A kind of refined glufosinate ammonium solid preparation and preparation method thereof

Abstract

The present invention relates to the field of pesticide technology, and in particular to a solid formulation of a refined glufosinate-ammonium salt and a preparation method thereof. The solid formulation comprises a refined glufosinate-ammonium salt slurry, an adsorbent, and an anti-caking agent. The solid formulation comprises, by mass percentage, 50-80% of the refined glufosinate-ammonium salt slurry; 1-50% of the adsorbent; 1-30% of the anti-caking agent; and 0-1% of the defoaming agent. The present invention directly uses the refined glufosinate-ammonium salt slurry as a raw material for granulation, abandoning the complex process of preparing the refined glufosinate-ammonium salt into crystals or other intermediates and then granulating them. This reduces costs, reduces production steps, and correspondingly reduces the generation and emission of pollutants such as wastewater and waste residue, thereby reducing pressure on the environment and meeting environmental protection requirements.

Description

Technical Field

[0001] The present invention relates to the technical field of pesticides, in particular to a refined glufosinate ammonium solid preparation and a preparation method thereof. Background Art

[0002] Glufosinate has two optical isomers, L-glufosinate and D-glufosinate. The L-type is phytotoxic and has twice the herbicidal activity of the racemic mixture. It is easily decomposed in the soil, has low toxicity to humans and animals, has a broad herbicidal spectrum, and is less destructive to the environment.

[0003] Among the many formulations of refined glufosinate ammonium, solid preparations offer significant savings in packaging and transportation costs compared to liquid formulations, especially for high-content soluble granules. Currently, conventional solid preparations are mostly made from refined glufosinate ammonium raw powder, which typically has a large particle size and a rough surface. During the granulation process, especially when using extrusion granulation, problems such as granulation difficulty forming and discharging granules can occur. This can also lead to extrusion slippage, pellet failure, and overheating in the rotary granulator. During the granulation process, if the raw powder is not evenly mixed with other raw materials (such as adjuvants and fillers), the active ingredient distribution in the product may be uneven, affecting the consistency and stability of the herbicidal effect and reducing product quality. Summary of the Invention

[0004] In order to solve the problems in the background technology, the present invention proposes a solid preparation of refined glufosinate ammonium salt and a preparation method thereof, which directly uses refined glufosinate ammonium salt slurry as raw material for granulation, abandoning the complicated process of making refined glufosinate ammonium salt into crystals or other intermediates and then granulating them, thereby reducing costs and production steps, and correspondingly reducing the generation and emission of pollutants such as wastewater and waste residues, reducing pressure on the environment, and meeting environmental protection requirements.

[0005] The technical solution adopted by the present invention to solve its technical problem is: to provide a refined glufosinate ammonium salt solid preparation, including a refined glufosinate ammonium salt slurry, an adsorbent and an anti-caking agent.

[0006] Furthermore, by mass percentage, it includes:

[0007] Refined glufosinate ammonium salt slurry, 50-80%; adsorbent, 1-50%; anti-caking agent, 1-30%; defoaming agent, 0-1%.

[0008] Furthermore, a refined glufosinate ammonium salt slurry is prepared by concentrating a mother liquor containing refined glufosinate ammonium salt; wherein the content of 3-(hydroxymethylphosphono)propionic acid in the refined glufosinate ammonium salt slurry is greater than 0.01%, preferably 0.01-1%. The refined glufosinate ammonium salt mother liquor is a concentrated solution in the pesticide production process.

[0009] The refined glufosinate ammonium salt slurry contains at least one of refined glufosinate ammonium salt, potassium salt, isopropylamine salt, sodium salt, monoethylamine salt, monomethylamine salt, and monoethanolamine salt.

[0010] The preparation of refined glufosinate ammonium salt slurry comprises: placing refined glufosinate acid and alkali metal hydroxide and / or nitrogen base in a mixed medium of volatile alcohol organic solvent and / or water at a molar ratio of 1:1-1.5, and obtaining refined glufosinate ammonium salt slurry through reaction.

[0011] Furthermore, the alkali metal hydroxide includes potassium hydroxide and / or sodium hydroxide; the nitrogen base includes ammonia, alkylamine and / or alkylolamine; the mass ratio of water and volatile alcohol organic solvent in the mixed medium is (80-60): (20-40); the volatile alcohol organic solvent includes C1-C3 alkyl alcohol.

[0012] Furthermore, the alkylamine includes methylamine, dimethylamine and / or isopropylamine; the alkylolamine includes monoethanolamine, diethanolamine and / or triethanolamine.

[0013] Furthermore, the content of refined glufosinate in the refined glufosinate salt slurry is 50-70%, and the viscosity at 30° C. is greater than 10,000 cp; preferably, the viscosity is 10,000-3,000,000 cp.

[0014] Furthermore, the anti-adhesive agent is composed of a composite of nanomaterials and surfactants, the surface of the nanomaterials is modified with hydrophilic groups, and the surfactants are adsorbed on the surface of the nanomaterials.

[0015] Furthermore, the nanomaterials include modified nano-silica, nano-silicon microspheres, modified nano-alumina and / or modified nano-kaolin; the surfactants include anionic surfactants, nonionic surfactants and / or zwitterionic surfactants.

