Method for preparing liquid fertilizer from tylosin waste liquid to improve crop yield

Abstract

The invention discloses a method for preparing a liquid fertilizer and improving crop yield by using tylosin waste liquid, and belongs to the technical field of agricultural waste resource utilization, and the method comprises the following steps: S1, preparing a novel liquid fertilizer: mixing the tylosin waste liquid with an antibiotic degradation agent for reaction, centrifuging, and collecting supernatant; adding nutrient substances and a mixed bacterial agent into the centrifugate for fermentation treatment, and filtering to obtain filtrate, namely the novel liquid fertilizer; s2, taking crop seeds, and soaking the crop seeds in a soaking solution before planting; s3, in the seed bud stage and the seedling stage, leaf surface spraying is conducted; wherein the antibiotic degradation agent is prepared by reacting modified silicon dioxide with sulfhydrylated sodium carboxymethyl cellulose. According to the method, resource utilization of the tylosin waste liquid is achieved, environmental pollution and use of chemical fertilizers are reduced, the agricultural production cost is reduced, and an effective way is provided for agricultural sustainable development.

Description

Technical Field

[0001] The present invention relates to the technical field of resource utilization of agricultural waste, and particularly relates to a method for preparing liquid fertilizer by using tylosin waste liquid and improving crop yield. Background Art

[0002] Tylosin is a macrolide antibiotic widely used in the prevention and treatment of animal diseases in the livestock industry. A large amount of waste liquid is generated during its production process, and this waste liquid contains residual antibiotics, organic substances, and various nutrient elements. Traditional treatment methods mainly involve harmless treatment through physical, chemical, or biological degradation and then discharging it. This not only has a high treatment cost but also wastes the nutrient resources in the waste liquid.

[0003] In recent years, with the improvement of environmental awareness and the development of the concept of circular economy, the resource utilization of waste has received increasing attention. If the antibiotic residues in wastewater are directly used in agriculture, it may cause soil and groundwater pollution, leading to the generation and spread of antibiotic-resistant bacteria, posing a threat to the ecosystem and human health.

[0004] Currently, the increase in crop yield mainly relies on the large application of chemical fertilizers. However, long-term excessive use of chemical fertilizers will cause environmental problems such as soil compaction, acidification, and groundwater pollution. As an environment-friendly fertilizer, biological fertilizer has the advantages of improving soil structure, enhancing soil fertility, and promoting crop growth, and is increasingly favored in agricultural production.

[0005] Traditional methods for antibiotic degradation mainly include physical methods, chemical methods, and biological methods, etc. Although physical methods are highly efficient, they have a high treatment cost and are prone to secondary pollution; chemical methods are environmentally friendly but the degradation is not thorough; biological methods are environmentally friendly and economical but are greatly affected by environmental factors and have a long treatment cycle. Summary of the Invention

[0006] The present invention provides a method for preparing liquid fertilizer from tylosin waste liquid to improve crop yield, which is used to solve the technical problems of low efficiency of antibiotic degradants in antibiotic waste liquid and low nutrient absorption efficiency of fertilizers in the prior art.

[0007] The method for preparing liquid fertilizer from tylosin waste liquid to improve crop yield disclosed by the present invention includes the following steps: S1. Prepare a novel liquid fertilizer: After mixing and reacting tylosin waste liquid with an antibiotic degradant, centrifuge, add nutrients and a mixed bacterial agent to the centrifugate for fermentation treatment, and then filter. The filtrate is the novel liquid fertilizer; S2. Take crop seeds and soak the crop seeds in a soaking solution before planting; S3. Perform foliar spraying during the seed germination stage and the seedling stage respectively; Among them, the antibiotic degrading agent is prepared by reacting modified silica with sodium mercapto carboxymethyl cellulose. The modified silica is prepared by reacting tetrabutyl titanate with mesoporous silica, and the sodium mercapto carboxymethyl cellulose is prepared by subjecting carboxymethyl cellulose sodium to a mercapto reaction; In the nutrient substances, the mass ratio of nitrogen, phosphorus, potassium, iron, manganese, and zinc is 15:15:15:1:1:1; In the mixed microbial agent, the mass ratio of Bacillus subtilis to yeast is 1:1; The crop is one of cucumber, corn, tomato, and wheat; The soaking solution is a mixture of a novel liquid fertilizer, glucose, and folic acid.

[0008] Preferably, the preparation method of the antibiotic degrading agent comprises the following steps: Step 1: Mix mesoporous silica with absolute ethanol, ultrasonicate for 20 - 40 min, add tetrabutyl titanate, deionized water, and glacial acetic acid, react at 110 - 130 °C for 10 - 12 h, cool to 20 - 40 °C, centrifuge, wash with absolute ethanol 3 - 5 times, and vacuum dry at 60 °C for 12 h to obtain modified silica; Step 2: Weigh sodium carboxymethyl cellulose, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC·HCl), N-hydroxysuccinimide (NHS), cysteine hydrochloride, absolute ethanol, and deionized water according to the mass-volume ratio of 10 g:8 g:4 g:10 g:200 ml:100 ml. Mix deionized water and sodium carboxymethyl cellulose, add EDC·HCl and NHS, stir at 20 - 30 °C for 1.5 - 2 h, add cysteine hydrochloride and deionized water, transfer the mixture to a dialysis bag, dialyze in deionized water for 48 h, and after dialysis, lyophilize the mixture to obtain sodium mercapto carboxymethyl cellulose; Step 3: Mix the modified silica with absolute ethanol, ultrasonicate for 30 min, add sodium mercapto carboxymethyl cellulose and deionized water, stir at 20 - 30 °C for 20 - 24 h, centrifuge the product, wash alternately with absolute ethanol and deionized water 3 - 5 times, and vacuum dry at 50 - 60 °C for 10 - 12 h to obtain the antibiotic degrading agent.

