Process for preparing organic fertilizer from vitamin B12 mushroom dregs

Abstract

The invention discloses a process for preparing an organic fertilizer from vitamin B12 mushroom dregs, and relates to the technical field of organic fertilizers. When the vitamin B12 mushroom dregs are used for preparing the organic fertilizer, firstly, the B12 mushroom dregs, bacillus subtilis and urea are mixed, and fertilizer particles are prepared through aerobic composting fermentation, aging, drying, smashing and granulation; secondly, carrying out ring opening polymerization on cyclosiloxane, and preparing modified polysiloxane by taking 3-bis (3-aminopropyl)-1, 1, 3, 3-tetramethyldisiloxane as an end-capping reagent; the preparation method comprises the following steps: reacting modified polysiloxane with dihydric alcohol and isocyanate to obtain a polyurethane emulsion, carrying out primary coating on fertilizer particles, dissolving the fertilizer particles with potassium chloride, carrying out secondary coating, carrying out tertiary coating by using the polyurethane emulsion and a natural photoinitiator, and irradiating under an ultraviolet lamp to obtain the organic fertilizer. The prepared organic fertilizer has a good slow release effect.

Description

Technical Field

[0001] The invention relates to the technical field of organic fertilizers, in particular to a process for preparing organic fertilizer from vitamin B12 fungus residues. Background Art

[0002] Mushroom residue, a byproduct of the microbial fermentation process, contains rich microbial metabolites and underutilized nutritional essences. Once these valuable ingredients are integrated into the soil, they can be quickly and efficiently decomposed and converted into nutrients that are easily absorbed and utilized by plants, such as nitrogen, phosphorus, potassium and various trace elements, providing a solid foundation for the healthy growth of crops. Not only that, the introduction of mushroom residue is like injecting a shot of adrenaline into the soil. It can effectively improve the soil structure, increase the organic matter content of the soil, significantly improve the soil's water and fertilizer retention capacity and air permeability, create a more ideal growth environment for the roots of crops, and promote the healthy development of crops and high yield and quality.

[0003] In order to maximize the effectiveness of this natural organic fertilizer and prolong its stability, researchers have cleverly introduced coating preparation technology. In this technology, the choice of coating materials plays a vital role. The ideal coating material must have excellent air permeability and water retention to ensure that the fertilizer can stably and slowly release nutrients in a complex and changeable soil environment to meet the different needs of the crop growth cycle. Polyurethane, a material that has demonstrated outstanding performance in many fields, stands out in the field of fertilizer coatings with its high-strength structural characteristics, wear-resistant and durable physical properties, excellent waterproof and anti-corrosion capabilities, and controlled-release properties that precisely control nutrient release, becoming a leader among many choices.

[0004] The polyurethane coating technology is like putting a layer of "smart coat" on the vitamin B12 fungus residue organic fertilizer. It can accurately control the nutrient release rate according to the growth rhythm and nutrient requirements of crops, and achieve continuous and balanced nutrient supply, thereby greatly improving the utilization rate of fertilizers and effectively reducing nutrient waste and loss. In addition, the polyurethane coating also gives the fertilizer excellent physical stability and environmental protection characteristics. Whether it is long-distance transportation or field application, it can ensure the integrity and safety of the fertilizer and reduce potential threats to the environment. Summary of the invention

[0005] The object of the present invention is to provide a process for preparing organic fertilizer from vitamin B12 fungus residue to solve the problems existing in the prior art.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions: A process for preparing organic fertilizer from vitamin B12 bacterial residues comprises the following preparation steps: (1) Mix vitamin B12 bacterial residue, Bacillus subtilis and urea, add pure water so that the moisture content of the vitamin B12 bacterial residue is 60%-70%, stir evenly, and then perform aerobic composting fermentation, aging, drying, crushing and granulation to obtain fertilizer granules; (2) Octamethylcyclotetrasiloxane and tetravinyltetramethylcyclotetrasiloxane were mixed evenly, heated to 80-90°C under nitrogen protection, reacted for 30-40 minutes, and then heated to 110-120°C. A 25wt% tetramethylammonium hydroxide aqueous solution with a mass of 0.02%-0.03% of the mass of octamethylcyclotetrasiloxane was added, and then 3-bis(3-aminopropyl)-1,1,3 ,3-tetramethyldisiloxane is stirred for 3-4h, heated to 150℃, reacted for 3-4h, reduced pressure to 2-2.5KPa, and reacted for 3-4h to obtain amino-terminated polysiloxane; under nitrogen protection and ice-water bath conditions, perylene tetracarboxylic anhydride, amino-terminated polysiloxane, and acetone are mixed at a mass ratio of 1:20.7:(50-60) for 40-50min, heated to room temperature for reaction for 2-3h, and filtered to obtain modified polysiloxane; (3) Weigh the following components: polycaprolactone diol, polyethylene glycol, modified polysiloxane, dibutyltin dilaurate, acetone, and isophorone diisocyanate; mix polycaprolactone diol and polyethylene glycol, dehydrate at 120°C for 0.5h under nitrogen protection, cool to 70-80°C, add modified polysiloxane and isophorone diisocyanate in sequence, stir for 2-3h, heat to 90-100°C, add dibutyltin dilaurate and acetone, continue to react until the isocyanate group content is 0%-0.1%, cool to room temperature, and after the reaction is completed, rotary evaporate at 50°C and -0.1MPa to obtain modified polyurethane; mix modified polyurethane, emulsifier, and pure water, and emulsify with a high-speed homogenizer at a speed of 16kr / min to obtain a modified polyurethane emulsion; (4) Put the fertilizer granules into a drum coating machine and heat them to 75-80°C. Spray 0.05-0.07 times the mass of the fertilizer granules with a modified polyurethane emulsion on the fertilizer granules in the drum. Heat at 75-80°C for 12 min, repeat twice, cool to room temperature to obtain a primary coated fertilizer, continue to spray 5-6 mg / L potassium chloride solution on the primary coated fertilizer, repeat twice to obtain a secondary coated fertilizer, spray 0.05-0.07 times the mass of the fertilizer granules with a modified polyurethane emulsion, 0.002-0.003 times the mass of the fertilizer granules with hesperidin, and 0.002-0.003 times the mass of the fertilizer granules with piperonal at room temperature on the secondary coated fertilizer, repeat twice, and irradiate under ultraviolet light for 5-10 min to obtain an organic fertilizer.

