Process for preparing liquid fertilizer from erythromycin thiocyanate waste liquid
By preparing potassium fertilizer particles of copper ion modified titanium dioxide and urea formaldehyde coating, mixing them with sulforoerythromycin waste liquid to produce liquid fertilizer, solving the problem of removal of antibiotics and thiocyanate in the waste liquid, and achieving the Sustained release effect and plant growth promotion.
Patent Information
- Application Number
- CN202411892491.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-20
- Publication Date
- 2025-02-14
AI Technical Summary
The residual antibiotics and thiocyanates in sulforomycin waste liquid pose a threat to the environment and human health, and it is difficult for the prior art to effectively remove these pollutants.
Titanium dioxide solid was prepared by tetrabutyl titanate and anhydrous ethanol under the action of ammonia water, and after ultrasonic treatment, copper ions were loaded with copper ions to produce copper ion modified titanium dioxide, combined with formaldehyde and urea to produce urea formaldehyde, and potassium chloride was used to produce potassium chloride. Grits are made for the coating to produce potassium fertilizer granules, and finally mix the potassium fertilizer granules with the waste liquid treatment liquid to produce sulforoerythromycin waste liquid fertilizer.
This process not only effectively removes sulfuromycin and thiocyanate from the waste liquid, but also has a good sustained release effect, can promote plant growth, have good fertilizer supply capabilities, and is environmentally friendly.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of liquid fertilizers, in particular to a process for preparing liquid fertilizer from thioerythromycin waste liquid. Background Art
[0002] The hazards of antibiotic production wastewater, in addition to the general characteristics of high organic matter concentration and complex composition, are aggravated by the large amount of antibiotic components remaining. The ecosystem in the environment can form naturally and maintain its own balance. The ecological environment is composed of different species of biological communities in the form of food chains. It is a very strict biological system. Most antibiotics have a very broad antibacterial spectrum (such as Gram-positive bacteria and Gram-negative bacteria). These antibiotics will kill certain species and groups of microorganisms in the environment or inhibit the growth and reproduction of microorganisms, which will destroy the inherent ecological balance in the environment and affect the food chain and human survival.
[0003] Thiorhiromycin, also known as erythromycin thiocyanate, is an erythromycin derivative and a veterinary drug. Erythromycin thiocyanate has two main functions. One is that it is a safe and efficient veterinary antibiotic based on its therapeutic effect on Gram-positive bacteria and mycoplasma infections; the other is that it is a key intermediate for the synthesis and production of erythromycin and its series of products, such as roxithromycin, azithromycin and clarithromycin, based on its parent nucleus belonging to the macrolide API. Erythromycin thiocyanate improves the solubility of erythromycin in water, reduces bitterness, improves pharmacokinetic properties, reduces toxic side effects, and retains the antibacterial activity of erythromycin. Therefore, it has been widely used. The demand for erythromycin thiocyanate in the market continues to rise, which has led to a sharp increase in the production of thioerythromycin. In addition to the hazards of antibiotic production wastewater, thioerythromycin pharmaceutical wastewater also contains thiocyanate, which aggravates its harm to the environment it contacts. Thiocyanate is a kind of highly toxic inorganic salt. It not only has an inhibitory effect on microbial activity, which has a great impact on the subsequent biochemical treatment of wastewater, but also affects aquatic organisms and human health after thiocyanate is discharged into the water body. In the water body, thiocyanate reacts with oxidants such as chlorine in the water to produce highly toxic cyanide, which harms aquatic organisms. After entering the human body, it can cause thyroid disease, dizziness and even loss of consciousness. Data show that excessive intake of thiocyanate can cause acute toxicity, which is mainly caused by the cyanide ions released in the body. Cyanide ions can bind to Fe (III) in cytochrome oxidase in the body, inhibiting the activity of the enzyme, making the tissue unable to use oxygen, causing nausea, vomiting, abdominal pain, diarrhea and other gastrointestinal disorders, blood pressure fluctuations, slow heart rate, and severe poisoning can cause significant renal damage; a small amount of intake can affect the body's use of iodine and cause thyroid disease, especially for the development of fetuses and infants. Therefore, the treatment of thioerythromycin waste liquid requires not only the removal of residual antibiotics, but also the removal of residual thiocyanate. Copper ions can react with thiocyanate to form precipitates, effectively removing thiocyanate from wastewater.
[0004] Liquid fertilizer is a fertilizer obtained by fusing organic fertilizer or chemical fertilizer with water, which can be directly sprayed on plant leaves or roots to allow them to absorb relatively quickly. The advantage of liquid fertilizer is that it can directly supply plants with effective nutrients, and the absorption and conversion of nutrients by leaves are faster than roots, which can timely supplement the needs of plants for nutrients. The present invention prepares liquid fertilizer with thioerythromycin waste liquid, can effectively remove thioerythromycin and thiocyanic acid in the thioerythromycin waste liquid, and has good slow-release effect, and has good market prospects. Summary of the invention
[0005] The object of the present invention is to provide a process for preparing liquid fertilizer from thioerythromycin waste liquid, so as 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: The invention discloses a process for preparing liquid fertilizer from thioerythromycin waste liquid. The liquid fertilizer from thioerythromycin waste liquid is prepared by preparing titanium dioxide solid by reacting tetrabutyl titanate and anhydrous ethanol under the action of ammonia water, and then loading copper ions on the titanium dioxide solid after ultrasonic treatment to prepare copper ion-modified titanium dioxide; reacting formaldehyde with urea to prepare urea formaldehyde, and using potassium chloride as a coating and urea formaldehyde as a coating layer, granulating with a disc granulator to prepare potash fertilizer particles; and mixing the potash fertilizer particles and waste liquid treatment liquid to prepare the liquid fertilizer.
