Innovative process for preparing liquid fertilizer from acetylisovaleryltylosin tartrate waste liquid for vegetable planting

Abstract

The invention discloses an innovative process for preparing a liquid fertilizer from an acetylisovaleryltylosin tartrate waste liquid for vegetable planting, and relates to the technical field of fertilizer preparation, and the innovative process comprises the following specific steps: step 1, preliminary pretreatment of the acetylisovaleryltylosin tartrate waste liquid; the preparation method has the advantages that the aminopropyltriethoxysilane enhances the dispersion stability of titanium dioxide in a waste liquid environment, the reduction of the effective surface area capable of participating in the reaction due to agglomeration is avoided, and the comprehensive and efficient promotion of the photocatalytic reaction is guaranteed; amino functional groups carried by aminopropyltriethoxysilane can be specifically combined with various organic substances in the waste liquid to guide a photocatalytic reaction to directionally act on specific organic macromolecules, so that the decomposition process is more targeted and efficient, the conversion efficiency of nutritional ingredients is greatly improved through the synergistic effect, and the photocatalytic effect of the waste liquid is improved. Macromolecular protein, polysaccharide and the like in the waste liquid are efficiently converted into micromolecular nutrients such as amino acid, monosaccharide and the like, and the content of effective nutritional ingredients in the liquid fertilizer is remarkably increased.

Description

Technical Field

[0001] The invention relates to the technical field of fertilizer preparation, and in particular to an innovative process for preparing liquid fertilizer from tyvalocin waste liquid for vegetable planting. Background Art

[0002] As an important veterinary antibiotic, tyvalosin is widely used in the field of animal husbandry. It belongs to the macrolide antibiotics. With its excellent antibacterial activity against a variety of common pathogens of livestock and poultry, such as mycoplasma and Gram-positive bacteria, it plays a key role in preventing and treating respiratory diseases and intestinal diseases of pigs, chickens and other animals, effectively ensuring the healthy growth of livestock and poultry, thereby improving breeding efficiency. However, the production of tyvalosin is a complex chemical process. During its fermentation, extraction and refining, a large amount of waste liquid will inevitably be generated. The composition of these waste liquids is complex, including incompletely reacted raw materials, by-products and microbial metabolites in the fermentation process. For example, they may contain residual sugars, protein substances, organic solvents and different types of salt components. If they are directly discharged without proper treatment, they will bring a heavy burden to the ecological environment, and may cause soil pollution, eutrophication of water bodies, and destruction of the balance of the surrounding ecosystem and many other environmental problems; The existing technology has certain defects. The first is the low efficiency of nutrient conversion. In the process of converting waste liquid into fertilizer, the nutrient conversion efficiency of some processes is not high, and the nutrients contained in the organic matter in the waste liquid cannot be fully released, resulting in poor fertilizer efficiency of the fertilizer. Secondly, the nutrient release characteristics are not good. The release rate of nutrients in the fertilizer is not synchronized with the growth needs of vegetables. Some fertilizers may release nutrients too quickly in the initial stage after being applied to the soil, resulting in "seedling burn", damaging the root system and growth points of vegetable seedlings, and hindering vegetable growth. On the contrary, there are also cases where some fertilizers release nutrients too slowly, and cannot provide sufficient nutrients in time during the critical period of vegetable growth, resulting in slow growth and poor development of vegetables. For this reason, we propose an innovative process for preparing liquid fertilizer from tyvalocin waste liquid for vegetable planting. Summary of the invention

[0003] The purpose of the present invention is to provide an innovative process for preparing liquid fertilizer from tyvalocin waste liquid for vegetable planting.

[0004] In order to solve the problems raised in the above background technology, the present invention provides the following technical solution: an innovative process for preparing liquid fertilizer from tyvalocin waste liquid for vegetable planting, the innovative process comprising the following specific steps: Step 1: Preliminary pretreatment of the tyvalosin waste liquid: collecting the tyvalosin waste liquid, transferring it to a multi-layer filter screen for preliminary filtration to remove unreacted raw material residues and solid impurities, and then adjusting the pH value of the waste liquid; Step 2: prepare a titanium dioxide nanomaterial coated with aminopropyltriethoxysilane on the surface, add it to the preliminarily pretreated waste liquid and stir to disperse it, then place the mixed solution in a photocatalytic reaction device for reaction, use the photocatalytic material to oxidize and reduce the complex organic macromolecules adsorbed in the waste liquid into small molecular nutrients, and collect the mixed solution; Step 3: preparing a bioelectrically sensitive nutrient carrier material, adding the carrier material to the collected mixed solution, stirring and dispersing the mixture, and forming a bioelectrically sensitive liquid fertilizer; Step 4: inoculating a microbial flora into the bioelectrically sensitive liquid fertilizer, then transferring the liquid fertilizer to a fermentation tank for microbial fermentation, sampling and testing during the fermentation process, and obtaining a fermentation liquid after the fermentation is completed; Step 5: Preliminarily filter and centrifuge the fermented liquid fertilizer in turn to obtain clear and transparent quasi-liquid fertilizer, then add urea to the quasi-liquid fertilizer to supplement the nitrogen source, add potassium dihydrogen phosphate to supplement the phosphorus element, add potassium sulfate to supplement the potassium element, add ferrous sulfate to supplement the iron element, add manganese sulfate to supplement the manganese element, and add zinc sulfate heptahydrate to supplement the zinc element. After the addition is completed, stir evenly to obtain liquid fertilizer.