[0007] As an optimization, the mass ratio of the vitamin B12 bacterial residue, Bacillus subtilis and urea in step (1) is 1:(0.1-0.2):(2-3).

[0008] As an optimization, the aerobic composting fermentation process in step (1) is as follows: the fermentation temperature is 60-75°C, the temperature is kept for 3-4 days, and then the compost is turned. The frequency of turning the compost is once every 1-2 days, and the fermentation time is 7-9 days.

[0009] As an optimization, the aging conditions in step (1) are: temperature of 30-50°C, fermentation period of 4-7 days; and the particle size of the fertilizer particles is 3-5 mm.

[0010] As an optimization, the mass ratio of octamethylcyclotetrasiloxane to tetravinyltetramethylcyclotetrasiloxane in step (2) is 1:(0.8-1).

[0011] As an optimization, the weighing amounts of the components in step (3) are: by mass, 10-11 parts of polycaprolactone diol, 20-30 parts of polyethylene glycol, 5-6 parts of modified polysiloxane, 0.002 parts of dibutyltin dilaurate, and 5-6 parts of acetone.

[0012] As an optimization, the molecular weights of the polycaprolactone diol and polyethylene glycol are both 2000.

[0013] As an optimization, the molar amount of the isocyanate group of the isophorone diisocyanate in step (3) is 1.1-1.2 times the molar amount of the hydroxyl group of the polycaprolactone diol and the polyethylene glycol.

[0014] As an optimization, the test method for the isocyanate group content in step (3) is the di-n-butylamine method.

[0015] As an optimization, the amount of the modified polyurethane, emulsifier and pure water in step (3) is: by mass, 100 parts of modified polyurethane, 10-12 parts of emulsifier, 40-50 parts of pure water, and the emulsifier is OP-10.

[0016] Compared with the prior art, the beneficial effects achieved by the present invention are: When the vitamin B12 bacterial residue is used to prepare the organic fertilizer, the present invention firstly mixes the B12 bacterial residue, bacillus subtilis and urea, and obtains the fertilizer particles through aerobic composting fermentation, aging, drying, crushing and granulation, wherein the aerobic fermentation process helps to kill harmful microorganisms in the bacterial residue, and realizes the stabilization of the bacterial residue; secondly, octamethylcyclotetrasiloxane and tetravinyltetramethylcyclotetrasiloxane are ring-opened and polymerized, and 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is used as a capping agent to prepare an amino-terminated polysiloxane containing a vinyl group in the side chain, and the amino-terminated polysiloxane reacts with perylene tetracarboxylic anhydride, and the anhydride is ring-opened to form a carboxyl group, thereby obtaining a modified polysiloxane containing a perylene structure and a carboxylic acid functional group; and the modified polysiloxane is Oxyalkyl reacts with diol and isocyanate to obtain polyurethane emulsion, and the fertilizer particles are coated once with the polyurethane emulsion as the coating material, and then the fertilizer particles are coated twice with potassium chloride solution. The carboxylic acid group on the polyurethane side chain can well complex potassium ions, thereby introducing potassium elements required for plant growth into the fertilizer, and then the polyurethane emulsion and natural photoinitiator are used for the third coating, and then irradiated under ultraviolet light. The presence of perylene structure allows ππ stacking between polyurethanes to form a cross-linked network. The vinyl on the polyurethane side chain induces double bond cross-linking under the action of natural photoinitiator to form a more complex cross-linked network. The presence of the cross-linked network can delay the release time of the fertilizer and improve the utilization rate of the fertilizer. DETAILED DESCRIPTION

[0017] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] The emulsifier used in the following examples and comparative examples is OP-10.

