Decomposing method for efficiently removing antibiotics in livestock and poultry manure based on mineral conditioner

Abstract

The invention discloses a decomposition method for efficiently removing antibiotics in livestock and poultry manure based on a mineral conditioner, the livestock and poultry manure and fermentation auxiliary materials are mixed to enable the water content of the livestock and poultry manure to be smaller than or equal to 85%, a fermentation raw material is obtained, the mineral conditioner is composed of 20-30% of CaO, 8-15% of MnFe2O4, 15-20% of zeolite powder, 25-30% of pyrolytic activated carbon powder and 5-10% of humic acid, and the mineral conditioner is composed of 20-30% of CaO, 8-15% of MnFe2O4, 15-20% of zeolite powder, 25-30% of pyrolytic activated carbon powder and 5-10% of humic acid. Then adding a mineral conditioner and a decomposing inoculant into the fermentation raw material, and fully mixing to obtain a blended fermentation raw material; performing maturing and composting on the blended fermentation raw material for 3-25 days to obtain a quickly matured fermentation raw material; and performing post-decomposition on the quickly decomposed and fermented raw material, and completing the treatment of the livestock and poultry manure after 15-20 days. Manganese oxide, pyrolytic activated carbon powder and the like are used as core components of the mineral conditioner, so that the removal of antibiotics in compost can be effectively enhanced.

Description

Technical Field

[0001] This invention relates to the field of livestock and poultry manure treatment technology, specifically to a composting method based on mineral conditioners for the efficient removal of antibiotics from livestock and poultry manure. Background Technology

[0002] Fertilizer utilization is the most important way to utilize agricultural organic waste such as livestock and poultry manure, accounting for over 60%. In recent years, relevant national departments have paid close attention to the resource utilization of livestock and poultry manure and have continuously increased their efforts to accelerate the promotion and application of organic fertilizers. They have proposed, following the principle of "nutrient balance and promoting crop production through livestock farming," to make livestock and poultry manure an important source of fertilizer to replace chemical fertilizers, aiming to achieve a comprehensive utilization rate of 90% for livestock and poultry manure by 2025. This is to accelerate the comprehensive green transformation of agricultural development.

[0003] Aerobic composting is currently the core technology for the harmless treatment and resource utilization of livestock and poultry manure. Its essence is to transform organic matter into stable humus through microbial-driven biochemical reactions. While previous national, industry, and local standards for livestock and poultry manure composting stipulated limits for harmful factors such as heavy metals, fecal coliform counts, and ascarid egg mortality, they neglected the efficient reduction of new pollutants such as antibiotics during the composting process. Nearly 50% of antibiotics globally are used in animal husbandry, making livestock and poultry manure a significant reservoir of antibiotic resistance genes (ARGs). Furthermore, manure application can cause a 28,000-fold increase in soil ARG abundance, threatening human health through the soil-crop system. Although traditional aerobic composting can partially remove antibiotics, the removal effect is still insufficient. Therefore, effectively controlling antibiotics in livestock and poultry manure has become a crucial issue in the safe recycling of waste and the ecological environment. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a composting method for efficiently removing antibiotics from livestock and poultry manure based on mineral conditioners.

[0005] The technical solution of this invention is: a composting method for efficiently removing antibiotics from livestock and poultry manure based on mineral conditioners, comprising the following steps: Step 1: Mix livestock and poultry manure with fermentation auxiliary materials to make the moisture content of livestock and poultry manure ≤85% to obtain fermentation raw materials. Then add mineral conditioner and composting agent to the fermentation raw materials and mix them thoroughly for 20~40 minutes to obtain the prepared fermentation raw materials. The mineral conditioner, by mass fraction, consists of 20-40% CaO, 10-15% MnFe2O4, 15-20% zeolite powder, 25-30% pyrolytic activated carbon powder, and 10-15% humic acid, and the amount of mineral conditioner added is 10-15 wt% of the dry weight of the fermentation raw materials. The composting agent is a mixture of *Trichoderma harzianum*, *Tricholoma thermophilum*, and *Bacillus stearothermophilus* in a mass ratio of 3-7:1-3:2-5, with an effective viable count ≥1×10⁻⁶. 9 CFU / g, and the amount of live bacteria added is 2~5wt‰ of the dry weight of the fermentation raw material; Step 2: Compost the prepared fermented raw materials, controlling the oxygen concentration inside the pile to ≥8%, and obtain rapidly composted raw materials after 3~25 days; Step 3: Subsequently, the rapidly composted raw materials are subjected to post-composting, and the oxygen concentration inside the pile is controlled to be ≥5%. The treatment of livestock and poultry manure is completed after 15~20 days.