[0016] Furthermore, the hydrophilic group includes at least one of a carboxyl group, an amino group, polyethylene glycol, or poly(methylpropionic acid) sulfobetaine.

[0017] Furthermore, the surfactant includes one or more of fatty alcohol ether sodium sulfate, dioctyl sulfosuccinate sodium salt, alkylbenzene sulfonate, fatty alcohol polyoxyethylene ether, alkyl glycoside, polyethylene glycol, betaine, polyacrylate surfactant, fatty acid ester surfactant, polysorbate, alkyl sulfate, acetylenic glycol, glycoside-modified polyether, silicone polymer or methacrylate polymer.

[0018] Furthermore, the surface of the modified nano-silica is modified by hydrophilic groups, with a particle size of 10-100 nanometers, a specific surface area of ​​300-500 m² / g, and a porosity of 80-90%.

[0019] The surface of the modified nano-silicon microspheres is modified by hydrophilic groups, with a particle size of 10-300 nanometers, a porosity of 70%-90%, a specific surface area of ​​100-500m² / g, and a water content of <1%.

[0020] Furthermore, the adsorbent includes a first adsorbent and / or a second adsorbent; the first adsorbent includes white carbon black, bentonite, diatomaceous earth, talc, activated alumina, soluble resin, soluble starch, chitosan, sodium alginate, magnesium aluminum silicate, polyvinyl pyrrolidone, polyvinyl alcohol, sodium carboxymethyl cellulose and / or lignin; the second adsorbent includes an anhydrous inorganic salt, and the anhydrous inorganic salt is preferably sodium pyrophosphate; the mass ratio of the first adsorbent to the second adsorbent is 1:(0.3-3);

[0021] Furthermore, the defoaming agent includes an organosilicon defoaming agent, a mineral oil defoaming agent, a vegetable oil defoaming agent or a polyether defoaming agent.

[0022] The present application also provides a method for preparing a solid formulation of refined glufosinate ammonium salt, comprising the following steps:

[0023] The refined glufosinate ammonium salt slurry is mixed with an anti-adhesive agent and an adsorbent until the material is in a solid or semi-solid state, and then granulated by extrusion or spray drying to obtain a refined glufosinate ammonium salt solid preparation.

[0024] Furthermore, a defoaming agent is further added during mixing.

[0025] The present application also provides a method for preparing a refined glufosinate ammonium solid preparation, comprising the following steps: S1, uniformly mixing a glufosinate ammonium slurry with an anti-caking agent, adding a first adsorbent to the mixture, and stirring evenly so that the material is in a solid or semi-solid state; S2, continuing to add a second adsorbent and mixing, and obtaining a refined glufosinate ammonium solid preparation by extrusion granulation or spray drying granulation.

[0026] Furthermore, a defoaming agent is further added during S1 mixing.

[0027] The beneficial effects of the present invention are:

[0028] 1. The present application directly uses refined glufosinate ammonium salt slurry as raw material for granulation, abandoning the complicated process of making refined glufosinate ammonium salt into crystals or other intermediates and then granulating them, thereby reducing costs and production steps, and correspondingly reducing the generation and discharge of pollutants such as wastewater and waste residues, reducing pressure on the environment, and meeting environmental protection requirements.

[0029] 2. The present application adopts a volatile organic solvent as a dispersion medium, which reduces the moisture content of the refined glufosinate ammonium salt slurry, improves the fluidity of the refined glufosinate ammonium salt, makes it easier to mix evenly, and is suitable for spray drying or extrusion granulation processes, reducing the difficulty of operation and the requirements for equipment, further reducing costs and improving production efficiency.

[0030] 3. The adsorbent selected in this application can adsorb the slurry and absorb part of the moisture in the slurry, thereby reducing the energy consumption of subsequent drying.

[0031] 4. The anti-adhesive agent of the present application reduces the surface tension of the slurry and the electrostatic repulsion effect between surface nanomaterials, thereby reducing the formation of sticky agglomerates, reducing the friction generated during the granulation process, and improving the disintegration performance of the particles. DETAILED DESCRIPTION

[0032] The following will be combined with the attached tables in the embodiments of the invention to clearly and completely describe the technical solutions in the embodiments of the invention. It should be understood that the specific embodiments described herein are only used to illustrate the present invention and are not intended to limit the present invention. It should also be noted that for ease of description, the attached tables only show some of the structures relevant to the present invention, not all of them.

[0033] Example 1: Preparation of 70% refined glufosinate ammonium slurry (acid basis).

[0034] The invention comprises, by mass percentage, 74% of 95% refined glufosinate ammonium, 6.6% of ammonia, 4% of ethanol, and 15.4% of water. 95% refined glufosinate ammonium is added to a kneading reactor according to the mass percentages, followed by a mixture of water and ethanol. The mixture is stirred continuously, and ammonia is added to the mixture for reaction, thereby producing a 70% refined glufosinate ammonium salt slurry having a viscosity of 1,920,000 cP at 30°C.

[0035] Example 2: Preparation of 65% refined glufosinate-ammonium potassium slurry (acid basis).

