organic humification.

[0075] Specifically, the fermentation products are aged to obtain a humification coefficient to determine whether to extend the aging time, and then dried to obtain a biocoupled powder. If the humification coefficient is greater than or equal to the preset humification coefficient, then drying treatment is required. If the humification coefficient is less than the preset humification coefficient, then the aging time should be extended by 3 to 5 days.

[0076] In this embodiment of the invention, the aging process involves piling up the fermentation products for 7 to 15 days, turning them over every 2 to 3 days.

[0077] In this embodiment of the invention, the process of obtaining the humification coefficient is as follows: the humic acid content of the fermentation product and the humic acid content of the aged material are measured. The humification coefficient is the ratio of the humic acid content of the aged material to the humic acid content of the fermentation product. The preset humification coefficient is in the range of 1.15 to 1.25, preferably set to 1.20. However, the above value is not limited to this. Those skilled in the art can also adjust the value according to actual needs.

[0078] In this embodiment of the invention, the drying process involves drying the aged and qualified material at a low temperature of 60℃~80℃ until the moisture content is ≤15%, then pulverizing it and passing it through an 80~100 mesh sieve to obtain a biocoupled powder.

[0079] Specifically, this invention quantifies the degree of aging through the humification coefficient, thereby determining the maturity state of fermentation products. This avoids instability of organic matter in biocoupled powder due to insufficient aging time, avoids extended production cycles and resource waste caused by excessive aging, and ensures the stability of biocoupled powder during storage and application.

[0080] The bio-coupling powder of this invention is prepared by mixing the following raw materials: activated potassium calcium magnesium sulfate, organic raw materials, and compound microbial agents, wherein, The organic raw materials are a mixture of livestock waste and feed processing waste. The livestock waste includes one or more of chicken manure, trough feed, and fallen feed, accounting for 50% to 70% of the total organic raw materials. The feed processing waste includes one or more of corn impurities, wheat impurities, mushroom residue, and corn stalk residue, accounting for 30% to 50% of the total organic raw materials. The compound microbial agent is composed of Bacillus subtilis, Bacillus licheniformis, Bacillus mucilaginosus, Streptomyces and Saccharomyces cerevisiae in a mass ratio of 2:1:1:0.5:0.5.

[0081] In this embodiment of the invention, the preset complexation rate is 75%, the preset increase in water-soluble calcium is 300 mg / kg, the preset pH change rate is +0.5, the preset minimum threshold for the water-soluble magnesium-calcium ratio is 0.10, the preset maximum threshold for the water-soluble magnesium-calcium ratio is 0.35, the preset pH range is 6.5–7.8, the preset change rate of the first water-soluble calcium content is 15%, the preset change rate of the second water-soluble calcium content is 20%, the preset change rate of the third water-soluble calcium content is 10%, and the preset humification coefficient is 1.20. Example 1

