Preparation process of ivermectin waste liquid liquid fertilizer

Abstract

The invention discloses a preparation process of an ivermectin waste liquid liquid fertilizer, and relates to the technical field of liquid fertilizers. When the ivermectin waste liquid liquid fertilizer is prepared, nitric acid, urea and tetrabutyl titanate react to prepare nano titanium dioxide; performing ultrasonic treatment on nano titanium dioxide and lanthanum nitrate to obtain a waste liquid treatment agent; the preparation method comprises the following steps: reacting cellulose with pentenedioic acid and N, N-methylene bisacrylamide to prepare modified cellulose; treating the ivermectin waste liquid by using a flocculating agent to obtain pretreated ivermectin waste liquid, treating the pretreated ivermectin waste liquid by using a waste liquid treating agent, and adding the modified cellulose to obtain the ivermectin waste liquid liquid fertilizer. The ivermectin waste liquid liquid fertilizer disclosed by the invention has good water retention and slow release effects and has a good degradation rate.

Description

Technical Field

[0001] The invention relates to the technical field of organic fertilizers, in particular to a preparation process of ivermectin waste liquid liquid fertilizer. Background Art

[0002] my country is a major producer and user of antibiotics, and its export volume of antibiotics accounts for a significant share in the international market. Antibiotic waste liquid discharge is one of the main sources of antibiotics in the environment. The water quality of antibiotic waste liquid is complex, and the residual antibiotics exposed to the environment can cause potential harm to the ecosystem and human health through the food chain. Ivermectin is a new type of broad-spectrum, highly effective, low-toxic antibiotic antiparasitic drug, which has a good expelling and killing effect on internal and external parasites, especially nematodes and arthropods. Ivermectin is widely used for gastrointestinal nematodes, lung nematodes and parasitic arthropods in cattle, sheep, horses and pigs, intestinal nematodes, ear mites, scabies, heartworms and microfilariae in dogs, and gastrointestinal nematodes and external parasites in poultry. Ivermectin is a macrolide antibiotic. Due to its extremely wide range of use, the residual level of macrolide antibiotics in traditional activated sludge systems is high, difficult to biodegrade, and difficult to treat. How to achieve harmless and resource-based treatment of macrolide antibiotic pharmaceutical waste liquid has become an urgent problem to be solved.

[0003] The antibiotic residue in ivermectin waste liquid is high, and direct application may cause pollution to soil and plants, affect the quality and safety of agricultural products, and may also cause microbial resistance problems, further exacerbating the spread and diffusion of antibiotic resistance; in addition, ivermectin waste liquid contains high concentrations of organic matter and nutrients such as nitrogen and phosphorus, which will cause serious pollution to water bodies if directly discharged into the environment, so effective measures must be taken to remove the antibiotic residue therein, and slow-release treatment of high concentrations of organic matter and substances such as nitrogen and phosphorus is performed to ensure the safety and effectiveness of liquid fertilizer. The ivermectin waste liquid liquid fertilizer prepared by the present invention not only effectively removes ivermectin in the waste liquid, but also retains the abundant phosphorus and nitrogen elements therein, and has good slow-release performance and water retention performance, and has broad market prospects. Summary of the invention

[0004] The purpose of the present invention is to provide a preparation process of ivermectin waste liquid liquid fertilizer to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: The invention discloses a method for preparing ivermectin waste liquid liquid fertilizer. The ivermectin waste liquid liquid fertilizer comprises the following steps: preparing nano titanium dioxide by reacting nitric acid, urea and tetrabutyl titanate; preparing a waste liquid treatment agent by ultrasonic treatment of the nano titanium dioxide and lanthanum nitrate; preparing modified cellulose by reacting cellulose, glutaconic acid and N,N-methylenebisacrylamide; preparing pretreated ivermectin waste liquid by treating the ivermectin waste liquid with a flocculant, and adding the modified cellulose after treating the pretreated ivermectin waste liquid with the waste liquid treatment agent.

[0006] A process for preparing ivermectin waste liquid liquid fertilizer comprises the following preparation steps: (1) Mix nitric acid, urea, tetrabutyl titanate, deionized water and anhydrous ethanol, stir at room temperature at 60-80 r / min for 2-3 h, age for 45-50 h, and dry at 65-75°C for 4-6 h to obtain nano titanium dioxide; mix nano titanium dioxide, lanthanum nitrate and deionized water, ultrasonically treat for 1-2 h, filter, wash the filter residue with deionized water for 3-5 times, heat in a muffle furnace at 650-750°C for 6-8 h, cool to room temperature, and grind into 350-450 mesh powder to obtain a waste liquid treatment agent; (2) Mix cellulose and potassium hydroxide solution of glutaconic acid, stir at 200-300 r / min for 25-35 min at room temperature, add potassium persulfate and N,N-methylenebisacrylamide, heat to 55-65°C under nitrogen atmosphere, stir at 400-600 r / min for 2-4 h, cool to room temperature, wash with deionized water for 3-5 times, freeze-dry for 4-8 hours, grind into powder of 180-220 mesh, and prepare modified cellulose; (3) The ivermectin waste liquid is treated with a flocculant to obtain a pretreated ivermectin waste liquid. The pretreated ivermectin waste liquid is treated with a waste liquid treating agent, and then 0.3 to 0.5 times the mass of the pretreated ivermectin waste liquid is added with modified cellulose, and the pretreated ivermectin waste liquid is allowed to stand for 10 to 14 hours to obtain an ivermectin waste liquid liquid fertilizer.

