Fine glufosinate-ammonium salt solid preparation and preparation method thereof

Abstract

The invention relates to the technical field of pesticides, in particular to a fine glufosinate-ammonium salt solid preparation and a preparation method thereof.The fine glufosinate-ammonium salt solid preparation is prepared from, by mass, 50-80% of fine glufosinate-ammonium salt slurry, 20-30% of adsorbent and 20-30% of anti-bonding agent. 1-50% of an adsorbent; 1-30% of an anti-adhesive agent; and 0-1% of a defoaming agent. According to the method, the refined glufosinate-ammonium salt slurry is directly used as the raw material for granulation, the complex process and cost of preparing the refined glufosinate-ammonium salt into crystals or other intermediates for re-granulation are abandoned, the production steps are reduced, the generation and emission of pollutants such as waste water and waste residues are correspondingly reduced, the pressure on the environment is reduced, and the method meets the environmental protection requirement.

Description

Technical Field

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

[0002] Glufosinate has two optical isomers, namely L-glufosinate and D-glufosinate. The L-form has phytotoxicity, and its herbicidal activity is twice that of the racemic mixture. It is easily decomposed in the soil, has less toxicity to humans and animals, has a wide herbicidal spectrum, and has little damage to the environment.

[0003] Among various dosage forms of glufosinate-ammonium, solid preparations can significantly save packaging costs and transportation costs compared with liquid preparations, especially the advantages of high-content soluble granules are more prominent. Currently, conventional solid preparations are mostly prepared from glufosinate-ammonium technical powder. The glufosinate-ammonium technical powder generally has a relatively large particle size and a rough surface. During the granulation process, especially when using extrusion granulation and other methods, problems such as difficult particle formation and difficult granule discharging are likely to occur, and abnormal situations such as extrusion slipping, no granule discharging, and overheating of the rotary granulator may also occur. During the granulation process, if the technical powder is not evenly mixed with other raw materials (auxiliaries, fillers, etc.), it may lead to uneven distribution of the active ingredient in the product, affecting the consistency and stability of the herbicidal effect and reducing the product quality. Summary of the Invention

[0004] In order to solve the problems in the background art, the present invention provides a solid preparation of glufosinate-ammonium salt and a preparation method thereof, which directly uses the glufosinate-ammonium salt paste as the raw material for granulation, abandons the complex process of making glufosinate-ammonium salt into crystals or other intermediates and then granulating, reduces costs and production steps, correspondingly reduces the generation and emission of pollutants such as waste water and waste residues, reduces the pressure on the environment, and meets the environmental protection requirements.

[0005] The technical solution adopted by the present invention to solve its technical problems is: to provide a solid preparation of glufosinate-ammonium salt, which includes glufosinate-ammonium salt paste, an adsorbent, and an anti-caking agent.

[0006] Further, by mass percentage, it includes: Glufosinate-ammonium salt paste, 50 - 80%; adsorbent, 1 - 50%; anti-caking agent, 1 - 30%; defoaming agent, 0 - 1%.

[0007] Further, the glufosinate-ammonium salt paste is prepared by concentrating the mother liquor containing glufosinate-ammonium salt; wherein, the content of 3-(hydroxymethylphosphinyl)propionic acid in the prepared glufosinate-ammonium salt paste is greater than 0.01%, and the preferred content is 0.01 - 1%. The glufosinate-ammonium salt mother liquor is a concentrated solution in the pesticide production process.

[0008] The ammonium glufosinate-ammonium salt slurry contains at least one of ammonium glufosinate-ammonium salt, potassium salt, isopropylamine salt, sodium salt, monoethylamine salt, monomethylamine salt, and monoethanolamine salt.

[0009] The preparation of the ammonium glufosinate-ammonium salt slurry includes: placing ammonium 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 to 1.5, and reacting to obtain the ammonium glufosinate-ammonium salt slurry.

[0010] Further, the alkali metal hydroxide includes potassium hydroxide and / or sodium hydroxide; the nitrogen base includes ammonia, alkylamine, and / or alkyl alkanolamine; the mass ratio of water to volatile alcohol organic solvent in the mixed medium is (80 - 60):(20 - 40); the volatile alcohol organic solvent includes C1 - C3 alkyl alcohols.

[0011] Further, the alkylamine includes methylamine, dimethylamine, and / or isopropylamine; the alkyl alkanolamine includes monoethanolamine, diethanolamine, and / or triethanolamine.

[0012] Further, the content of ammonium glufosinate in the ammonium glufosinate-ammonium salt slurry is 50 - 70%, and the viscosity at 30 °C > 10000 cp; preferably, the viscosity is 10000 - 3000000 cp.

[0013] Further, the anti-caking agent is composed of a composite of nanomaterials and surfactants. The nanomaterials are surface-modified with hydrophilic groups, and the surfactants are adsorbed on the surface of the nanomaterials.

[0014] Further, the nanomaterials include modified nano-silica, nano-silica microspheres, modified nano-alumina, and / or modified nano-kaolin; the surfactants include anionic surfactants, non-ionic surfactants, and / or zwitterionic surfactants.