[0009] Preferably, in Step 1, the mass-volume ratio of the mesoporous silica, tetrabutyl titanate, absolute ethanol, deionized water, and glacial acetic acid is 8 - 10 g:40 - 50 ml:200 ml:10 - 12 ml:3 - 5 ml.

[0010] Preferably, in Step 1, the mesh number of the mesoporous silica is 80 - 120.

[0011] Preferably, in step three, the mass-volume ratio of the modified silica, mercapto carboxymethyl cellulose sodium, absolute ethanol, and deionized water is 5 g: 3 g: 100 ml: 50 ml.

[0012] Preferably, in S1, the mixing reaction is to mix the tylosin antibiotic degrading agent at a mass-volume ratio of 88 - 95 L: 5 - 10 kg, stir evenly, irradiate with a UV lamp with a wavelength of 240 - 260 nm and a power of 30 W for 3 - 5 days, and introduce ozone for 30 min every 1 - 2 h during this period; Among them, the ozone concentration is 0.8 - 1.0 ppm.

[0013] Preferably, in S1, the centrifugation speed is 3000 - 5000 r / min, and the centrifugation time is 15 - 20 min.

[0014] Preferably, in S2, the mass ratio of the novel liquid fertilizer, glucose, and folic acid in the soaking solution is 50: 5 - 10: 0.5 - 1.

[0015] Preferably, in S2, select plump wheat, corn, cucumber, or tomato seeds without pests and diseases, completely immerse the seeds in the soaking solution, take them out after soaking for 30 min, and place them in a cool and ventilated place to dry.

[0016] Preferably, in S3, during the seed germination stage and seedling stage, foliar spraying is carried out respectively. The novel liquid is prepared into a novel liquid fertilizer dilution with water at a volume ratio of 1:50. 30 - 40 L of the novel liquid fertilizer dilution is sprayed per mu during the germination stage, and 40 - 50 L of the novel liquid fertilizer dilution is sprayed per mu during the seedling stage.

[0017] The present invention has at least the following beneficial effects: (1) Tetrabutyl titanate is a metal alkoxide, which will undergo a hydrolysis reaction under the action of water, and glacial acetic acid acts as a catalyst to accelerate the hydrolysis of tetrabutyl titanate. The specific reaction is as follows:

[0018] Polycondensation reactions will occur between the hydrolysis products: Titanium oxide polymer particles are formed; mesoporous silica has a large specific surface area and a rich pore structure. When the titanium oxide polymer particles generated by the hydrolysis and polycondensation of tetrabutyl titanate are formed, the silanol groups on the surface of mesoporous silica will undergo a condensation reaction with the hydroxyl groups on the surface of the titanium oxide polymer particles, so that titanium oxide is tightly combined with mesoporous silica, and thus titanium dioxide is attached to the surface of mesoporous silica, making it have excellent antibiotic photocatalytic degradation effect.

[0019] (2) It can be understood that in the embodiments of the present application, under the stirring condition of 20 - 30 °C, EDC·HCl first reacts with the carboxyl group on the sodium carboxymethylcellulose molecule to form an unstable O-acylisourea intermediate. This intermediate is prone to react with water and hydrolyze, resulting in a decrease in the activation efficiency. The addition of NHS can react with the O-acylisourea intermediate to generate a more stable N-hydroxysuccinimide ester. Representing the carboxyl group on sodium carboxymethylcellulose with CMC-COOH, the reaction equation can be expressed as follows: CMC-COOH + EDC·HCl → CMC-CO-O-C(=NH)-N(CH 2 CH 2 CH 2 NCH 32 )CH 2 CH 3 +HCl, CMC-CO-O-C(=NH)-N(CH 2 CH 2 CH 2 NCH 32 )CH 2 CH 3 + NHS → CMC-CO-NHS + EDC-urea derivative; Cysteine hydrochloride undergoes a nucleophilic substitution reaction with the activated NHS ester on sodium carboxymethylcellulose. The amino group attacks the carbonyl carbon in the NHS ester, and NHS leaves as a leaving group, thereby connecting cysteine to the sodium carboxymethylcellulose molecule and introducing a mercapto group at the same time. The reaction equation is as follows: CMC-CO-NHS + HS-CH 2 -CH(NH 2 )-COOH·HCl → CMC-CO-NH-CH(COOH)-CH 2 -SH + NHS + HCl; Among them, as a functional group with relatively high nucleophilicity, the mercapto group can initiate a nucleophilic attack on the electrophilic center in the tylosin molecule and destroy the unsaturated bond therein. Specifically, the mercapto group can combine with the carbonyl group, thereby destroying the molecular structure of tylosin.

[0020] (3) The sodium carboxymethyl cellulose with mercapto groups contains a large number of hydroxyl and carboxyl groups, and these groups can form hydrogen bonds with the silicon-hydrogen bonds on the surface of the modified silica, thereby loading the modified silica onto the sodium carboxymethyl cellulose with mercapto groups; the macromolecular structure of the sodium carboxymethyl cellulose with mercapto groups can increase the uniformity and stability of the modified silica in the tylosin waste liquid, thereby improving the degradation efficiency, and can reduce the aggregation and inactivation of the modified silica during the reaction, thereby increasing the lifespan of the antibiotic degrading agent; meanwhile, the surface of the modified silica has a large specific surface area and excellent adsorption properties, and can adsorb tylosin molecules, while the sodium carboxymethyl cellulose with mercapto groups can chelate metal ions, and the mercapto groups on it can attack tylosin through nucleophilic reaction, thereby realizing the synergistic effect of the two on the degradation of tylosin.