[0082] During the process, potassium calcium magnesium sulfate was pulverized to 325 mesh and added to the reaction vessel at a mass ratio of 1:4 with a 10% humic acid solution. The pH was adjusted to 6.0, the temperature was controlled at 60℃, the stirring speed was 300 r / min, and the reaction time was 3 hours. After solid-liquid separation, the solid phase was dried to obtain activated potassium calcium magnesium sulfate. The complexation rate of activated potassium calcium magnesium sulfate was determined to be 78%, and the activation treatment was deemed qualified. The organic raw materials were crushed to a particle size of ≤2cm. The organic raw materials, by mass percentage, were: chicken manure 35%, trough cleaning material 20%, fallen material 15%, and livestock waste totaling 70%; corn impurities 10%, wheat impurities 10%, mushroom residue 5%, corn sucrose residue 5%, and feed processing waste totaling 30%. Activated potassium calcium magnesium sulfate and corn sucrose residue were added to a premixer and mixed at a stirring speed of 80r / min for 8 minutes to obtain premixed powder. The premixed powder and the remaining organic raw materials were added to a twin-shaft paddle mixer and mixed at a stirring speed of 100r / min for 15 minutes to obtain a mixed material. The water-soluble calcium content of activated potassium calcium magnesium sulfate was determined to be 3200 mg / kg, while the water-soluble calcium content of the organic raw material was 850 mg / kg. The mass fraction of activated potassium calcium magnesium sulfate in the mixture was 20%, and the mass fraction of the organic raw material was 80%. The theoretical weighted water-soluble calcium content was calculated to be 1320 mg / kg. A sample of the mixture was taken and extracted at a solid-to-water ratio of 1:10. The actual water-soluble calcium content was determined to be 1680 mg / kg, and the increase in water-soluble calcium was 360 mg / kg, which is greater than the preset increase in water-soluble calcium of 300 mg / kg. The pH value of the mixture was determined to be 7.5, while the pH value of the organic raw material without activated potassium calcium magnesium sulfate was 6.8. The pH change rate was +0.7, confirming that the affinity dissociation between activated potassium calcium magnesium sulfate and the organic raw material met the standard. The water-soluble calcium content of the mixture was determined to be 1680 mg / kg, and the water-soluble magnesium content was determined to be 235 mg / kg, which translates to a molar magnesium-to-calcium ratio of 0.18. The pH value of the mixture was determined to be 7.5, indicating that no equilibration treatment was required for the mixture. The fermentation substrate was placed into the fermentation tank, with an initial temperature of 28℃ and an aeration rate of 0.2m³. 3 / min˙m 3The material was first sprayed with a first compound microbial agent composed of Bacillus subtilis and Saccharomyces cerevisiae in a 2:1 mass ratio, with an inoculation amount of 0.5% of the fermentation substrate. After turning the pile, the first water-soluble calcium content was measured to be 1980 mg / kg, and the change rate of the first water-soluble calcium content was calculated to be 17.9%. No additional microbial agent was added. On the third day of fermentation, when the temperature rose to 52℃, a second compound microbial agent composed of Bacillus licheniformis and Bacillus mucilaginosus in a 1:1 mass ratio was sprayed, with an inoculation amount of [missing information - likely a percentage] of the fermentation substrate. The content of the second water-soluble calcium was 0.4%. After turning the pile, the content of the second water-soluble calcium was measured to be 2680 mg / kg. The change rate of the second water-soluble calcium content was calculated to be 35.4%. No additional inoculant was added. The temperature was maintained for 6 days and then began to decrease. On the 10th day, the temperature dropped to 43℃. A third compound inoculant composed of Streptomyces was sprayed. The inoculum amount was 0.2% of the fermentation substrate mass. After turning the pile, the content of the third water-soluble calcium was measured to be 3150 mg / kg. The change rate of the third water-soluble calcium content was calculated to be 17.5%. No additional inoculant was added. The fermentation products were piled up and aged for 10 days, and turned over every 2 days. The humic acid content of the fermentation products was measured to be 85 g / kg. The humic acid content of the aged material was 112 g / kg, and the humification coefficient was 1.32. The qualified aged material was dried at a low temperature of 70℃ to a moisture content of 12%, crushed, and passed through a 100-mesh sieve to obtain the first biological coupling powder.

[0083] The raw materials required for preparing 1 kg of the first bio-coupling powder in Example 1 are as follows: (1) Activate 200g of potassium calcium magnesium sulfate; (2) 800g of organic raw materials, including: 280g of chicken manure, 160g of cleaning feed, 120g of ground feed, 80g of corn impurities, 80g of wheat impurities, 40g of mushroom residue, and 40g of corn sugar core residue; (3) 5g of compound microbial agent, including 2g of Bacillus subtilis, 1g of Bacillus licheniformis, 1g of Bacillus mucilaginosus, 0.5g of Streptomyces and 0.5g of Saccharomyces cerevisiae.