[0005] As a further solution of the present invention: in the step one, the pore sizes of the multi-layer filter mesh are 100μm-150μm, 60μm-80μm and 10μm-50μm from top to bottom, respectively, and 1.0mol / L dilute hydrochloric acid solution and 1.0mol / L sodium hydroxide solution are used to adjust the pH value of the waste liquid to 6.5-7.5.

[0006] As a further scheme of the present invention: in the step 2, 80mL-100mL of tetrabutyl titanate is dissolved in 400mL-550mL of anhydrous ethanol, and stirred at a stirring speed of 400r / min-600r / min for 20min-40min to form a solution A, 4mL-6mL of aminopropyltriethoxysilane is dissolved in 80mL-100mL of anhydrous ethanol, 8mL-10mL of deionized water is added and the pH value is adjusted to 3.0-4.0 with hydrochloric acid to form a solution B, and the solution B is added dropwise to the solution A at a dropping speed of 1mL / min-2mL / min, and after a transparent sol is formed, it is dried at 50℃-80℃ for 4h-10h to form a gel, and the gel is calcined at 400℃-550℃ for 1.5h-3.5h to obtain a nanomaterial.

[0007] As a further solution of the present invention: in the step 2, 6g-8g of nanomaterials are added per liter of waste liquid, and the mixture is dispersed by stirring at 200r / min-400r / min for 10min-20min. The wavelength of the light source of the photocatalytic reaction device is 220nm-380nm, the light intensity is 60mW / cm²-80mW / cm², the reaction temperature is 20℃-40℃, and the reaction time is 3h-5h.

[0008] As a further scheme of the present invention: in the step three, 12g-18g of polylactic acid-glycolic acid copolymer is weighed and dissolved in 120mL-150mL of dichloromethane, 6g-8g of methacryloyloxyethyltrimethylammonium chloride and 0.6g-0.8g of azobisisobutyronitrile are added, and the mixture is stirred at 60°C-70°C and a stirring speed of 300r / min-500r / min for 4h-6h to prepare a bioelectrically sensitive nutrient carrier material.

[0009] As a further solution of the present invention: in the step three, the prepared bioelectrically sensitive nutrient carrier material is weighed and added to the collected mixed solution at a ratio of 120g-180g per kilogram of liquid fertilizer, and then stirred with a magnetic stirrer at a speed of 150r / min-250r / min for 8min-12min to form a bioelectrically sensitive liquid fertilizer.

[0010] As a further solution of the present invention: in step 4, the microbial flora includes Bacillus, yeast and lactic acid bacteria, and is inoculated at 1.0×10 6 CFU-1.0×10 7 The inoculation amount of CFU is used for inoculation, the temperature of the fermentation tank for fermentation treatment is 28℃-32℃, the humidity is 65%-75%, the ventilation volume is 0.5vvm-1.0vvm, the fermentation time is 3-5 days, and sampling is carried out every 6 hours during the fermentation process. The fermentation time is 3-5 days.

[0011] As a further solution of the present invention: in the step five, preliminary filtration is performed using a deep filter with a pore size of 10 μm-20 μm, the centrifugal speed is 3500 r / min-4500 r / min, and the centrifugal time is 15 min-20 min.

[0012] As a further scheme of the present invention: in the step 5, urea is added in an amount of 3g-5g per kilogram of quasi-liquid fertilizer, potassium dihydrogen phosphate is added in an amount of 6g-8g per kilogram of quasi-liquid fertilizer, potassium sulfate is added in an amount of 4g-6g per kilogram of quasi-liquid fertilizer, ferrous sulfate is added in an amount of 0.5mg-1.0mg per kilogram of quasi-liquid fertilizer, manganese sulfate is added in an amount of 0.3mg-0.6mg per kilogram of quasi-liquid fertilizer, and zinc sulfate heptahydrate is added in an amount of 0.3mg-0.5mg per kilogram of quasi-liquid fertilizer, and the mixture is stirred at a stirring speed of 100r / min-120r / min for 30min-45min.