[0015] Further, the hydrophilic groups include at least one of carboxyl group, amino group, polyethylene glycol, or sulfobetaine polymethylpropanecarboxylate.

[0016] Further, the surfactants include one or more of sodium lauryl ether sulfate, sodium dioctyl sulfosuccinate, alkylbenzene sulfonate, fatty alcohol polyoxyethylene ether, alkyl glycoside, polyethylene glycol, betaine, polyacrylate surfactants, fatty acid ester surfactants, polysorbate, alkyl sulfate, alkynediol, glycoside-modified polyether, organosilicon polymer, or polymer of methacrylate.

[0017] Further, the surface of the modified nano-silica is modified with hydrophilic groups, particle size: 10 - 100 nanometers, specific surface area: 300 - 500 m² / g, porosity: 80 - 90%; The surface of the modified nano-silica 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 - 500 m² / g, and a moisture content of <1%.

[0018] Furthermore, the adsorbent includes a first adsorbent and / or a second adsorbent; the first adsorbent includes silica white, bentonite, diatomite, talc, activated alumina, soluble resin, soluble starch, chitosan, sodium alginate, magnesium aluminum silicate, polyvinylpyrrolidone, polyvinyl alcohol, sodium carboxymethyl cellulose, and / or lignin; the second adsorbent includes anhydrous inorganic salts, and the anhydrous inorganic salts are preferably sodium pyrophosphate; the mass ratio of the first adsorbent to the second adsorbent is 1:(0.3 - 3); Furthermore, the defoamer includes silicone defoamers, mineral oil defoamers, vegetable oil defoamers, or polyether defoamers.

[0019] This application also provides a preparation method for a solid preparation of glufosinate-ammonium salt, comprising the following steps: Mix the glufosinate-ammonium salt paste with an anti-caking agent and an adsorbent until the material becomes solid or semi-solid, and obtain the solid preparation of glufosinate-ammonium salt by extrusion granulation or spray drying granulation.

[0020] Furthermore, a defoamer is further added during mixing.

[0021] This application also provides a preparation method for a solid preparation of glufosinate-ammonium salt, comprising the following steps: S1. Mix the glufosinate-ammonium salt paste with an anti-caking agent evenly, add the first adsorbent to the mixture, and stir evenly to make the material present a solid or semi-solid state; S2. Continue to add the second adsorbent for mixing, and obtain the solid preparation of glufosinate-ammonium salt by extrusion granulation or spray drying granulation.

[0022] Furthermore, a defoamer is further added during the mixing in S1.

[0023] The beneficial effects of the present invention are: 1. This application directly uses the glufosinate-ammonium salt paste as the raw material for granulation, abandoning the complex process of making the glufosinate-ammonium salt into crystals or other intermediates and then granulating, reducing costs and production steps, correspondingly reducing the generation and emission of pollutants such as wastewater and waste residues, reducing the pressure on the environment, and meeting the environmental protection requirements.

[0024] 2. This application uses a volatile organic solvent as the dispersion medium, reducing the moisture content of the glufosinate-ammonium salt paste, improving the fluidity of the glufosinate-ammonium salt, making it easier to mix evenly, and being suitable for spray drying or extrusion granulation processes, reducing the operation difficulty and requirements for equipment, and further reducing costs and improving production efficiency.

[0025] 3. The adsorbent selected in this application can adsorb the paste, adsorb part of the water in the paste, and reduce the energy consumption of subsequent drying.

[0026] 4. The anti-adhesive agent of this application reduces the generation of viscous lumps and the friction generated during the granulation process by reducing the surface tension of the paste and the electrostatic repulsion effect between surface nanomaterials, and at the same time improves the particle disintegration performance. Specific embodiments

[0027] Next, the technical solutions in the embodiments of the invention will be clearly and completely described in conjunction with the attached tables in the embodiments of the invention. It can be understood that the specific embodiments described herein are only used to explain the present invention, rather than limiting the present invention. In addition, it should be noted that for the convenience of description, only part of the structures related to the present invention rather than all structures are shown in the attached tables.

[0028] Example 1: Prepare 70% ammonium glufosinate-ammonium paste (calculated as acid).

[0029] By mass percentage, it includes 74% of 95% glufosinate acid, 6.6% of ammonia, 4% of ethanol, and 15.4% of water. Put 95% glufosinate acid into the kneading reactor according to the mass percentage, then add the mixed solution of water and ethanol, continuously stir, add ammonia and mix for reaction to obtain 70% ammonium glufosinate-ammonium paste with a viscosity of 1920000 cP at 30°C.

[0030] Example 2: Prepare 65% potassium glufosinate paste (calculated as acid).

[0031] By mass percentage, it includes 68.5% of 95% glufosinate acid, 20.5% of potassium hydroxide, 3% of ethanol, and 8% of water. Put 95% glufosinate acid into the kneading reactor according to the mass percentage, then add the mixed solution of water and ethanol, continuously stir, add potassium hydroxide and mix for reaction to obtain 65% potassium glufosinate paste with a viscosity of 1860000 cP at 30°C.