[0006] Furthermore, the fermentation auxiliary material is any one or a mixture of crop straw, sawdust, edible fungus residue, wheat bran, rapeseed cake, soybean cake, and rice husk; wherein, the crop straw needs to be crushed to 2-5 cm; the sawdust needs to be piled up and aged for 1-2 weeks; the edible fungus residue needs to be dried to a moisture content of <40%; and the wheat bran, rapeseed cake, and soybean cake need to be crushed into powder with a particle size of <2 mm.

[0007] Note: Straw, rice husks, and sawdust are high-carbon auxiliary materials, while bran, soybean cake, rapeseed cake, and mushroom residue are high-nitrogen auxiliary materials. Rice husks and sawdust can form a "skeleton support" to prevent the pile from compacting, ensure oxygen permeability, and avoid anaerobic odor production. Rapeseed cake and soybean cake can provide protein nitrogen, mushroom residue releases polysaccharides and trace elements, and rice husks supplement silicon and potassium. The use of fermentation auxiliary materials can form a synergistic fertilizer effect of "organic-inorganic-biological".

[0008] Furthermore, the moisture content of the modified fermentation raw material is 50%~60%, the carbon-nitrogen ratio is 20:1~30:1, the free space content is >15%, and the pH value is 6.0~9.0.

[0009] Note: By controlling the moisture content to 50%~60%, the necessary water environment for microbial metabolism can be provided, which ensures the dissolution and transport of nutrients and avoids excessive moisture clogging the pores and causing anaerobic fermentation. When the moisture content is below 30%, microbial activity is inhibited, and when it is above 70%, ventilation is blocked, which can easily lead to foul odors and nitrogen loss. By controlling the carbon-to-nitrogen ratio to 20:1 to 30:1, the balance between the microorganisms' "energy (carbon)" and "structural raw materials (nitrogen)" can be maintained. When the carbon source is insufficient (C / N < 20:1), ammonia volatilization and nitrogen loss are likely to occur. When the carbon source is excessive (C / N > 30:1), the composting process is likely to be delayed and the fermentation cycle is prolonged. By controlling the free airspace to ≥15%, continuous oxygen infiltration can be ensured, supporting the efficient degradation of organic matter by aerobic microbial communities (such as thermophilic bacteria). If the airspace is insufficient, the system will be forced to switch to an anaerobic pathway, producing harmful gases such as hydrogen sulfide and methane. By adjusting the pH value to 6.0-9.0, the optimal activity range of microbial enzyme systems (such as proteases and cellulases) can be maintained. When pH < 5.0, aerobic bacteria will be inhibited, while when pH > 9.0, ammonia volatilization will be promoted. Within this range, a natural buffer can be formed. Furthermore, the pH can be adjusted according to the actual situation by using a certain amount of chemical conditioner to adjust the pH value of the fermentation raw materials to 6.0-9.0. Since a large amount of ammonia gas is produced by the decomposition of nitrogen-containing organic matter in the early stage of composting, which volatilizes in gaseous form, resulting in the loss of total nitrogen in the compost, these conditioners can significantly retain nitrogen nutrients, greatly reduce the release of irritating ammonia odor from the source, and increase the nitrogen content of the final compost product. They also adjust the pH back to neutral or slightly acidic, creating a more suitable living environment for microorganisms (including bacteria and fungi) and promoting the decomposition of organic matter.

[0010] Furthermore, the preparation method of the mineral conditioner is as follows: First, the first coating material is composed of CaO and pyrolytic activated carbon powder, and the second coating material is composed of MnFe2O4, zeolite powder, and humic acid. Secondly, a type A multilayer spherical conditioner and / or a type B multilayer spherical conditioner are formed by sequentially coating the spherical core with the first coating material and the second coating material; The diameter of the sphere is 2-5 mm, and the sphere is made of a first coating material or a second coating material. The thickness of the first coating material is 2-3 mm, and the thickness of the second coating material is 1-2 mm.