[0019] Embodiment 1: (1) Mix vitamin B12 bacterial residue, Bacillus subtilis and urea in a mass ratio of 1:0.1:2, add pure water to make the moisture content of the vitamin B12 bacterial residue 70%, stir evenly and perform aerobic composting fermentation, the fermentation temperature is 75°C, keep warm for 4 days, and then turn the compost, the turning frequency is once every 2 days, and the fermentation time is 9 days; then age, the ageing conditions are: temperature is 50°C, and the fermentation cycle is 7 days; after the ageing is completed, dry, crush and granulate to obtain fertilizer granules, and the particle size of the fertilizer granules is 5 mm; (2) Octamethylcyclotetrasiloxane and tetravinyltetramethylcyclotetrasiloxane were mixed uniformly in a mass ratio of 1:0.8, heated to 90°C under nitrogen protection, reacted for 40 minutes, and then heated to 120°C, and a 25wt% tetramethylammonium hydroxide aqueous solution of 0.02% by mass of octamethylcyclotetrasiloxane was added, and then 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane of 1 times the mass of octamethylcyclotetrasiloxane was added and stirred for 4 hours, and then heated to 150°C, reacted for 4 hours, and reduced pressure to 2.5KPa, and continued to react for 4 hours to obtain amino-terminated polysiloxane; under nitrogen protection and ice-water bath conditions, perylene tetracarboxylic anhydride, amino-terminated polysiloxane, and acetone were mixed in a mass ratio of 1:20.7:50 for 50 minutes, heated to room temperature for reaction for 3 hours, and filtered to obtain modified polysiloxane; (3) Weigh the following components: 10 parts by mass of polycaprolactone diol, 20 parts by mass of polyethylene glycol, 5 parts by mass of modified polysiloxane, 0.002 parts by mass of dibutyltin dilaurate, and 5 parts by mass of acetone; the molecular weight of polycaprolactone diol and polyethylene glycol are both 2000; weigh isophorone diisocyanate, wherein the molar amount of the isocyanate group of isophorone diisocyanate is 1.1 times the molar amount of the hydroxyl group of polycaprolactone diol and polyethylene glycol; mix the polycaprolactone diol and polyethylene glycol, dehydrate them at 120°C for 0.5 h under nitrogen protection, cool them to 80°C, and add modified polysiloxane, isophorone diisocyanate, and acetone in sequence; diisocyanate, stirred for 3h, heated to 100℃, added dibutyltin dilaurate and acetone, continued the reaction until the isocyanate group content was 0.1%, cooled to room temperature, and the isocyanate group content was tested by di-n-butylamine method; after the reaction, rotary evaporation was performed at 50℃ and -0.1MPa to obtain modified polyurethane; the following components were weighed, calculated by mass: 100 parts of modified polyurethane, 10 parts of emulsifier, and 40 parts of pure water. The modified polyurethane, emulsifier, and pure water were mixed, and emulsified with a high-speed homogenizing emulsifier at a speed of 16kr / min to obtain a modified polyurethane emulsion; (4) Put the fertilizer granules into a drum coating machine and heat them to 80°C. Spray 0.05 times the mass of the fertilizer granules with a modified polyurethane emulsion on the fertilizer granules in the drum. Heat at 80°C for 12 min. Repeat twice. Cool to room temperature to obtain a primary coated fertilizer. Continue to spray 5 mg / L potassium chloride solution on the primary coated fertilizer. Repeat twice to obtain a secondary coated fertilizer. Spray 0.05 times the mass of the fertilizer granules with a modified polyurethane emulsion, 0.002 times the mass of the fertilizer granules with hesperidin, and 0.002 times the mass of the fertilizer granules with piperonal on the secondary coated fertilizer at room temperature. Repeat twice. Irradiate under ultraviolet light for 10 min to obtain an organic fertilizer.