[0007] As an optimization, the mass ratio of nitric acid, urea, tetrabutyl titanate, deionized water and anhydrous ethanol in step (1) is 1: (4.5-5.5): (6-6.5): (35-40): (15-20).

[0008] As an optimization, the mass ratio of nano-titanium dioxide, lanthanum nitrate and deionized water in step (1) is 1: (0.1-0.2): (10-20).

[0009] As an optimization, the potassium hydroxide solution of glutaconic acid in step (2) is prepared by mixing glutaconic acid and 0.02 g / ml potassium hydroxide solution in a mass ratio of 1:18.

[0010] As an optimization, the preparation method of cellulose in step (2) is as follows: drying corn stalks at 65-75° C. for 10-14 h, crushing and passing through an 80-mesh sieve to obtain stalk powder, mixing the stalk powder and a 10% nitric acid solution at a mass ratio of 1:30, stirring at 400-600 r / min at 90-110° C. for 3-5 h, filtering, washing the filter residue with deionized water for 3-5 times, and drying at 65-75° C. for 4-8 h to obtain cellulose.

[0011] As an optimization, the mass ratio of the cellulose to the potassium hydroxide solution of glutaconic acid in step (2) is 1:(15-20).

[0012] As an optimization, the mass of potassium persulfate in step (2) is 0.004 to 0.006 times the mass of cellulose, and the mass of N,N-methylenebisacrylamide is 0.02 to 0.04 times the mass of cellulose.

[0013] As an optimization, the flocculant in step (3) is 400 mg / L polyaluminium chloride and the flocculant aid is 15 mg / L polyacrylamide.

[0014] As an optimization, the method for treating ivermectin waste liquid with the flocculant in step (3) is as follows: the flocculant, ivermectin waste liquid and flocculant aid are mixed in a mass ratio of 1:0.8:0.3, stirred at room temperature at 60-80 r / min for 5-15 min, filtered with a filter with a pore diameter of 75 μm, and the filtrate is retained as the pretreated ivermectin waste liquid.

[0015] As an optimization, the method for treating the pretreated ivermectin waste liquid with the waste liquid treatment agent in step (3) is as follows: the waste liquid treatment agent and the pretreated ivermectin waste liquid are mixed in a transparent container at a mass ratio of 1: (25-35), ozone is introduced at a rate of 3.0 g / h, stirred at 400-600 r / min for 5 min at room temperature, irradiated with an ultraviolet lamp, continued to stir for 5-7 h, filtered, and the filtrate is retained.

[0016] Compared with the prior art, the beneficial effects achieved by the present invention are: When preparing ivermectin waste liquid liquid fertilizer, the present invention comprises the following steps: reacting nitric acid, urea and tetrabutyl titanate to obtain nano titanium dioxide; ultrasonically treating the nano titanium dioxide and lanthanum nitrate to obtain a waste liquid treating agent; reacting cellulose, glutaconic acid and N,N-methylenebisacrylamide to obtain modified cellulose; treating the ivermectin waste liquid with a flocculant to obtain a pretreated ivermectin waste liquid; treating the pretreated ivermectin waste liquid with a waste liquid treating agent, and then adding the modified cellulose to obtain the ivermectin waste liquid liquid fertilizer.

[0017] Firstly, nitric acid, urea and tetrabutyl titanate are reacted to prepare nano titanium dioxide, which is photoexcited to generate electron-hole pairs under the irradiation of ultraviolet rays. The electron-hole pairs react with water and oxygen to generate active oxygen species, which can effectively oxidize and degrade ivermectin. A large amount of ivermectin is contained in ivermectin waste liquid. When titanium dioxide is irradiated with ultraviolet rays, active oxygen species generated under the photocatalytic action have the effect of removing ivermectin from ivermectin waste liquid. Nano titanium dioxide and lanthanum nitrate are ultrasonically treated to prepare waste liquid treatment agent. Lanthanum ions can broaden the light response range of titanium dioxide and increase the light absorption capacity of titanium dioxide. Lanthanum ions can form Ti-O-La bonds with titanium dioxide, which can effectively inhibit the recombination of electron-hole pairs and prolong the life of photogenerated carriers, thereby further improving the degradation effect of the waste liquid treatment agent on ivermectin in ivermectin waste liquid and effectively improving the ivermectin removal rate.