[0011] Explanation: CaO can react with the moisture in the feces to release heat, enabling self-heating within the fermentation raw materials. At the same time, the multi-layer spherical design of this invention can avoid the problem of excessive local temperature and prolong the effect of the mineral conditioner. The use of pyrolytic activated carbon powder can achieve a >500 m 2 With a specific surface area and microporous structure of / g, it strongly adsorbs odorous substances such as NH3, H2S, and VOCs, thereby significantly improving the air quality in the composting environment. Through physical adsorption and the combination of surface functional groups, it can effectively fix volatile nitrogen compounds, increasing the total nitrogen content of compost products by 20-35%. Due to the multivalence of manganese (Mn) 2+ Mn 3+ Mn 4+MnFe2O4, with its unique catalytic redox properties and regulatory effect on microbial metabolic processes, has attracted widespread attention in aerobic composting. As a typical representative of spinel ferrite catalysts (such as MnFe2O4, ZnFe2O4, and CuFe2O4), MnFe2O4 exhibits superior catalytic activity in all aspects compared to single metal oxides such as manganese oxides. Therefore, by using the novel spinel ferrite catalyst MnFe2O4, the goal of efficient catalytic composting and rapid maturation can be achieved. By introducing a certain amount of zeolite powder into MnFe2O4, its three-dimensional porous structure can selectively adsorb odorous substances such as ammonia and hydrogen sulfide, fixing 40%–60% of ammonia nitrogen, significantly reducing ammonia escape, regulating fecal permeability, and also controlling Cd. 2+ Pb 2+ Cu 2+ It has a strong affinity for manure, which reduces the bioavailability of heavy metals in manure and improves agricultural safety. On the other hand, the addition of zeolite powder can synergize with MnFe2O4 to effectively improve the conditioning effect. Humic acid can promote the polymerization of small organic molecules into large humic molecules, increase the compost humification index, enhance the long-term fertilizer effect of organic fertilizer, and effectively activate the proliferation of microorganisms, improve nutrient conversion efficiency, thereby achieving "biological-organic" synergistic improvement. By layering the components of the aforementioned mineral conditioner with a first coating material and a second coating material, this multi-layered coating method can prevent excessively high local temperatures in the fermentation raw materials after addition, and also enable each component to achieve a slow-release effect. This slow-release structure inhibits NH4+. 4+ It is rapidly converted into NH3, and combined with the dual mechanisms of zeolite ion exchange and activated carbon adsorption, it significantly reduces ammonia emission during the storage and application of manure, alleviates odor pollution in the surrounding area, and enables some mineral conditioners to play a slow-release role in subsequent composting, thereby improving the removal effect of antibiotics in livestock and poultry manure.

[0012] Furthermore, the core of the type A multilayer spherical conditioner is the second coating material, and it is coated from the inside out by the first coating material and the second coating material, with the first coating material as the outermost layer. The core of the type B multilayer spherical conditioner is the first coating material, and it is coated from the inside out by the second coating material and the first coating material, with the second coating material as the outermost layer. The number of coating layers of the type A multilayer spherical conditioner and the type B multilayer spherical conditioner is N, where N∈[1,7] and N is an odd number.

[0013] Note: By combining the multi-layer spherical conditioner into Type A and Type B, the application effect of the multi-layer spherical conditioner can be further improved, avoiding excessively high local temperatures in the fermentation raw materials after addition, and enhancing the slow-release effect of each component. By configuring and using them in a certain proportion, type A can pre-release heat and type B can pre-release the novel spinel ferrite catalyst MnFe2O4. The alternating release of these two substances enhances the conditioning effect of the mineral conditioner, thereby significantly inhibiting NH4+. 4+ It is rapidly converted into NH3, and with the combined effect of zeolite ion exchange and activated carbon adsorption, it significantly reduces ammonia release during the storage and application of manure, alleviates odor pollution in the surrounding area, and allows some mineral conditioners to continue to be released slowly in subsequent composting, thereby enhancing the removal effect of antibiotics in livestock and poultry manure.

[0014] Furthermore, the type A multilayer spherical conditioner and the type B multilayer spherical conditioner are mixed and used at a particle ratio of 40~50:80.

[0015] Note: By configuring and using the above particle ratio, the alternating synergistic effect of type A and type B release can be achieved at a relatively ideal state, maximizing the conditioning effect of the mineral conditioner when applied in combination with type A and type B, and significantly inhibiting NH4+. 4+ It is rapidly converted into NH3, which significantly reduces ammonia release during the storage and application of manure, alleviates odor pollution, and allows the mineral conditioner to continue to play a slow-release role in subsequent composting.

[0016] Furthermore, the Type A multilayer spherical conditioner and the Type B multilayer spherical conditioner are wrapped with a biodegradable protective film, which is either glutinous rice paper or PLA film.

[0017] Note: By using a biodegradable protective film for encapsulation, the storage time of Type A multilayer spherical conditioner and Type B multilayer spherical conditioner can be extended, and the action time can be prolonged to avoid burst release and maintain the dosage effect.

[0018] Furthermore, the fully decomposed livestock and poultry manure is used in farmland. The treated livestock and poultry manure is comprehensively considered in terms of hygiene and safety, nutrient availability and environmental risks. Through strict quality control, scientific application management and dynamic monitoring, the safety and economy of the decomposed products are ensured.

[0019] The beneficial effects of this invention are: (1) This invention uses manganese oxide as the core component of a mineral conditioner, which has the coupling effect of humic acid on antibiotics and the property of MnFe2O4 to catalyze the generation of hydroxyl radicals ·OH from H2O2 and the effect of ·OH on antibiotic removal, thus enhancing the removal of antibiotics from compost.