[0007] A process for preparing liquid fertilizer from thioerythromycin waste liquid comprises the following preparation steps: (1) Tetrabutyl titanate and anhydrous ethanol are mixed in a mass ratio of 1: (6-8), an ammonia ethanol solution of 13-17 times the mass of tetrabutyl titanate is added, the mixture is stirred at 200-300 r / min for 20-30 hours at room temperature, the precipitate is separated by centrifugation, and the precipitate is washed with deionized water for 3-5 times to obtain titanium dioxide solid; the titanium dioxide solid is diluted to a titanium dioxide mixed solution with a solid content of 15%-25%, a 50 g / L copper chloride dihydrate aqueous solution of 5%-15% of the mass of the titanium dioxide mixed solution is added, the mixture is mixed, sealed, ultrasonicated at 25°C for 4-6 hours, the precipitate is separated by centrifugation, and the precipitate is calcined at 700-800°C for 6-8 hours to obtain copper ion modified titanium dioxide; (2) Mix the formaldehyde solution and urea, adjust the pH to 9.0 with sodium hydroxide solution, react at 45-55°C for 1-2 hours, adjust the pH to 5.0 with hydrochloric acid solution, continue to react for 1-2 hours, dry at 85-95°C until the liquid disappears, then cool to 50-60°C, and continue to dry for 4-6 hours to obtain urea formaldehyde; mix urea formaldehyde with water to obtain urea formaldehyde suspension, use potassium chloride as coating and urea formaldehyde as coating layer, granulate with a disc granulator, sieve out particles with a particle size of 2 mm, and dry at 105-115°C for 3-5 hours to obtain potash fertilizer granules; (3) Mix the erythromycin waste liquid and copper ion modified titanium dioxide, stir at room temperature at 50-100 r / min, treat with ultraviolet irradiation for 1-2 h, continue stirring for 10-12 h, centrifuge to separate the precipitate, retain the filtrate, and prepare the waste liquid treatment liquid; mix the potassium fertilizer granules and the waste liquid treatment liquid to prepare the erythromycin waste liquid liquid fertilizer.
[0008] As an optimization, the preparation method of the ammonia ethanol solution in step (1) is: mixing ammonia water and anhydrous ethanol in a volume ratio of 1:3.
[0009] As an optimization, the formaldehyde solution in step (2) is a formaldehyde solution with a mass concentration of 37%; the sodium hydroxide solution is a sodium hydroxide solution with a mass concentration of 5%; and the hydrochloric acid solution is a hydrochloric acid solution with a mass concentration of 1%.
[0010] As an optimization, the mass ratio of the formaldehyde solution to urea in step (2) is 1:(0.3~0.5).
[0011] As an optimization, the mass ratio of urea formaldehyde to water in step (2) is 1:(6-8).
[0012] As an optimization, the mass ratio of urea formaldehyde suspension to potassium chloride during granulation by the disc granulator in step (2) is 1:(0.5-0.7).
[0013] As an optimization, the mass ratio of the erythromycin waste liquid and the copper ion modified titanium dioxide in step (3) is 1: (0.1~0.2).
[0014] As an optimization, the ultraviolet irradiation power in step (3) is 180W.
[0015] As an optimization, the mass ratio of the potassium fertilizer particles to the waste liquid treatment liquid in step (3) is 1: (10-20).
[0016] Compared with the prior art, the beneficial effects achieved by the present invention are: When preparing the thioerythromycin waste liquid liquid fertilizer, the present invention comprises the following steps: tetrabutyl titanate and anhydrous ethanol are reacted with ammonia water to obtain titanium dioxide solid, and the titanium dioxide solid is subjected to ultrasonic treatment and then loaded with copper ions to obtain copper ion modified titanium dioxide; formaldehyde and urea are reacted to obtain urea formaldehyde, and potassium chloride is used as a coating and the urea formaldehyde is used as a coating layer, and granulation is performed by a disc granulator to obtain potash fertilizer particles; and the potash fertilizer particles and waste liquid treatment liquid are mixed to obtain the thioerythromycin waste liquid liquid fertilizer.