[0020] Embodiment 2: A process for preparing organic fertilizer from vitamin B12 fungus residue, the process for preparing organic fertilizer from vitamin B12 fungus residue comprising the following preparation steps: (1) Mix vitamin B12 bacterial residue, Bacillus subtilis and urea in a mass ratio of 1:0.15:2.5, add pure water to make the moisture content of the vitamin B12 bacterial residue 65%, stir evenly and perform aerobic composting fermentation, keep the fermentation temperature at 65°C for 3 days, turn the compost, turn the compost once every 2 days, and ferment for 8 days; then age the compost, the ageing conditions are: temperature 40°C, fermentation cycle 6 days; after the ageing, dry, crush and granulate to obtain fertilizer granules, the particle size of the fertilizer granules is 4 mm; (2) Octamethylcyclotetrasiloxane and tetravinyltetramethylcyclotetrasiloxane were mixed uniformly in a mass ratio of 1:0.9, heated to 85°C under nitrogen protection, reacted for 35 minutes, and then heated to 115°C, and a 25wt% tetramethylammonium hydroxide aqueous solution of 0.025% of the mass of octamethylcyclotetrasiloxane was added, and then 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane of 1.5 times the mass of octamethylcyclotetrasiloxane was added, and the mixture was stirred for 3.5 hours. The mixture was heated to 150°C, reacted for 3.5 hours, and the pressure was reduced to 2.3 KPa, and the reaction was continued for 3.5 hours to obtain amino-terminated polysiloxane. Under nitrogen protection and ice-water bath conditions, perylene tetracarboxylic anhydride, amino-terminated polysiloxane, and acetone were mixed in a mass ratio of 1:20.7:55 for 45 minutes, heated to room temperature for reaction for 2.5 hours, and filtered to obtain modified polysiloxane. (3) Weigh the following components: 10 parts by mass of polycaprolactone diol, 25 parts of polyethylene glycol, 5.5 parts of modified polysiloxane, 0.002 parts of dibutyltin dilaurate, and 5.5 parts of acetone; the molecular weight of polycaprolactone diol and polyethylene glycol are both 2000; weigh isophorone diisocyanate, wherein the molar amount of the isocyanate group of isophorone diisocyanate is 1.15 times the molar amount of the hydroxyl group of polycaprolactone diol and polyethylene glycol; mix the polycaprolactone diol and polyethylene glycol, dehydrate them at 120°C for 0.5 h under nitrogen protection, cool them to 75°C, and add modified polysiloxane, isophorone diisocyanate, and acetone in sequence; 1, 2, 4, 5, 10, 15, 20, 30, 40, 50, 80, 100, 150, 200, 300, 400, 800, 1000, 200, 300, 400, 8 ... (4) Place the fertilizer granules in a drum coating machine and heat them to 77°C. Spray 0.06 times the mass of the fertilizer granules with a modified polyurethane emulsion on the fertilizer granules in the drum. Heat at 76°C for 12 min, repeat twice, cool to room temperature to obtain a primary coated fertilizer, continue to spray 5.5 mg / L potassium chloride solution on the primary coated fertilizer, repeat twice to obtain a secondary coated fertilizer, spray 0.06 times the mass of the fertilizer granules with a modified polyurethane emulsion, 0.003 times the mass of the fertilizer granules with hesperidin, and 0.003 times the mass of the fertilizer granules with piperonal on the secondary coated fertilizer at room temperature, repeat twice, and irradiate under ultraviolet light for 7 min to obtain an organic fertilizer.

[0021] Embodiment 3: A process for preparing organic fertilizer from vitamin B12 fungus residue, the process for preparing organic fertilizer from vitamin B12 fungus residue comprising the following preparation steps: (1) Mix vitamin B12 bacterial residue, Bacillus subtilis and urea in a mass ratio of 1:0.2:3, add pure water to make the moisture content of the vitamin B12 bacterial residue 60%, stir evenly and then perform aerobic composting fermentation, the fermentation temperature is 60°C, keep warm for 3 days, and then turn the compost, the turning frequency is once a day, and the fermentation time is 7 days; then age, the ageing conditions are: temperature is 30°C, and the fermentation cycle is 4 days; after the ageing is completed, dry, crush and granulate to obtain fertilizer granules; the particle size of the fertilizer granules is 3 mm; (2) Octamethylcyclotetrasiloxane and tetravinyltetramethylcyclotetrasiloxane were mixed uniformly in a mass ratio of 1:1, heated to 80°C under nitrogen protection, reacted for 30 minutes, and then heated to 110°C, and a 25wt% tetramethylammonium hydroxide aqueous solution of 0.03% of the mass of octamethylcyclotetrasiloxane was added, and then 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane of twice the mass of octamethylcyclotetrasiloxane was added and stirred for 3 hours, and then heated to 150°C, reacted for 3 hours, and reduced pressure to 2KPa, and continued to react for 3 hours to obtain amino-terminated polysiloxane; under nitrogen protection and ice-water bath conditions, perylene tetracarboxylic anhydride, amino-terminated polysiloxane, and acetone were mixed in a mass ratio of 1:20.7:60 for 40 minutes, heated to room temperature for reaction for 2 hours, and filtered to obtain modified polysiloxane; (3) Weigh the following components: 11 parts of polycaprolactone diol, 30 parts of polyethylene glycol, 6 parts of modified polysiloxane, 0.002 parts of dibutyltin dilaurate, and 6 parts of acetone, by mass; the molecular weight of polycaprolactone diol and polyethylene glycol are both 2000; then weigh isophorone diisocyanate, the molar amount of the isocyanate group of isophorone diisocyanate is 1.2 times the molar amount of the hydroxyl group of polycaprolactone diol and polyethylene glycol; mix the polycaprolactone diol and polyethylene glycol, dehydrate them at 120°C for 0.5h under nitrogen protection, cool them to 70°C, and add modified polysiloxane, isophorone diisocyanate, and acetone in sequence; diisocyanate, stirred for 2h, heated to 90°C, added dibutyltin dilaurate and acetone, continued to react until the isocyanate group content was 0.1%, cooled to room temperature, and the isocyanate group content was tested by di-n-butylamine method; after the reaction was completed, the modified polyurethane was obtained by rotary evaporation at 50°C and -0.1MPa; the following components were weighed, calculated by mass: 100 parts of modified polyurethane, 12 parts of emulsifier, and 50 parts of pure water. The modified polyurethane, emulsifier, and pure water were mixed, and emulsified with a high-speed homogenizing emulsifier at a speed of 16kr / min to obtain a modified polyurethane emulsion; (4) Place the fertilizer granules in a drum coating machine and heat them to 75°C. Spray 0.07 times the mass of the fertilizer granules with a modified polyurethane emulsion on the fertilizer granules in the drum. Heat at 75°C for 12 min. Repeat twice. Cool to room temperature to obtain a primary coated fertilizer. Continue to spray 6 mg / L potassium chloride solution on the primary coated fertilizer. Repeat twice to obtain a secondary coated fertilizer. Spray 0.07 times the mass of the fertilizer granules with a modified polyurethane emulsion, 0.003 times the mass of the fertilizer granules with hesperidin, and 0.003 times the mass of the fertilizer granules with piperonal on the secondary coated fertilizer at room temperature. Repeat twice. Irradiate under ultraviolet light for 5 min to obtain an organic fertilizer.