[0032] Example 3: Prepare 65% sodium glufosinate paste (calculated as acid).

[0033] By mass percentage, it includes 68.5% of 95% glufosinate acid, 14.5% of sodium hydroxide, 5% of ethanol, and 12% of water. Put 95% glufosinate acid into the kneading reactor according to the mass percentage, then add the mixed solution of water and ethanol, continuously stir, add sodium hydroxide and mix for reaction to obtain 65% sodium glufosinate paste with a viscosity of 1810000 cP at 30°C.

[0034] Example 4: Prepare 65% isopropylammonium glufosinate paste (calculated as acid).

[0035] By mass percentage, it includes 68.5% of 95% glufosinate acid, 21.5% of isopropylamine, 3% of ethanol, and 7% of water. Put 95% glufosinate acid into a kneading reactor according to the mass percentage, then add the mixed solution of water and ethanol, continuously stir, add isopropylamine and mix for reaction to obtain a 65% glufosinate-ammonium salt paste with a viscosity of 1,900,000 cP at 30°C.

[0036] Example 5: Prepare a 70% glufosinate-ammonium salt and glufosinate-sodium salt paste (calculated as acid).

[0037] By mass percentage, it includes 74% of 95% glufosinate acid, 7.7% of sodium hydroxide, 3.4% of ammonia, 4.5% of ethanol, and 10.4% of water. Put 95% glufosinate acid into a kneading reactor according to the mass percentage, then add the mixed solution of water and ethanol, continuously stir, add sodium hydroxide and ammonia and mix for reaction to obtain a 70% glufosinate-ammonium salt and glufosinate-sodium salt paste with a viscosity of 1,930,000 cP at 30°C.

[0038] Example 6: Prepare a 70% glufosinate-ammonium salt and glufosinate-potassium salt paste (calculated as acid).

[0039] By mass percentage, it includes 74% of 95% glufosinate acid, 5.4% of potassium hydroxide, 5.1% of ammonia, 4% of ethanol, and 11.5% of water. Put 95% glufosinate acid into a kneading reactor according to the mass percentage, then add the mixed solution of water and ethanol, continuously stir, add potassium hydroxide and ammonia and mix for reaction to obtain a 70% glufosinate-ammonium salt and glufosinate-potassium salt paste with a viscosity of 1,940,000 cP at 30°C.

[0040] Example 7: Prepare a 70% glufosinate-ammonium salt and glufosinate-isopropylamine salt paste (calculated as acid).

[0041] By mass percentage, it includes 74% of 95% glufosinate acid, 9.2% of isopropylamine, 4.0% of ammonia, 3.8% of ethanol, and 9.0% of water. Put 95% glufosinate acid into a kneading reactor according to the mass percentage, then add the mixed solution of water and ethanol, continuously stir, add isopropylamine and ammonia and mix for reaction to obtain a 70% glufosinate-ammonium salt and glufosinate-isopropylamine salt paste with a viscosity of 1,980,000 cP at 30°C.

[0042] Example 8: Prepare a 70% glufosinate-ammonium salt and glufosinate-monoethanolamine salt paste (calculated as acid).

[0043] By mass percentage, it includes 74% of 95% glufosinate-ammonium acid, 7.2% of monoethanolamine, 4.6% of ammonia, 3.5% of ethanol, and 10.7% of water. Add 95% glufosinate-ammonium acid into a kneading reactor according to the mass percentage, then add the mixed solution of water and ethanol, continuously stir, add monoethanolamine and ammonia for mixed reaction to obtain a slurry of 70% glufosinate-ammonium salt and glufosinate monoethanolamine salt with a viscosity of 1,960,000 cP at 30°C.

[0044] Example 9: Preparation of a slurry of 70% glufosinate-ammonium salt and glufosinate monomethylamine salt (calculated as acid).

[0045] By mass percentage, it includes 74% of 95% glufosinate-ammonium acid, 6.2% of monomethylamine, 3.3% of ammonia, 4.5% of ethanol, and 12% of water. Add 95% glufosinate-ammonium acid into a kneading reactor according to the mass percentage, then add the mixed solution of water and ethanol, continuously stir, add monomethylamine and ammonia for mixed reaction to obtain a slurry of 70% glufosinate-ammonium salt and glufosinate monomethylamine salt with a viscosity of 1,940,000 cP at 30°C.

[0046] Example 10: Preparation of a slurry of 64.5% glufosinate-ammonium salt (calculated as acid).

[0047] 100 g of 10% glufosinate-ammonium salt mother liquor is heated and concentrated at 110°C to remove 84.5 g of water, obtaining a slurry of 64.5% glufosinate-ammonium salt with a viscosity of 1,800,000 cP at 30°C.

[0048] Example 11: Preparation of a slurry of 65.2% glufosinate-potassium salt (calculated as acid).

[0049] 100 g of 15% glufosinate-potassium salt mother liquor is heated and concentrated at 110°C to remove 77 g of water, obtaining a slurry of 65.2% glufosinate-potassium salt with a viscosity of 1,840,000 cP at 30°C.