[0018] Secondly, cellulose is reacted with glutaric acid and N,N-methylenebisacrylamide to obtain modified cellulose. On the one hand, cellulose cross-linking can form a three-dimensional network structure, and its porous structure can effectively extend the diffusion path of water molecules, thereby limiting the diffusion rate of water molecules and delaying the release of water. The network structure can more effectively wrap more water molecules and has a better water absorption effect. It can be combined with its good advantage of delaying water release efficiency to effectively improve the water retention effect of the fertilizer; on the other hand, the imine structure introduced by N,N-methylenebisacrylamide can effectively complex the metal elements and nitrogen elements in the waste liquid. After complexation, the three-dimensional network structure of cellulose can effectively wrap and slowly release them, thereby achieving a slow-release effect; the abundant microorganisms in the soil can secrete a large amount of cellulase, thereby effectively destroying the molecular structure of cellulose and decomposing cellulose into small molecular organic matter, so that the ivermectin waste liquid liquid fertilizer has good biodegradability. 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 ivermectin waste liquid liquid fertilizer comprises the following preparation steps: (1) Nitric acid, urea, tetrabutyl titanate, deionized water, and anhydrous ethanol were mixed in a mass ratio of 1:5:6.25:37.5:17.5, stirred at 70 r / min for 2.5 h at room temperature, aged for 47.5 h, and dried at 70°C for 5 h to obtain nano titanium dioxide; nano titanium dioxide, lanthanum nitrate, and deionized water were mixed in a mass ratio of 1:0.15:15, ultrasonically treated for 1.5 h, filtered, and the residue was washed with deionized water for 4 times, heated at 700°C in a muffle furnace for 7 h, cooled to room temperature, and ground into a 400-mesh powder to obtain a waste liquid treatment agent; (2) Dry corn stalks at 70°C for 12 h, crush and pass through an 80-mesh sieve to obtain stalk powder, mix the stalk powder and 10% nitric acid solution at a mass ratio of 1:30, stir at 100°C for 4 h at 500 r / min, filter, wash the residue with deionized water 4 times, and dry at 70°C for 6 h to obtain cellulose; mix glutaric acid and 0.02 g / ml potassium hydroxide solution at a mass ratio of 1:18 to obtain a potassium hydroxide solution of glutaric acid; , potassium hydroxide solution of glutaric acid and glutaric acid were mixed in a mass ratio of 1:17.5, stirred at 250r / min for 30min at room temperature, added with potassium persulfate (0.005 times the mass of cellulose) and N,N-methylenebisacrylamide (0.03 times the mass of cellulose), heated to 60°C in a nitrogen atmosphere, stirred at 500r / min for 3h, cooled to room temperature, washed with deionized water for 4 times, freeze-dried for 6h, ground into 200-mesh powder, and obtained modified cellulose; (3) The flocculant, ivermectin waste liquid and flocculant aid were mixed in a mass ratio of 1:0.8:0.3, stirred at 70 r / min for 10 min at room temperature, filtered with a filter with a pore diameter of 75 μm, and the filtrate was retained as the pretreated ivermectin waste liquid; the waste liquid treatment agent and the pretreated ivermectin waste liquid were mixed in a mass ratio of 1:30 in a transparent container, ozone was introduced at a rate of 3.0 g / h, stirred at 500 r / min for 5 min at room temperature, irradiated with ultraviolet light, continued to stir for 6 h, filtered, retained the filtrate, added 0.4 times the mass of modified cellulose to the filtrate, and allowed to stand for 12 h to obtain ivermectin waste liquid liquid fertilizer.