[0020] (2) The present invention uses a type A multilayer spherical conditioner and / or a type B multilayer spherical conditioner, which are composed of a first coating material and a second coating material to coat the spherical core in sequence, to enable the phased slow release during the conditioning stage, promote subsequent composting, and improve the removal effect of antibiotics in compost. Attached Figure Description

[0021] Figure 1 This is a process flow diagram of the composting method for efficiently removing antibiotics from livestock and poultry manure based on mineral conditioners, which is based on the present invention. Detailed Implementation

[0022] The present invention will now be described in more detail with reference to specific embodiments, so as to better demonstrate the advantages of the present invention.

[0023] Example 1: A composting method for efficiently removing antibiotics from livestock and poultry manure based on mineral conditioners, comprising the following steps: Step 1: Mix livestock and poultry manure with fermentation auxiliary materials to obtain fermentation raw materials with a moisture content of ≤85%. Then, add mineral conditioner and composting agent to the fermentation raw materials and mix thoroughly for 35 minutes to obtain the prepared fermentation raw materials. The prepared fermentation raw materials have a moisture content of 55%, a carbon-nitrogen ratio of 25:1, a free space content of 18%, and a pH value of 8.0. It should be noted that: livestock and poultry manure mainly consists of pig manure, cow manure, poultry manure, sheep manure, etc. It must not contain stones, bricks, soil clods or other debris. If there is debris, it must be removed mechanically or manually. Before fermentation, the blocky manure of poultry must be mechanically crushed into small particles. The mineral conditioner, by mass fraction, consists of 28% CaO, 10% MnFe2O4, 18% zeolite powder, 29% pyrolytic activated carbon powder, and 15% humic acid, and the amount of mineral conditioner added is 12.8 wt% of the dry weight of the fermentation raw materials. The composting agent is a mixture of *Trichoderma harzianum*, *Tricholoma thermophilum*, and *Bacillus stearothermophilus* in a mass ratio of 2:4:1, with an effective viable count ≥1×10⁻⁶. 9 The live bacteria content was 4.5 wt‰ of the dry weight of the fermentation raw materials. Trichoderma harzianum was purchased from Shandong Xinxiong Biotechnology Co., Ltd., Thermophilus harzianum was purchased from Guangzhou Ceyan Technology Co., Ltd., and Thermophilus stearothermophilus was purchased from Shanghai Beinuo Biotechnology Co., Ltd. Taking 1000 kg of pig manure as an example, the fermentation auxiliary materials are 120 kg of crop straw, 50 kg of sawdust, 60 kg of edible fungus residue, 30 kg of wheat bran, 50 kg of rapeseed cake, and 40 kg of rice husks. The crop straw needs to be crushed to 2-5 cm; the sawdust needs to be piled and aged for 2 weeks; the edible fungus residue needs to be dried until the moisture content is <40%; the wheat bran, rapeseed cake, and soybean cake need to be crushed into powder with a particle size <2 mm. 34% of the crop straw serves as the main framework, absorbing a large amount of moisture from the pig manure; 17% of the edible fungus residue strongly absorbs ammonia odor and provides active mycelium. 14% of the sawdust fills the micropores, keeping the pile loose and aiding in water absorption. 11% of the rice husks increases macroscopic permeability, preventing collapse and anaerobic digestion during pig manure fermentation. 14% of the rapeseed cake / soybean cake, while high in nitrogen, is low in carbon, supplementing carbon and raising the fermentation temperature to 65℃+. Mix 10% of the wheat bran with the inoculum and sprinkle it in as a quick-acting nutrient to "ignite" the fire. Step 2: The prepared fermentation raw materials are composted, and the oxygen concentration inside the compost pile is controlled to be ≥8%. After 24 days, the rapidly composted fermentation raw materials are obtained. By using auxiliary methods, the formation of humic acid can be accelerated, the total nitrogen loss can be reduced, and the removal efficiency of antibiotic indicators can be improved. The high-temperature fermentation in troughs should be maintained for at least 5 days. The fermentation equipment mainly includes turning equipment and ventilation equipment. Turning machines should be used, equipped with a transfer cart to facilitate changing troughs. Ventilation equipment should use fans, and depending on the required air pressure and volume, a single fan for a single trough or multiple fans in multiple trough sections should be selected. Specifically, the aeration air volume is 0.15 m³ / s. 3 / min.

[0024] Step 3: Subsequently, the rapidly composted raw materials are subjected to post-composting, and the oxygen concentration inside the pile is controlled to be ≥5%. The treatment of livestock and poultry manure is completed after 18 days.