[0084] Example 2 Potassium calcium magnesium sulfate was pulverized to 325 mesh and added to a reaction vessel at a mass ratio of 1:5 with a 12% amino acid solution. The pH was adjusted to 5.5, the temperature was controlled at 65℃, the stirring speed was 350 r / min, and the reaction time was 4 hours. After solid-liquid separation, the solid phase was dried to obtain activated potassium calcium magnesium sulfate. The complexation rate of activated potassium calcium magnesium sulfate was determined to be 82%, confirming that the activation treatment was qualified. The organic raw materials are crushed to a particle size of ≤2cm. The organic raw materials are as follows by mass percentage: 50% of the cleaning material, 25% of the wheat impurities, 15% of the mushroom residue, and 10% of the corn succulent residue. The activated potassium calcium magnesium sulfate and the corn succulent residue are added to a premixer and stirred at 60r / min for 10 minutes to obtain a premixed powder. The premixed powder and the remaining organic raw materials are added to a twin-shaft paddle mixer and stirred at 120r / min for 20 minutes to obtain a mixed material. The water-soluble calcium content of activated potassium calcium magnesium sulfate was determined to be 3560 mg / kg, while the water-soluble calcium content of the organic raw material was 720 mg / kg. The mass fraction of activated potassium calcium magnesium sulfate in the mixture was 16.7%, and the mass fraction of the organic raw material was 83.3%. The theoretical weighted average water-soluble calcium content was calculated to be 1198 mg / kg. A sample of the mixture was taken and extracted at a solid-to-water ratio of 1:10, and the actual water-soluble calcium content was determined to be 1580 mg / kg. The increase in water-soluble calcium was 382 mg / kg, which is greater than the preset increase in water-soluble calcium of 300 mg / kg. The pH value of the mixture was determined to be 7.3, while the pH value of the organic raw material without activated potassium calcium magnesium sulfate was 6.5. The pH change rate was +0.8, confirming that the affinity dissociation between activated potassium calcium magnesium sulfate and the organic raw material met the standard. The water-soluble calcium content of the mixture was determined to be 1580 mg / kg, and the water-soluble magnesium content was determined to be 206 mg / kg, which translates to a molar magnesium-to-calcium ratio of 0.17. The pH value of the mixture was determined to be 7.3, indicating that no equilibration treatment was required for the mixture. The fermentation substrate was placed into the fermentation tank, with an initial temperature of 30℃ and an aeration rate of 0.25m³. 3 / min˙m 3 The material was first sprayed with a first compound microbial agent composed of Bacillus subtilis and Saccharomyces cerevisiae in a 2:1 mass ratio, with an inoculum amount of 0.6% of the fermentation substrate mass. After turning the pile, the first water-soluble calcium content was measured to be 1860 mg / kg, and the calculated change rate of the first water-soluble calcium content was 17.7%. No additional microbial agent was added. On the fourth day of fermentation, when the temperature rose to 55℃, a second compound microbial agent composed of Bacillus licheniformis and Bacillus mucilaginosus in a 1:1 mass ratio was sprayed, with an inoculum amount of 0.6% of the fermentation substrate mass. After turning the compost pile, the content of the second water-soluble calcium was measured to be 2520 mg / kg, and the change rate of the second water-soluble calcium content was calculated to be 35.5%. No additional microbial agent was added. After maintaining the high temperature period for 7 days, the temperature began to drop. On the 12th day, the temperature dropped to 42℃. A third compound microbial agent composed of Streptomyces was sprayed, with an inoculum amount of 0.3% of the fermentation substrate mass. After turning the compost pile, the content of the third water-soluble calcium was measured to be 2980 mg / kg, and the change rate of the third water-soluble calcium content was calculated to be 18.3%. No additional microbial agent was added. The fermentation products were piled up and aged for 12 days, and turned over every 3 days. The humic acid content of the fermentation products was measured to be 92 g / kg. The humic acid content of the aged material was 126 g / kg, and the humification coefficient was 1.37. The qualified aged material was dried at a low temperature of 65℃ to a moisture content of 10%, crushed, and passed through a 100-mesh sieve to obtain the second biological coupling powder.

[0085] The raw materials required for preparing 1 kg of the second bio-coupling powder in Example 2 are as follows: (1) Activate 167g of potassium calcium magnesium sulfate; (2) 833g of organic raw materials, including: 416.5g of cleaning material, 208.25g of wheat impurities, 124.95g of mushroom residue, and 83.3g of corn sugar core residue; (3) 6g of compound microbial agent, including 2.4g of Bacillus subtilis, 1.2g of Bacillus licheniformis, 1.2g of Bacillus mucilaginosus, 0.6g of Streptomyces and 0.6g of Saccharomyces cerevisiae.

[0086] Table 1.1 Physicochemical properties of the biocoupled powder prepared in the examples.

[0087] ; The standard parameters are the physicochemical properties of ordinary organic-inorganic compound fertilizers.