[0021] Embodiment 2: A process for preparing ivermectin waste liquid liquid fertilizer comprises the following preparation steps: (1) Nitric acid, urea, tetrabutyl titanate, deionized water, and anhydrous ethanol were mixed in a mass ratio of 1:4.5:6:35:15, stirred at 70 r / min for 2.5 h at room temperature, aged for 47.5 h, and dried at 70°C for 5 h to obtain nano titanium dioxide; nano titanium dioxide, lanthanum nitrate, and deionized water were mixed in a mass ratio of 1:0.1:10, ultrasonically treated for 1.5 h, filtered, and the residue was washed with deionized water for 4 times, heated at 700°C in a muffle furnace for 7 h, cooled to room temperature, and ground into a 400-mesh powder to obtain a waste liquid treatment agent; (2) Dry corn stalks at 70°C for 12 h, crush and pass through an 80-mesh sieve to obtain stalk powder, mix the stalk powder and 10% nitric acid solution at a mass ratio of 1:30, stir at 100°C and 500 r / min for 4 h, filter, wash the filter residue with deionized water 4 times, and dry at 70°C for 6 h to obtain cellulose; mix glutaric acid and 0.02 g / ml potassium hydroxide solution at a mass ratio of 1:18 to obtain a potassium hydroxide solution of glutaric acid; The cellulose was mixed with potassium hydroxide solution of glutaric acid and cellulose in a mass ratio of 1:15, stirred at 250 r / min for 30 min at room temperature, and potassium persulfate (0.004 times the mass of cellulose) and N,N-methylenebisacrylamide (0.02 times the mass of cellulose) were added. The mixture was heated to 60°C and stirred at 500 r / min for 3 h under a nitrogen atmosphere. The mixture was cooled to room temperature, washed with deionized water for 4 times, freeze-dried for 6 hours, and ground into 200-mesh powder to obtain modified cellulose. (3) The flocculant, ivermectin waste liquid and flocculant aid were mixed in a mass ratio of 1:0.8:0.3, stirred at 70 r / min for 10 min at room temperature, filtered with a filter with a pore diameter of 75 μm, and the filtrate was retained as the pretreated ivermectin waste liquid; the waste liquid treatment agent and the pretreated ivermectin waste liquid were mixed in a mass ratio of 1:25 in a transparent container, ozone was introduced at a rate of 3.0 g / h, stirred at 500 r / min for 5 min at room temperature, irradiated with ultraviolet light, continued to stir for 6 h, filtered, retained the filtrate, added 0.3 times the mass of modified cellulose to the filtrate, and allowed to stand for 12 h to obtain ivermectin waste liquid liquid fertilizer.

[0022] Embodiment 3: A process for preparing ivermectin waste liquid liquid fertilizer comprises the following preparation steps: (1) Nitric acid, urea, tetrabutyl titanate, deionized water, and anhydrous ethanol were mixed in a mass ratio of 1:5.5:6.5:40:20, stirred at 70 r / min for 2.5 h at room temperature, aged for 47.5 h, and dried at 70°C for 5 h to obtain nano titanium dioxide; nano titanium dioxide, lanthanum nitrate, and deionized water were mixed in a mass ratio of 1:0.2:20, ultrasonically treated for 1.5 h, filtered, and the residue was washed with deionized water for 4 times, heated at 700°C in a muffle furnace for 7 h, cooled to room temperature, and ground into a 400-mesh powder to obtain a waste liquid treatment agent; (2) Dry corn stalks at 70°C for 12 h, crush and pass through an 80-mesh sieve to obtain stalk powder, mix the stalk powder and 10% nitric acid solution at a mass ratio of 1:30, stir at 100°C and 500 r / min for 4 h, filter, wash the filter residue with deionized water 4 times, and dry at 70°C for 6 h to obtain cellulose; mix glutaric acid and 0.02 g / ml potassium hydroxide solution at a mass ratio of 1:18 to obtain a potassium hydroxide solution of glutaric acid; The cellulose was mixed with potassium hydroxide solution of glutaric acid and cellulose in a mass ratio of 1:20, stirred at 250 r / min for 30 min at room temperature, and potassium persulfate (0.006 times the mass of cellulose) and N,N-methylenebisacrylamide (0.04 times the mass of cellulose) were added. The mixture was heated to 60°C and stirred at 500 r / min for 3 h under a nitrogen atmosphere. The mixture was cooled to room temperature, washed with deionized water for 4 times, freeze-dried for 6 hours, and ground into 200-mesh powder to obtain modified cellulose. (3) The flocculant, ivermectin waste liquid and flocculant aid were mixed in a mass ratio of 1:0.8:0.3, stirred at 70 r / min for 10 min at room temperature, filtered with a filter with a pore diameter of 75 μm, and the filtrate was retained as the pretreated ivermectin waste liquid; the waste liquid treatment agent and the pretreated ivermectin waste liquid were mixed in a mass ratio of 1:35 in a transparent container, ozone was introduced at a rate of 3.0 g / h, stirred at 500 r / min for 5 min at room temperature, irradiated with ultraviolet light, continued to stir for 6 h, filtered, retained the filtrate, added 0.4 times the mass of modified cellulose to the filtrate, and allowed to stand for 12 h to obtain ivermectin waste liquid liquid fertilizer.