[0025] Example 2: The difference between this example and Example 1 is that the mixture was thoroughly mixed for 20 minutes, and the moisture content of the fermentation raw material after preparation was 50%, the carbon-nitrogen ratio was 20:1, the free space content was 18%, and the pH value was 6.0.

[0026] Example 3: The difference between this example and Example 1 is that the mixture was thoroughly mixed for 40 minutes, and the moisture content of the fermentation raw material after preparation was 60%, the carbon-nitrogen ratio was 30:1, the free space content was 18%, and the pH value was 9.0.

[0027] Example 4: This example differs from Example 1 in that, by mass fraction, the mineral conditioner consists of 20% CaO, 15% MnFe2O4, 20% zeolite powder, 30% pyrolytic activated carbon powder, and 15% humic acid, and the amount of mineral conditioner added is 10 wt% of the dry weight of the fermentation raw material.

[0028] Example 5: This example differs from Example 1 in that, by mass fraction, the mineral conditioner consists of 40% CaO, 10% MnFe2O4, 15% zeolite powder, 25% pyrolytic activated carbon powder, and 10% humic acid, and the amount of mineral conditioner added is 15 wt% of the dry weight of the fermentation raw material.

[0029] Example 6: This example differs from Example 1 in that the composting agent is a mixture of *Trichoderma harzianum*, *Tricholoma thermophilum*, and *Bacillus stearothermophilus* in a mass ratio of 3:1:2, with an effective viable count ≥1×10⁻⁶. 9 The concentration of live bacteria is CFU / g, and the amount of live bacteria added is 2 wt‰ of the dry weight of the fermentation raw materials.

[0030] Example 7: This example differs from Example 1 in that the composting agent is a mixture of *Trichoderma harzianum*, *Tricholoma thermophilum*, and *Bacillus stearothermophilus* in a mass ratio of 7:3:5, with an effective viable count ≥1×10⁻⁶. 9 The concentration of live bacteria is CFU / g, and the amount of live bacteria added is 5 wt‰ of the dry weight of the fermentation raw materials.

[0031] Example 8: This example differs from Example 1 in that, taking 1000 kg of chicken manure as an example, the fermentation auxiliary materials are 130 kg of crop straw, 60 kg of sawdust, 80 kg of edible mushroom residue, 40 kg of wheat bran, 40 kg of soybean cake, and 50 kg of rice husks. Specifically, the crop straw needs to be crushed to 2-5 cm; the sawdust needs to be piled and aged for one week; the edible mushroom residue needs to be dried until the moisture content is <40%; and the wheat bran, rapeseed cake, and soybean cake need to be crushed into powder with a particle size <2 mm. The crop straw (32%) provides a large carbon source, diluting the high concentration of chicken manure and preventing seedling burn. The edible mushroom residue (20%) has the best adsorption effect due to the strong odor of chicken manure. The sawdust (15%) locks in nitrogen, reduces ammonia volatilization, and increases volume. The rice husks (12%) provide physical support, making the finished fertilizer granular and easy to apply. The soybean cake (10%) is sufficient because chicken manure itself has enough nitrogen, and an appropriate amount of cake fertilizer is needed, mainly to balance the C / N ratio. 11% wheat bran promotes rapid heating in the early stages and kills parasite eggs in chicken manure.

[0032] Example 9: The difference between this example and Example 1 is that the prepared fermentation raw materials are composted, and the oxygen concentration inside the pile is controlled to be ≥8%. After 3 days, rapidly composted fermentation raw materials are obtained.

[0033] Example 10: The difference between this example and Example 1 is that the prepared fermentation raw materials are composted, and the oxygen concentration inside the compost pile is controlled to be ≥8%. After 25 days, rapidly composted fermentation raw materials are obtained.

[0034] Example 11: The difference between this example and Example 1 is that the rapidly composted raw materials are subsequently subjected to post-composting, and the oxygen concentration inside the pile is controlled to be ≥5%. The treatment of livestock and poultry manure is completed after 15 days.

[0035] Example 12: The difference between this example and Example 1 is that the rapidly composted raw materials are subsequently subjected to post-composting, and the oxygen concentration inside the pile is controlled to be ≥5%. The treatment of livestock and poultry manure is completed after 20 days.

[0036] Example 13: This example differs from Example 1 in that the preparation method of the mineral conditioner is as follows: First, the first coating material is composed of CaO and pyrolytic activated carbon powder, and the second coating material is composed of MnFe2O4, zeolite powder, and humic acid. Secondly, a type A multilayer spherical conditioning agent is formed by sequentially coating the spherical core with the first coating material and the second coating material; The core of the type A multilayer spherical conditioner is the second coating material, and it is coated from the inside out by the first coating material and the second coating material, with the first coating material as the outermost layer. The diameter of the sphere is 4mm, the thickness of the first coating material is 3mm, and the thickness of the second coating material is 2mm; The A-type multilayer spherical conditioner has N coating layers, where N∈[1,7] and N is an odd number, with N being 5.