[0021] (4) The tylosin waste liquid contains organic matter and residual tylosin. In the present invention, the tylosin waste liquid is mixed with the antibiotic degrading agent, and combined with the treatment methods of ultraviolet irradiation and ozone introduction, which can effectively degrade the antibiotic residues in the waste liquid; the new liquid fertilizer is added with a compound fertilizer containing nitrogen, phosphorus and potassium and trace elements such as iron, zinc and manganese, which can provide comprehensive and balanced nutrients for crop growth; nitrogen promotes the growth of crop stems and leaves, phosphorus helps root development and flowering and fruiting, and potassium enhances the stress resistance of crops; using the tylosin waste liquid as a raw material to prepare the liquid fertilizer reduces the raw material cost while reducing the usage amount of traditional chemical fertilizers, saves the agricultural production cost, and realizes the recycling of resources.

[0022] (5) The present invention realizes the resource utilization of the tylosin waste liquid, reduces the environmental pollution of the waste liquid, and reduces the treatment cost; the prepared new liquid fertilizer can partially replace chemical fertilizers, reduces the agricultural production cost, improves the crop yield at the same time, and increases the income of farmers; the use of the mixed microbial agent helps to improve the soil microbial environment, enhance the soil fertility, reduce the damage of chemical fertilizers to the soil structure, and is beneficial to the sustainable development of agriculture. Specific embodiments

[0023] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative work shall fall within the protection scope of the present invention.

[0024] In one embodiment, the present invention discloses a preparation method of an antibiotic degrading agent: Step 1: Weigh mesoporous silica, tetrabutyl titanate, absolute ethanol, deionized water, and glacial acetic acid according to the mass-volume ratio of 8-10 g: 40-50 ml: 200 ml: 10-12 ml: 3-5 ml. Mix mesoporous silica and absolute ethanol, and ultrasonicate for 20-40 min. Then add tetrabutyl titanate, deionized water, and glacial acetic acid, and react at 110-130 °C for 10-12 h. Cool to 20-40 °C, centrifuge, wash with absolute ethanol 3-5 times, and vacuum dry at 60 °C for 12 h to obtain modified silica; Among them, the mesh number of mesoporous silica is 80-120; It can be understood that in the embodiments of the present application, tetrabutyl titanate is a metal alkoxide, which will undergo a hydrolysis reaction under the action of water, and glacial acetic acid acts as a catalyst to accelerate the hydrolysis of tetrabutyl titanate. The specific reaction is as follows:

[0025] Polycondensation reactions will occur between the hydrolysis products: Titanium oxide polymer particles are formed; mesoporous silica has a large specific surface area and a rich pore structure. When titanium oxide polymer particles generated by the hydrolysis and polycondensation of tetrabutyl titanate are formed, the silanol groups on the surface of mesoporous silica will undergo a condensation reaction with the hydroxyl groups on the surface of titanium oxide polymer particles, so that titanium oxide is tightly combined with mesoporous silica, and thus titanium dioxide is attached to the surface of mesoporous silica, making it have excellent antibiotic photocatalytic degradation effect.

[0026] Step 2: Weigh sodium carboxymethyl cellulose, 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC·HCl), N-hydroxysuccinimide (NHS), cysteine hydrochloride, absolute ethanol, and deionized water according to the mass-volume ratio of 10 g: 8 g: 4 g: 10 g: 200 ml: 100 ml. Mix deionized water and sodium carboxymethyl cellulose, add EDC·HCl and NHS, stir at 20-30 °C for 1.5-2 h, add cysteine hydrochloride and deionized water, transfer the mixture to a dialysis bag, and dialyze in deionized water for 48 h. After dialysis, lyophilize the mixture to obtain thiolated sodium carboxymethyl cellulose; It can be understood that in the embodiments of the present application, under the stirring condition of 20-30 °C, EDC·HCl first reacts with the carboxyl group on the sodium carboxymethyl cellulose molecule to form an unstable O-acylisourea intermediate, which is prone to hydrolysis when reacting with water, resulting in a decrease in activation efficiency. The addition of NHS can react with the O-acylisourea intermediate to generate a more stable N-hydroxysuccinimide ester (NHS ester). Representing the carboxyl group on sodium carboxymethyl cellulose with CMC-COOH, the reaction equation can be expressed as follows: CMC-COOH + EDC·HCl → CMC-CO-O-C(=NH)-N(CH 2 CH 2 CH 2 NCH 32 )CH 2 CH 3 + HCl, CMC-CO-O-C(=NH)-N(CH 2 CH 2 CH 2 NCH 32 )CH 2 CH 3 + NHS → CMC-CO-NHS + EDC-urea derivative; The nucleophilic substitution reaction occurs between cysteine hydrochloride and the activated NHS ester on sodium carboxymethyl cellulose. The amino group attacks the carbonyl carbon in the NHS ester, and NHS leaves as a leaving group, thus connecting cysteine to the sodium carboxymethyl cellulose molecule and introducing a mercapto group at the same time. The reaction equation is as follows: CMC-CO-NHS + HS-CH 2 -CH(NH 2 )-COOH·HCl → CMC-CO-NH-CH(COOH)-CH 2 -SH + NHS + HCl; Among them, the mercapto group, as a functional group with high nucleophilicity, can initiate a nucleophilic attack on the electrophilic center in the tylosin molecule and break the unsaturated bond therein. For example, the mercapto group can combine with the carbonyl group, thus destroying the molecular structure of tylosin.

[0027] Step 3: Weigh modified silica, mercapto-functionalized sodium carboxymethyl cellulose, absolute ethanol, and deionized water according to the mass-to-volume ratio of 5 g: 3 g: 100 ml: 50 ml. Mix the modified silica and absolute ethanol, ultrasonicate for 30 min, add mercapto-functionalized sodium carboxymethyl cellulose and deionized water, stir at 20 - 30 °C for 20 - 24 h, centrifuge the product, wash it alternately with absolute ethanol and deionized water for 3 - 5 times, and vacuum dry it at 50 - 60 °C for 10 - 12 h to obtain the antibiotic degrading agent.