[0036] The mixture comprises, by mass percentage, 68.5% of 95% refined glufosinate ammonium, 20.5% of potassium hydroxide, 3% of ethanol, and 8% of water. The 95% refined glufosinate ammonium is added to a kneading reaction kettle according to the mass percentages, followed by a mixture of water and ethanol. The mixture is stirred continuously, and potassium hydroxide is added for mixing and reaction to produce a 65% refined glufosinate ammonium potassium salt slurry having a viscosity of 1,860,000 cP at 30°C.

[0037] Example 3: Preparation of 65% refined glufosinate sodium salt slurry (acid basis).

[0038] The mixture comprises, by mass percentage, 68.5% of 95% refined glufosinate ammonium, 14.5% of sodium hydroxide, 5% of ethanol, and 12% of water. The 95% refined glufosinate ammonium is added to a kneading reaction kettle according to the mass percentages, followed by a mixture of water and ethanol. The mixture is stirred continuously, and sodium hydroxide is added for mixing and reaction to produce a 65% refined glufosinate ammonium sodium salt slurry having a viscosity of 1,810,000 cP at 30°C.

[0039] Example 4: Preparation of 65% glufosinate-ammonium isopropylamine salt slurry (acid basis).

[0040] The mixture comprises, by mass percentage, 68.5% of 95% refined glufosinate ammonium, 21.5% of isopropylamine, 3% of ethanol, and 7% of water. The 95% refined glufosinate ammonium isopropylamine salt slurry having a viscosity of 1,900,000 cP at 30°C is prepared. The mixture is then added with a mixture of water and ethanol. The mixture is stirred continuously, and isopropylamine is added for reaction.

[0041] Example 5: Preparation of 70% refined glufosinate ammonium salt and refined glufosinate sodium salt slurry (acid basis).

[0042] The mixture comprises, by mass percentage, 74% of 95% refined glufosinate ammonium, 7.7% of sodium hydroxide, 3.4% of ammonia, 4.5% of ethanol, and 10.4% of water. 95% refined glufosinate ammonium is added to a kneading reactor according to the mass percentages, followed by a mixture of water and ethanol. The mixture is stirred continuously, and then sodium hydroxide and ammonia are added for reaction to produce a slurry of 70% refined glufosinate ammonium salt and refined glufosinate sodium salt having a viscosity of 1,930,000 cP at 30°C.

[0043] Example 6: Preparation of 70% refined glufosinate ammonium and refined glufosinate potassium slurry (acid basis).

[0044] The mixture comprises, by mass percentage, 74% of 95% refined glufosinate ammonium, 5.4% of potassium hydroxide, 5.1% of ammonia, 4% of ethanol, and 11.5% of water. 95% refined glufosinate ammonium is added to a kneading reactor, followed by a mixture of water and ethanol. The mixture is stirred continuously, and potassium hydroxide and ammonia are added for reaction to produce a slurry of 70% refined glufosinate ammonium salt and refined glufosinate potassium salt having a viscosity of 1,940,000 cP at 30°C.

[0045] Example 7: Preparation of 70% refined glufosinate ammonium salt and refined glufosinate isopropylamine salt slurry (acid basis).

[0046] The mixture comprises, by mass percentage, 74% of 95% refined glufosinate ammonium, 9.2% of isopropylamine, 4.0% of ammonia, 3.8% of ethanol, and 9.0% of water. 95% refined glufosinate ammonium is added to a kneading reactor according to the mass percentages, followed by a mixture of water and ethanol. The mixture is stirred continuously, and isopropylamine and ammonia are added for reaction to produce a slurry of 70% refined glufosinate ammonium salt and refined glufosinate isopropylamine salt having a viscosity of 1,980,000 cP at 30°C.

[0047] Example 8: Preparation of 70% refined glufosinate ammonium salt and refined glufosinate monoethanolamine salt slurry (acid basis).

[0048] The mixture comprises, by mass percentage, 74% of 95% refined glufosinate ammonium, 7.2% of monoethanolamine, 4.6% of ammonia, 3.5% of ethanol, and 10.7% of water. 95% refined glufosinate ammonium is added to a kneading reactor according to the mass percentages, followed by a mixture of water and ethanol. The mixture is stirred continuously, and then monoethanolamine and ammonia are added and reacted to produce a slurry of 70% refined glufosinate ammonium salt and refined glufosinate monoethanolamine salt having a viscosity of 1,960,000 cP at 30°C.

[0049] Example 9: Preparation of 70% refined glufosinate ammonium salt and refined glufosinate monomethylamine salt slurry (acid basis).

[0050] The mixture comprises, by mass percentage, 74% of 95% refined glufosinate ammonium, 6.2% of monomethylamine, 3.3% of ammonia, 4.5% of ethanol, and 12% of water. 95% refined glufosinate ammonium is added to a kneading reactor, followed by a mixture of water and ethanol. The mixture is stirred continuously, and monomethylamine and ammonia are added for reaction to produce a slurry of 70% refined glufosinate ammonium salt and refined glufosinate monomethylamine salt having a viscosity of 1,940,000 cP at 30°C.

[0051] Example 10: Preparation of 64.5% refined glufosinate ammonium slurry (acid basis).