[0050] Example 12: Preparation of a slurry of 64.5% glufosinate-ammonium salt and glufosinate-isopropylamine salt (calculated as acid).

[0051] 100 g of a mixed mother liquor of 10% glufosinate-ammonium salt and glufosinate-isopropylamine salt is heated and concentrated at 110°C to remove 84.5 g of water, obtaining a slurry of 64.5% glufosinate-ammonium salt and glufosinate-isopropylamine salt with a viscosity of 1,965,000 cP at 30°C.

[0052] Example 13: Preparation of a slurry of 64.5% glufosinate-ammonium salt and glufosinate monomethylamine salt (calculated as acid).

[0053] 100 g of a mixed mother liquor of 12% glufosinate-ammonium and glufosinate-N-methylamine was concentrated by heating at 110 °C to remove 81.5 g of water, obtaining a 64.9% glufosinate-ammonium and glufosinate-N-methylamine paste with a viscosity of 1,940,000 cP at 30 °C.

[0054] Example 14: Preparation of a 65.2% glufosinate-ammonium, glufosinate-potassium and glufosinate-N-methylamine paste (calculated as acid).

[0055] 100 g of a mixed mother liquor of 15% glufosinate-ammonium, glufosinate-potassium and glufosinate-N-methylamine was concentrated by heating at 110 °C to remove 77 g of water, obtaining a 65.2% glufosinate-ammonium, glufosinate-potassium and glufosinate-N-methylamine paste with a viscosity of 1,910,000 cP at 30 °C.

[0056] Example 15: Preparation of a 50% glufosinate-ammonium solid preparation (calculated as acid).

[0057] Take 71.5 g of the 70% glufosinate-ammonium paste prepared in Example 1, 4 g of carboxyl-modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%), 4 g of alkynediol, 7 g of sodium lauryl ether sulfate, 10 g of sodium carboxymethyl cellulose, 15 g of sodium pyrophosphate, 7.3 g of ammonium sulfate, and 0.2 g of defoamer.

[0058] Put the 70% glufosinate-ammonium paste, carboxyl-modified nano-silica, alkynediol, sodium carboxymethyl cellulose, sodium lauryl ether sulfate and defoamer into a high-speed mixer, start stirring, set the mixing speed at 1000 r / min and the mixing temperature at 40 °C. After mixing evenly, add sodium pyrophosphate to the mixture and stir evenly until the material presents a solid or semi-solid state; continue to add ammonium sulfate for mixing. After mixing evenly, granulate by extrusion or spray drying to obtain a glufosinate salt solid preparation.

[0059] Example 16: Preparation of a 50% glufosinate-potassium solid preparation (calculated as acid).

[0060] The difference between Example 16 and Example 15 is that: Take 77 g of the 65% glufosinate-potassium paste prepared in Example 2, 4 g of carboxyl-modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%), 2 g of alkynediol, 7 g of sodium lauryl ether sulfate, 10 g of sodium carboxymethyl cellulose, 15 g of anhydrous calcium chloride, 1.5 g of potassium sulfate, and 0.2 g of defoamer.

[0061] Example 17: Preparation of a 50% glufosinate-sodium solid preparation (calculated as acid).

[0062] Example 17 is different from Example 15 in that: Take 77 g of the 65% ammonium glufosinate-ammonium sodium salt paste prepared in Example 3, 4 g of amino-modified modified nano-silica (particle size 100 nm, specific surface area 400 m 2 / g, porosity 85%), 2 g of alkynediol, 7 g of sodium lauryl ether sulfate, 10 g of sodium carboxymethyl cellulose, 15 g of sodium pyrophosphate, 5.9 g of sodium sulfate, and 0.2 g of defoamer.

[0063] Example 18: Preparation of a 50% solid preparation of ammonium glufosinate-ammonium and ammonium glufosinate-sodium (calculated as acid).

[0064] Example 18 is different from Example 15 in that: Take 71.5 g of the 70% ammonium glufosinate-ammonium and ammonium glufosinate-sodium salt paste prepared in Example 5, 4 g of carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%), 2 g of alkynediol, 7 g of sodium lauryl ether sulfate, 10 g of sodium carboxymethyl cellulose, 15 g of sodium pyrophosphate, 6.5 g of ammonium sulfate, and 0.2 g of defoamer.

[0065] Example 19: Preparation of a 50% solid preparation of ammonium glufosinate-ammonium and ammonium glufosinate-potassium (calculated as acid).

[0066] Example 19 is different from Example 15 in that: Take 71.5 g of the 70% ammonium glufosinate-ammonium and ammonium glufosinate-potassium salt paste prepared in Example 6, 4 g of carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%), 2 g of glycoside-modified organosilicon polyether, 7 g of sodium dioctyl sulfosuccinate, 10 g of sodium carboxymethyl cellulose, 15 g of sodium pyrophosphate, 2.4 g of ammonium sulfate, 2.45 g of potassium sulfate, and 0.2 g of defoamer.

[0067] Example 20: Preparation of a 50% solid preparation of ammonium glufosinate-ammonium and ammonium glufosinate-monoethanolamine (calculated as acid).