[0013] By adopting the above technical solution, compared with the prior art, the beneficial effects of the present invention are: 1. The present invention introduces a nano-scale photocatalytic material-assisted conversion process, and a titanium dioxide nanomaterial prepared with tetrabutyl titanate as a precursor constitutes a photocatalytic core. The characteristic of the titanium dioxide nanomaterial producing strong oxidizing substances under light can act on complex organic macromolecules in the waste liquid. Aminopropyl triethoxysilane is coated on the surface of titanium dioxide nanoparticles, and aminopropyl triethoxysilane enhances the dispersion stability of titanium dioxide in the waste liquid environment, avoids the reduction of the effective surface area that can participate in the reaction due to agglomeration, and ensures that the photocatalytic reaction is fully and efficiently promoted. The amino functional group carried by aminopropyl triethoxysilane can specifically combine with a variety of organic substances in the waste liquid, guide the photocatalytic reaction to act on specific organic macromolecules, and make the decomposition process more targeted and efficient. This synergistic effect greatly improves the conversion efficiency of nutrients, and efficiently converts macromolecular proteins, polysaccharides, etc. in the waste liquid into small molecular nutrients such as amino acids and monosaccharides, significantly improves the content of effective nutrients in liquid fertilizer, and provides a better and sufficient nutrient basis for vegetable growth; 2. The present invention has achieved remarkable beneficial effects by creating a bioelectric stimulation nutrient release regulation system. Polylactic acid-glycolic acid copolymer is selected as the basic material, and quaternary ammonium salt groups are introduced by emulsion polymerization to prepare a bioelectrically sensitive nutrient carrier material. The polylactic acid-glycolic acid copolymer has good biocompatibility and degradability, can effectively encapsulate nutrients and can be naturally decomposed in the soil without causing residual pollution to the environment. The introduction of quaternary ammonium salt groups makes the material electrically sensitive and can respond to bioelectric stimulation. The bioelectric stimulation device composed of carbon nanotube fiber electrodes, power supplies, controllers and sensors is combined. The sensor monitors the electrical signals of vegetable roots and soil microorganisms and transmits them to the controller. The controller regulates the power output according to a preset algorithm. In the seedling stage of vegetables, the root electrical activity is weak, and low-voltage current stimulation causes the modified PLGA material structure to change slowly, and nutrients are slowly released. In the vigorous growth period, the root electrical activity is strong, and high-voltage current promotes accelerated changes in the material structure and accelerated nutrient release. The needs of vegetables at each stage are accurately matched, the fertilizer utilization rate is improved, the healthy growth of vegetables is promoted, the quality and yield of vegetables are improved, and an intelligent solution is provided for vegetable planting and fertilization. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 Schematic diagram of the process steps in an embodiment of the present invention. DETAILED DESCRIPTION

[0015] The specific embodiments of the present invention will be further described below in conjunction with the accompanying drawings. It should be noted that the description of these embodiments is used to help understand the present invention, but does not constitute a limitation of the present invention.

[0016] In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0017] Please see attached Figure 1 The present invention discloses an innovative process for preparing liquid fertilizer from tyvalocin waste liquid for vegetable planting, and the innovative process comprises the following specific steps: Step 1: Preliminary pretreatment of the tyvalosin waste liquid: collecting the tyvalosin waste liquid, transferring it to a multi-layer filter screen for preliminary filtration to remove unreacted raw material residues and solid impurities, and then adjusting the pH value of the waste liquid; Step 2: prepare a titanium dioxide nanomaterial coated with aminopropyltriethoxysilane on the surface, add it to the preliminarily pretreated waste liquid and stir to disperse it, then place the mixed solution in a photocatalytic reaction device for reaction, use the photocatalytic material to oxidize and reduce the complex organic macromolecules adsorbed in the waste liquid into small molecular nutrients, and collect the mixed solution; Step 3: preparing a bioelectrically sensitive nutrient carrier material, adding the carrier material to the collected mixed solution, stirring and dispersing the mixture, and forming a bioelectrically sensitive liquid fertilizer; Step 4: inoculating a microbial flora into the bioelectrically sensitive liquid fertilizer, then transferring the liquid fertilizer to a fermentation tank for microbial fermentation, sampling and testing during the fermentation process, and obtaining a fermentation liquid after the fermentation is completed; Step 5: Preliminarily filter and centrifuge the fermented liquid fertilizer in turn to obtain clear and transparent quasi-liquid fertilizer, then add urea to the quasi-liquid fertilizer to supplement the nitrogen source, add potassium dihydrogen phosphate to supplement the phosphorus element, add potassium sulfate to supplement the potassium element, add ferrous sulfate to supplement the iron element, add manganese sulfate to supplement the manganese element, and add zinc sulfate heptahydrate to supplement the zinc element. After the addition is completed, stir evenly to obtain liquid fertilizer.

