Preparation method of glyphosate-triclopyr soluble powder

Abstract

The present application provides a preparation method of glyphosate and triclopyr soluble powder, comprising the following process steps: triclopyr, inorganic base and appropriate amount of water are put into a kneader, stirring is started, the mixing temperature of the materials is 40-50 DEG C, the materials are unloaded after stirring and mixing, the materials are stored for three days, then dried and crushed. Triclopyr salt, filler are put into a mixer, glyphosate salt and adjuvant are added and mixed, then taken out and crushed. The glyphosate and triclopyr soluble powder product prepared by the present application has stable quality, excellent solubility and wetting performance, has good control effect on weeds, and the preparation method is simple in operation, lower in energy consumption and less in wastewater.

Description

Technical Field

[0001] This invention discloses a method for preparing glyphosate-triclopyroxyacetic acid soluble powder, which belongs to the field of herbicides. It not only solves the problems of high energy consumption and large wastewater volume of the crystallization method, but also ensures stable product quality and excellent weed control effect. Background Technology

[0002] Glyphosate, chemically known as N-(methyl phosphate)glycine, is an organophosphorus herbicide. It is a systemic, broad-spectrum, non-selective herbicide with characteristics such as broad spectrum, low toxicity, no residue, systemic action, and excellent non-selective properties. It is widely used for weed control in genetically modified crops or non-arable land.

[0003] Triclopyralid (Greengrass) is a pyridineoxycarboxylic acid herbicide, a systemic selective herbicide. It is absorbed by the leaves and roots of plants and translocated throughout the entire plant, causing root, stem, and leaf malformation, vascular bundle blockage or rupture, and gradual plant death. It is effective only against broadleaf plants and almost ineffective against grassy weeds. It is widely used in non-arable land for the control of broadleaf weeds and shrubs.

[0004] A soluble powder formulated with glyphosate and triclopyralid can be used to control weeds and shrubs on non-arable land, suitable for eucalyptus forests, firebreaks, and other similar applications. It offers excellent control of weeds and shrubs at a low cost. The preparation of glyphosate·triclopyralid soluble powder requires the technical grade glyphosate and triclopyralid to be converted into a salt, which is then formulated into a soluble powder. Salt formation significantly increases the solubility of the technical grade; if salt formation is inadequate, the solubility of the soluble powder will not meet quality standards. The crystallization method for preparing triclopyralid salt involves reacting triclopyralid with an alkali in solution, heating to complete the reaction, continuing to heat to evaporate some of the solvent, and then cooling to allow the triclopyralid salt to crystallize out. While crystallization produces good salt formation and stable quality, it requires heating and cooling the solution, resulting in high energy consumption. Furthermore, some triclopyroxyacetate remains unprecipitated in the mother liquor, leading to large volumes of difficult-to-treat wastewater. Each ton of potassium triclopyroxyacetate produces 1.7 tons of wastewater and consumes 1.3 tons of steam. Considering water recycling, the kneading mixing method of this invention produces no process wastewater and consumes only 130 kWh of electricity per ton of potassium triclopyroxyacetate, significantly reducing energy consumption.

[0005] Furthermore, experiments revealed that the soluble powder formulated with glyphosate and triclopyralid is prone to instability in solubility and poor resistance to hard water due to the properties of triclopyralid. Commercially available 60% glyphosate·triclopyralid soluble powder exhibits slight precipitation after dilution with water. Based on these reasons, an experimental method was developed to prepare glyphosate·triclopyralid soluble powder that is simple to operate, consumes less energy, produces no process wastewater, and yields stable product quality. The resulting 60% glyphosate·triclopyralid soluble powder is clear and transparent without precipitation after dilution with water, and all indicators meet the standard requirements, demonstrating good weed control efficacy, thus completing this invention. Summary of the Invention

[0006] To address the problems of high energy consumption, large wastewater volume, unstable solubility index, and poor hard water resistance in the original process, the purpose of this invention is to develop a method for preparing glyphosate-triclopyroxyacetic acid soluble powder, which makes the preparation of glyphosate-triclopyroxyacetic acid soluble powder simpler, consumes less energy, produces less wastewater, and results in more stable product quality.