[0028] It can be understood that in the embodiments of the present application, the thiolated sodium carboxymethyl cellulose molecule contains a large number of hydroxyl and carboxyl groups. These groups can form hydrogen bonds with the silicon-hydrogen bonds on the surface of the modified silica, thereby loading the modified silica on the thiolated sodium carboxymethyl cellulose. The macromolecular structure of the thiolated sodium carboxymethyl cellulose can increase the uniformity and stability of the modified silica in tylosin waste liquid, thereby improving the degradation efficiency, and can reduce the aggregation and inactivation of the modified silica during the reaction, thereby increasing the lifespan of the antibiotic degrader. At the same time, the surface of the modified silica has a large specific surface area and excellent adsorption properties, and can adsorb tylosin molecules. The thiolated sodium carboxymethyl cellulose can chelate metal ions, and the sulfhydryl group on it can attack tylosin through a nucleophilic reaction, thereby realizing the synergistic effect of the two on the degradation of tylosin.

[0029] In one embodiment, the present invention discloses a preparation method of a novel liquid fertilizer: Mix the tylosin antibiotic degrader in a mass-volume ratio of 88 - 95 L : 5 - 10 kg, stir evenly, irradiate with an ultraviolet lamp with a wavelength of 240 - 260 nm and a power of 30 W for 3 - 5 days. During this period, ozone is introduced for 30 min every 1 - 2 h. After the reaction is completed, centrifuge at a speed of 3000 - 5000 r / min for 15 - 20 min, collect the centrifugate. For the compound fertilizer, add 5 - 8 kg per 100 L of the centrifugate. Add nutrients and microbial agents to the centrifugate. The nutrients include a compound fertilizer prepared in a mass ratio of N:P:K = 15:15:15, and the addition amount of the compound fertilizer is 5 - 8 kg per 100 L of the centrifugate, as well as trace elements such as iron, zinc, and manganese, and the addition amount of the trace elements is 0.5 - 1 kg per 100 L of the centrifugate. The microbial agent is a mixed microbial agent of Bacillus subtilis and Saccharomyces cerevisiae with a mass ratio of 1:1, and the addition amount of the mixed microbial agent is 0.2 - 0.3 kg per 100 L of the centrifugate. After stirring evenly, ferment at 28 - 32 °C in an aerobic environment for 5 - 7 days. After fermentation is completed, sterilize the mixed liquid at 121 °C and 0.1 MPa for 20 - 30 min, and then filter through a 100 - 200 mesh filter to obtain the novel liquid fertilizer.

[0030] It is understandable that in the embodiments of the present application, the tylosin waste liquid contains organic matter and residual tylosin. The present invention mixes the tylosin waste liquid with an antibiotic degrading agent and combines the treatment methods of ultraviolet irradiation and ozone introduction, which can effectively degrade the antibiotic residues in the waste liquid; the novel liquid fertilizer is added with a compound fertilizer containing nitrogen, phosphorus and potassium and trace elements such as iron, zinc and manganese, which can provide comprehensive and balanced nutrients for crop growth; nitrogen promotes the growth of crop stems and leaves, phosphorus helps root development and flowering and fruiting, and potassium enhances the stress resistance of crops; using tylosin waste liquid as a raw material to prepare liquid fertilizer reduces the raw material cost while reducing the usage amount of traditional chemical fertilizers, saves the agricultural production cost, and realizes the recycling of resources.

[0031] Example 1-1 This example discloses a preparation method of a novel liquid fertilizer.

[0032] Prepare modified silica: Weigh 8 g of 80-mesh mesoporous silica, add 200 ml of absolute ethanol, ultrasonicate for 20 min, sequentially add 40 ml of tetrabutyl titanate, 10 ml of deionized water, and 3 ml of glacial acetic acid, react at 110 °C for 10 h, centrifuge after cooling to 20 °C, wash 3 times with absolute ethanol, and vacuum dry at 60 °C for 12 h to obtain modified silica.

[0033] Prepare mercapto-carboxymethyl cellulose sodium: Weigh carboxymethyl cellulose sodium, EDC·HCl, NHS, cysteine hydrochloride, absolute ethanol, and deionized water according to the mass-volume ratio of 10 g: 8 g: 4 g: 10 g: 200 ml: 100 ml. Mix deionized water and carboxymethyl cellulose sodium, add EDC·HCl and NHS, stir at 20 °C for 1.5 h, add cysteine hydrochloride and the remaining deionized water, dialyze for 48 h and then freeze-dry to obtain mercapto-carboxymethyl cellulose sodium.

[0034] Prepare an antibiotic degrading agent: Mix 5 g of modified silica with 100 ml of absolute ethanol, ultrasonicate for 30 min, add 3 g of mercapto-carboxymethyl cellulose sodium and 50 ml of deionized water, stir at 20 °C for 20 h, centrifuge and separate, wash 3 times alternately with absolute ethanol and deionized water, and vacuum dry at 50 °C for 10 h to obtain an antibiotic degrading agent.

[0035] Preparation of a new type of liquid fertilizer: Take 88 L of tylosin waste liquid, add 5 kg of the above-mentioned antibiotic degrading agent, stir evenly, irradiate with an ultraviolet lamp at a wavelength of 240 nm and a power of 30 W for 3 days, and introduce ozone for 30 min every 1 h during this period. Centrifuge at 3000 r / min for 15 min, collect the centrifugate, add 5 kg of compound fertilizer prepared according to N:P:K = 15:15:15, 0.5 kg of trace elements such as iron, zinc, and manganese, and 0.2 kg of a mixed microbial agent with a mass ratio of Bacillus subtilis to yeast of 1:1 to 100 L of the centrifugate, ferment aerobically at 28 °C for 5 days, then sterilize at 121 °C and 0.1 MPa for 20 min, and filter through a 100-mesh filter to obtain the new type of liquid fertilizer.