[0018] In one embodiment of the present invention: in step one, the pore sizes of the multi-layer filter mesh are 100 μm-150 μm, 60 μm-80 μm and 10 μm-50 μm from top to bottom, respectively, and 1.0 mol / L dilute hydrochloric acid solution and 1.0 mol / L sodium hydroxide solution are used to adjust the pH value of the waste liquid to 6.5-7.5.

[0019] In one embodiment of the present invention: in step 2, 80mL-100mL of tetrabutyl titanate is dissolved in 400mL-550mL of anhydrous ethanol, and stirred at a stirring speed of 400r / min-600r / min for 20min-40min to form solution A, 4mL-6mL of aminopropyltriethoxysilane is dissolved in 80mL-100mL of anhydrous ethanol, 8mL-10mL of deionized water is added and the pH value is adjusted to 3.0-4.0 with hydrochloric acid to form solution B, and solution B is added dropwise to solution A at a dropping speed of 1mL / min-2mL / min, and after forming a transparent sol, it is dried at 50℃-80℃ for 4h-10h to form a gel, and the gel is calcined at 400℃-550℃ for 1.5h-3.5h to obtain a nanomaterial.

[0020] In one embodiment of the present invention: in step 2, 6g-8g of nanomaterials are added per liter of waste liquid, and the mixture is dispersed by stirring at 200r / min-400r / min for 10min-20min. The wavelength of the light source of the photocatalytic reaction device is 220nm-380nm, the light intensity is 60mW / cm²-80mW / cm², the reaction temperature is 20℃-40℃, and the reaction time is 3h-5h.

[0021] In one embodiment of the present invention: in step three, 12g-18g of polylactic acid-glycolic acid copolymer is weighed and dissolved in 120mL-150mL of dichloromethane, 6g-8g of methacryloyloxyethyltrimethylammonium chloride and 0.6g-0.8g of azobisisobutyronitrile are added, and the mixture is stirred at 60°C-70°C and a stirring speed of 300r / min-500r / min for 4h-6h to prepare a bioelectrically sensitive nutrient carrier material.

[0022] In one embodiment of the present invention: in step three, the prepared bioelectrically sensitive nutrient carrier material is weighed and added to the collected mixed solution at a ratio of 120g-180g per kilogram of liquid fertilizer, and then stirred with a magnetic stirrer at a speed of 150r / min-250r / min for 8min-12min to form a bioelectrically sensitive liquid fertilizer.

[0023] In one embodiment of the present invention: in step 4, the microbial flora includes Bacillus, yeast and lactic acid bacteria, and is inoculated at 1.0×10 6 CFU-1.0×10 7 The inoculation amount of CFU is used for inoculation, the temperature of the fermentation tank for fermentation treatment is 28℃-32℃, the humidity is 65%-75%, the ventilation volume is 0.5vvm-1.0vvm, the fermentation time is 3-5 days, and sampling is carried out every 6 hours during the fermentation process. The fermentation time is 3-5 days.

[0024] In one embodiment of the present invention: in step five, preliminary filtration is performed using a deep filter with a pore size of 10 μm-20 μm, the centrifugal speed is 3500 r / min-4500 r / min, and the centrifugal time is 15 min-20 min.

[0025] In one embodiment of the present invention: in step 5, urea is added in an amount of 3g-5g per kilogram of quasi-liquid fertilizer, potassium dihydrogen phosphate is added in an amount of 6g-8g per kilogram of quasi-liquid fertilizer, potassium sulfate is added in an amount of 4g-6g per kilogram of quasi-liquid fertilizer, ferrous sulfate is added in an amount of 0.5mg-1.0mg per kilogram of quasi-liquid fertilizer, manganese sulfate is added in an amount of 0.3mg-0.6mg per kilogram of quasi-liquid fertilizer, and zinc sulfate heptahydrate is added in an amount of 0.3mg-0.5mg per kilogram of quasi-liquid fertilizer, and the mixture is stirred at a stirring speed of 100r / min-120r / min for 30min-45min.