[0068] Example 20 is different from Example 15 in that: Take 71.5 g of the 70% ammonium glufosinate-ammonium and ammonium glufosinate-monoethanolamine salt paste prepared in Example 8, 4 g of carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%), 2 g of alkynediol, 7 g of sodium dioctyl sulfosuccinate, 10 g of sodium carboxymethyl cellulose, 15 g of anhydrous trisodium phosphate, and 0.2 g of defoamer.

[0069] Example 21: Preparation of a 50% solid preparation of glufosinate-ammonium and glufosinate-N-methylamine (calculated as acid).

[0070] The difference between Example 21 and Example 15 is that: Take 71.5 g of the 70% glufosinate-ammonium and glufosinate-N-methylamine paste prepared in Example 9, 4 g of carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%), 2 g of glycoside-modified silicone polyether, 3.5 g of sodium lauryl ether sulfate, 3.5 g of sodium dioctyl sulfosuccinate, 10 g of sodium carboxymethyl cellulose, 15 g of sodium pyrophosphate, 5 g of ammonium sulfate, and 0.2 g of defoamer.

[0071] Example 22: Preparation of a 50% solid preparation of glufosinate-ammonium (calculated as acid).

[0072] The difference between Example 22 and Example 15 is that: Take 77.6 g of the 64.5% glufosinate-ammonium paste prepared in Example 10, 4 g of carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%), 2 g of acetylenic diol, 7 g of sodium lauryl ether sulfate, 10 g of sodium carboxymethyl cellulose, 15 g of sodium pyrophosphate, 7.3 g of ammonium sulfate, and 0.2 g of defoamer.

[0073] Example 23: Preparation of a 50% solid preparation of glufosinate-potassium (calculated as acid).

[0074] The difference between Example 23 and Example 15 is that: Take 76.7 g of the 65.2% glufosinate-potassium paste prepared in Example 11, 4 g of carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%), 2 g of acetylenic diol, 7 g of sodium lauryl ether sulfate, 10 g of sodium carboxymethyl cellulose, 15 g of anhydrous trisodium phosphate, 1.5 g of ammonium sulfate, and 0.2 g of defoamer.

[0075] Example 24: Preparation of a 50% solid preparation of glufosinate-ammonium and glufosinate-isopropylamine (calculated as acid).

[0076] The difference between Example 24 and Example 15 is that: Take 77.6 g of the 64.5% glufosinate-ammonium and glufosinate-isopropylamine paste prepared in Example 12, 4 g of carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 24 g of carboxyl group-modified modified nano-silica (particle size 50 nm, specific surface area 500 m

[0077] Example 25: Preparation of a solid preparation of 50% glufosinate-ammonium and glufosinate monomethylammonium (calculated as acid).

[0078] The difference between Example 25 and Example 15 is that: Take 77.6 g of the 64.5% glufosinate-ammonium and glufosinate monomethylammonium paste prepared in Example 13, carboxyl group-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 4 g, alkynediol 2 g, sodium docusate 7 g, sodium carboxymethyl cellulose 10 g, sodium pyrophosphate 15 g, ammonium sulfate 2.7 g, defoaming agent 0.2 g.

[0079] Example 26: Preparation of a solid preparation of 50% glufosinate-ammonium, glufosinate-potassium and glufosinate monomethylammonium (calculated as acid).

[0080] The difference between Example 26 and Example 15 is that: Take 77.6 g of the 64.5% glufosinate-ammonium, glufosinate-potassium and glufosinate monomethylammonium paste prepared in Example 14, carboxyl group-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 4 g, alkynediol 2 g, sodium docusate 3.5 g, sodium docusate sulfonate 3.5 g, sodium carboxymethyl cellulose 10 g, sodium pyrophosphate 15 g, ammonium sulfate 4.6 g, defoaming agent 0.2 g.

[0081] Example 27: Preparation of an 88% glufosinate-ammonium solid preparation (calculated as salt).

[0082] The difference between Example 27 and Example 15 is that: Take 115 g of the 70% glufosinate-ammonium paste prepared in Example 1, carboxyl group-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 2 g, alkynediol 1 g, sodium docusate 1 g, polyvinylpyrrolidone 3 g, sodium pyrophosphate 5 g, defoaming agent 0.2 g.

[0083] Example 28: Preparation of an 88% glufosinate-potassium solid preparation (calculated as salt).

[0084] The difference between Example 28 and Example 15 is that: Take 112 g of the 65% glufosinate-ammonium potassium salt paste prepared in Example 2, 2 g of carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%), 1 g of alkynediol, 1 g of sodium lauryl polyoxyethylene ether sulfate, 3 g of polyvinylpyrrolidone, 5 g of anhydrous trisodium phosphate, and 0.2 g of defoamer.

[0085] Example 29: Preparation of 88% glufosinate-ammonium sodium salt solid preparation (calculated as salt).