[0036] Examples 1 - 2 This example discloses a preparation method of a new type of liquid fertilizer.

[0037] Preparation of modified silica: Weigh 9 g of 90-mesh mesoporous silica, add 220 ml of anhydrous ethanol, ultrasonicate for 25 min, successively add 42 ml of tetrabutyl titanate, 11 ml of deionized water, and 4 ml of glacial acetic acid, react at 115 °C for 10.5 h, centrifuge after cooling to 25 °C, wash 4 times with anhydrous ethanol, and vacuum dry at 60 °C for 12 h to obtain modified silica.

[0038] Preparation of mercapto-carboxymethyl cellulose sodium: Weigh carboxymethyl cellulose sodium, EDC·HCl, NHS, cysteine hydrochloride, anhydrous ethanol, and deionized water according to the mass-volume ratio of 11 g:9 g:5 g:11 g:220 ml:110 ml. Mix deionized water with carboxymethyl cellulose sodium, add EDC·HCl and NHS, stir at 22 °C for 1.6 h, add cysteine hydrochloride and the remaining deionized water, dialyze for 48 h and then freeze-dry to obtain mercapto-carboxymethyl cellulose sodium.

[0039] Preparation of antibiotic degrading agent: Mix 6 g of modified silica with 110 ml of anhydrous ethanol, ultrasonicate for 32 min, add 3.5 g of mercapto-carboxymethyl cellulose sodium and 55 ml of deionized water, stir at 22 °C for 21 h. Centrifuge and separate, wash 4 times alternately with anhydrous ethanol and deionized water, and vacuum dry at 52 °C for 10.5 h to obtain the antibiotic degrading agent.

[0040] Preparation of a new type of liquid fertilizer: Take 90 L of tylosin waste liquid, add 6 kg of the above-mentioned antibiotic degrading agent, stir evenly, irradiate with an ultraviolet lamp at a wavelength of 245 nm and a power of 30 W for 3.5 days, and introduce ozone for 30 min every 1.2 h during this period. Centrifuge at 3500 r / min for 16 min, collect the centrifugate, add 5.5 kg of compound fertilizer prepared according to N:P:K = 15:15:15, 0.6 kg of trace elements such as iron, zinc, and manganese, and 0.22 kg of a mixed bacterium agent with a mass ratio of Bacillus subtilis to yeast of 1:1 to 100 L of the centrifugate, ferment aerobically at 29 °C for 5.5 days, sterilize at 121 °C and 0.1 MPa for 22 min, and filter through a 120-mesh filter screen to obtain the new type of liquid fertilizer.

[0041] Examples 1 - 3 This example discloses a preparation method of a new type of liquid fertilizer Preparation of modified silica: Weigh 10 g of 100-mesh mesoporous silica, add 240 ml of anhydrous ethanol, ultrasonicate for 30 min, successively add 45 ml of tetrabutyl titanate, 12 ml of deionized water, and 5 ml of glacial acetic acid, react at 120 °C for 11 h, centrifuge after cooling to 30 °C, wash 5 times with anhydrous ethanol, and vacuum dry at 60 °C for 12 h to obtain modified silica.

[0042] Preparation of mercapto-carboxymethyl cellulose sodium: Weigh carboxymethyl cellulose sodium, EDC·HCl, NHS, cysteine hydrochloride, anhydrous ethanol, and deionized water according to the mass-volume ratio of 12 g:10 g:6 g:12 g:240 ml:120 ml. Mix deionized water with carboxymethyl cellulose sodium, add EDC·HCl and NHS, stir at 25 °C for 1.8 h, add cysteine hydrochloride and the remaining deionized water, dialyze for 48 h and then freeze-dry to obtain mercapto-carboxymethyl cellulose sodium.

[0043] Preparation of antibiotic degrading agent: Mix 7 g of modified silica with 120 ml of anhydrous ethanol, ultrasonicate for 35 min, add 4 g of mercapto-carboxymethyl cellulose sodium and 60 ml of deionized water, stir at 25 °C for 22 h. Centrifuge and separate, wash 5 times alternately with anhydrous ethanol and deionized water, and vacuum dry at 55 °C for 11 h to obtain the antibiotic degrading agent.

[0044] Preparation of a new type of liquid fertilizer: Take 92 L of tylosin waste liquid, add 7 kg of the above-mentioned antibiotic degrading agent, stir evenly, irradiate with an ultraviolet lamp at a wavelength of 250 nm and a power of 30 W for 4 days, and introduce ozone for 30 min every 1.5 h during this period. Centrifuge at 4000 r / min for 18 min, collect the centrifugate, add 6 kg of compound fertilizer prepared according to N:P:K = 15:15:15, 0.7 kg of trace elements such as iron, zinc, and manganese, 0.25 kg of a mixed microbial agent with a mass ratio of Bacillus subtilis to yeast of 1:1 to 100 L of the centrifugate, ferment aerobically at 30 °C for 6 days, sterilize at 121 °C and 0.1 MPa for 25 min, and filter through a 150-mesh filter to obtain the new type of liquid fertilizer.

[0045] Comparative Example 1-1 This comparative example discloses a preparation method of a new type of liquid fertilizer. When preparing the new type of liquid fertilizer in this comparative example, no antibiotic degrading agent was added.