[0026] In one embodiment of the present invention: the introduction of quaternary ammonium salt groups makes the material electrically sensitive and can respond to bioelectric stimulation. A bioelectric stimulation device consisting of a carbon nanotube fiber electrode, a power supply, a controller and a sensor is combined. The electrode of the bioelectric stimulation device is made of carbon nanotube fiber, one end of which is inserted into the soil near the vegetable root system to which bioelectric sensitive liquid fertilizer is applied, and the other end is connected to the power supply and the controller. The sensor monitors the action potential of the vegetable roots in the soil in real time within the range of 0-50mV and the soil microbial metabolic electrical signal within the range of 10μV-30μV, and transmits the signal to the controller; the controller presets an algorithm to set different voltage and current output thresholds according to different growth stages of the vegetables. When the root action potential of the vegetable seedlings is lower than 20mV and the soil microbial metabolic electrical signal is lower than 15μV, the output voltage is 2-5V and the current is 0.5-1.0A to achieve nutrient slow release. When the root action potential of the vegetable is higher than 30mV and the soil microbial metabolic electrical signal is higher than 20μV during the vigorous growth period, the output voltage is 8-12V and the current is 2.0-3.0A to accelerate nutrient release.

[0027] In one embodiment of the present invention: In step 2, a stirring blade with adjustable angle and position is provided inside the photocatalytic reaction device. The rotation speed of the stirring blade can be dynamically adjusted according to the reaction time during the photocatalytic reaction. It runs at 200r / min-300r / min for 1h-2h before the reaction, increases to 300r / min-400r / min for 1h-2h in the middle, and drops back to 200r / min-300r / min for the last 1h, so as to optimize the contact effect between the photocatalytic material and the waste liquid and improve the conversion efficiency of the nutrient components.

[0028] In one embodiment of the present invention: In step three, before adding the bioelectrically sensitive nutrient carrier material to the mixed solution, it is first placed in an ultrasonic oscillator for 10 minutes to 20 minutes, and the ultrasonic frequency is 30kHz to 50kHz, so that the internal structure of the material is further loosened, so as to facilitate the subsequent more stable and efficient encapsulation and release of nutrients in the liquid fertilizer.

[0029] In one embodiment of the present invention: In step four, a multi-layer temperature zoning control device is provided inside the fermentation tank. During the microbial fermentation process, according to the needs of the microbial flora at different growth stages, the inside of the fermentation tank is divided into 2-3 temperature zones, the upper temperature is maintained at 28°C-30°C, the middle temperature is controlled at 30°C-32°C, and the lower temperature is at 26°C-28°C, so that the microorganisms in different areas can be in a relatively suitable growth environment, thereby promoting the efficient progress of the fermentation process.

[0030] Example 1, please refer to the attached Figure 1First, the waste liquid of tyvalocin was collected and transferred to a multi-layer filter for preliminary filtration. The pore sizes of the filter were 150 μm, 80 μm and 50 μm from top to bottom, respectively. The unreacted raw material residues and mixed solid impurities were removed to make the waste liquid initially clear. 1.0 mol / L dilute hydrochloric acid solution or 1.0 mol / L sodium hydroxide solution was added to adjust the pH value of the waste liquid to 7.5. Then, 100 mL of tetrabutyl titanate was measured as a precursor of titanium dioxide, dissolved in 550 mL of anhydrous ethanol, and stirred on a magnetic stirrer at a speed of 600 r / min for 40 min to form a uniform solution A. Another 6 mL of aminopropyltriethoxysilane was dissolved in 100 mL of anhydrous ethanol, 10 mL of deionized water was added, and the pH value was adjusted to 4.0 with hydrochloric acid to form solution B. Solution B was slowly added to solution A at a dropping rate of 2 mL / min to form a transparent sol, which was then dried at 80 ° C for 10 h to form a gel, and placed in a muffle furnace and calcined at 550 ° C for 3.5 h to obtain a titanium dioxide nanomaterial coated with aminopropyltriethoxysilane on the surface. The waste liquid after preliminary pretreatment was transferred to a container, and the nanomaterial was weighed and added to the container at a ratio of 8 g per liter of waste liquid. The solution was stirred with a magnetic stirrer. The agitator was stirred at a speed of 400r / min for 20min to make it evenly dispersed, and then the reaction container containing the mixed solution was placed in a photocatalytic reaction device equipped with a high-intensity ultraviolet light source (wavelength 380nm), and the light intensity was set to 80mW / cm² and the reaction temperature was 40℃. The photocatalytic reaction was started for 5h, and the holes and electron pairs generated on the surface of the photocatalytic material were used to oxidize and reduce the complex organic macromolecules adsorbed in the waste liquid into small molecular nutrients and collect the mixed solution. Then 18g of polylactic acid-glycolic acid copolymer was weighed and dissolved in 150mL of dichloromethane to form a uniform solution, and 8g of Methacryloyloxyethyl trimethylammonium chloride with a quaternary ammonium salt group and 0.8 g of azobisisobutyronitrile were used as initiators, and stirred on a magnetic stirrer at a temperature of 70°C and a speed of 500 r / min for 6 hours to obtain a bioelectrically sensitive nutrient carrier material, and the material was weighed and added to the collected mixed solution at a ratio of 180 g per kilogram of liquid fertilizer, and stirred with a magnetic stirrer at a speed of 250 r / min for 12 minutes to form a bioelectrically sensitive liquid fertilizer, and a microbial flora including Bacillus, yeast and lactic acid bacteria was inoculated into the bioelectrically sensitive liquid fertilizer at a rate of 1.0×10 7The inoculation amount of CFU was inoculated, and the liquid fertilizer was transferred to the fermentation tank after inoculation. The temperature of the fermentation tank was set to 32°C, the humidity was set to 75%, and the ventilation volume was set to 1.0vvm. During the fermentation process, the fermentation liquid was sampled and tested every 6 hours. The fermentation time was 5 days. Finally, the fermented liquid fertilizer was transferred to the filtration equipment. First, a deep filter with a pore size of 20μm was used for preliminary filtration to remove microbial cells and incompletely decomposed residues. Then, the filtered liquid was centrifuged, and the centrifugal speed was set to 4500r / min and the centrifugal time was 20min. A clear and transparent quasi-liquid fertilizer was obtained, and then urea (5 g per kilogram of quasi-liquid fertilizer) was added to the quasi-liquid fertilizer to supplement the nitrogen source, potassium dihydrogen phosphate (8 g per kilogram of quasi-liquid fertilizer) was added to supplement the phosphorus element, potassium sulfate (6 g per kilogram of quasi-liquid fertilizer) was added to supplement the potassium element, ferrous sulfate (1.0 mg per kilogram of quasi-liquid fertilizer) was added to supplement the iron element, manganese sulfate (0.6 mg per kilogram of quasi-liquid fertilizer) was added to supplement the manganese element, and zinc sulfate heptahydrate (0.5 mg per kilogram of quasi-liquid fertilizer) was added to the quasi-liquid fertilizer, and the mixture was stirred at a stirring speed of 120 r / min for 45 min to obtain liquid fertilizer.