[0022] Embodiment 4: (1) Mix vitamin B12 bacterial residue, Bacillus subtilis and urea in a mass ratio of 1:0.13:2.2, add pure water to make the moisture content of the vitamin B12 bacterial residue 63%, stir evenly and then perform aerobic composting fermentation at a fermentation temperature of 64°C for 3 days, then turn the compost once a day for 7 days; then age the compost at a temperature of 36°C and a fermentation cycle of 6 days; after the ageing, dry, crush and granulate the compost to obtain fertilizer granules; the particle size of the fertilizer granules is 4 mm; (2) Octamethylcyclotetrasiloxane and tetravinyltetramethylcyclotetrasiloxane were mixed uniformly in a mass ratio of 1:0.86, heated to 87°C under nitrogen protection, reacted for 34 minutes, and then heated to 112°C, and a 25wt% tetramethylammonium hydroxide aqueous solution of 0.02% by weight of octamethylcyclotetrasiloxane was added, and then 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane of 1.7 times by weight of octamethylcyclotetrasiloxane was added, and the mixture was stirred for 3.6 hours. The mixture was heated to 150°C, reacted for 3.4 hours, and the pressure was reduced to 2KPa, and the reaction was continued for 3.6 hours to obtain amino-terminated polysiloxane. Under nitrogen protection and ice-water bath conditions, perylene tetracarboxylic anhydride, amino-terminated polysiloxane, and acetone were mixed in a mass ratio of 1:20.7:57 for 47 minutes, heated to room temperature for reaction for 2.6 hours, and filtered to obtain modified polysiloxane. (3) Weigh the following components by mass: 10.4 parts of polycaprolactone diol, 23 parts of polyethylene glycol, 5.6 parts of modified polysiloxane, 0.002 parts of dibutyltin dilaurate, and 5.6 parts of acetone; the molecular weight of polycaprolactone diol and polyethylene glycol are both 2000; the molar amount of the isocyanate group of the isophorone diisocyanate is 1.14 times the molar amount of the hydroxyl group of the polycaprolactone diol and the polyethylene glycol; mix the polycaprolactone diol and the polyethylene glycol, dehydrate them at 120°C for 0.5h under nitrogen protection, cool them to 73°C, and add the modified polysiloxane, isophorone diisocyanate, and acetone in sequence; Cyanate, stir for 2h, heat to 95℃, add dibutyltin dilaurate and acetone, continue to react until the isocyanate group content is 0%, cool to room temperature, and the isocyanate group content is tested by di-n-butylamine method; after the reaction is completed, rotary evaporate at 50℃ and -0.1MPa to obtain modified polyurethane; weigh the following components, by mass, 100 parts of modified polyurethane, 11 parts of emulsifier, and 44 parts of pure water, mix the modified polyurethane, emulsifier and pure water, and emulsify with a high-speed homogenizing emulsifier at a speed of 16kr / min to obtain a modified polyurethane emulsion; (4) The fertilizer granules were placed in a drum coating machine and heated to 76°C. A modified polyurethane emulsion at a concentration of 0.059 times the mass of the fertilizer granules was sprayed on the fertilizer granules in the drum. The mixture was heated at 76°C for 12 min and repeated twice. The mixture was cooled to room temperature to obtain a primary coated fertilizer. A 5.6 mg / L potassium chloride solution was sprayed on the primary coated fertilizer and repeated twice to obtain a secondary coated fertilizer. A modified polyurethane emulsion at a concentration of 0.056 times the mass of the fertilizer granules, hesperidin at a concentration of 0.002 times the mass of the fertilizer granules, and piperonal at a concentration of 0.002 times the mass of the fertilizer granules were sprayed on the secondary coated fertilizer at room temperature and repeated twice. The mixture was irradiated under ultraviolet light for 7 min to obtain an organic fertilizer.