[0037] Example 14: This example differs from Example 13 in that the diameter of the sphere is 2mm, the thickness of the first coating material is 2mm, and the thickness of the second coating material is 1mm; the number of coating layers of the type A multilayer spherical conditioner is N, N∈[1,7], and N is an odd number, N is 1.

[0038] Example 15: This example differs from Example 13 in that the diameter of the sphere is 5mm, the thickness of the first coating material is 3mm, and the thickness of the second coating material is 2mm; the number of coating layers of the type A multilayer spherical conditioner is N, N∈[1,7], and N is an odd number, with N being 7.

[0039] Example 16: This example differs from Example 1 in that the preparation method of the mineral conditioner is as follows: First, the first coating material is composed of CaO and pyrolytic activated carbon powder, and the second coating material is composed of MnFe2O4, zeolite powder, and humic acid. Secondly, a type B multilayer spherical conditioning agent is formed by sequentially coating the spherical core with the first coating material and the second coating material; The core of the type B multilayer spherical conditioner is the first coating material, and it is coated from the inside out by the second coating material and the first coating material, with the second coating material as the outermost layer. The diameter of the sphere is 4mm, the thickness of the first coating material is 3mm, and the thickness of the second coating material is 2mm; The number of coating layers of the type B multilayer spherical conditioner is N, where N∈[1,7], and N is an odd number, with N being 5.

[0040] Example 17: This example differs from Example 16 in that the diameter of the sphere is 2mm, the thickness of the first coating material is 2mm, and the thickness of the second coating material is 1mm; the number of coating layers of the type B multilayer spherical conditioner is N, N∈[1,7], and N is an odd number, N is 1.

[0041] Example 18: This example differs from Example 16 in that the diameter of the sphere is 5mm, the thickness of the first coating material is 3mm, and the thickness of the second coating material is 2mm; the number of coating layers of the type B multilayer spherical conditioner is N, N∈[1,7], and N is an odd number, with N being 7.

[0042] Example 19: This example differs from Example 1 in that the preparation method of the mineral conditioner is as follows: First, the first coating material is composed of CaO and pyrolytic activated carbon powder, and the second coating material is composed of MnFe2O4, zeolite powder, and humic acid. Secondly, a type A multilayer spherical conditioner and a type B multilayer spherical conditioner are prepared by sequentially coating the spherical core with the first coating material and the second coating material; the type A multilayer spherical conditioner and the type B multilayer spherical conditioner are mixed and used at a particle ratio of 9:16; The core of the type A multilayer spherical conditioner is the second coating material, and it is coated with the first coating material and the second coating material in sequence from the inside to the outside, with the first coating material as the outermost layer; the core of the type B multilayer spherical conditioner is the first coating material, and it is coated with the second coating material and the first coating material in sequence from the inside to the outside, with the second coating material as the outermost layer; and the number of coating layers of the type A multilayer spherical conditioner and the type B multilayer spherical conditioner is N, N∈[1,7], and N is an odd number, N is 5; The core has a diameter of 4 mm and is made of a first coating material or a second coating material, the first coating material having a thickness of 3 mm and the second coating material having a thickness of 2 mm.

[0043] Example 20: This example differs from Example 19 in that the Type A multilayer spherical conditioner and the Type B multilayer spherical conditioner are mixed and used at a particle ratio of 1:2.

[0044] Example 21: The difference between this example and Example 19 is that the Type A multilayer spherical conditioner and the Type B multilayer spherical conditioner are mixed and used at a particle ratio of 5:8.

[0045] Example 22: This example differs from Example 19 in that the number of coating layers of the type A multilayer spherical conditioner and the type B multilayer spherical conditioner is N, N∈[1,7], and N is an odd number, N is 1; the diameter of the sphere is 2mm, and the sphere is made of a first coating material or a second coating material, the thickness of the first coating material is 2mm, and the thickness of the second coating material is 1mm.

[0046] Example 23: This example differs from Example 19 in that the number of coating layers of the type A multilayer spherical conditioner and the type B multilayer spherical conditioner is N, N∈[1,7], and N is an odd number, N is 7; the diameter of the sphere is 5mm, and the sphere is made of a first coating material or a second coating material, the thickness of the first coating material is 3mm, and the thickness of the second coating material is 2mm.

[0047] Example 24: The difference between this example and Example 19 is that the Type A multi-layer spherical conditioner and the Type B multi-layer spherical conditioner are wrapped with a biodegradable protective film, which is glutinous rice paper.

[0048] Example 25: The difference between this example and Example 19 is that the Type A multilayer spherical conditioner and the Type B multilayer spherical conditioner are wrapped with a biodegradable protective film, which is a PLA film.