[0023] Embodiment 4: A process for preparing ivermectin waste liquid liquid fertilizer comprises the following preparation steps: (1) Nitric acid, urea, tetrabutyl titanate, deionized water, and anhydrous ethanol were mixed in a mass ratio of 1:5:6.25:37.5:17.5, stirred at 70 r / min for 2 h at room temperature, aged for 45 h, and dried at 70°C for 4 to obtain nano titanium dioxide; nano titanium dioxide, lanthanum nitrate, and deionized water were mixed in a mass ratio of 1:0.15:15, ultrasonically treated for 1 h, filtered, and the residue was washed with deionized water for 4 times, heated at 700°C in a muffle furnace for 6 h, cooled to room temperature, and ground into a 400-mesh powder to obtain a waste liquid treatment agent; (2) Dry corn stalks at 70°C for 10 h, crush and pass through an 80-mesh sieve to obtain stalk powder, mix the stalk powder and 10% nitric acid solution at a mass ratio of 1:30, stir at 100°C and 500 r / min for 3 h, filter, wash the residue with deionized water 4 times, and dry at 70°C for 4 h to obtain cellulose; mix glutaric acid and 0.02 g / ml potassium hydroxide solution at a mass ratio of 1:18 to obtain a potassium hydroxide solution of glutaric acid; , potassium hydroxide solution of glutaric acid and glutaric acid were mixed in a mass ratio of 1:17.5, stirred at 250 r / min for 25 min at room temperature, added with potassium persulfate (0.005 times the mass of cellulose) and N,N-methylenebisacrylamide (0.03 times the mass of cellulose), heated to 60°C in a nitrogen atmosphere, stirred at 500 r / min for 2 h, cooled to room temperature, washed with deionized water for 4 times, freeze-dried for 4 hours, ground into 200-mesh powder, and obtained modified cellulose; (3) The flocculant, ivermectin waste liquid and flocculant aid were mixed in a mass ratio of 1:0.8:0.3, stirred at 70 r / min for 5 min at room temperature, filtered with a filter with a pore diameter of 75 μm, and the filtrate was retained as the pretreated ivermectin waste liquid; the waste liquid treatment agent and the pretreated ivermectin waste liquid were mixed in a mass ratio of 1:30 in a transparent container, ozone was introduced at a rate of 3.0 g / h, stirred at 500 r / min for 5 min at room temperature, irradiated with ultraviolet light, continued to stir for 5 h, filtered, retained the filtrate, added 0.4 times the mass of modified cellulose to the filtrate, and allowed to stand for 10 h to obtain ivermectin waste liquid liquid fertilizer.

[0024] Embodiment 5: A process for preparing ivermectin waste liquid liquid fertilizer comprises the following preparation steps: (1) Nitric acid, urea, tetrabutyl titanate, deionized water, and anhydrous ethanol were mixed in a mass ratio of 1:5:6.25:37.5:17.5, stirred at 70 r / min for 3 h at room temperature, aged for 50 h, and dried at 70°C for 6 h to obtain nano titanium dioxide; nano titanium dioxide, lanthanum nitrate, and deionized water were mixed in a mass ratio of 1:0.15:15, ultrasonically treated for 2 h, filtered, and the filter residue was washed with deionized water for 4 times, heated at 700°C in a muffle furnace for 8 h, cooled to room temperature, and ground into a 400-mesh powder to obtain a waste liquid treatment agent; (2) Dry corn stalks at 70°C for 14 h, crush and pass through an 80-mesh sieve to obtain stalk powder, mix the stalk powder and 10% nitric acid solution at a mass ratio of 1:30, stir at 100°C and 500 r / min for 5 h, filter, wash the residue with deionized water 4 times, and dry at 70°C for 8 h to obtain cellulose; mix glutaric acid and 0.02 g / ml potassium hydroxide solution at a mass ratio of 1:18 to obtain a potassium hydroxide solution of glutaric acid; , potassium hydroxide solution of glutaric acid and glutaric acid were mixed in a mass ratio of 1:17.5, stirred at 250r / min for 35min at room temperature, added with potassium persulfate (0.005 times the mass of cellulose) and N,N-methylenebisacrylamide (0.03 times the mass of cellulose), heated to 60°C in a nitrogen atmosphere, stirred at 500r / min for 4h, cooled to room temperature, washed with deionized water for 4 times, freeze-dried for 8h, ground into 200-mesh powder, and obtained modified cellulose; (3) The flocculant, ivermectin waste liquid and flocculant aid were mixed in a mass ratio of 1:0.8:0.3, stirred at 70 r / min for 15 min at room temperature, filtered with a filter with a pore diameter of 75 μm, and the filtrate was retained as the pretreated ivermectin waste liquid; the waste liquid treatment agent and the pretreated ivermectin waste liquid were mixed in a mass ratio of 1:30 in a transparent container, ozone was introduced at a rate of 3.0 g / h, stirred at 500 r / min for 5 min at room temperature, irradiated with ultraviolet light, continued to stir for 7 h, filtered, retained the filtrate, added 0.4 times the mass of modified cellulose to the filtrate, and allowed to stand for 14 h to obtain ivermectin waste liquid liquid fertilizer.