[0017] First, titanium dioxide solid is prepared by tetrabutyl titanate and anhydrous ethanol under the action of ammonia water. After ultrasonic treatment, copper ions are loaded on the titanium dioxide solid to obtain copper ion-modified titanium dioxide. Titanium dioxide can generate a large number of electron-hole pairs under ultraviolet irradiation. Oxygen or water molecules in the air can combine with holes to generate active free radicals. Free radicals can destroy the molecular structure of thioerythromycin, thereby achieving the effect of degrading thioerythromycin and removing residual antibiotics in the waste liquid. There is a large amount of thiocyanate in the thioerythromycin waste liquid. Copper ions can react with thiocyanic acid in the waste liquid to form precipitation, thereby effectively removing thiocyanate in the thioerythromycin waste liquid.
[0018] Secondly, formaldehyde is reacted with urea to obtain urea formaldehyde, and potassium chloride is used as a coating material and urea formaldehyde is used as a coating layer. The potash fertilizer particles are obtained by granulating with a disc granulator. On the one hand, potassium chloride has poor adhesion and plasticity, and it is difficult to obtain smooth particles with high hardness. However, urea formaldehyde has strong adhesion properties, so it has good coating properties for potassium chloride. The urea formaldehyde obtained by the reaction of formaldehyde and urea as a coating layer can be slowly degraded under the action of microorganisms in the soil, so that potassium ions are gradually released, thereby achieving a slow-release effect; on the other hand, urea formaldehyde as a coating layer can be decomposed into ammonium nitrogen, carbon dioxide and water under the action of microorganisms in the soil. Ammonium nitrogen can be used as a nitrogen fertilizer to provide fertilizer for plant growth, and urea formaldehyde can be completely degraded in the soil, which is environmentally friendly; the slow-released potassium chloride and the urea formaldehyde degraded by microorganisms in the soil can provide sufficient potassium fertilizer and nitrogen fertilizer for plant growth, effectively promote plant growth, and make the liquid fertilizer have a good fertilizer supply capacity. DETAILED DESCRIPTION
[0019] 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 making creative work are within the scope of protection of the present invention.
[0020] Embodiment 1: A process for preparing liquid fertilizer from thioerythromycin waste liquid comprises the following preparation steps: (1) Ammonia water and anhydrous ethanol are mixed in a volume ratio of 1:3 to obtain an ammonia ethanol solution; tetrabutyl titanate and anhydrous ethanol are mixed in a mass ratio of 1:7, and an ammonia ethanol solution of 15 times the mass of tetrabutyl titanate is added, and the mixture is stirred at room temperature at 250 r / min for 25 hours, and the precipitate is separated by centrifugation, and the precipitate is washed with deionized water for 4 times to obtain titanium dioxide solid; the titanium dioxide solid is diluted to a titanium dioxide mixed solution with a solid content of 20%, and a 50 g / L copper chloride dihydrate aqueous solution of 10% of the mass of the titanium dioxide mixed solution is added and mixed, and the mixture is sealed, ultrasonicated at 25°C for 5 hours, and the precipitate is separated by centrifugation, and the precipitate is calcined at 750°C for 7 hours to obtain copper ion modified titanium dioxide; (2) Formaldehyde solution and urea were mixed in a mass ratio of 1:0.2, the pH was adjusted to 9.0 with sodium hydroxide solution, the reaction was carried out at 50°C for 1.5 hours, the pH was adjusted to 5.0 with hydrochloric acid solution, the reaction was continued for 1.5 hours, and the mixture was dried at 90°C until the liquid disappeared, then cooled to 55°C and dried for 5 hours to obtain urea formaldehyde. The coating layer and water were mixed in a mass ratio of 1:7 to obtain a urea formaldehyde suspension, potassium chloride was used as the coating material and urea formaldehyde was used as the coating layer, the mass ratio of urea formaldehyde suspension to potassium chloride was 1:0.6, and granulation was carried out using a disc granulator, and particles with a particle size of 2 mm were screened out, and the particles were dried at 110°C for 4 hours to obtain potassium fertilizer particles; (3) The erythromycin waste liquid and copper ion modified titanium dioxide were mixed at a mass ratio of 1:0.15, stirred at room temperature at 75 r / min, irradiated with ultraviolet light at a power of 180 W for 1.5 h, continued stirring for 11 h, centrifuged to separate the precipitate, retained the filtrate, and obtained the waste liquid treatment liquid; the potassium fertilizer granules and the waste liquid treatment liquid were mixed at a mass ratio of 1:15 to obtain the erythromycin waste liquid liquid fertilizer.