[0052] 100 g of 10% refined glufosinate ammonium salt mother liquor was heated at 110°C and concentrated to remove 84.5 g of water to obtain a 64.5% refined glufosinate ammonium salt slurry having a viscosity of 1,800,000 cP at 30°C.

[0053] Example 11: Preparation of 65.2% refined glufosinate-ammonium potassium slurry (acid basis).

[0054] 100 g of 15% refined glufosinate potassium ammonium mother liquor was heated at 110°C and concentrated to remove 77 g of water to obtain a 65.2% refined glufosinate potassium ammonium slurry having a viscosity of 1,840,000 cP at 30°C.

[0055] Example 12: Preparation of a 64.5% slurry of refined glufosinate ammonium salt and refined glufosinate isopropylamine salt (acid basis).

[0056] 100 g of a mixed mother liquor of 10% refined glufosinate ammonium salt and refined glufosinate isopropylamine salt was heated at 110° C. and concentrated to remove 84.5 g of water to obtain a slurry of 64.5% refined glufosinate ammonium salt and refined glufosinate isopropylamine salt having a viscosity of 1965000 cP at 30° C.

[0057] Example 13: Preparation of a 64.5% slurry of refined glufosinate ammonium salt and refined glufosinate monomethylamine salt (acid basis).

[0058] 100 g of a mixed mother liquor of 12% refined glufosinate ammonium salt and refined glufosinate monomethylamine salt was heated at 110° C. and concentrated to remove 81.5 g of water to obtain a slurry of 64.9% refined glufosinate ammonium salt and refined glufosinate monomethylamine salt having a viscosity of 1940000 cP at 30° C.

[0059] Example 14: Preparation of a 65.2% slurry of refined glufosinate ammonium salt, refined glufosinate potassium salt and refined glufosinate monomethylamine salt (acid basis).

[0060] 100 g of a mixed mother liquor of 15% refined glufosinate ammonium salt, refined glufosinate potassium salt and refined glufosinate monomethylamine salt was heated and concentrated at 110° C. to remove 77 g of water, thereby obtaining a slurry of 65.2% refined glufosinate ammonium salt, refined glufosinate potassium salt and refined glufosinate monomethylamine salt having a viscosity of 1910000 cP at 30° C.

[0061] Example 15: Preparation of 50% refined glufosinate ammonium solid preparation (acid basis).

[0062] 71.5 g of the 70% refined glufosinate ammonium salt slurry prepared in Example 1, carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 4g, acetylenic glycol 4g, sodium fatty alcohol polyoxyethylene ether sulfate 7g, sodium carboxymethyl cellulose 10g, sodium pyrophosphate 15g, ammonium sulfate 7.3g, defoaming agent 0.2g.

[0063] 70% refined glufosinate ammonium salt slurry is mixed with carboxyl-modified modified nano-silica, acetylene glycol, sodium carboxymethyl cellulose, sodium fatty alcohol polyoxyethylene ether sulfate and a defoamer; the mixture is put into a high-speed mixer, stirring is started, the mixing speed is set to 1000 r / min, the mixing temperature is set to 40°C, and the mixture is mixed evenly; sodium pyrophosphate is added to the mixture, and the mixture is stirred evenly to make the material present a solid or semi-solid state; ammonium sulfate is continuously added and mixed, and after mixing evenly, the mixture is granulated by extrusion or spray drying to obtain a refined glufosinate ammonium salt solid preparation.

[0064] Example 16: Preparation of 50% refined glufosinate-ammonium potassium salt solid preparation (acid basis).

[0065] The difference between Example 16 and Example 15 is that:

[0066] 77 g of the 65% refined glufosinate potassium slurry prepared in Example 2, carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 4g, acetylenic glycol 2g, fatty alcohol polyoxyethylene ether sodium sulfate 7g, sodium carboxymethyl cellulose 10g, anhydrous calcium chloride 15g, potassium sulfate 1.5g, defoaming agent 0.2g.

[0067] Example 17: Preparation of 50% refined glufosinate sodium salt solid preparation (acid basis).

[0068] The difference between Example 17 and Example 15 is that:

[0069] Take 77g of the 65% refined glufosinate sodium slurry prepared in Example 3, amino-modified modified nano-silica (particle size 100nm, specific surface area 400m 2 / g, porosity 85%) 4g, acetylenic glycol 2g, sodium fatty alcohol polyoxyethylene ether sulfate 7g, sodium carboxymethyl cellulose 10g, sodium pyrophosphate 15g, sodium sulfate 5.9g, defoaming agent 0.2g.

[0070] Example 18: Preparation of 50% refined glufosinate ammonium salt and refined glufosinate sodium salt solid preparation (acid basis).

[0071] The difference between Example 18 and Example 15 is that:

[0072] Take 71.5 g of the slurry of 70% refined glufosinate ammonium salt and refined glufosinate sodium salt prepared in Example 5, carboxyl modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 4g, acetylenic glycol 2g, sodium fatty alcohol polyoxyethylene ether sulfate 7g, sodium carboxymethyl cellulose 10g, sodium pyrophosphate 15g, ammonium sulfate 6.5g, defoaming agent 0.2g.

[0073] Example 19: Preparation of 50% refined glufosinate ammonium salt and refined glufosinate potassium salt solid preparation (acid basis).