[0088] The specific preparation process of the control parameters is as follows: potassium calcium magnesium sulfate is directly pulverized to 325 mesh without activation treatment; the organic raw materials are 60% chicken manure, 20% corn impurities, 10% mushroom residue, and 10% corn sucrose residue by mass percentage; 200g of pulverized potassium calcium magnesium sulfate is mixed with 800g of organic raw materials at a stirring speed of 100r / min for 15 minutes; after mixing, no affinity dissociation determination or equilibration treatment is performed, and it is directly used as the fermentation substrate; the fermentation, aging, and drying steps are the same as in Example 1. The control parameters are used to characterize the product characteristics after the unactivated potassium calcium magnesium sulfate is directly mixed with organic raw materials and fermented.

[0089] To verify the technical effects of the key steps of the present invention, the following comparative examples were set up. Except for the differences described below, all other steps in each comparative example (including the composition and ratio of organic raw materials, mixing conditions after activation treatment, turning frequency, ventilation volume, temperature control, inoculation and replenishment of compound microbial agents at each stage, aging and drying, etc.) were exactly the same as in Example 1. All comparative examples used the same batch of raw materials as in Example 1, and the waiting time and placement time of each step were consistent with those in Example 1 to ensure a single variable.

[0090] Table 2.1 Comparison of different process treatments.

[0091] ; Table 3.1 Performance Comparison.

[0092] ; Table 4.1 Comparison of effects.

[0093] ; In this embodiment of the invention, based on the data in Tables 3.1 and 4.1, a comparison between Comparative Example 1 (CE1) and Example 1 revealed that when potassium calcium magnesium sulfate was used directly without activation treatment, the proportion of organic complexed calcium and the content of water-soluble calcium in the bio-coupling powder were significantly reduced, and the corn sugar content decreased by 23.7%. Omitting the activation treatment would result in potassium calcium magnesium sulfate only playing a filling role in the system and failing to achieve bio-coupling. A comparison between Comparative Example 2 (CE2) and Example 1 revealed that although the performance was better than CE1 when the affinity dissociation determination step was omitted, the water-soluble calcium content and the proportion of organic complexed calcium were still lower than in Example 1, and the corn sugar content decreased by 12.4%. This indicates that the affinity dissociation determination can effectively identify the degree of chemical coupling between the activated mineral and the organic raw material, ensuring the formation of a stable organic-inorganic composite interface. Omitting the determination may lead to insufficient coupling in some batches of materials, affecting the overall quality.

[0094] Comparing Comparative Example 3 (CE3) with Example 1, it was found that omitting the equilibration treatment step resulted in a magnesium-calcium ratio deviating from the optimal range, a lower content of water-soluble magnesium, and an 8.1% decrease in corn sugar content. This indicates that the equilibration treatment, by regulating the magnesium-calcium ratio and pH environment, provides a suitable micro-ecological environment for microbial metabolism. Omitting the equilibration treatment would lead to problems with ion competition and nutrient fixation.

[0095] Comparing Comparative Example 4 (CE4) with Example 1, it was found that the use of a single inoculation instead of staged spraying during the fermentation stage significantly reduced the proportion of organic complexed calcium and the content of water-soluble calcium, and reduced the sugar content of corn by 16.7%. This indicates that staged inoculation achieved dynamic matching between microbial community succession and fermentation temperature stages. A single inoculation cannot meet the functional requirements of different stages, resulting in insufficient mineral activation.

[0096] Comparing Comparative Example 5 (CE5) with Example 1, it was found that by omitting the determination of the humification coefficient and fixing the aging time, the humic acid content and storage stability were lower than those of Example 1, and the corn sugar content decreased by 4.3%. This indicates that the determination of the humification coefficient can dynamically adjust the aging time according to the actual degree of decomposition of the material, avoiding the instability of organic matter and nutrient loss caused by insufficient aging.

[0097] The control example (CK) used only ordinary organic fertilizer, and all indicators were lower than those of the example and the control example, indicating that adding activating minerals and compound microbial agents is the key to improving performance. Ordinary organic fertilizer cannot provide sufficient mineral nutrition and microbial activity.

[0098] A comparison of Example 1 and Example 2 revealed that increasing the activation treatment temperature, extending the reaction time, and optimizing the inoculum amount further improved the various physicochemical properties and application effects of the biocoupled powder. This indicates that the technical solution of the present invention has room for parameter optimization, and those skilled in the art can make adjustments according to actual needs.