[0021] Embodiment 2: A process for preparing liquid fertilizer from thioerythromycin waste liquid comprises the following preparation steps: (1) Ammonia water and anhydrous ethanol are mixed in a volume ratio of 1:3 to obtain an ammonia ethanol solution; tetrabutyl titanate and anhydrous ethanol are mixed in a mass ratio of 1:6, and an ammonia ethanol solution 13 times the mass of tetrabutyl titanate is added, and the mixture is stirred at 250 r / min at room temperature for 25 hours, and the precipitate is separated by centrifugation, and the precipitate is washed with deionized water for 4 times to obtain titanium dioxide solid; the titanium dioxide solid is diluted to a titanium dioxide mixed solution with a solid content of 15%, and a 50 g / L copper chloride dihydrate aqueous solution with a mass content of 5% of the titanium dioxide mixed solution is added and mixed, and the mixture is sealed, ultrasonicated at 25°C for 5 hours, and the precipitate is separated by centrifugation, and the precipitate is calcined at 750°C for 7 hours to obtain copper ion modified titanium dioxide; (2) Formaldehyde solution and urea were mixed in a mass ratio of 1:0.3, the pH was adjusted to 9.0 with sodium hydroxide solution, the reaction was carried out at 50°C for 1.5 hours, the pH was adjusted to 5.0 with hydrochloric acid solution, the reaction was continued for 1.5 hours, the mixture was dried at 90°C until the liquid disappeared, the temperature was lowered to 55°C, and the drying was continued for 5 hours to obtain urea formaldehyde, the coating layer was mixed with water in a mass ratio of 1:6 to obtain a urea formaldehyde suspension, potassium chloride was used as the coating material and urea formaldehyde was used as the coating layer, the mass ratio of urea formaldehyde suspension to potassium chloride was 1:0.5, granulation was carried out with a disc granulator, particles with a particle size of 2 mm were screened out, and the particles were dried at 110°C for 4 hours to obtain potassium fertilizer particles; (3) The erythromycin waste liquid and copper ion modified titanium dioxide were mixed at a mass ratio of 1:0.1, stirred at room temperature at 75 r / min, irradiated with ultraviolet light at a power of 180 W for 1.5 h, continued stirring for 11 h, centrifuged to separate the precipitate, retained the filtrate, and obtained the waste liquid treatment liquid; the potassium fertilizer granules and the waste liquid treatment liquid were mixed at a mass ratio of 1:10 to obtain the erythromycin waste liquid liquid fertilizer.
[0022] Embodiment 3: A process for preparing liquid fertilizer from thioerythromycin waste liquid comprises the following preparation steps: (1) Ammonia water and anhydrous ethanol are mixed in a volume ratio of 1:3 to obtain an ammonia ethanol solution; tetrabutyl titanate and anhydrous ethanol are mixed in a mass ratio of 1:8, and an ammonia ethanol solution with a mass of 17 times that of tetrabutyl titanate is added, and the mixture is stirred at 250 r / min for 25 seconds at room temperature, and the precipitate is separated by centrifugation, and the precipitate is washed with deionized water for 4 times to obtain titanium dioxide solid; the titanium dioxide solid is diluted to a titanium dioxide mixed solution with a solid content of 25%, and a 50 g / L copper chloride dihydrate aqueous solution with a mass of 15% of the titanium dioxide mixed solution is added and mixed, and the mixture is sealed, ultrasonicated at 25°C for 5 hours, and the precipitate is separated by centrifugation, and the precipitate is calcined at 750°C for 7 hours to obtain copper ion modified titanium dioxide; (2) Formaldehyde solution and urea were mixed in a mass ratio of 1:0.5, the pH was adjusted to 9.0 with sodium hydroxide solution, the reaction was carried out at 55°C for 1-2 hours, the pH was adjusted to 5.0 with hydrochloric acid solution, the reaction was continued for 1.5 hours, and the mixture was dried at 90°C until the liquid disappeared, then cooled to 55°C and dried for 5 hours to obtain urea formaldehyde. The coating layer and water were mixed in a mass ratio of 1:8 to obtain a urea formaldehyde suspension, potassium chloride was used as the coating material and urea formaldehyde was used as the coating layer, the mass ratio of urea formaldehyde suspension to potassium chloride was 1:0.7, and granulation was carried out using a disc granulator, and particles with a particle size of 2 mm were screened out, and the mixture was dried at 110°C for 4 hours to obtain potassium fertilizer particles; (3) The erythromycin waste liquid and copper ion modified titanium dioxide were mixed at a mass ratio of 1:0.2, stirred at room temperature at 75 r / min, irradiated with ultraviolet light at a power of 180 W for 1.5 h, continued stirring for 11 h, centrifuged to separate the precipitate, retained the filtrate, and obtained the waste liquid treatment liquid; the potassium fertilizer granules and the waste liquid treatment liquid were mixed at a mass ratio of 1:20 to obtain the erythromycin waste liquid liquid fertilizer.