[0049] Example 26: This example demonstrates the application of the composted livestock and poultry manure products from Examples 1-22. The finally composted manure is used in farmland. The treated manure undergoes comprehensive consideration of hygiene and safety, nutrient availability, and environmental risks. Strict quality control, scientific application management, and dynamic monitoring are implemented to ensure the safety and economic viability of the composted products. Specific requirements are as follows: The sample should have a uniform appearance, no foul odor, and an organic matter content (on a dried basis) ≥30%, a total nutrient (N+P2O3+K2O) mass fraction (on a dried basis) ≥4.0%, a moisture (fresh sample) mass fraction ≤30%, a pH value of 5.5~8.5, a seed germination index (GI) ≥70%, a mechanical impurity mass fraction ≤0.5%, an ascarid egg mortality rate ≥95%, a fecal coliform count ≤100 CFU / g, and a total arsenic (As) (on a dried basis) ≤15%. mg / kg, total mercury (Hg) (on a dried basis) ≤2mg / kg, total lead (Pb) (on a dried basis) ≤50mg / kg, total cadmium (Cd) (on a dried basis) ≤3mg / kg, total chromium (Cr) (on a dried basis) ≤150mg / kg, total antibiotics (on a dried basis) ≤3.25mg / kg. Total antibiotics refer to the sum of four substances: oxytetracycline, tetracycline, chlortetracycline, and doxycycline. At the same time, there are no live maggots, pupae, or newly emerged adult flies.

[0050] Application Experiment Example: To verify the effectiveness of mineral conditioners in treating rapidly composted livestock and poultry manure, measurements were taken on rapidly composted livestock and poultry manure processed using various methods, and the following control groups were set up: Control 1: This control is based on Example 1 with changes to the conditions. Specifically, only the same mass of pyrolytic activated carbon powder, humic acid and MnFe2O4 as in Example 1 were added, while the other treatment conditions remained unchanged. Using seed germination rate as the main indicator of composting maturity, the germination index was measured under various processes after inoculation 20 days later, as shown in Table 1 below: Table 1 Germination Index of Composted Livestock and Poultry Manure

[0051] By using the mineral conditioner, the germination index was significantly higher than that of control 1 (60.3%) after 20 days of composting. This shows that the mineral conditioner provided by the present invention can effectively shorten the composting period by more than 20 days, as shown in Table 1.

[0052] Meanwhile, a comparison of the data in Table 1 shows that, compared with the mineral conditioner addition method in Example 1, the use of Type A multilayer spherical conditioner, Type B multilayer spherical conditioner, and Type A-B multilayer spherical conditioner can further improve the effect of livestock and poultry manure composting products; among them, the mixed use of Type A-B multilayer spherical conditioners in Examples 19, 24, and 25 shows the most significant improvement in effect. Furthermore, to further investigate the effects of various parameters of the Type A multilayer spherical conditioner, Type B multilayer spherical conditioner, and Type A-B multilayer spherical conditioner on the effectiveness of livestock and poultry manure composting products, seed germination rate was used as the main composting indicator. The germination index was measured under each process after 20 days of composting, as shown in Tables 2, 3, and 4 below. For Type A multi-layer spherical conditioning agents: Table 2 Germination Index of Composted Livestock and Poultry Manure

[0053] The addition of type A multilayer spherical conditioner under different process parameters has a certain impact on the composting products of livestock and poultry manure. Among them, the effect of the addition method in Example 13 is the best, as shown in Table 2.

[0054] For Type B multi-layer spherical conditioning agents: Table 3 Germination Index of Composted Livestock and Poultry Manure

[0055] The addition of type B multilayer spherical conditioner under different process parameters has a certain impact on the composting products of livestock and poultry manure. Among them, the effect of the addition method in Example 16 is the best, as shown in Table 3.

[0056] For Type A-B multilayer spherical conditioning agents: Table 4 Germination Index of Composted Livestock and Poultry Manure

[0057] The addition of type A-B multilayer spherical conditioner under different process parameters has a certain impact on the composting products of livestock and poultry manure. Among them, the effects of the addition in Examples 19 and 23 are the best. However, considering factors such as manufacturing cost, the overall effect of Example 19 is better. Through the above comparison, it can be seen that by combining type A and type B multilayer spherical conditioner, type A pre-releases heat and type B pre-releases the novel spinel ferrite catalyst MnFe2O4. The alternating release of the two enhances the conditioning effect of the mineral conditioner, thereby significantly inhibiting NH4+. 4+ It is rapidly converted into NH3, and with the combined effect of zeolite ion exchange and activated carbon adsorption, it significantly reduces ammonia release during the storage and application of manure, alleviates odor pollution in the surrounding area, and allows some mineral conditioners to continue to be released slowly in subsequent composting, enhancing the removal effect of antibiotics in livestock and poultry manure. This improves the application effect of multi-layer spherical conditioners, avoids excessively high local temperatures in fermentation raw materials after addition, and enhances the slow-release effect of each component (see Table 4).