[0099] The technical solution of the present invention has been described above with reference to the preferred embodiments shown in the accompanying drawings. However, it will be readily understood by those skilled in the art that the scope of protection of the present invention is obviously not limited to these specific embodiments. Without departing from the principles of the present invention, those skilled in the art can make equivalent changes or substitutions to the relevant technical features, and the technical solutions after these changes or substitutions will all fall within the scope of protection of the present invention.

Claims

1. A method for preparing a biocoupled powder rich in mineral nutrients, characterized in that, Including: Activating potassium calcium magnesium sulfate to obtain activated potassium calcium magnesium sulfate, and determining whether the activation treatment is qualified based on the complexation rate of the activated potassium calcium magnesium sulfate; In response to the qualified activation treatment, mixing potassium calcium magnesium sulfate with organic raw materials to obtain a mixed material, obtaining the water-soluble calcium increment and pH change rate of the mixed material, and comparing them with the preset water-soluble calcium increment and preset pH change rate respectively to determine whether the affinity dissociation of the activated potassium calcium magnesium sulfate and the organic raw material in the mixed material meets the standard; In response to the affinity dissociation of the activated potassium calcium magnesium sulfate and the organic raw material meeting the standard, determining the water-soluble magnesium-calcium ratio based on the water-soluble calcium content, water-soluble magnesium content and pH value of the mixed material, and determining the equilibrium treatment of the mixed material according to the water-soluble magnesium-calcium ratio and pH value to obtain a fermentation substrate; Spraying a compound bacterial agent into the fermentation substrate in several preset stages for solid-state aerobic fermentation treatment to obtain a fermentation product, obtaining the water-soluble calcium content of the fermentation material in a single stage, and calculating the change rate of the water-soluble calcium content in adjacent stages to determine the supplementary addition of the compound bacterial agent; Performing aging treatment on the fermentation product to obtain a humification coefficient to determine whether to extend the aging time, and performing drying treatment to obtain a biological coupling powder.

2. The method for preparing the mineral-rich biocoupled powder according to claim 1, characterized in that, Determining that the activation treatment is qualified based on the complexation rate of the activated potassium calcium magnesium sulfate being greater than or equal to the preset complexation rate, where The conditions for the activation treatment are that potassium calcium magnesium sulfate is pulverized to below 325 mesh, added to a reaction kettle with an organic active liquid in a mass ratio of 1:3 to 1:5, the pH is adjusted to 5.0 to 6.5, the temperature is controlled at 50°C to 70°C, the stirring speed is 200 to 400 r / min, the reaction time is 2 to 4 hours, and the solid phase is taken and dried to obtain activated potassium calcium magnesium sulfate; The complexation rate is the percentage of the result of the ratio of the content of organically complexed calcium to the total calcium content.

3. The method for preparing the mineral-rich biocoupled powder according to claim 1, characterized in that, The process of the mixing treatment includes: Crushing the organic raw material to a particle size of ≤2 cm to obtain a pretreated organic raw material; Using the step-by-step mixing method, putting the activated potassium calcium magnesium sulfate and corn sugar heart residue into a premixer in a mass ratio of 1:5 to 1:10, mixing at a stirring speed of 60 to 100 r / min for 5 to 10 minutes to obtain a premixed powder; Putting the premixed powder and the organic raw material into a double-shaft paddle mixer in a mass ratio of 1:3 to 1:5, and mixing at a stirring speed of 60 to 120 r / min for 10 to 20 minutes to obtain a mixed material.

4. The method for preparing the mineral-rich biocoupled powder according to claim 3, characterized in that, Determining that the affinity dissociation of the activated potassium calcium magnesium sulfate and the organic raw material in the mixed material meets the standard based on the water-soluble calcium increment of the mixed material being greater than or equal to the preset water-soluble calcium increment and the pH change rate being greater than or equal to the preset pH change rate, where The water-soluble calcium increment is the difference between the actual water-soluble calcium content and the theoretical weighted water-soluble calcium content; The theoretical weighted water-soluble calcium content is the sum of the product of the water-soluble calcium content of the activated potassium calcium magnesium sulfate and the mass fraction of the activated potassium calcium magnesium sulfate in the mixed material, and the product of the water-soluble calcium content of the organic raw material and the mass fraction of the organic raw material in the mixed material.