[0023] Embodiment 5: (1) Mix vitamin B12 bacterial residue, Bacillus subtilis and urea in a mass ratio of 1:0.18:2.7, add pure water to make the moisture content of the vitamin B12 bacterial residue 67%, stir evenly and then perform aerobic composting fermentation at a fermentation temperature of 72°C for 3 days, then turn the compost once every 2 days for 7 days; then age the compost under the following conditions: a temperature of 42°C and a fermentation cycle of 5 days; after the ageing, dry, crush and granulate the compost to obtain fertilizer granules; the particle size of the fertilizer granules is 4 mm; (2) Octamethylcyclotetrasiloxane and tetravinyltetramethylcyclotetrasiloxane were mixed uniformly in a mass ratio of 1:0.9, heated to 88°C under nitrogen protection, reacted for 36 minutes, and then heated to 118°C, and a 25wt% tetramethylammonium hydroxide aqueous solution of 0.03% by mass of octamethylcyclotetrasiloxane was added, and then 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane of 1.4 times by mass of octamethylcyclotetrasiloxane was added, and the mixture was stirred for 3.6 hours. The mixture was heated to 150°C, reacted for 4 hours, and the pressure was reduced to 2.5 KPa, and the reaction was continued for 4 hours to obtain amino-terminated polysiloxane. Under nitrogen protection and ice-water bath conditions, perylene tetracarboxylic anhydride, amino-terminated polysiloxane, and acetone were mixed in a mass ratio of 1:20.7:58 for 46 minutes, heated to room temperature for reaction for 2.7 hours, and filtered to obtain modified polysiloxane. (3) Weigh the following components by mass: 11 parts of polycaprolactone diol, 26 parts of polyethylene glycol, 5 parts of modified polysiloxane, 0.002 parts of dibutyltin dilaurate, and 5 parts of acetone; the molecular weight of polycaprolactone diol and polyethylene glycol are both 2000; the molar amount of the isocyanate group of the isophorone diisocyanate is 1.1 times the molar amount of the hydroxyl group of the polycaprolactone diol and the polyethylene glycol; mix the polycaprolactone diol and the polyethylene glycol, dehydrate them at 120°C for 0.5h under nitrogen protection, cool them to 76°C, add the modified polysiloxane and isophorone diisocyanate in turn, and stir them. Stir for 2h, heat to 94°C, add dibutyltin dilaurate and acetone, continue to react until the isocyanate group content is 0.1%, cool to room temperature, and the isocyanate group content is tested by di-n-butylamine method; after the reaction is completed, rotary evaporate at 50°C and -0.1MPa to obtain modified polyurethane; weigh the following components, calculated by mass, 100 parts of modified polyurethane, 11 parts of emulsifier, and 47 parts of pure water, mix the modified polyurethane, emulsifier, and pure water, and emulsify with a high-speed homogenizer at a speed of 16kr / min to obtain a modified polyurethane emulsion; (4) The fertilizer granules were placed in a drum coating machine and heated to 76°C. A modified polyurethane emulsion at a concentration of 0.063 times the mass of the fertilizer granules was sprayed on the fertilizer granules in the drum. The mixture was heated at 77°C for 12 min, and the process was repeated twice. The mixture was cooled to room temperature to obtain a primary coated fertilizer. A 5.4 mg / L potassium chloride solution was sprayed on the primary coated fertilizer, and the process was repeated twice to obtain a secondary coated fertilizer. A modified polyurethane emulsion at a concentration of 0.056 times the mass of the fertilizer granules, hesperidin at a concentration of 0.002 times the mass of the fertilizer granules, and piperonal at a concentration of 0.003 times the mass of the fertilizer granules were sprayed on the secondary coated fertilizer at room temperature, and the process was repeated twice. The mixture was irradiated under ultraviolet light for 7 min to obtain an organic fertilizer.