[0086] The difference between Example 29 and Example 15 is that: Take 121 g of the 65% glufosinate-ammonium sodium salt paste prepared in Example 3, 2 g of carboxyl-modified modified nano-silica microspheres (particle size 15 nm, specific surface area 500 m 2 / g, moisture content: 0.76%, porosity 85%), 1 g of glycoside-modified organosilicon polyether, 1 g of sodium lauryl polyoxyethylene ether sulfate, 3 g of polyvinylpyrrolidone, 5 g of anhydrous trisodium phosphate, and 0.2 g of defoamer.

[0087] Example 30: Preparation of 88% glufosinate-ammonium and sodium salt solid preparation (calculated as salt).

[0088] The difference between Example 30 and Example 15 is that: Take 113.3 g of the 70% glufosinate-ammonium and sodium salt paste prepared in Example 5, 2 g of amino-modified modified nano-silica microspheres (particle size 20 nm, specific surface area 450 m 2 / g, moisture content: 0.53%, porosity 81%), 1 g of alkynediol, 1 g of sodium lauryl polyoxyethylene ether sulfate, 3 g of polyvinylpyrrolidone, 5 g of sodium pyrophosphate, and 0.2 g of defoamer.

[0089] Example 31: Preparation of 88% glufosinate-ammonium and potassium salt solid preparation (calculated as salt).

[0090] The difference between Example 31 and Example 15 is that: Take 110 g of the 70% glufosinate-ammonium and potassium salt paste prepared in Example 6, 2 g of carboxyl-modified modified nano-silica microspheres (particle size 15 nm, specific surface area 500 m 2 / g, moisture content: 0.76%, porosity 85%), 1 g of alkynediol, 1 g of sodium lauryl polyoxyethylene ether sulfate, 3 g of polyvinylpyrrolidone, 5 g of sodium pyrophosphate, and 0.2 g of defoamer.

[0091] Example 32: Preparation of 88% glufosinate-ammonium and monomethylamine salt solid preparation (calculated as salt).

[0092] The difference between Example 32 and Example 15 is that: Take 110.3 g of the 70% glufosinate-ammonium and monomethylamine salt paste prepared in Example 9, 2 g of carboxyl-modified modified nano-silica microspheres (particle size 15 nm, specific surface area 500 m 2 / g, moisture content: 0.76%, porosity 85%), 1 g of glycoside-modified organosilicon polyether, 1 g of sodium dioctyl sulfosuccinate, 3 g of polyvinylpyrrolidone, 5 g of anhydrous calcium chloride, and 0.2 g of defoamer.

[0093] Example 33: Preparation of 50% glufosinate-ammonium solid preparation (calculated as acid).

[0094] The difference between Example 33 and Example 15 is that: Take 71.5 g of the 70% glufosinate-ammonium paste prepared in Example 1, 4 g of carboxyl-modified modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%), 2 g of alkynediol, 7 g of fatty alcohol polyoxyethylene ether sodium sulfate, 10 g of sodium carboxymethyl cellulose, 15 g of sodium pyrophosphate, and 7.3 g of ammonium sulfate.

[0095] Example 34: Preparation of 88% glufosinate-ammonium and potassium salt solid preparation (calculated as salt).

[0096] The difference between Example 34 and Example 31 is that: Take 110 g of the 70% glufosinate-ammonium and potassium salt paste prepared in Example 6, 2 g of carboxyl-modified modified nano-silica microspheres (particle size 15 nm, specific surface area 500 m 2 / g, moisture content: 0.76%, porosity 85%), 1 g of alkynediol, 1 g of fatty alcohol polyoxyethylene ether sodium sulfate, 3 g of polyvinylpyrrolidone, and 5 g of sodium pyrophosphate.

[0097] Example 35: Preparation of 50% glufosinate-ammonium solid preparation (calculated as acid).

[0098] The difference between Example 35 and Example 15 is that: Take 71.5 g of the 70% glufosinate-ammonium paste prepared in Example 1, fumed silica (particle size 450 nm, specific surface area 300 m 2 / g, porosity 55%) 10 g, 2 g of alkynediol, 7 g of fatty alcohol polyoxyethylene ether sodium sulfate, 10 of sodium carboxymethyl cellulose, 15 g of sodium pyrophosphate, 7.3 g of ammonium sulfate, and 0.2 g of defoamer.

[0099] Example 36: Preparation of 88% glufosinate-ammonium and potassium salt paste (calculated as salt).

[0100] The difference between Example 36 and Example 31 is that: Take 110 g of the 70% glufosinate-ammonium and potassium salt paste prepared in Example 6, 2 g of microsilica (particle size 400 nm, specific surface area 30 m 2 / g, moisture content 2.8%, porosity 65%), 1 g of alkynediol, 1 g of sodium lauryl polyoxyethylene ether sulfate, 3 g of polyvinylpyrrolidone, 5 g of sodium pyrophosphate, and 0.2 g of defoamer.

[0101] Example 37: Preparation of 50% glufosinate-ammonium solid preparation (calculated as acid).

[0102] The difference between Example 37 and Example 15 is that: Take 71.5 g of the 70% glufosinate-ammonium paste prepared in Example 1, carboxyl-modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 4 g, alkynediol 2 g, sodium lauryl polyoxyethylene ether sulfate 7 g, sodium carboxymethyl cellulose 10 g, sodium pyrophosphate 15 g, ammonium sulfate 7.3 g, and defoamer 0.2 g.