[0074] The difference between Example 19 and Example 15 is that:

[0075] 71.5 g of the slurry of 70% refined glufosinate ammonium salt and refined glufosinate potassium salt prepared in Example 6, carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 4g, glycoside modified silicone polyether 2g, dioctyl sulfosuccinate sodium salt 7g, sodium carboxymethyl cellulose 10g, sodium pyrophosphate 15g, ammonium sulfate 2.4g, potassium sulfate 2.45g, defoamer 0.2g.

[0076] Example 20: Preparation of 50% refined glufosinate ammonium salt and refined glufosinate monoethanolamine salt solid preparations (acid basis).

[0077] The difference between Example 20 and Example 15 is that:

[0078] 71.5 g of the slurry of 70% refined glufosinate ammonium salt and refined glufosinate monoethanolamine salt prepared in Example 8, carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 4g, acetylenediol 2g, dioctyl sodium sulfosuccinate 7g, sodium carboxymethyl cellulose 10g, anhydrous trisodium phosphate 15g, defoamer 0.2g.

[0079] Example 21: Preparation of 50% refined glufosinate ammonium salt and refined glufosinate monomethylamine salt solid preparation (acid basis).

[0080] The difference between Example 21 and Example 15 is that:

[0081] Take 71.5 g of the slurry of 70% refined glufosinate ammonium salt and refined glufosinate monomethylamine salt prepared in Example 9, carboxyl modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 4g, glycoside modified silicone polyether 2g, fatty alcohol polyoxyethylene ether sodium sulfate 3.5g, dioctyl sulfosuccinate sodium salt 3.5g, sodium carboxymethyl cellulose 10g, sodium pyrophosphate 15g, ammonium sulfate 5g, defoamer 0.2g.

[0082] Example 22: Preparation of 50% refined glufosinate ammonium solid preparation (acid basis).

[0083] The difference between Example 22 and Example 15 is:

[0084] 77.6 g of the 64.5% refined glufosinate ammonium salt slurry prepared in Example 10, carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 4g, acetylenic glycol 2g, sodium fatty alcohol polyoxyethylene ether sulfate 7g, sodium carboxymethyl cellulose 10g, sodium pyrophosphate 15g, ammonium sulfate 7.3g, defoaming agent 0.2g.

[0085] Example 23: Preparation of 50% refined glufosinate-ammonium potassium salt solid preparation (acid basis).

[0086] The difference between Example 23 and Example 15 is that:

[0087] 76.7 g of the 65.2% refined glufosinate potassium slurry prepared in Example 11, carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 4g, acetylenic glycol 2g, fatty alcohol polyoxyethylene ether sodium sulfate 7g, sodium carboxymethyl cellulose 10g, anhydrous trisodium phosphate 15g, ammonium sulfate 1.5g, defoaming agent 0.2g.

[0088] Example 24: Preparation of 50% refined glufosinate ammonium salt and refined glufosinate isopropylamine salt solid preparation (acid basis).

[0089] The difference between Example 24 and Example 15 is that:

[0090] Take 77.6 g of the slurry of 64.5% refined glufosinate ammonium salt and refined glufosinate isopropylamine salt prepared in Example 12, carboxyl modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 4g, acetylenic glycol 2g, sodium fatty alcohol polyoxyethylene ether sulfate 7g, sodium carboxymethyl cellulose 10g, sodium pyrophosphate 15g, ammonium sulfate 2.7g, defoaming agent 0.2g.

[0091] Example 25: Preparation of 50% refined glufosinate ammonium salt and refined glufosinate monomethylamine salt solid preparation (acid basis).

[0092] The difference between Example 25 and Example 15 is that:

[0093] 77.6 g of the slurry of 64.5% refined glufosinate ammonium salt and refined glufosinate monomethylamine salt prepared in Example 13, carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 4g, acetylenediol 2g, dioctyl sodium sulfosuccinate 7g, sodium carboxymethyl cellulose 10g, sodium pyrophosphate 15g, ammonium sulfate 5.7g, defoamer 0.2g.

[0094] Example 26: Preparation of 50% solid preparations of refined glufosinate ammonium salt, refined glufosinate potassium salt and refined glufosinate monomethylamine salt (acid basis).

[0095] The difference between Example 26 and Example 15 is that:

[0096] 77.6 g of the slurry of 64.5% refined glufosinate ammonium salt, refined glufosinate potassium salt and refined glufosinate monomethylamine salt prepared in Example 14, carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 4g, acetylenic glycol 2g, sodium polyoxyethylene fatty alcohol ether sulfate 3.5g, sodium dioctyl sulfosuccinate 3.5g, sodium carboxymethyl cellulose 10g, sodium pyrophosphate 15g, ammonium sulfate 4.6g, defoaming agent 0.2g.

[0097] Example 27: Preparation of 88% refined glufosinate ammonium solid preparation (calculated as salt).

[0098] The difference between Example 27 and Example 15 is that:

[0099] Take 115g of the 70% refined glufosinate ammonium salt slurry prepared in Example 1, carboxyl modified nano-silica (particle size 50nm, specific surface area 500m 2 / g, porosity 88%) 2g, acetylenic glycol 1g, sodium fatty alcohol polyoxyethylene ether sulfate 1g, polyvinyl pyrrolidone 3g, sodium pyrophosphate 5g, defoaming agent 0.2g.