[0024] Comparative Example 1: (1) Mix vitamin B12 bacterial residue, Bacillus subtilis and urea in a mass ratio of 1:0.15:2.5, add pure water to make the moisture content of the vitamin B12 bacterial residue 65%, stir evenly and perform aerobic composting fermentation, keep the fermentation temperature at 65°C for 3 days, turn the compost, turn the compost once every 2 days, and ferment for 8 days; then age the compost, the ageing conditions are: temperature 40°C, fermentation cycle 6 days; after the ageing, dry, crush and granulate to obtain fertilizer granules, the particle size of the fertilizer granules is 4 mm; (2) Octamethylcyclotetrasiloxane and tetravinyltetramethylcyclotetrasiloxane were mixed uniformly in a mass ratio of 1:0.9, heated to 85°C under nitrogen protection, reacted for 35 minutes, and then heated to 115°C, and a 25wt% tetramethylammonium hydroxide aqueous solution of 0.025% of the mass of octamethylcyclotetrasiloxane was added, and then 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane of 1.5 times the mass of octamethylcyclotetrasiloxane was added, and the mixture was stirred for 3.5 hours. The mixture was heated to 150°C, reacted for 3.5 hours, and the pressure was reduced to 2.3 KPa, and the reaction was continued for 3.5 hours to obtain amino-terminated polysiloxane. Under nitrogen protection and ice-water bath conditions, perylene tetracarboxylic anhydride, amino-terminated polysiloxane, and acetone were mixed in a mass ratio of 1:20.7:55 for 45 minutes, heated to room temperature for reaction for 2.5 hours, and filtered to obtain modified polysiloxane. (3) Weigh the following components: 10 parts by mass of polycaprolactone diol, 25 parts of polyethylene glycol, 5.5 parts of modified polysiloxane, 0.002 parts of dibutyltin dilaurate, and 5.5 parts of acetone; the molecular weight of polycaprolactone diol and polyethylene glycol are both 2000; weigh isophorone diisocyanate, wherein the molar amount of the isocyanate group of isophorone diisocyanate is 1.15 times the molar amount of the hydroxyl group of polycaprolactone diol and polyethylene glycol; mix the polycaprolactone diol and polyethylene glycol, dehydrate them at 120°C for 0.5 h under nitrogen protection, cool them to 75°C, and add modified polysiloxane, isophorone diisocyanate, and acetone in sequence; 1, 2, 4, 5, 10, 15, 20, 30, 40, 50, 80, 100, 150, 200, 300, 400, 800, 1000, 200, 300, 400, 8 ... (4) The fertilizer particles are placed in a drum coating machine and heated to 77°C. The modified polyurethane emulsion at a concentration of 0.06 times the mass of the fertilizer particles is sprayed on the fertilizer particles in the drum. The mixture is heated at 76°C for 12 min. This process is repeated twice. The mixture is cooled to room temperature to obtain organic fertilizer.

[0025] Test Example 1: Test of sustained release performance: The sustained release performance of the organic fertilizers prepared in the examples and comparative examples was tested using the water dissolution rate method. 10.0 g of the organic fertilizer sample was weighed and placed in a 100-mesh nylon mesh bag, which was sealed and added to a glass container containing 200.0 mL of distilled water. After sealing, the bag was placed in a constant temperature incubator at 25°C, and the release rate was measured for 30 days. The results are shown in Table 1.

[0026] Table 1

[0027] From the comparison of the experimental data of Examples 1 to 3 and Comparative Example 1 in Table 1, it can be found that the organic fertilizer prepared by the present invention has good slow-release performance.

[0028] By comparison, the release rates of Examples 1 to 3 and are less than that of Comparative Example 1, indicating that, firstly, B12 fungus residue, Bacillus subtilis, and urea are mixed, and fertilizer granules are obtained by aerobic composting fermentation, aging, drying, crushing, and granulation. The aerobic fermentation process helps to kill harmful microorganisms in the fungus residue and achieve stabilization of the fungus residue; secondly, octamethylcyclotetrasiloxane and tetravinyltetramethylcyclotetrasiloxane are ring-opened and polymerized, and 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is used as a capping agent to prepare an amino-terminated polysiloxane containing a vinyl group in the side chain, and the amino-terminated polysiloxane reacts with perylene tetracarboxylic anhydride, and the anhydride is ring-opened to form a carboxyl group, thereby obtaining a modified polysiloxane containing a perylene structure and a carboxylic acid functional group; Modified polysiloxane is reacted with diol and isocyanate to obtain polyurethane emulsion, which is used as a coating material to coat the fertilizer particles once, and then coated with potassium chloride solution for a second time. The carboxylic acid groups on the polyurethane side chains can well complex potassium ions, thereby introducing potassium elements required for plant growth into the fertilizer. Polyurethane emulsion and natural photoinitiator are used for a third coating, and the fertilizer is irradiated under ultraviolet light. The presence of perylene structure allows ππ stacking between polyurethanes to form a cross-linked network. The vinyl groups on the polyurethane side chains induce double bond cross-linking under the action of natural photoinitiators to form a more complex cross-linked network. The presence of the cross-linked network can delay the release time of the fertilizer and improve the utilization rate of the fertilizer.