[0031] Example 2, please refer to the attached Figure 1First, the waste liquid of tyvalocin was collected and transferred to a multi-layer filter for preliminary filtration. The pore sizes of the filter were 100 μm, 60 μm and 10 μm from top to bottom, respectively. The unreacted raw material residues and mixed solid impurities were removed to make the waste liquid initially clear. A 1.0 mol / L dilute hydrochloric acid solution or a 1.0 mol / L sodium hydroxide solution was added to adjust the pH value of the waste liquid to 6.5. Then, 80 mL of tetrabutyl titanate was measured as a precursor of titanium dioxide, dissolved in 400 mL of anhydrous ethanol, and stirred on a magnetic stirrer at a speed of 400 r / min for 20 min to form a uniform solution A. , take another 4 mL of aminopropyltriethoxysilane and dissolve it in 80 mL of anhydrous ethanol, add 8 mL of deionized water, adjust the pH value to 3.0 with hydrochloric acid to form solution B, slowly add solution B to solution A at a drop rate of 1 mL / min to form a transparent sol, then dry it at 50°C for 4 h to form a gel, put it into a muffle furnace and calcine it at 400°C for 1.5 h to obtain a titanium dioxide nanomaterial coated with aminopropyltriethoxysilane on the surface, transfer the preliminarily pretreated waste liquid to a container, weigh the nanomaterial at a ratio of 6 g per liter of waste liquid and add it to the container, stir it with a magnetic stirrer. The mixture was stirred at a speed of 200r / min for 10min to make it evenly dispersed, and then the reaction container containing the mixed solution was placed in a photocatalytic reaction device equipped with a high-intensity ultraviolet light source (wavelength 220nm), and the light intensity was set to 60mW / cm² and the reaction temperature was 20℃. The photocatalytic reaction was started for 3h, and the holes and electron pairs generated on the surface of the photocatalytic material were used to oxidize and reduce the complex organic macromolecules adsorbed in the waste liquid into small molecular nutrients and collect the mixed solution. Then 12g of polylactic acid-glycolic acid copolymer was weighed and dissolved in 120mL of dichloromethane to form a uniform solution, and 6g of Methacryloyloxyethyl trimethylammonium chloride with a quaternary ammonium salt group and 0.6 g of azobisisobutyronitrile were used as initiators, and stirred on a magnetic stirrer at a temperature of 60°C and a speed of 300 r / min for 4 h to obtain a bioelectrically sensitive nutrient carrier material, and the material was weighed and added to the collected mixed solution at a ratio of 120 g per kilogram of liquid fertilizer, and stirred with a magnetic stirrer at a speed of 150 r / min for 8 min to form a bioelectrically sensitive liquid fertilizer, and a microbial flora including Bacillus, yeast and lactic acid bacteria was inoculated into the bioelectrically sensitive liquid fertilizer at a rate of 1.0×10 6The inoculation amount of CFU was inoculated, and the liquid fertilizer was transferred to the fermentation tank after inoculation. The temperature of the fermentation tank was set to 28°C, the humidity was set to 65%, and the ventilation volume was set to 0.5vvm. During the fermentation process, the fermentation liquid was sampled and tested every 6 hours. The fermentation time was 3 days. Finally, the fermented liquid fertilizer was transferred to the filtration equipment. First, a deep filter with a pore size of 10μm was used for preliminary filtration to remove microbial cells and incompletely decomposed residues. Then, the filtered liquid was centrifuged, and the centrifugal speed was set to 3500r / min and the centrifugal time was 15min. A clear and transparent quasi-liquid fertilizer was obtained, and then urea (3 g per kilogram of quasi-liquid fertilizer) was added to the quasi-liquid fertilizer to supplement the nitrogen source, potassium dihydrogen phosphate (6 g per kilogram of quasi-liquid fertilizer) was added to supplement the phosphorus element, potassium sulfate (4 g per kilogram of quasi-liquid fertilizer) was added to supplement the potassium element, ferrous sulfate (0.5 mg per kilogram of quasi-liquid fertilizer) was added to supplement the iron element, manganese sulfate (0.3 mg per kilogram of quasi-liquid fertilizer) was added to supplement the manganese element, and zinc sulfate heptahydrate (0.3 mg per kilogram of quasi-liquid fertilizer) was added to the quasi-liquid fertilizer, and the mixture was stirred at a stirring speed of 100 r / min for 30 minutes to obtain liquid fertilizer.