[0100] Example 28: Preparation of 88% refined glufosinate-ammonium potassium salt solid preparation (calculated as salt).

[0101] The difference between Example 28 and Example 15 is that:

[0102] Take 112 g of the 65% refined glufosinate potassium slurry prepared in Example 2, carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 2g, acetylenic glycol 1g, sodium fatty alcohol polyoxyethylene ether sulfate 1g, polyvinyl pyrrolidone 3g, anhydrous trisodium phosphate 5g, defoaming agent 0.2g.

[0103] Example 29: Preparation of 88% refined glufosinate sodium salt solid preparation (calculated as salt).

[0104] The difference between Example 29 and Example 15 is that:

[0105] Take 121g of the 65% refined glufosinate sodium salt slurry prepared in Example 3, carboxyl modified nano-silicon microspheres (particle size 15nm, specific surface area 500m 2 / g, water content: 0.76%, porosity 85%) 2g, glycoside modified silicone polyether 1g, fatty alcohol polyoxyethylene ether sodium sulfate 1g, polyvinyl pyrrolidone 3g, anhydrous trisodium phosphate 5g, defoaming agent 0.2g.

[0106] Example 30: Preparation of 88% refined glufosinate ammonium and sodium salt solid preparations (calculated as salt).

[0107] The difference between Example 30 and Example 15 is that:

[0108] Take 113.3 g of the 70% refined glufosinate ammonium and sodium salt slurry prepared in Example 5, amino-modified modified nano-silicon microspheres (particle size 20 nm, specific surface area 450 m 2 / g, water content: 0.53%, porosity 81%) 2g, acetylenic glycol 1g, sodium fatty alcohol polyoxyethylene ether sulfate 1g, polyvinyl pyrrolidone 3g, sodium pyrophosphate 5g, defoaming agent 0.2g.

[0109] Example 31: Preparation of 88% refined glufosinate ammonium and potassium salt solid preparation (calculated as salt).

[0110] The difference between Example 31 and Example 15 is that:

[0111] Take 110 g of the 70% refined glufosinate ammonium and potassium salt slurry prepared in Example 6, carboxyl modified nano-silicon microspheres (particle size 15 nm, specific surface area 500 m 2 / g, water content: 0.76%, porosity 85%) 2g, acetylenic glycol 1g, sodium fatty alcohol polyoxyethylene ether sulfate 1g, polyvinyl pyrrolidone 3g, sodium pyrophosphate 5g, defoaming agent 0.2g.

[0112] Example 32: Preparation of 88% refined solid preparation of glufosinate ammonium salt and monomethylamine salt (calculated as salt).

[0113] The difference between Example 32 and Example 15 is that:

[0114] Take 110.3 g of the 70% refined glufosinate ammonium salt and monomethylamine salt slurry prepared in Example 9, carboxyl modified nano-silicon microspheres (particle size 15 nm, specific surface area 500 m 2 / g, water content: 0.76%, porosity 85%) 2g, glycoside modified silicone polyether 1g, dioctyl sulfosuccinate sodium salt 1g, polyvinyl pyrrolidone 3g, anhydrous calcium chloride 5g, defoaming agent 0.2g.

[0115] Example 33: Preparation of 50% refined glufosinate ammonium solid preparation (acid basis).

[0116] The difference between Example 33 and Example 15 is that:

[0117] 71.5 g of the 70% refined glufosinate ammonium salt slurry prepared in Example 1, carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 4g, acetylenic glycol 2g, sodium fatty alcohol polyoxyethylene ether sulfate 7g, sodium carboxymethyl cellulose 10g, sodium pyrophosphate 15g, ammonium sulfate 7.3g.

[0118] Example 34: Preparation of 88% refined glufosinate ammonium and potassium salt solid preparation (calculated as salt).

[0119] The difference between Example 34 and Example 31 is that:

[0120] Take 110 g of the 70% refined glufosinate ammonium salt and potassium salt slurry prepared in Example 6, carboxyl modified nano-silicon microspheres (particle size 15 nm, specific surface area 500 m 2 / g, water content: 0.76%, porosity 85%) 2g, acetylenic glycol 1g, sodium fatty alcohol polyoxyethylene ether sulfate 1g, polyvinyl pyrrolidone 3g, sodium pyrophosphate 5g.

[0121] Example 35: Preparation of 50% refined glufosinate ammonium solid preparation (acid basis).

[0122] The difference between Example 35 and Example 15 is that:

[0123] Take 71.5g of the 70% refined glufosinate ammonium salt slurry prepared in Example 1, fumed silica (particle size 450nm, specific surface area 300m 2 / g, porosity 55%) 10g, acetylenic glycol 2g, sodium fatty alcohol polyoxyethylene ether sulfate 7g, sodium carboxymethyl cellulose 10g, sodium pyrophosphate 15g, ammonium sulfate 7.3g, defoaming agent 0.2g.

[0124] Example 36: Preparation of 88% refined glufosinate ammonium and potassium slurry (based on salt).