[0029] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A process for preparing organic fertilizer from vitamin B12 fungus residue, characterized in that: The method comprises the following preparation steps: (1) Mix vitamin B12 bacterial residue, Bacillus subtilis and urea, add pure water so that the moisture content of the vitamin B12 bacterial residue is 60%-70%, stir evenly, and then perform aerobic composting fermentation, aging, drying, crushing and granulation to obtain fertilizer granules; (2) Octamethylcyclotetrasiloxane and tetravinyltetramethylcyclotetrasiloxane were mixed evenly, heated to 80-90°C under nitrogen protection, reacted for 30-40 minutes, and then heated to 110-120°C. A 25wt% tetramethylammonium hydroxide aqueous solution with a mass of 0.02%-0.03% of the mass of octamethylcyclotetrasiloxane was added, and then 3-bis(3-aminopropyl)-1,1,3 ,3-tetramethyldisiloxane is stirred for 3-4h, heated to 150℃, reacted for 3-4h, reduced pressure to 2-2.5KPa, and reacted for 3-4h to obtain amino-terminated polysiloxane; under nitrogen protection and ice-water bath conditions, perylene tetracarboxylic anhydride, amino-terminated polysiloxane, and acetone are mixed at a mass ratio of 1:20.7:(50-60) for 40-50min, heated to room temperature for reaction for 2-3h, and filtered to obtain modified polysiloxane; (3) Weigh the following components: polycaprolactone diol, polyethylene glycol, modified polysiloxane, dibutyltin dilaurate, acetone, and isophorone diisocyanate; mix polycaprolactone diol and polyethylene glycol, dehydrate at 120°C for 0.5h under nitrogen protection, cool to 70-80°C, add modified polysiloxane and isophorone diisocyanate in sequence, stir for 2-3h, heat to 90-100°C, add dibutyltin dilaurate and acetone, continue to react until the isocyanate group content is 0%-0.1%, cool to room temperature, and after the reaction is completed, rotary evaporate at 50°C and -0.1MPa to obtain modified polyurethane; mix modified polyurethane, emulsifier, and pure water, and emulsify with a high-speed homogenizer at a speed of 16kr / min to obtain a modified polyurethane emulsion; (4) Put the fertilizer granules into a drum coating machine and heat them to 75-80°C. Spray 0.05-0.07 times the mass of the fertilizer granules with a modified polyurethane emulsion on the fertilizer granules in the drum. Heat at 75-80°C for 12 min, repeat twice, cool to room temperature to obtain a primary coated fertilizer, continue to spray 5-6 mg / L potassium chloride solution on the primary coated fertilizer, repeat twice to obtain a secondary coated fertilizer, spray 0.05-0.07 times the mass of the fertilizer granules with a modified polyurethane emulsion, 0.002-0.003 times the mass of the fertilizer granules with hesperidin, and 0.002-0.003 times the mass of the fertilizer granules with piperonal at room temperature on the secondary coated fertilizer, repeat twice, and irradiate under ultraviolet light for 5-10 min to obtain an organic fertilizer.

2. A process for preparing organic fertilizer from vitamin B12 fungus residue according to claim 1, characterized in that: In step (1), the mass ratio of the vitamin B12 bacterial residue, Bacillus subtilis and urea is 1:(0.1-0.2):(2-3).

3. A process for preparing organic fertilizer from vitamin B12 fungus residue according to claim 1, characterized in that: The aerobic composting fermentation process in step (1) is as follows: the fermentation temperature is 60-75° C., the temperature is kept for 3-4 days, and then the compost is turned. The frequency of turning the compost is once every 1-2 days, and the fermentation time is 7-9 days.

4. A process for preparing organic fertilizer from vitamin B12 fungus residue according to claim 1, characterized in that: The aging conditions in step (1) are: a temperature of 30-50° C., a fermentation period of 4-7 days; and a particle size of the fertilizer particles of 3-5 mm.

5. A process for preparing organic fertilizer from vitamin B12 fungus residue according to claim 1, characterized in that: The mass ratio of octamethylcyclotetrasiloxane to tetravinyltetramethylcyclotetrasiloxane in step (2) is 1:(0.8-1).

6. A process for preparing organic fertilizer from vitamin B12 fungus residue according to claim 1, characterized in that: The weighed amounts of the components in step (3) are: 10-11 parts of polycaprolactone diol, 20-30 parts of polyethylene glycol, 5-6 parts of modified polysiloxane, 0.002 parts of dibutyltin dilaurate, and 5-6 parts of acetone, by mass.

7. A process for preparing organic fertilizer from vitamin B12 fungus residue according to claim 4, characterized in that: The molecular weights of the polycaprolactone diol and polyethylene glycol are both 2000.

8. A process for preparing organic fertilizer from vitamin B12 fungus residue according to claim 1, characterized in that: The molar amount of the isocyanate group of the isophorone diisocyanate in step (3) is 1.1-1.2 times the molar amount of the hydroxyl group of the polycaprolactone diol and the polyethylene glycol.

9. A process for preparing organic fertilizer from vitamin B12 fungus residue according to claim 1, characterized in that: The test method for the isocyanate group content in step (3) is the di-n-butylamine method.

10. A process for preparing organic fertilizer from vitamin B12 fungus residue according to claim 1, characterized in that: The amounts of the modified polyurethane, emulsifier and pure water used in step (3) are: by mass: 100 parts of modified polyurethane, 10-12 parts of emulsifier and 40-50 parts of pure water, and the emulsifier is OP-10.

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