[0046] Take 88 L of tylosin waste liquid, without adding an antibiotic degrading agent, directly irradiate with an ultraviolet lamp at a wavelength of 240 nm and a power of 30 W for 3 days, introduce ozone for 30 min every 1 h during this period, centrifuge at 3000 r / min for 15 min, collect the centrifugate, add 5 kg of compound fertilizer prepared according to N:P:K = 15:15:15, 0.5 kg of trace elements such as iron, zinc, and manganese, 0.2 kg of a mixed microbial agent with a mass ratio of Bacillus subtilis to yeast of 1:1 to 100 L of the centrifugate, ferment aerobically at 28 °C for 5 days, sterilize at 121 °C and 0.1 MPa for 20 min, and filter through a 100-mesh filter to obtain the new type of liquid fertilizer.

[0047] Comparative Example 1-2 This comparative example discloses a preparation method of a new type of liquid fertilizer.

[0048] In this comparative example, no modified silica was added when preparing the antibiotic degrading agent.

[0049] Weigh carboxymethyl cellulose sodium, EDC·HCl, NHS, cysteine hydrochloride, absolute ethanol, and deionized water according to the mass-to-volume ratio of 10 g:8 g:4 g:10 g:200 ml:100 ml. Mix deionized water with carboxymethyl cellulose sodium, add EDC·HCl and NHS, stir at 20 °C for 1.5 h, add cysteine hydrochloride and the remaining deionized water, dialyze for 48 h and then freeze-dry to obtain thiolated carboxymethyl cellulose sodium.

[0050] Weigh 3 g of thiolated carboxymethyl cellulose sodium, add 100 ml of absolute ethanol and 50 ml of deionized water, stir at 20 °C for 20 h, centrifuge and separate, wash alternately with absolute ethanol and deionized water 3 times, and vacuum-dry at 50 °C for 10 h to obtain the antibiotic degrading agent.

[0051] Take 88 L of tylosin waste liquid, add the above-mentioned antibiotic degrading agent, stir evenly, irradiate with an ultraviolet lamp with a wavelength of 240 nm and a power of 30 W for 3 days, introduce ozone for 30 min every 1 h during this period, centrifuge at 3000 r / min for 15 min, collect the centrifugate, add 5 kg of compound fertilizer prepared according to N:P:K = 15:15:15, 0.5 kg of trace elements such as iron, zinc, and manganese, and 0.2 kg of a mixed microbial agent of Bacillus subtilis and yeast in a mass ratio of 1:1 to 100 L of the centrifugate, and perform aerobic fermentation at 28 °C for 5 days. Sterilize at 121 °C and 0.1 MPa for 20 min, and filter through a 100-mesh filter to obtain a novel liquid fertilizer.

[0052] Comparative Examples 1 - 3 This comparative example discloses a preparation method of a novel liquid fertilizer In this comparative example, sodium carboxymethyl cellulose mercaptan was not added during the preparation of the antibiotic degrading agent.

[0053] Weigh 8 g of 80-mesh mesoporous silica, add 200 ml of anhydrous ethanol, ultrasonicate for 20 min, sequentially add 40 ml of tetrabutyl titanate, 10 ml of deionized water, and 3 ml of glacial acetic acid, react at 110 °C for 10 h, centrifuge after cooling to 20 °C, wash 3 times with anhydrous ethanol, and vacuum dry at 60 °C for 12 h to obtain modified silica.

[0054] Mix 5 g of modified silica with 100 ml of anhydrous ethanol and ultrasonicate for 30 min. Add 50 ml of deionized water, stir at 20 °C for 20 h, perform centrifugal separation, wash 3 times alternately with anhydrous ethanol and deionized water, and vacuum dry at 50 °C for 10 h to obtain the antibiotic degrading agent.

[0055] Take 88 L of tylosin waste liquid, add the above-mentioned antibiotic degrading agent, stir evenly, irradiate with an ultraviolet lamp with a wavelength of 240 nm and a power of 30 W for 3 days, introduce ozone for 30 min every 1 h during this period, centrifuge at 3000 r / min for 15 min, collect the centrifugate, add 5 kg of compound fertilizer prepared according to N:P:K = 15:15:15, 0.5 kg of trace elements such as iron, zinc, and manganese, and 0.2 kg of a mixed microbial agent of Bacillus subtilis and yeast in a mass ratio of 1:1 to 100 L of the centrifugate, perform aerobic fermentation at 28 °C for 5 days, sterilize at 121 °C and 0.1 MPa for 20 min, and filter through a 100-mesh filter to obtain a novel liquid fertilizer.

[0056] Performance detection Detection Example 1: Detection of antibiotic degradation effect At the start of the ultraviolet lamp irradiation during the preparation process of the examples and comparative examples, detect the tylosin concentration, use high-performance liquid chromatography, sample and measure once every 24 h, continuously monitor for 3 days, and calculate the tylosin degradation rate.

[0057] Degradation rate (%) = (Initial concentration - Concentration after treatment) / Initial concentration × 100%.

[0058] Table 1 Data table of tylosin degradation rate Time (h) 0 24 48 72 Example 1-1 0% 43.50% 76.20% 95.50% Example 1-2 0% 45.00% 78.50% 96.80% Example 1-3 0% 47.50% 81.20% 97.80% Comparative Example 1-1 0% 15.20% 25.80% 38.40% Comparative Example 1-2 0% 28.70% 46.30% 65.70% Comparative Example 1-3 0% 32.40% 52.10% 71.20% Detection Example 2, Wheat planting experiment Test site: Select the test base of the Agricultural Technology Extension Station in Fengning Manchu Autonomous County, Hebei Province. The geographical coordinates are 41°14' north latitude and 116°24' east longitude. The climate characteristics belong to the temperate semi-humid and semi-arid continental monsoon climate. The average annual temperature is 12.1°C, the frost-free period is 180 days, the annual precipitation is 530 mm, the soil type is cinnamon soil, the tillage layer thickness is 25 cm, the organic matter content is 1.3%, pH is 7.2, the available nitrogen is 95 mg / kg, the available phosphorus is 22 mg / kg, and the available potassium is 135 mg / kg.