[0032] According to the above two groups of embodiments, it can be concluded that by subjecting the tyvalosin waste liquid to a multi-step fine treatment, firstly, the waste liquid is pre-treated to effectively remove impurities and adjust the pH, the nano-scale photocatalytic material-assisted conversion process significantly improves the nutrient conversion efficiency, the preparation and application of bio-electrically sensitive nutrient carrier materials realize the intelligent regulation of nutrient release, the microbial enhanced treatment optimizes the nutrient structure, and then after strict post-treatment and precise nutrient addition, each step is closely coordinated and synergistic, so that the tyvalosin waste liquid can be efficiently converted into high-quality liquid fertilizer. The method has significant technical innovation and good application prospects, and can provide high-quality fertilizer guarantee for vegetable planting.

[0033] Although the present invention is disclosed as above in terms of preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art may make possible changes and modifications without departing from the spirit and scope of the present invention. Therefore, any modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention shall fall within the scope of protection defined by the claims of the present invention.

Claims

1. An innovative process for preparing liquid fertilizer from tyvalocin waste liquid for vegetable planting, characterized in that: The innovative process comprises the following specific steps: Step 1: Preliminary pretreatment of the tyvalosin waste liquid: collecting the tyvalosin waste liquid, transferring it to a multi-layer filter screen for preliminary filtration to remove unreacted raw material residues and solid impurities, and then adjusting the pH value of the waste liquid; Step 2: prepare a titanium dioxide nanomaterial coated with aminopropyltriethoxysilane on the surface, add it to the preliminarily pretreated waste liquid and stir to disperse it, then place the mixed solution in a photocatalytic reaction device for reaction, use the photocatalytic material to oxidize and reduce the complex organic macromolecules adsorbed in the waste liquid into small molecular nutrients, and collect the mixed solution; Step 3: preparing a bioelectrically sensitive nutrient carrier material, adding the carrier material to the collected mixed solution, stirring and dispersing the mixture, and forming a bioelectrically sensitive liquid fertilizer; Step 4: inoculating a microbial flora into the bioelectrically sensitive liquid fertilizer, then transferring the liquid fertilizer to a fermentation tank for microbial fermentation, sampling and testing during the fermentation process, and obtaining a fermentation liquid after the fermentation is completed; Step 5: Preliminarily filter and centrifuge the fermented liquid fertilizer in turn to obtain clear and transparent quasi-liquid fertilizer, then add urea to the quasi-liquid fertilizer to supplement the nitrogen source, add potassium dihydrogen phosphate to supplement the phosphorus element, add potassium sulfate to supplement the potassium element, add ferrous sulfate to supplement the iron element, add manganese sulfate to supplement the manganese element, and add zinc sulfate heptahydrate to supplement the zinc element. After the addition is completed, stir evenly to obtain liquid fertilizer.