[0023] Embodiment 4: A process for preparing liquid fertilizer from thioerythromycin waste liquid comprises the following preparation steps: (1) Ammonia water and anhydrous ethanol are mixed in a volume ratio of 1:3 to obtain an ammonia ethanol solution; tetrabutyl titanate and anhydrous ethanol are mixed in a mass ratio of 1:7, and an ammonia ethanol solution of 15 times the mass of tetrabutyl titanate is added, and the mixture is stirred at 250 r / min for 20 hours at room temperature, and the precipitate is separated by centrifugation, and the precipitate is washed with deionized water for 4 times to obtain titanium dioxide solid; the titanium dioxide solid is diluted to a titanium dioxide mixed solution with a solid content of 20%, and a 50 g / L copper chloride dihydrate aqueous solution of 10% of the mass of the titanium dioxide mixed solution is added and mixed, and the mixture is sealed, ultrasonicated at 25°C for 4 hours, and the precipitate is separated by centrifugation, and the precipitate is calcined at 750°C for 6 hours to obtain copper ion modified titanium dioxide; (2) Formaldehyde solution and urea were mixed at a mass ratio of 1:0.4, the pH was adjusted to 9.0 with sodium hydroxide solution, the reaction was carried out at 50°C for 1 hour, the pH was adjusted to 5.0 with hydrochloric acid solution, the reaction was continued for 1 hour, and the mixture was dried at 90°C until the liquid disappeared, then cooled to 55°C and dried for 4 hours to obtain urea formaldehyde. The coating layer and water were mixed at a mass ratio of 1:7 to obtain a urea formaldehyde suspension, potassium chloride was used as the coating material and urea formaldehyde was used as the coating layer, the mass ratio of urea formaldehyde suspension to potassium chloride was 1:0.6, and granulation was carried out using a disc granulator, and particles with a particle size of 2 mm were screened out, and the particles were dried at 110°C for 3 hours to obtain potassium fertilizer particles; (3) The erythromycin waste liquid and copper ion modified titanium dioxide were mixed at a mass ratio of 1:0.15, stirred at room temperature at 75 r / min, irradiated with ultraviolet light at a power of 180 W for 1 hour, continued stirring for 10 hours, centrifuged to separate the precipitate, retained the filtrate, and obtained the waste liquid treatment liquid; the potassium fertilizer granules and the waste liquid treatment liquid were mixed at a mass ratio of 1:15 to obtain the erythromycin waste liquid liquid fertilizer.
[0024] Embodiment 5: A process for preparing liquid fertilizer from thioerythromycin waste liquid comprises the following preparation steps: (1) Ammonia water and anhydrous ethanol are mixed in a volume ratio of 1:3 to obtain an ammonia ethanol solution; tetrabutyl titanate and anhydrous ethanol are mixed in a mass ratio of 1:7, and an ammonia ethanol solution of 15 times the mass of tetrabutyl titanate is added, and the mixture is stirred at room temperature at 250 r / min for 30 hours, and the precipitate is separated by centrifugation, and the precipitate is washed with deionized water for 4 times to obtain titanium dioxide solid; the titanium dioxide solid is diluted to a titanium dioxide mixed solution with a solid content of 20%, and a 50 g / L copper chloride dihydrate aqueous solution of 10% of the mass of the titanium dioxide mixed solution is added and mixed, and the mixture is sealed, ultrasonicated at 25°C for 6 hours, and the precipitate is separated by centrifugation, and the precipitate is calcined at 750°C for 8 hours to obtain copper ion modified titanium dioxide; (2) Formaldehyde solution and urea were mixed in a mass ratio of 1:0.4, the pH was adjusted to 9.0 with sodium hydroxide solution, the reaction was carried out at 50°C for 2 hours, the pH was adjusted to 5.0 with hydrochloric acid solution, the reaction was continued for 2 hours, the mixture was dried at 90°C until the liquid disappeared, the temperature was lowered to 55°C, and the drying was continued for 6 hours to obtain urea formaldehyde, the coating layer was mixed with water in a mass ratio of 1:7 to obtain a urea formaldehyde suspension, potassium chloride was used as the coating material and urea formaldehyde was used as the coating layer, the mass ratio of urea formaldehyde suspension to potassium chloride was 1:0.6, granulation was carried out with a disc granulator, particles with a particle size of 2 mm were screened out, and the particles were dried at 110°C for 5 hours to obtain potassium fertilizer particles; (3) The erythromycin waste liquid and copper ion modified titanium dioxide were mixed at a mass ratio of 1:0.15, stirred at room temperature at 75 r / min, irradiated with ultraviolet light at a power of 180 W for 2 h, continued to stir for 12 h, centrifuged to separate the precipitate, retained the filtrate, and obtained the waste liquid treatment liquid; the potassium fertilizer granules and the waste liquid treatment liquid were mixed at a mass ratio of 1:15 to obtain the erythromycin waste liquid liquid fertilizer.
[0025] Comparative Example 1: A process for preparing liquid fertilizer from thioerythromycin waste liquid comprises the following preparation steps: (1) Ammonia water and anhydrous ethanol are mixed at a volume ratio of 1:3 to obtain an ammonia-ethanol solution; tetrabutyl titanate and anhydrous ethanol are mixed at a mass ratio of 1:7, and an ammonia-ethanol solution with a mass of 15 times that of tetrabutyl titanate is added, and the mixture is stirred at room temperature at 250 r / min for 25 h, and the precipitate is separated by centrifugation, and the precipitate is washed 4 times with deionized water to obtain titanium dioxide solid; (2) Mix 37% formaldehyde solution and urea in a mass ratio of 1:0.4, adjust the pH to 9.0 with sodium hydroxide solution, react at 50°C for 1.5 hours, adjust the pH to 5.0 with 1% hydrochloric acid solution, continue to react for 1.5 hours, dry at 90°C until the liquid disappears, then cool to 55°C and continue to dry for 5 hours to obtain urea formaldehyde, mix the coating layer with water in a mass ratio of 1:7 to obtain a urea formaldehyde suspension, use potassium chloride as the coating and urea formaldehyde as the coating, use a disc granulator to granulate, screen out particles with a particle size of 3.5 mm, and dry at 110°C for 4 hours to obtain potash fertilizer particles; (3) The erythromycin waste liquid and titanium dioxide solid were mixed at a mass ratio of 1:0.15, stirred at room temperature at 75 r / min, irradiated with ultraviolet light at a power of 180 W for 1.5 h, continued stirring for 11 h, centrifuged to separate the precipitate, retained the filtrate, and obtained the waste liquid treatment liquid; the potassium fertilizer granules and the waste liquid treatment liquid were mixed at a mass ratio of 1:15 to obtain the erythromycin waste liquid liquid fertilizer.