[0103] Mix the 70% glufosinate-ammonium paste with carboxyl-modified nano-silica, alkynediol, glycoside-modified organosilicon polyether, sodium lauryl polyoxyethylene ether sulfate and defoamer, sodium pyrophosphate, ammonium sulfate, and stir evenly until the material presents a solid or semi-solid state. After mixing evenly, granulate by extrusion granulation or spray drying granulation to obtain the glufosinate-ammonium solid preparation.

[0104] Comparative Example: Preparation of 50% glufosinate-ammonium solid preparation (calculated as acid).

[0105] Select 58.8 g (calculated as acid) of 85% glufosinate-ammonium technical powder, carboxyl-modified nano-silica (particle size 50 nm, specific surface area 500 m 2 / g, porosity 88%) 4 g, alkynediol 2 g, sodium lauryl polyoxyethylene ether sulfate 7 g, sodium carboxymethyl cellulose 10 g, sodium pyrophosphate 15 g, ammonium sulfate 3 g, defoamer 0.2 g, and 3 g of ammonium sulfate are put into a high-speed mixer, start stirring, set the mixing speed at 1000 r / min, the mixing temperature at 40 °C, mix for 20 min, and granulate by an extrusion granulator after mixing evenly.

[0106] For the glufosinate-ammonium solid preparations prepared in Examples 15 to 37 and the comparative example, test the product content uniformity, persistent foaming property, and disintegration property. The specific results are shown in Table 1.

[0107] Table 1 Detection results of the indicators of the glufosinate-ammonium solid preparation.

[0108]

[0109]

[0110] As can be seen from Table 1, no heat generation occurred during the extrusion granulation process in Examples 15 - 36, and the granulation was smooth with uniform appearance, indicating that the process using the glufosinate - ammonium salt paste as the raw material effectively solved the problems of slipping and heat generation in traditional raw powder granulation. Comparing Examples 22 - 26 with Examples 15 - 21 shows that the pastes prepared by concentrating the glufosinate - ammonium salt mother liquor and the paste prepared by reacting glufosinate - ammonium acid with alkali metal hydroxides and / or nitrogen - containing bases are similar and there is no difference in performance indicators. Severe foaming occurred in Examples 33 and 34, highlighting the importance of defoamers. The fumed silica in Example 35 and the microsilica powder in Example 36 affected the final form and performance of the product compared with 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, strong ammonia smell during the process, and uneven content of the final product with poor indicators. Compared with the heat generation during raw powder granulation in the comparative example, the present invention uses the glufosinate - ammonium salt paste, reducing the equipment energy consumption and operation difficulty and improving the production efficiency.

[0111] The weeding control effects of the glufosinate - ammonium salt solid preparations prepared in Examples 15 to 32 and the comparative example were tested. For controlling weeds in wasteland, with the mass concentration of glufosinate - ammonium being 40 g / mu and the spraying liquid volume being 40 L / mu, 4 replicates were set, and the plot area was 30 m 2 , and the total weeding control effect of the wasteland weeds 10 days after treatment with 40 g / mu of glufosinate - ammonium was statistically analyzed. The specific results are shown in Table 2.

[0112] Table 2 Pharmacodynamic test results of glufosinate - ammonium salt solid preparations

[0113]

[0114] As can be seen from Table 2, in the actual application of 88% glufosinate - ammonium salt solid preparations, both the overall plant control effect and the fresh weight control effect showed good trends. Due to the relatively low addition amount of surfactants in this preparation, its drug efficacy was slightly inferior to that of 50% glufosinate - ammonium salt solid preparations, which is a normal phenomenon. The 50% glufosinate - ammonium salt solid preparation prepared by granulating with glufosinate - ammonium salt paste showed excellent drug efficacy, and there was basically no difference in its plant control effect and fresh weight control effect compared with the solid preparation granulated with glufosinate - ammonium raw powder, which strongly indicates that there is no substantial difference in the drug efficacy of the final products when using two different raw materials to prepare glufosinate - ammonium salt solid preparations.

[0115] The preparation process of traditional glufosinate-ammonium powder requires complex powder extraction and refining processes, which are not only cumbersome and energy-consuming, but also accompanied by environmental problems such as wastewater and waste residue emissions. The present invention breakthroughly adopts the direct granulation technology of glufosinate-ammonium salt paste, completely avoiding the pollutant generation links in the traditional process and eliminating the hidden danger of wastewater and waste residue emissions from the source. In addition, the innovative introduction of a volatile organic solvent system significantly reduces the energy consumption in the drying process, further reducing the impact of production activities on the ecological environment and achieving the dual goals of efficient resource utilization and low-carbon emissions.

[0116] Through the deep integration of raw material innovation and process optimization, the present invention has successfully constructed an efficient and green production system. It not only greatly improves production efficiency and optimizes the quality stability of products, but also realizes the coordinated development of environmental benefits and economic benefits. This technical solution combines technological foresight, economic feasibility and environmental friendliness, providing a new path for the large-scale industrial production of glufosinate-ammonium salt solid preparations. In the context of the era of agricultural green development transformation, it shows great market application potential and industry demonstration value, and is expected to become the core technical solution to promote the upgrading of the pesticide industry.