2. The innovative process for preparing liquid fertilizer from tyvalocin waste liquid for vegetable planting according to claim 1, characterized in that: In the step 1, the pore sizes of the multi-layer filter are 100 μm-150 μm, 60 μm-80 μm and 10 μm-50 μm from top to bottom, respectively, and a 1.0 mol / L dilute hydrochloric acid solution and a 1.0 mol / L sodium hydroxide solution are used to adjust the pH value of the waste liquid to 6.5-7.

5.

3. The innovative process for preparing liquid fertilizer from tyvalocin waste liquid for vegetable planting according to claim 1, characterized in that: In the step 2, 80 mL-100 mL of tetrabutyl titanate is dissolved in 400 mL-550 mL of anhydrous ethanol, and stirred at a stirring speed of 400 r / min-600 r / min for 20 min-40 min to form a solution A, 4 mL-6 mL of aminopropyl triethoxysilane is dissolved in 80 mL-100 mL of anhydrous ethanol, 8 mL-10 mL of deionized water is added, and the pH value is adjusted to 3.0-4.0 with hydrochloric acid to form a solution B, and the solution B is added dropwise to the solution A at a dropping speed of 1 mL / min-2 mL / min, and after forming a transparent sol, it is dried at 50° C.-80° C. for 4 h-10 h to form a gel, and the gel is calcined at 400° C.-550° C. for 1.5 h-3.5 h to obtain the nanomaterial.

4. The innovative process for preparing liquid fertilizer from tyvalosin waste liquid for vegetable planting according to claim 1, characterized in that: In the step 2, 6g-8g of nanomaterial is added per liter of waste liquid, and the mixture is dispersed by stirring at 200r / min-400r / min for 10min-20min. The wavelength of the light source of the photocatalytic reaction device is 220nm-380nm, the light intensity is 60mW / cm²-80mW / cm², the reaction temperature is 20℃-40℃, and the reaction time is 3h-5h.

5. The innovative process for preparing liquid fertilizer from tyvalocin waste liquid for vegetable planting according to claim 1, characterized in that: In the step three, 12 g to 18 g of polylactic acid-glycolic acid copolymer is weighed and dissolved in 120 mL to 150 mL of dichloromethane, 6 g to 8 g of methacryloyloxyethyl trimethylammonium chloride and 0.6 g to 0.8 g of azobisisobutyronitrile are added, and the mixture is stirred at 60° C. to 70° C. and a stirring speed of 300 r / min to 500 r / min for 4 h to 6 h to prepare a bioelectrically sensitive nutrient carrier material.

6. The innovative process for preparing liquid fertilizer from tyvalocin waste liquid for vegetable planting according to claim 1, characterized in that: In the step three, the prepared bioelectrically sensitive nutrient carrier material is weighed and added to the collected mixed solution at a ratio of 120 g to 180 g per kilogram of liquid fertilizer, and then stirred for 8 min to 12 min at a speed of 150 r / min to 250 r / min using a magnetic stirrer to form a bioelectrically sensitive liquid fertilizer.

7. The innovative process for preparing liquid fertilizer from tyvalocin waste liquid for vegetable planting according to claim 1, characterized in that: In step 4, the microbial flora includes Bacillus, yeast and lactic acid bacteria, and is inoculated at 1.0×10 6 CFU-1.0×10 7 The inoculation amount of CFU is used for inoculation, the temperature of the fermentation tank for fermentation treatment is 28℃-32℃, the humidity is 65%-75%, the ventilation volume is 0.5vvm-1.0vvm, the fermentation time is 3-5 days, and sampling is carried out every 6 hours during the fermentation process. The fermentation time is 3-5 days.

8. The innovative process for preparing liquid fertilizer from tyvalocin waste liquid for vegetable planting according to claim 1, characterized in that: In the step 5, a deep filter with a pore size of 10 μm-20 μm is used for preliminary filtration, the centrifugal speed is 3500 r / min-4500 r / min, and the centrifugal time is 15 min-20 min.

9. The innovative process for preparing liquid fertilizer from tyvalocin waste liquid for vegetable planting according to claim 1, characterized in that: In the step 5, urea is added in an amount of 3g-5g per kilogram of quasi-liquid fertilizer, potassium dihydrogen phosphate is added in an amount of 6g-8g per kilogram of quasi-liquid fertilizer, potassium sulfate is added in an amount of 4g-6g per kilogram of quasi-liquid fertilizer, ferrous sulfate is added in an amount of 0.5mg-1.0mg per kilogram of quasi-liquid fertilizer, manganese sulfate is added in an amount of 0.3mg-0.6mg per kilogram of quasi-liquid fertilizer, and zinc sulfate heptahydrate is added in an amount of 0.3mg-0.5mg per kilogram of quasi-liquid fertilizer, and the mixture is stirred at a stirring speed of 100r / min-120r / min for 30min-45min.

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