[0059] Wheat variety: Jimai 22

[0060] Experimental design: Set 7 groups, including 6 experimental groups and 1 blank control group. Each group has 4 replicates, a total of 28 plots, randomly arranged in blocks with a plot spacing of 1.5 m.

[0061] Planting density: Wheat seeding rate is 15 kg / mu.

[0062] Seed treatment: Take 300 seeds for each group and place them in a 500 ml beaker. Add 500 ml of soaking solution to the experimental groups and an equal amount of distilled water to the blank control group to ensure that the seeds are completely immersed. Soak at 25°C for 30 min, stir once every 10 min during this period, pick out the seeds with tweezers, spread them on a clean filter paper, and dry them in a cool and ventilated place for 2 h.

[0063] Among them, the preparation method of the soaking solution for the experimental groups is: Mix 50 g of the new liquid fertilizer, 5 g of glucose, and 0.5 g of folic acid, add distilled water to 1000 ml, and stir evenly to obtain the soaking solution. Fertilization plan: Experimental groups: 14 days after sowing, at the wheat seedling stage, spray with a knapsack sprayer, and spray 1.05 L of a 1:50 dilution of the liquid fertilizer on each plot; 35 days after sowing, at the wheat seedling stage, spray 1.35 L of a 1:50 dilution of the liquid fertilizer on each plot.

[0064] The blank control group sprays an equal amount of distilled water.

[0065] Pest and disease control: Uniformly spray a 2000-fold solution of 5% acetamiprid emulsifiable concentrate to control aphids.

[0066] Record the germination rate, bud length, and root length of wheat during the germination period, the plant height and tiller number of wheat during the growth period, and the spike length, spike number, and 1000-grain weight of wheat during the maturity period.

[0067] The HPLC method was used to detect antibiotic residues in liquid fertilizers, soil, and grains.

[0068] One-way analysis of variance was performed using SPSS 26.0, and Duncan's test (P < 0.05).

[0069] Table 2 Record table of index data during the wheat germination period Group Germination rate (%) Bud length (cm) Root length (cm) Example 1-1 92.3a 3.8a 5.2a Example 1-2 93.5a 4.1a 5.5a Example 1-3 94.8a 4.3a 5.8a Comparative Example 1-1 78.5b 2.3b 3.1b Comparative Example 1-2 82.1b 2.6b 3.5b Comparative Example 1-3 84.3b 2.8b 3.7b Blank control 65.2c 1.8c 2.4c Note: Different lowercase letters indicate significant differences between groups (P < 0.05), and the same applies hereinafter.

[0070] Table 3 Record table of index data during the wheat growth period Group Plant height (cm) Tiller number (pcs) Example 1-1 68.5a 3.5a Example 1-2 71.2a 3.8a Example 1-3 73.6a 4.1a Comparative Example 1-1 52.3b 2.1b Comparative Example 1-2 55.7b 2.4b Comparative Example 1-3 58.9b 2.7b Blank control 45.6c 1.8c Table 4 Record table of index data during the wheat maturity period Group Panicle length (cm) Panicle number (pcs / m²) 1000-grain weight (g) Example 1-1 8.5a 450a 42.3a Example 1-2 8.8a 465a 43.5a Example 1-3 9.2a 480a 44.8a Comparative Example 1-1 6.2b 320b 35.2b Comparative Example 1-2 6.8b 345b 36.7b Comparative Example 1-3 7.1b 360b 37.9b Blank control 5.5c 280c 32.1c Table 5 Record table of antibiotic residue detection Group Liquid fertilizer residue Soil residue Grain residue Example 1-1 <0.01 <0.01 <0.01 Example 1-2 <0.01 <0.01 <0.01 Example 1-3 <0.01 <0.01 <0.01 Comparative Example 1-1 0.85 0.32 0.15 Comparative Example 1-2 0.58 0.21 0.08 Comparative Example 1-3 0.43 0.17 0.06 Blank control - - - Note: The detection limit was 0.01 mg / kg, and no residues were detected in the experimental groups.

[0071] Data analysis As can be seen from Table 1, the degradation rates of tylosin in Examples 1-1, 1-2, and 1-3 were significantly higher than those in Comparative Example 1-1, indicating that the antibiotic degrading agent of the present invention achieved efficient degradation of antibiotic residues; significantly higher than those in Comparative Examples 1-2 and 1-3, indicating that modified silica and mercapto-carboxymethyl cellulose sodium had a synergistic effect on the degradation of tylosin.

[0072] As can be seen from Table 2, the root length of the experimental group was significantly increased compared with that of the blank group during the wheat germination period. This was because the chelating effect of mercapto-carboxymethyl cellulose sodium promoted the absorption of trace elements such as iron and zinc by plants, accelerating root elongation.

[0073] As can be seen from Table 3, the plant height of each experimental group was significantly increased compared with that of Comparative Example 1-2, indicating that the mesoporous silica supported by TiO 2 could adsorb heavy metals and release silicon elements, relieve soil compaction, and thus promote plant growth.

[0074] As can be seen from Table 4, the experimental group of mature wheat was significantly higher than the comparative and blank control groups, indicating that the novel liquid fertilizer of the present invention had a positive effect on promoting crop yield.

[0075] As can be seen from Table 5, the tylosin residues in the soil and grains of the liquid fertilizer prepared by the preparation method of the novel liquid fertilizer of the present invention met the national standards and were worthy of promotion.