[0025] Comparative Example 1: A process for preparing ivermectin waste liquid liquid fertilizer comprises the following preparation steps: (1) Glutaric acid and 0.02 g / ml potassium hydroxide solution were mixed in a mass ratio of 1:18 to obtain a potassium hydroxide solution of glutaric acid; corn stalks were dried at 70°C for 12 h, crushed and sieved through an 80-mesh sieve to obtain stalk powder; the stalk powder and 10% nitric acid solution were mixed in a mass ratio of 1:30, stirred at 100°C for 4 h at 500 r / min, filtered, and the residue was washed with deionized water for 4 times, and dried at 70°C for 6 h to obtain cellulose; the cellulose , potassium hydroxide solution of glutaric acid and glutaric acid were mixed in a mass ratio of 1:17.5, stirred at 250r / min for 30min at room temperature, added with potassium persulfate (0.005 times the mass of cellulose) and N,N-methylenebisacrylamide (0.03 times the mass of cellulose), heated to 60°C in a nitrogen atmosphere, stirred at 500r / min for 3h, cooled to room temperature, washed with deionized water for 4 times, freeze-dried for 6h, ground into 200-mesh powder, and obtained modified cellulose; (2) The flocculant and ivermectin waste liquid were mixed in a mass ratio of 1:0.8, stirred at 70 r / min for 10 min at room temperature, filtered with a filter with a pore diameter of 75 μm, and the filtrate was retained as the pretreated ivermectin waste liquid; 0.4 times the mass of modified cellulose was added to the pretreated ivermectin waste liquid, and the mixture was allowed to stand for 12 h to obtain ivermectin waste liquid liquid fertilizer.

[0026] Comparative Example 2: A process for preparing ivermectin waste liquid liquid fertilizer comprises the following preparation steps: (1) Nitric acid, urea, tetrabutyl titanate, deionized water and anhydrous ethanol were mixed at a mass ratio of 1:5:6.25:37.5:17.5, stirred at room temperature at 70 r / min for 2.5 h, aged for 47.5 h, and dried at 70 °C for 5 h to prepare a waste liquid treatment agent; (2) Glutaric acid and 0.02 g / ml potassium hydroxide solution were mixed in a mass ratio of 1:18 to obtain a potassium hydroxide solution of glutaric acid; corn stalks were dried at 70°C for 12 h, crushed and sieved through an 80-mesh sieve to obtain stalk powder; the stalk powder and 10% nitric acid solution were mixed in a mass ratio of 1:30, stirred at 100°C for 4 h at 500 r / min, filtered, and the residue was washed with deionized water for 4 times, and dried at 70°C for 6 h to obtain cellulose; the cellulose , potassium hydroxide solution of glutaric acid and glutaric acid were mixed in a mass ratio of 1:17.5, stirred at 250r / min for 30min at room temperature, added with potassium persulfate (0.005 times the mass of cellulose) and N,N-methylenebisacrylamide (0.03 times the mass of cellulose), heated to 60°C in a nitrogen atmosphere, stirred at 500r / min for 3h, cooled to room temperature, washed with deionized water for 4 times, freeze-dried for 6h, ground into 200-mesh powder, and obtained modified cellulose; (3) The flocculant and ivermectin waste liquid were mixed at a mass ratio of 1:0.8, stirred at 70 r / min for 10 min at room temperature, filtered with a filter with a pore diameter of 75 μm, and the filtrate was retained as the pretreated ivermectin waste liquid; the waste liquid treatment agent and the pretreated ivermectin waste liquid were mixed at a mass ratio of 1:30 in a transparent container, ozone was introduced at a rate of 3.0 g / h, stirred at 500 r / min for 5 min at room temperature, irradiated with ultraviolet light, continued to stir for 6 h, filtered, and the filtrate was retained; 0.4 times the mass of modified cellulose was added to the filtrate, and the filtrate was allowed to stand for 12 h to obtain ivermectin waste liquid liquid fertilizer.

[0027] Comparative Example 3 A process for preparing ivermectin waste liquid liquid fertilizer comprises the following preparation steps: (1) Nitric acid, urea, tetrabutyl titanate, deionized water, and anhydrous ethanol were mixed in a mass ratio of 1:5:6.25:37.5:17.5, stirred at 70 r / min for 2.5 h at room temperature, aged for 47.5 h, and dried at 70°C for 5 h to obtain nano titanium dioxide; nano titanium dioxide, lanthanum nitrate, and deionized water were mixed in a mass ratio of 1:0.15:15, ultrasonically treated for 1.5 h, filtered, and the residue was washed with deionized water for 4 times, heated at 700°C in a muffle furnace for 7 h, cooled to room temperature, and ground into a 400-mesh powder to obtain a waste liquid treatment agent; (2) Mix the flocculant and ivermectin waste liquid in a mass ratio of 1:0.8, stir at 70 r / min for 10 min at room temperature, filter with a filter with a pore diameter of 75 μm, and retain the filtrate as the pretreated ivermectin waste liquid; mix the waste liquid treatment agent and the pretreated ivermectin waste liquid in a mass ratio of 1:30 in a transparent container, introduce ozone at a rate of 3.0 g / h, stir at 500 r / min for 5 min at room temperature, irradiate with ultraviolet light, continue stirring for 6 h, filter, and retain the filtrate as the ivermectin waste liquid liquid fertilizer.