[0026] Comparative Example 2: A process for preparing liquid fertilizer from thioerythromycin waste liquid comprises the following preparation steps: (1) A 37% formaldehyde solution and urea were mixed in a mass ratio of 1:0.4, the pH was adjusted to 9.0 with a sodium hydroxide solution, the reaction was carried out at 50°C for 1.5 hours, the pH was adjusted to 5.0 with a 1% hydrochloric acid solution, the reaction was continued for 1.5 hours, the solution was dried at 90°C until the liquid disappeared, the temperature was lowered to 55°C, and the drying was continued for 5 hours to obtain urea formaldehyde, the coating layer was mixed with water in a mass ratio of 1:7 to obtain a urea formaldehyde suspension, potassium chloride was used as the coating material and urea formaldehyde was used as the coating layer, and granulation was carried out using a disc granulator, particles with a particle size of 3.5 mm were screened out, and the particles were dried at 110°C for 4 hours to obtain potassium fertilizer particles; (2) The erythromycin waste liquid and copper ion modified titanium dioxide were mixed at a mass ratio of 1:0.15, stirred at room temperature at 75 r / min, irradiated with ultraviolet light at a power of 180 W for 1.5 h, continued stirring for 11 h, centrifuged to separate the precipitate, retained the filtrate, and obtained the waste liquid treatment liquid; the potassium fertilizer particles and the waste liquid treatment liquid were mixed at a mass ratio of 1:15 to obtain the erythromycin waste liquid liquid fertilizer.
[0027] Comparative Example 3: A process for preparing liquid fertilizer from thioerythromycin waste liquid comprises the following preparation steps: (1) Ammonia water and anhydrous ethanol are mixed in a volume ratio of 1:3 to obtain an ammonia ethanol solution; tetrabutyl titanate and anhydrous ethanol are mixed in a mass ratio of 1:7, and an ammonia ethanol solution of 15 times the mass of tetrabutyl titanate is added, and the mixture is stirred at room temperature at 250 r / min for 25 hours, and the precipitate is separated by centrifugation, and the precipitate is washed with deionized water for 4 times to obtain titanium dioxide solid; the titanium dioxide solid is diluted to a titanium dioxide mixed solution with a solid content of 20%, and a 50 g / L copper chloride dihydrate aqueous solution of 10% of the mass of the titanium dioxide mixed solution is added and mixed, and the mixture is sealed, ultrasonicated at 25°C for 5 hours, and the precipitate is separated by centrifugation, and freeze-dried for 24 hours to obtain copper ion modified titanium dioxide; (2) Gypsum and water are mixed in a mass ratio of 1:7 to obtain a gypsum suspension, potassium chloride is used as a coating material and gypsum is used as a coating layer, and granulation is performed using a disc granulator. Particles with a particle size of 3.5 mm are screened out, and dried at 110° C. for 4 h to obtain potassium fertilizer granules; (3) The erythromycin waste liquid and copper ion modified titanium dioxide were mixed at a mass ratio of 1:0.15, stirred at room temperature at 75 r / min, irradiated with ultraviolet light at a power of 180 W for 1.5 h, continued stirring for 11 h, centrifuged to separate the precipitate, retained the filtrate, and obtained the waste liquid treatment liquid; the potassium fertilizer granules and the waste liquid treatment liquid were mixed at a mass ratio of 1:15 to obtain the erythromycin waste liquid liquid fertilizer.
[0028] Test Example 1: Sustained release rate test: The liquid fertilizer prepared from the thioerythromycin waste liquid of each embodiment and comparative example was filtered through a 1.00 mm test sieve. After filtering, the material on the sieve was rinsed with water for 3 times, and then the water on the surface of the particles was dried with absorbent paper. 12.50 g of the above particles were put into a 150 μm (100 mesh) finger-shaped nylon mesh bag (the specifications of the nylon mesh bag are 2 to 3 cm wide and 15 to 20 cm long, and a sealing rope is left at the sealing point, and a label is tied). After sealing (the label tied on the sealing rope of the mesh bag is left outside the bottle when sealing, and then the lid is tightly closed, the same below), it was placed in a plastic bottle or glass bottle with 250 mL of water at 25°C (the fertilizer-water ratio is 1:20), placed in a biochemical constant temperature incubator at 25°C and cultured for 20 days, and the sustained release rate was tested by sampling. Each group was tested 3 times, and the average value was recorded. The results are shown in Table 1.