[0076] Although embodiments of the present invention have been shown and described, those of ordinary skill in the art will appreciate that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. All equivalent changes and improvements made in accordance with the scope of the present invention application shall still fall within the scope covered by the patent of the present invention.

Claims

1. A method for preparing liquid fertilizer from tylosin waste liquid to increase crop yield, characterized in that: The following steps are involved: S1. Preparation of new liquid fertilizer: mixing tylosin waste liquid with an antibiotic degradation agent for reaction, centrifuging, adding nutrients and mixed bacterial agents to the centrifuge for fermentation, filtering, and obtaining the filtrate as the new liquid fertilizer; S2, taking crop seeds, and soaking the crop seeds in a soaking liquid before planting; S3, spray on the leaves at the seed bud stage and seedling stage; The antibiotic degradation agent is prepared by reacting modified silicon dioxide with thiolated sodium carboxymethyl cellulose, wherein the modified silicon dioxide is prepared by reacting tetrabutyl titanate with mesoporous silicon dioxide, and the thiolated sodium carboxymethyl cellulose is prepared by thiolation of sodium carboxymethyl cellulose; Among the nutrients, the mass ratio of nitrogen, phosphorus, potassium, iron, manganese and zinc is 15:15:15:1:1:1; In the mixed bacterial agent, the mass ratio of Bacillus subtilis to yeast is 1:1; The crop is one of cucumber, corn, tomato and wheat; The soaking liquid is a mixture of novel liquid fertilizer, glucose and folic acid.

2. The method for preparing liquid fertilizer from tylosin waste liquid to increase crop yield according to claim 1, characterized in that: The preparation method of the antibiotic degradation agent comprises the following steps: Step 1: Mix mesoporous silica with anhydrous ethanol, perform ultrasonic treatment for 20-40 minutes, add tetrabutyl titanate, deionized water, and glacial acetic acid, react at 110-130°C for 10-12 hours, cool to 20-40°C, centrifuge, wash with anhydrous ethanol for 3-5 times, and vacuum dry at 60°C for 12 hours to obtain modified silica; Step 2: weigh sodium carboxymethyl cellulose, EDC・HCl (1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride), NHS (N-hydroxysuccinimide), cysteine ​​hydrochloride, anhydrous ethanol, and deionized water in a mass volume ratio of 10g:8g:4g:10g:200ml:100ml, mix the deionized water and sodium carboxymethyl cellulose, add EDC・HCl and NHS, stir at 20-30°C for 1.5-2h, add cysteine ​​hydrochloride and deionized water, transfer the mixture to a dialysis bag, dialyze in deionized water for 48h, and after the dialysis, freeze-dry the mixture to obtain thiolated sodium carboxymethyl cellulose; Step 3: Mix the modified silica and anhydrous ethanol, ultrasonicate for 30 minutes, add thiolated sodium carboxymethyl cellulose and deionized water, stir at 20-30° C. for 20-24 hours, centrifuge the product, wash it alternately with anhydrous ethanol and deionized water for 3-5 times, and vacuum dry it at 50-60° C. for 10-12 hours to obtain an antibiotic degrader.

3. A method for increasing crop yield by preparing liquid fertilizer from tylosin waste liquid according to claim 2, characterized in that: In step 1, the mass volume ratio of the mesoporous silica, tetrabutyl titanate, anhydrous ethanol, deionized water and glacial acetic acid is 8-10g:40-50ml:200ml:10-12ml:3-5ml.

4. The method for preparing liquid fertilizer from tylosin waste liquid to increase crop yield according to claim 2, characterized in that: In step 1, the mesh size of the mesoporous silica is 80-120.

5. The method for preparing liquid fertilizer from tylosin waste liquid to increase crop yield according to claim 2, characterized in that: In step 3, the mass volume ratio of the modified silicon dioxide, thiolated sodium carboxymethyl cellulose, anhydrous ethanol and deionized water is 5g:3g:100ml:50ml.

6. The method for preparing liquid fertilizer from tylosin waste liquid to increase crop yield according to claim 1, characterized in that: In S1, the mixing reaction is to mix the tylosin antibiotic degradation agent in a mass volume ratio of 88-95L:5-10kg, stir evenly, and irradiate with an ultraviolet lamp with a wavelength of 240-260nm and a power of 30W for 3-5 days, during which ozone is introduced for 30 minutes every 1-2 hours; Wherein, the ozone concentration is 0.8-1.0ppm.

7. The method for preparing liquid fertilizer from tylosin waste liquid to increase crop yield according to claim 1, characterized in that: In S1, the centrifugal speed is 3000-5000 r / min, and the centrifugal time is 15-20 min.

8. The method for preparing liquid fertilizer from tylosin waste liquid to increase crop yield according to claim 1, characterized in that: In S2, the mass ratio of the new liquid fertilizer, glucose and folic acid in the soaking liquid is 50:5-10:0.5-1.

9. The method for preparing liquid fertilizer from tylosin waste liquid to increase crop yield according to claim 1, characterized in that: In S2, plump wheat, corn, cucumber or tomato seeds without diseases and insect pests are selected, the seeds are completely immersed in the soaking liquid, the seeds are taken out after soaking for 30 minutes, and placed in a cool and ventilated place to dry.

10. The method for preparing liquid fertilizer from tylosin waste liquid to increase crop yield according to claim 1, characterized in that: In S3, foliar spraying is performed at the seed budding stage and the seedling stage, respectively. The new liquid and water are mixed into a new liquid fertilizer dilution solution at a volume ratio of 1:

50. 30-40 L of the new liquid fertilizer dilution solution is sprayed per mu at the budding stage, and 40-50 L of the new liquid fertilizer dilution solution is sprayed per mu at the seedling stage.

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