[0125] The difference between Example 36 and Example 31 is that:

[0126] Take 110g of the 70% refined glufosinate ammonium salt and potassium salt slurry prepared in Example 6, microsilica powder (particle size 400nm, specific surface area 30m 2 / g, water content 2.8%, porosity 65%) 2g, acetylenic glycol 1g, sodium fatty alcohol polyoxyethylene ether sulfate 1g, polyvinyl pyrrolidone 3g, sodium pyrophosphate 5g, defoaming agent 0.2g.

[0127] Example 37: Preparation of 50% refined glufosinate ammonium solid preparation (acid basis).

[0128] The difference between Example 37 and Example 15 is that:

[0129] 71.5 g of the 70% refined glufosinate ammonium slurry prepared in Example 1, carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 4g, acetylenic glycol 2g, sodium fatty alcohol polyoxyethylene ether sulfate 7g, sodium carboxymethyl cellulose 10g, sodium pyrophosphate 15g, ammonium sulfate 7.3g, defoaming agent 0.2g.

[0130] A 70% refined glufosinate ammonium salt slurry is mixed with carboxyl-modified modified nano-silica, acetylene glycol, glycoside-modified silicone polyether, fatty alcohol polyoxyethylene ether sodium sulfate and defoaming agent, sodium pyrophosphate and ammonium sulfate, and stirred evenly to make the material present a solid or semi-solid state. After mixing evenly, the mixture is granulated by extrusion or spray drying to obtain a refined glufosinate ammonium salt solid preparation.

[0131] Comparative Example: Preparation of 50% refined glufosinate ammonium solid preparation (acid basis).

[0132] 58.8g of 85% refined glufosinate ammonium salt powder (acid), carboxyl modified nano-silica (particle size 50nm, specific surface area 500m 2 / g, porosity 88%), 4g of acetylene glycol, 2g of acetylene glycol, 7g of sodium fatty alcohol polyoxyethylene ether sulfate, 10g of sodium carboxymethyl cellulose, 15g of sodium pyrophosphate, 3g of ammonium sulfate, 0.2g of defoamer, and 3g of ammonium sulfate were put into a high-speed mixer, and stirring was started. The mixing speed was set to 1000r / min and the mixing temperature was 40°C. The mixture was mixed for 20min and granulated by an extrusion granulator after uniform mixing.

[0133] The refined glufosinate ammonium solid preparations prepared in Examples 15 to 37 and the comparative example were tested for product content uniformity, sustained foaming, and disintegration. The specific results are shown in Table 1.

[0134] Table 1 Test results of indicators of refined glufosinate ammonium solid preparation.

[0135]

[0136]

[0137] As shown in Table 1, no heat generation occurred in Examples 15-36 during the extrusion granulation process, and the granules were smoothly formed and had a uniform appearance, indicating that the process using refined glufosinate ammonium salt slurry as raw material effectively solved the problems of slippage and heat generation in traditional raw powder granulation. Comparison of Examples 22-26 with Examples 15-21 shows that the slurry obtained by concentrating refined glufosinate ammonium salt mother liquor and the slurry obtained by reacting refined glufosinate acid with alkali metal hydroxide and / or nitrogen base are similar, with no difference in performance indicators. Examples 33 and 34 had severe foaming, highlighting the importance of defoamers. The fumed silica of Example 35 and the microsilica powder of Example 36 affected the final morphology and performance of the product compared to nano carbon dioxide and nano silicon microspheres. In Example 37, all materials were mixed and granulated at one time, resulting in a wet and sticky mixture, poor adsorption effect, a strong ammonia smell during the process, uneven content of the final product, and poor indicators. Compared with the comparative example in which heat is generated when raw powder is used for granulation, the present invention reduces equipment energy consumption and operation difficulty and improves production efficiency by using a slurry of refined glufosinate ammonium salt.

[0138] The weed control effect of the refined glufosinate ammonium solid formulations prepared in Examples 15 to 32 and the comparative example was tested. The weed control was carried out on wasteland with a refined glufosinate ammonium concentration of 40 g / mu and a spray volume of 40 L / mu, with 4 repetitions and a plot area of ​​30 m 2 The total control effect of weeds in wasteland was calculated based on the treatment with 40g glufosinate ammonium per mu 10 days after treatment. The specific results are shown in Table 2.

[0139] Table 2 Efficacy test results of refined glufosinate ammonium solid preparation

[0140]

[0141]

[0142] As shown in Table 2, the 88% refined glufosinate solid formulation demonstrated good overall plant-to-plant efficacy and fresh-weight efficacy in practical applications. Due to the relatively low level of surfactant added to this formulation, its efficacy was slightly inferior to that of the 50% refined glufosinate solid formulation, which is normal. The 50% refined glufosinate solid formulation prepared using refined glufosinate slurry granulation exhibited excellent efficacy, with virtually no difference in plant-to-plant efficacy and fresh-weight efficacy compared to the solid formulation granulated with refined grass flour. This strongly suggests that there is no substantial difference in the efficacy of the final product when the refined glufosinate solid formulations are prepared using these two different raw materials.