[0029] Thioerythromycin removal rate test: Use high performance liquid chromatography to test the content of thioerythromycin in liquid fertilizer, and calculate the thioerythromycin removal rate in liquid fertilizer. The results are shown in Table 1.
[0030] Thiocyanate removal rate test: The thiocyanate content in liquid fertilizer was tested using the iron salt complexation method, and the thiocyanate removal rate was calculated. The results are shown in Table 1.
[0031] Table 1
[0032] From the comparison of the experimental data of Examples 1 to 5 and Comparative Examples 1 to 3 in the table, it can be found that the organic fertilizer prepared by the present invention has good slow-release performance, thioerythromycin removal rate and thiocyanate removal rate.
[0033] By comparison, the average potassium release rates of Examples 1 to 3 are significantly lower than that of Comparative Example 3, indicating that urea formaldehyde is prepared by the reaction of formaldehyde and urea, potassium chloride is used as a coating, urea formaldehyde is used as a coating layer, and potash fertilizer particles are prepared by granulation using a disc granulator. The urea formaldehyde prepared by the reaction of formaldehyde and urea has strong adhesion as a coating layer and has good coating properties for potassium chloride. The urea formaldehyde prepared by the reaction of formaldehyde and urea as a coating layer can be slowly degraded under the action of microorganisms in the soil, so that potassium ions are gradually released, thereby achieving a sustained release effect.
[0034] By comparison, the thiocyanate removal rates of Examples 1 to 5 are significantly greater than that of Comparative Example 1, indicating that the abundant copper ions on the copper ion-modified titanium dioxide obtained by loading copper ions on titanium dioxide solid after ultrasonic treatment can react with thiocyanate in the waste liquid to form a precipitate, thereby effectively removing thiocyanate in the erythromycin waste liquid.
[0035] By comparison, the thioerythromycin removal rates of Examples 1 to 5 are significantly greater than the thioerythromycin removal rate of Comparative Example 2, indicating that titanium dioxide solid is prepared by tetrabutyl titanate and anhydrous ethanol under the action of ammonia water, and copper ions are loaded on the titanium dioxide solid after ultrasonic treatment to prepare copper ion-modified titanium dioxide. Titanium dioxide can generate a large number of electron-hole pairs under ultraviolet irradiation, and oxygen or water molecules in the air can combine with the holes to generate active free radicals. The free radicals can destroy the molecular structure of thioerythromycin, thereby achieving the effect of degrading thioerythromycin and effectively removing residual thioerythromycin in the waste liquid.
[0036] Test Example 2: Degradability test: The liquid fertilizer prepared in each embodiment was dried at 110°C for 6h to obtain a solid, weighed, recorded as M0, and buried 6cm below the soil. At room temperature, the soil moisture was controlled to be 20%-25%. After 45 days, it was taken out, washed with distilled water, vacuum dried to constant weight, weighed at room temperature, recorded as M1, and the degradation rate was calculated according to the degradation rate = (M0-M1) / M0*100%. The results are shown in Table 2.
[0037] Table 2
[0038] By comparison, Examples 1 to 5 all have good degradation rates, indicating that urea formaldehyde as a coating layer can be effectively degraded under the action of microorganisms in the soil and is environmentally friendly.
[0039] Test Example 3: Plant growth test: The test adopts potted planting method, the pot height is 13cm, the diameter is 21cm, and each pot contains 1500g soil. Soak the tomato seeds in 30℃ warm water for 20 minutes to make the pathogens on the surface of the seeds absorb water and germinate, so that they can be killed more easily in the future high temperature. Then place the seeds in 55-60℃ hot water 6-7 times its volume, add cold water after keeping warm for 15 minutes, and keep 25-30℃ to soak for 6 hours. Pull out the seeds to drain excess water, wrap them with wet gauze and place them in a 30℃ constant temperature box for germination, rinse them with warm water once every 12h, pull them out for 48h, sow them in the hole tray, sow 3 seeds in each pot, thin out the seedlings after germination, leave 1 seedling in each pot, apply 100ml of liquid fertilizer prepared in each embodiment 10 days after the tomato seedlings emerge, and use clear water treatment as a control, and repeat 3 for each treatment. After that, treat them every 3 days, for a total of 4 times. Other operations are the same as normal management. After the tomatoes were borne, the number of fruits and total yield of each treatment were counted. The results are shown in Table 3.
[0040] Table 3
[0041] By comparison, the yield and diameter of Examples 1 to 5 are significantly greater than those of the control group, indicating that potassium chloride is used as a coating and urea formaldehyde is used as a coating layer, and potash fertilizer particles are prepared by granulation with a disc granulator, and then the potash fertilizer particles and the waste liquid treatment liquid are mixed to prepare liquid fertilizer, wherein potassium chloride effectively releases potash fertilizer through slow release, and the urea formaldehyde coating layer is degraded into ammonium nitrogen by the action of microorganisms in the soil, and the ammonium nitrogen can be used as a nitrogen source to provide nutrients for plant growth, and the combined action of the nitrogen source and the potassium source can effectively promote plant growth, and the fertility is sufficient; the yield and diameter of Examples 1 to 5 are significantly greater than those of Comparative Example 5, indicating that urea formaldehyde, as a coating layer, can be slowly decomposed into ammonium nitrogen, carbon dioxide and water under the action of microorganisms in the soil, and the ammonium nitrogen can be used as a nitrogen fertilizer to provide nutrients for plant growth and promote plant growth, thereby having good fertilizer supply capacity.