[0028] Test example: Water retention rate test: Soil and liquid fertilizer prepared in each embodiment and comparative example were mixed at a mass ratio of 1:0.5, stored in a glass beaker, weighed and recorded as W1, and the transparent beaker containing the mixture of soil and liquid fertilizer was placed at room temperature for 20 days, weighed and recorded as W2, and the water retention rate was calculated according to water retention rate = (W1-W2) / W1*100%, and the results are shown in Table 1; Sustained release rate test: The liquid fertilizer prepared in each embodiment and comparative example was dried at 110° C. for 6 h to obtain a solid, which was weighed and recorded as M0. The solid was immersed in a urea solution with a mass concentration of 10%, and the solid was separated by centrifugation. The solid was dried at 110° C. for 6 h, and the solid was weighed and recorded as M1. The solid was placed in a 100-mesh nylon bag and placed in 500 mL of deionized water. The solution after release was removed, and the urea concentration in the solution was detected by para-dimethylaminobenzaldehyde colorimetric spectrophotometry. The sustained release rate was calculated according to sustained release rate = concentration * 500 / (M1-M0) * 100%. The results are shown in Table 1; The content of ivermectin in liquid fertilizer was tested by high performance liquid chromatography, and the removal rate of ivermectin in liquid fertilizer was calculated. The results are shown in Table 1; Table 1

[0029] By comparison, the water retention rates of Examples 1 to 5 are significantly greater than that of Comparative Example 3, indicating that cellulose cross-linking can form a three-dimensional network structure, and its porous structure can effectively extend the diffusion path of water molecules, thereby limiting the diffusion rate of water molecules and delaying the release of water. In addition, the network structure can more effectively wrap more water molecules and has a better water absorption effect. It can be combined with its good advantage of delaying water release efficiency to effectively improve the water retention effect of the fertilizer.

[0030] By comparison, the sustained release rates of Examples 1 to 5 are significantly greater than that of Comparative Example 3, indicating that the modified cellulose is prepared by reacting cellulose with glutaconic acid and N,N-methylenebisacrylamide, and the imine structure introduced by N,N-methylenebisacrylamide can effectively complex the metal elements and nitrogen elements in the waste liquid. After the complexation, the three-dimensional network structure of the cellulose can effectively wrap and slowly release, thereby achieving a sustained release effect.

[0031] By comparison, the ivermectin removal rates of Examples 1 to 5 are significantly higher than that of Comparative Example 2, indicating that nano titanium dioxide is prepared by the reaction of nitric acid, urea and tetrabutyl titanate, and electron-hole pairs are generated by photoexcitation under ultraviolet irradiation. The electron-hole pairs react with water and oxygen to generate active oxygen species, which can effectively oxidize and degrade ivermectin. The ivermectin waste liquid contains a large amount of ivermectin. The active oxygen species generated by titanium dioxide under the photocatalytic action of ultraviolet irradiation play a role in removing ivermectin from the ivermectin waste liquid. effect; the ivermectin removal rate of comparative example 1 is lower than that of comparative example 2, indicating that the waste liquid treatment agent is prepared by ultrasonic treatment of nano titanium dioxide and lanthanum nitrate, lanthanum ions can broaden the light response range of titanium dioxide, increase the light absorption capacity of titanium dioxide, and lanthanum ions can form Ti-O-La bonds with titanium dioxide, which can effectively inhibit the recombination of electron-hole pairs and prolong the life of photogenerated carriers, thereby further improving the degradation effect of the waste liquid treatment agent on ivermectin in ivermectin waste liquid, and effectively improving the ivermectin removal rate.

[0032] 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, cleaned 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; Table 2

[0033] As can be seen from Table 2, the cellulose solids in the ivermectin waste liquid liquid fertilizers prepared in Examples 1 to 5 have a good degradation rate, indicating that the molecular structure of cellulose can be destroyed by the cellulase secreted by microorganisms in the soil, and the cellulose is decomposed into small molecular organic matter, thereby making the ivermectin waste liquid liquid fertilizer have good biodegradability.