[0143] The traditional process for preparing refined glufosinate flour requires complex extraction and refining steps, which are not only cumbersome and energy-intensive, but also associated with environmental issues such as wastewater and waste residue emissions. This invention utilizes a breakthrough technology for direct granulation of refined glufosinate ammonium salt slurry, completely circumventing the pollutant generation process in traditional processes and eliminating the potential for wastewater and waste residue emissions at the source. Furthermore, the innovative introduction of a volatile organic solvent system significantly reduces energy consumption during the drying process, further mitigating the impact of production activities on the ecological environment, and achieving the dual goals of efficient resource utilization and low carbon emissions.

[0144] The present invention successfully builds an efficient and green production system through the deep integration of raw material innovation and process optimization. It not only greatly improves production efficiency and optimizes product quality stability, but also achieves the coordinated development of environmental and economic benefits. This technical solution combines technical foresight, economic feasibility and environmental friendliness, and provides a new path for the large-scale industrial production of refined glufosinate ammonium solid preparations. In the context of the era of green development and transformation of agriculture, it shows huge market application potential and industry demonstration value, and is expected to become the core technical solution for promoting the upgrading of the pesticide industry.

[0145] The present invention has been described in detail above with reference to the embodiments and comparative examples. However, the present invention is not limited to the above embodiments. Various modifications can be made within the scope of knowledge possessed by those skilled in the art without departing from the spirit of the present invention. Any content not described in detail in the present invention may be adapted from existing technologies.

Claims

1. A refined glufosinate ammonium solid preparation, characterized in that: Calculated by mass percentage, including: Refined glufosinate ammonium salt slurry, 50-80%; adsorbent, 1-50%; anti-caking agent, 1-30%; defoaming agent, 0-1%; The content of refined glufosinate in the refined glufosinate slurry is 45-70%, and the viscosity is >10000cp at 30°C; The anti-adhesive agent is composed of a composite of nanomaterials and surfactants. The surface of the nanomaterials is modified with hydrophilic groups, and the surfactants are adsorbed on the surface of the nanomaterials. Nanomaterials include modified nano-silica, modified nano-silicon microspheres, modified nano-alumina and / or modified nano-kaolin; The adsorbent includes a first adsorbent and / or a second adsorbent; the mass ratio of the first adsorbent to the second adsorbent is 1:(0.3-3).

2. The refined glufosinate-ammonium solid preparation according to claim 1, characterized in that The refined glufosinate ammonium salt slurry is prepared by concentrating the mother liquor containing the refined glufosinate ammonium salt; The content of 3-(hydroxymethylphosphono)propionic acid in the prepared refined glufosinate ammonium salt slurry is greater than 0.01%.

3. The refined glufosinate-ammonium solid preparation according to claim 1, wherein: The preparation of refined glufosinate ammonium salt slurry comprises: Refined glufosinate ammonium acid and alkali metal hydroxide and / or nitrogen base are placed in a mixed medium of a volatile alcohol organic solvent and / or water at a molar ratio of 1:1-1.5, and a refined glufosinate ammonium salt slurry is prepared through reaction.

4. The refined glufosinate-ammonium solid preparation according to claim 3, characterized in that: The alkali metal hydroxide includes potassium hydroxide and / or sodium hydroxide; the nitrogen base includes ammonia, alkylamine and / or alkylolamine; the mass ratio of water and volatile alcohol organic solvent in the mixed medium is (80-60): (20-40); the volatile alcohol organic solvent includes C1-C3 alkyl alcohol.

5. The refined glufosinate-ammonium solid preparation according to claim 1, characterized in that: Surfactants include anionic surfactants, nonionic surfactants and / or zwitterionic surfactants; Hydrophilic groups include carboxyl, amino, polyethylene glycol and / or poly(methylpropional) sulfobetaine.

6. The refined glufosinate-ammonium solid preparation according to claim 1, characterized in that: The surface of modified nano-silica is modified by hydrophilic groups, with a particle size of 10-100 nanometers, a specific surface area of ​​300-500 m² / g, and a porosity of 80-90%. The surface of the modified nano-silicon microspheres is modified by hydrophilic groups, with a particle size of 10-300 nanometers, a porosity of 70%-90%, and a specific surface area of ​​100-500 m² / g.

7. The refined glufosinate-ammonium solid preparation according to claim 1, characterized in that: The first adsorbent includes white carbon black, bentonite, diatomaceous earth, talc, activated alumina, soluble resin, soluble starch, chitosan, sodium alginate, magnesium aluminum silicate, polyvinyl pyrrolidone, polyvinyl alcohol, sodium carboxymethyl cellulose and / or lignin; The second adsorbent includes an anhydrous inorganic salt.

8. The refined glufosinate-ammonium solid preparation according to claim 1, characterized in that: Defoaming agents include silicone defoaming agents, mineral oil defoaming agents, vegetable oil defoaming agents or polyether defoaming agents.

9. A method for preparing the refined glufosinate-ammonium solid preparation according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Evenly mix the glufosinate-ammonium salt slurry and the anti-adhesive agent, add the first adsorbent to the mixture, and stir evenly until the material is in a solid or semi-solid state; S2. Continue to add the second adsorbent and mix, and obtain the refined glufosinate ammonium solid preparation by extrusion granulation or spray drying granulation.

10. The method for preparing the refined glufosinate ammonium solid preparation according to claim 9, wherein: S1 further adds defoamer during mixing.

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