5. The method for preparing the mineral-rich biocoupled powder according to claim 1, characterized in that, Based on the fact that the water-soluble magnesium-calcium ratio is less than the minimum threshold of the preset water-soluble magnesium-calcium ratio, the mixture is determined to undergo the first equilibrium treatment. Based on the fact that the water-soluble magnesium-calcium ratio is greater than or equal to the minimum threshold of the preset water-soluble magnesium-calcium ratio and less than the maximum threshold of the preset water-soluble magnesium-calcium ratio, and the pH value is less than the preset first pH value or greater than the preset second pH value, the mixture is determined to undergo a second equilibrium treatment. Wherein, the water-soluble magnesium-calcium ratio is the molar ratio of the water-soluble magnesium content to the water-soluble calcium content; The first balancing treatment involves adding a water-soluble magnesium salt, which is magnesium sulfate heptahydrate or magnesium chloride hexahydrate, to the mixture. The amount added is 0.5% to 2.0% of the dry weight of the mixture. The stirring speed is 60 to 120 r / min, the stirring time is 15 to 30 min, and the settling time is 30 to 60 min. The second balancing process involves adding an acidic or alkaline regulator to the mixture. The alkaline regulator is one or more of calcium hydroxide, calcium carbonate, or wood ash, and the amount added is 0.5% to 2.0% of the dry weight of the mixture. The acidic regulator is one or more of citric acid, malic acid, or humic acid solution, and the amount added is 0.3% to 1.0% of the dry weight of the mixture.

6. The method for preparing the mineral-rich biocoupled powder according to claim 1, characterized in that, Based on the fact that the change rate of the first water-soluble calcium content is less than the preset change rate of the first water-soluble calcium content, 0.1% to 0.2% of the first compound bacterial agent is added, wherein, The first rate of change of water-soluble calcium content is a percentage of the ratio of the difference between the first water-soluble calcium content and the water-soluble calcium content of the fermentation substrate to the water-soluble calcium content of the fermentation substrate.

7. The method for preparing the mineral-rich biocoupled powder according to claim 6, characterized in that, Based on the fact that the change rate of the second water-soluble calcium content is less than the preset change rate of the second water-soluble calcium content, 0.1% to 0.2% of the second compound bacterial agent is added, wherein... The change rate of the second water-soluble calcium content is the percentage of the difference between the second water-soluble calcium content and the first water-soluble calcium content to the ratio of the first water-soluble calcium content.

8. The method for preparing the mineral-rich biocoupled powder according to claim 7, characterized in that, Based on the fact that the change rate of the third water-soluble calcium content is less than the preset change rate of the third water-soluble calcium content, 0.1% to 0.2% of the third compound bacterial agent is added, of which, The rate of change of the third water-soluble calcium content is the percentage of the difference between the third water-soluble calcium content and the second water-soluble calcium content to the ratio of the second water-soluble calcium content.

9. The method for preparing the mineral-rich biocoupled powder according to claim 1, characterized in that, Based on the fact that the humification coefficient is less than the preset humification coefficient, the aging time is extended by 3-5 days. The aging process is as follows: the fermentation product is piled up and aged for 7 to 15 days, and the pile is turned over every 2 to 3 days. The humification coefficient is the ratio of the humic acid content of the aged material to the humic acid content of the fermentation product.

10. A biocoupled powder prepared by the method for preparing the mineral-rich biocoupled powder according to any one of claims 1-9, characterized in that, The bio-coupling powder is made from a mixture of the following raw materials: activated potassium calcium magnesium sulfate, organic raw materials, and compound microbial agents, wherein, The organic raw materials are a mixture of livestock waste and feed processing waste. The livestock waste includes one or more of chicken manure, trough feed, and fallen feed, accounting for 50% to 70% of the total organic raw materials. The feed processing waste includes one or more of corn impurities, wheat impurities, mushroom residue, and corn stalk residue, accounting for 30% to 50% of the total organic raw materials. The compound microbial agent is composed of Bacillus subtilis, Bacillus licheniformis, Bacillus mucilaginosus, Streptomyces and Saccharomyces cerevisiae in a mass ratio of 2:1:1:0.5:0.5.

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