[0117] The present invention has been described in detail above in combination with examples and comparative examples. However, the present invention is not limited to the above embodiments, and various changes can be made without departing from the purpose of the present invention within the scope of knowledge possessed by those of ordinary skill in the art. The content not described in detail in the present invention can all adopt the prior art.

Claims

1. A solid preparation of glufosinate-ammonium salt, characterized in that: It includes glufosinate-ammonium salt paste, adsorbent and anti-caking agent.

2. The solid preparation of the ammonium glufosinate-ammonium according to claim 1, wherein By mass percentage, it includes: Glufosinate-ammonium salt paste, 50 - 80%; adsorbent, 1 - 50%; anti-caking agent, 1 - 30%; defoamer, 0 - 1%.

3. The glufosinate-ammonium salt solid preparation according to claim 1, wherein The glufosinate-ammonium salt paste is prepared by concentrating the mother liquor containing glufosinate-ammonium salt; Among them, the content of 3-(hydroxymethylphosphinyl)propionic acid in the prepared glufosinate-ammonium salt paste is greater than 0.01%.

4. The glufosinate-ammonium salt solid preparation according to claim 1, characterized in that: The preparation of the glufosinate-ammonium salt paste includes: Put glufosinate acid and alkali metal hydroxide and / or nitrogen base in a mixed medium of volatile alcohol organic solvent and / or water in a molar ratio of 1:1 - 1.5, and react to obtain the glufosinate-ammonium salt paste.

5. The glufosinate-ammonium salt solid preparation according to claim 4, wherein: The alkali metal hydroxide includes potassium hydroxide and / or sodium hydroxide; The nitrogen base includes ammonia, alkylamine and / or alkyl alkanolamine; 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.

6. The glufosinate-ammonium salt solid preparation according to claim 1, wherein: The content of glufosinate in the glufosinate-ammonium salt paste is 45 - 70%, and the viscosity at 30 °C > 10000 cp.

7. The solid preparation of the ammonium glufosinate-ammonium according to claim 1, characterized in that: The anti-caking agent is composed of a composite of nano material and surfactant. The surface of the nano material is modified with hydrophilic groups, and the surfactant is adsorbed on the surface of the nano material; The nano material includes modified nano silica, modified nano silicon microspheres, modified nano alumina and / or modified nano kaolin; The surfactant includes anionic surfactant, non-ionic surfactant and / or zwitterionic surfactant; The hydrophilic groups include carboxyl group, amino group, polyethylene glycol and / or poly(methylpropylcarboxylic acid)sulfobetaine.

8. The glufosinate-ammonium salt solid preparation according to claim 7, wherein: The surface of the modified nano silica is modified with hydrophilic groups, particle size: 10 - 100 nm, specific surface area: 300 - 500 m² / g, porosity: 80 - 90%; The surface of the modified nano silicon microspheres is modified with hydrophilic groups, particle size: 10 - 300 nm, porosity: 70% - 90%, specific surface area: 100 - 500 m² / g.

9. The glufosinate-ammonium salt solid preparation according to claim 2, wherein: The adsorbent includes a first adsorbent and / or a second adsorbent; The first adsorbent includes silica white, bentonite, diatomite, talc, activated alumina, soluble resin, soluble starch, chitosan, sodium alginate, magnesium aluminum silicate, polyvinylpyrrolidone, polyvinyl alcohol, sodium carboxymethyl cellulose and / or lignin; The second adsorbent includes anhydrous inorganic salts; The mass ratio of the first adsorbent to the second adsorbent is 1:(0.3 - 3).

10. The glufosinate-ammonium salt solid preparation according to claim 2, wherein: The defoamer includes silicone defoamer, mineral oil defoamer, vegetable oil defoamer or polyether defoamer.

11. A preparation method of the glufosinate-ammonium solid preparation according to any one of claims 1-10, characterized in that, It includes the following steps: Mix the glufosinate-ammonium salt paste with an anti-caking agent and an adsorbent until the material becomes solid or semi-solid, and obtain the glufosinate-ammonium salt solid preparation by extrusion granulation or spray drying granulation.

12. The preparation method of the solid preparation of the ammonium glufosinate-ammonium according to claim 11, characterized in that Add an antifoaming agent during mixing.

13. A preparation method of the solid preparation of the ammonium glufosinate-ammonium salt as described in any one of claims 1-10, characterized in that, It includes the following steps: S1. Mix the glufosinate-ammonium salt paste with the anti-caking agent evenly, add the first adsorbent to the mixture, and stir evenly to make the material present a solid or semi-solid state; S2. Continue to add the second adsorbent for mixing, and obtain the glufosinate-ammonium salt solid preparation by extrusion granulation or spray drying granulation.

14. The preparation method of the solid preparation of the ammonium glufosinate-ammonium according to claim 13, characterized in that, Add an antifoaming agent during the mixing in S1.

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