[0042] 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 producing liquid fertilizer from thioerythromycin waste liquid, characterized in that: The thioerythromycin waste liquid liquid fertilizer is prepared by treating the thioerythromycin waste liquid with copper ion-modified titanium dioxide and then mixing it with potash fertilizer particles; The copper ion modified titanium dioxide is prepared by reacting tetrabutyl titanate with an ammonia ethanol solution to prepare titanium dioxide solid, which is then ultrasonically treated to load the copper ions. The potash fertilizer granules are prepared by granulating urea formaldehyde by reacting formaldehyde with urea, using potassium chloride as a coating and urea formaldehyde as a coating layer, using a disc granulator for granulation.
2. A process for producing liquid fertilizer from thioerythromycin waste liquid, characterized in that: The method comprises the following preparation steps: (1) Tetrabutyl titanate and anhydrous ethanol are mixed in a mass ratio of 1: (6-8), an ammonia ethanol solution of 13-17 times the mass of tetrabutyl titanate is added, the mixture is stirred at 200-300 r / min for 20-30 hours at room temperature, the precipitate is separated by centrifugation, and the precipitate is washed with deionized water for 3-5 times to obtain titanium dioxide solid; the titanium dioxide solid is diluted to a titanium dioxide mixed solution with a solid content of 15%-25%, a 50 g / L copper chloride dihydrate aqueous solution of 5%-15% of the mass of the titanium dioxide mixed solution is added, the mixture is mixed, sealed, ultrasonicated at 25°C for 4-6 hours, the precipitate is separated by centrifugation, and the precipitate is calcined at 700-800°C for 6-8 hours to obtain copper ion modified titanium dioxide; (2) Mix the formaldehyde solution and urea, adjust the pH to 9.0 with sodium hydroxide solution, react at 45-55°C for 1-2 hours, adjust the pH to 5.0 with hydrochloric acid solution, continue to react for 1-2 hours, dry at 85-95°C until the liquid disappears, then cool to 50-60°C, and continue to dry for 4-6 hours to obtain urea formaldehyde; mix urea formaldehyde with water to obtain urea formaldehyde suspension, use potassium chloride as coating and urea formaldehyde as coating layer, granulate with a disc granulator, sieve out particles with a particle size of 2 mm, and dry at 105-115°C for 3-5 hours to obtain potash fertilizer granules; (3) Mix the erythromycin waste liquid and copper ion modified titanium dioxide, stir at room temperature at 50-100 r / min, treat with ultraviolet irradiation for 1-2 h, continue stirring for 10-12 h, centrifuge to separate the precipitate, retain the filtrate, and prepare the waste liquid treatment liquid; mix the potassium fertilizer granules and the waste liquid treatment liquid to prepare the erythromycin waste liquid liquid fertilizer.
3. a process for preparing liquid fertilizer from a kind of thioerythromycin waste liquid according to claim 2, is characterized in that, The preparation method of the ammonia ethanol solution in step (1) is: mixing ammonia water and anhydrous ethanol in a volume ratio of 1:
3.
4. a process for preparing liquid fertilizer from a kind of thioerythromycin waste liquid according to claim 2, is characterized in that, The formaldehyde solution in step (2) is a formaldehyde solution with a mass concentration of 37%; the sodium hydroxide solution is a sodium hydroxide solution with a mass concentration of 5%; and the hydrochloric acid solution is a hydrochloric acid solution with a mass concentration of 1%.
5. a process for preparing liquid fertilizer from a kind of thioerythromycin waste liquid according to claim 2, is characterized in that, The mass ratio of the formaldehyde solution to urea in step (2) is 1:(0.3-0.5).
6. a process for preparing liquid fertilizer from a kind of thioerythromycin waste liquid according to claim 2, is characterized in that, The mass ratio of urea formaldehyde to water in step (2) is 1:(6-8).
7. a process for preparing liquid fertilizer from a kind of thioerythromycin waste liquid according to claim 2, is characterized in that, In step (2), the mass ratio of the urea formaldehyde suspension to potassium chloride during granulation by the disc granulator is 1:(0.5-0.7).
8. a process for preparing liquid fertilizer from a kind of thioerythromycin waste liquid according to claim 2, is characterized in that, The mass ratio of the erythromycin waste liquid and the copper ion modified titanium dioxide in step (3) is 1: (0.1-0.2).
9. a process for preparing liquid fertilizer from a kind of thioerythromycin waste liquid according to claim 2, is characterized in that, The ultraviolet irradiation power in step (3) is 180W.
10. A process for preparing liquid fertilizer from thioerythromycin waste liquid according to claim 2, characterized in that, In step (3), the mass ratio of the potash fertilizer particles to the waste liquid treatment liquid is 1:(10-20).