[0034] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A process for preparing ivermectin waste liquid liquid fertilizer, characterized in that: The ivermectin waste liquid liquid fertilizer is prepared by adding modified cellulose to the ivermectin waste liquid after the waste liquid treatment agent is treated; The waste liquid treatment agent is prepared by reacting nitric acid, urea and tetrabutyl titanate to obtain nano titanium dioxide, and then ultrasonically treating the nano titanium dioxide with lanthanum nitrate. Modified cellulose is prepared by reacting cellulose with potassium hydroxide solution of glutaconic acid and then reacting with N,N-methylenebisacrylamide under the action of potassium persulfate to obtain modified cellulose; A preparation process of ivermectin waste liquid liquid fertilizer, characterized by comprising the following preparation steps: (1) Mix nitric acid, urea, tetrabutyl titanate, deionized water and anhydrous ethanol, stir at room temperature at 60-80 r / min for 2-3 h, age for 45-50 h, and dry at 65-75°C for 4-6 h to obtain nano titanium dioxide; mix nano titanium dioxide, lanthanum nitrate and deionized water, ultrasonically treat for 1-2 h, filter, wash the filter residue with deionized water for 3-5 times, heat in a muffle furnace at 650-750°C for 6-8 h, cool to room temperature, and grind into 350-450 mesh powder to obtain a waste liquid treatment agent; (2) Mix cellulose and potassium hydroxide solution of glutaconic acid, stir at 200-300 r / min for 25-35 min at room temperature, add potassium persulfate and N,N-methylenebisacrylamide, heat to 55-65°C under nitrogen atmosphere, stir at 400-600 r / min for 2-4 h, cool to room temperature, wash with deionized water for 3-5 times, freeze-dry for 4-8 hours, grind into powder of 180-220 mesh, and prepare modified cellulose; (3) The ivermectin waste liquid is treated with a flocculant to obtain a pretreated ivermectin waste liquid. The pretreated ivermectin waste liquid is treated with a waste liquid treating agent, and then 0.3 to 0.5 times the mass of the pretreated ivermectin waste liquid is added with modified cellulose, and the pretreated ivermectin waste liquid is allowed to stand for 10 to 14 hours to obtain an ivermectin waste liquid liquid fertilizer.

2. A process for preparing ivermectin waste liquid fertilizer according to claim 2, characterized in that: The mass ratio of nitric acid, urea, tetrabutyl titanate, deionized water and anhydrous ethanol in step (1) is 1: (4.5-5.5): (6-6.5): (35-40): (15-20).

3. A process for preparing ivermectin waste liquid fertilizer according to claim 2, characterized in that: The mass ratio of nano-titanium dioxide, lanthanum nitrate and deionized water in step (1) is 1: (0.1-0.2): (10-20).

4. A process for preparing ivermectin waste liquid fertilizer according to claim 2, characterized in that: The potassium hydroxide solution of glutaconic acid in step (2) is prepared by mixing glutaconic acid and 0.02 g / ml potassium hydroxide solution in a mass ratio of 1:

18.

5. A process for preparing ivermectin waste liquid fertilizer according to claim 2, characterized in that: The preparation method of the cellulose in step (2) is as follows: drying corn stalks at 65-75° C. for 10-14 h, crushing and passing through an 80-mesh sieve to obtain stalk powder, mixing the stalk powder and a 10% nitric acid solution at a mass ratio of 1:30, stirring at 400-600 r / min at 90-110° C. for 3-5 h, filtering, washing the filter residue with deionized water for 3-5 times, and drying at 65-75° C. for 4-8 h to obtain cellulose.

6. A process for preparing ivermectin waste liquid liquid fertilizer according to claim 2, characterized in that: In step (2), the mass ratio of the cellulose to the potassium hydroxide solution of glutaconic acid is 1:(15-20).

7. A process for preparing ivermectin waste liquid fertilizer according to claim 2, characterized in that: In step (2), the mass of potassium persulfate is 0.004 to 0.006 times the mass of cellulose, and the mass of N,N-methylenebisacrylamide is 0.02 to 0.04 times the mass of cellulose.

8. The process for preparing a liquid fertilizer from ivermectin waste liquid according to claim 2, characterized in that: In step (3), the flocculant is 400 mg / L polyaluminium chloride and the flocculant aid is 15 mg / L polyacrylamide.

9. A process for preparing ivermectin waste liquid fertilizer according to claim 2, characterized in that: The method for treating ivermectin waste liquid with a flocculant in step (3) is as follows: mixing the flocculant, ivermectin waste liquid and flocculant aid in a mass ratio of 1:0.8:0.3, stirring at room temperature at 60-80 r / min for 5-15 min, filtering with a filter with a pore diameter of 75 μm, and retaining the filtrate as the pretreated ivermectin waste liquid.

10. The process for preparing ivermectin waste liquid fertilizer according to claim 2, characterized in that: The method for treating the pretreated ivermectin waste liquid with the waste liquid treatment agent in step (3) is as follows: the waste liquid treatment agent and the pretreated ivermectin waste liquid are mixed in a transparent container at a mass ratio of 1: (25-35), ozone is introduced at a rate of 3.0 g / h, stirred at 400-600 r / min for 5 min at room temperature, irradiated with an ultraviolet lamp, continued to stir for 5-7 h, filtered, and the filtrate is retained.

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