Claims

1. A composting method for efficiently removing antibiotics from livestock and poultry manure based on mineral conditioners, characterized in that, Includes the following steps: Step 1: Mix livestock and poultry manure with fermentation auxiliary materials to make the moisture content of livestock and poultry manure ≤85% to obtain fermentation raw materials. Then add mineral conditioner and composting agent to the fermentation raw materials and mix them thoroughly for 20~40 minutes to obtain the prepared fermentation raw materials. The mineral conditioner, by mass fraction, consists of 20-40% CaO, 10-15% MnFe2O4, 15-20% zeolite powder, 25-30% pyrolytic activated carbon powder, and 10-15% humic acid, and the amount of mineral conditioner added is 10-15 wt% of the dry weight of the fermentation raw materials. The composting agent is a mixture of *Trichoderma harzianum*, *Tricholoma thermophilum*, and *Bacillus stearothermophilus* in a mass ratio of 3-7:1-3:2-5, with an effective viable count ≥1×10⁻⁶. 9 CFU / g, and the amount of live bacteria added is 2~5 wt‰ of the dry weight of the fermentation raw material; Step 2: Compost the prepared fermented raw materials, controlling the oxygen concentration inside the pile to ≥8%, and obtain rapidly composted raw materials after 3~25 days; Step 3: Subsequently, the rapidly composted raw materials are subjected to post-composting, and the oxygen concentration inside the pile is controlled to be ≥5%. The treatment of livestock and poultry manure is completed after 15~20 days.

2. The composting method for efficiently removing antibiotics from livestock and poultry manure based on mineral conditioners according to claim 1, characterized in that, The fermentation auxiliary materials are any one or a mixture of crop straw, sawdust, edible fungus residue, wheat bran, rapeseed cake, soybean cake, and rice husk; wherein, the crop straw needs to be crushed to 2-5 cm; the sawdust needs to be piled up and aged for 1-2 weeks; the edible fungus residue needs to be dried to a moisture content of <40%; and the wheat bran, rapeseed cake, and soybean cake need to be crushed into powder with a particle size of <2 mm.

3. The composting method for efficiently removing antibiotics from livestock and poultry manure based on mineral conditioners according to claim 1, characterized in that, By adding mineral conditioners and composting agents to the fermentation feedstock, the moisture content of the prepared fermentation feedstock is made to be 50%~60%, the carbon-nitrogen ratio is 20:1~30:1, the free space content is >15%, and the pH value is 6.0~9.

0.

4. The composting method for efficiently removing antibiotics from livestock and poultry manure based on mineral conditioners according to claim 1, characterized in that, The preparation method of the mineral conditioner is as follows: First, the first coating material is composed of CaO and pyrolytic activated carbon powder, and the second coating material is composed of MnFe2O4, zeolite powder, and humic acid. Secondly, a type A multilayer spherical conditioner and / or a type B multilayer spherical conditioner are formed by sequentially coating the spherical core with the first coating material and the second coating material; The diameter of the sphere is 2-5 mm, and the sphere is made of a first coating material or a second coating material. The thickness of the first coating material is 2-3 mm, and the thickness of the second coating material is 1-2 mm.

5. The composting method for efficiently removing antibiotics from livestock and poultry manure based on mineral conditioners according to claim 4, characterized in that, The core of the type A multilayer spherical conditioner is the second coating material, and it is coated from the inside out by the first coating material and the second coating material, with the first coating material as the outermost layer. The core of the type B multilayer spherical conditioner is the first coating material, and it is coated from the inside out by the second coating material and the first coating material, with the second coating material as the outermost layer. The number of coating layers of the type A multilayer spherical conditioner and the type B multilayer spherical conditioner is N, where N∈[1,7] and N is an odd number.

6. The composting method for efficiently removing antibiotics from livestock and poultry manure based on mineral conditioners according to claim 4, characterized in that, The type A multi-layer spherical conditioner and the type B multi-layer spherical conditioner are mixed and used at a particle ratio of 40~50:

80.

7. The composting method for efficiently removing antibiotics from livestock and poultry manure based on mineral conditioners according to claim 4, characterized in that, The Type A multi-layer spherical conditioner and the Type B multi-layer spherical conditioner are wrapped with a biodegradable protective film, which is either glutinous rice paper or PLA film.

8. The composting method for efficiently removing antibiotics from livestock and poultry manure based on mineral conditioners according to claim 1, characterized in that, The fully decomposed livestock and poultry manure is then used in farmland.

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