[0007] The preparation method of the glyphosate·triclopyroxyacetic acid soluble powder includes the following process steps:

[0008] (1) Put triclopyroxyacetic acid, inorganic alkali and appropriate amount of water into a kneader, turn on the stirring, stir and mix evenly, unload the material, store the material for 2-3 days, then dry and crush it to obtain the salt of triclopyroxyacetic acid.

[0009] Compared to traditional crystallization methods, this step significantly reduces wastewater volume and energy consumption. Traditional crystallization methods require dissolution, reaction, and recrystallization processes, necessitating the use of large amounts of water as a solvent and steam for heating. Considering water recycling, each ton of potassium triclopyralid generates 1.7 tons of wastewater and consumes 1.3 tons of steam. In contrast, the kneading mixing method of this invention produces no process wastewater, and each ton of potassium triclopyralid consumes 130 kWh of electricity, resulting in a significant reduction in energy consumption.

[0010] (2) Add triclopyroxyacetic acid salt and filler into a mixer, mix evenly, then add adjuvants and glyphosate salt and mix evenly, then take out and crush to obtain glyphosate·triclopyroxyacetic acid soluble powder.

[0011] In step (1), the material mixing temperature is 40-50℃, the stirring and mixing time is 2 hours, the storage temperature is 35℃, and the triclopyroxyacetic acid content of the obtained triclopyroxyacetic acid salt is not less than 80%; in step (2), the mixing time is 30 minutes, and the soluble powder obtained by crushing should not contain large particles or lumps; the inorganic base mentioned in step (1) is either sodium hydroxide solution or potassium hydroxide solution.

[0012] The filler mentioned in step (2) is one or a mixture of potassium chloride, sodium chloride, and ammonium sulfate; the amount of filler added is 20-30 wt% of the total amount of raw materials.

[0013] The filler also contains pentasodium diethylenetriaminepentaacetate and / or 2-phosphonobutane-1,2,4-tricarboxylic acid, wherein the amount of pentasodium diethylenetriaminepentaacetate and / or 2-phosphonobutane-1,2,4-tricarboxylic acid added is 5-50 wt% of the total filler volume.

[0014] The additives mentioned in step (2) are one or more of the following: sodium salt of naphthalene sulfonate formaldehyde condensate, sodium salt of alkyl naphthalene sulfonate, isomeric dodecyl alcohol polyoxyethylene ether, and alkyl glycoside. The amount of additives added is 10-15 wt% of the total amount of raw materials.

[0015] Potassium chloride, sodium chloride, and ammonium sulfate serve as fillers to aid dissolution, while diethylenetriaminepentaacetic acid pentasodium and 2-phosphonobutane-1,2,4-tricarboxylic acid help resist hard water and reduce precipitation. Commercially available 60% glyphosate·triclopyroxyacetic acid soluble powder has poor resistance to hard water and precipitates after dilution, which not only reduces pesticide utilization but may also damage pesticide application equipment. This set of fillers significantly improves the problem of partial precipitation in glyphosate·triclopyroxyacetic acid soluble powder after dilution, resulting in a clear, transparent solution without precipitation.

[0016] The above-mentioned method for preparing glyphosate·triclopyroxyacetic acid soluble powder is simple to operate, has low energy consumption, low wastewater volume, stable product quality, and excellent control effect on weeds and shrubs.

[0017] Unless otherwise stated, all percentage contents mentioned in this patent application are weight percentage contents. Detailed Implementation

[0018] The present invention will be further described below with reference to specific embodiments. The glyphosate-triclopyroxyacetic acid soluble powder of the present invention is composed of 50% glyphosate, 10% triclopyroxyacetic acid, and other adjuvants and fillers. Both glyphosate and triclopyroxyacetic acid are acidic and can react with alkalis to form salts. After salt formation, the molecular weight increases; therefore, the content needs to be converted when calculating in salt form. The glyphosate content, calculated as acid, is 50%, and after salt formation, it is 56.5% as glyphosate ammonium salt; the triclopyroxyacetic acid content, calculated as acid, is 10%, as triclopyroxyacetic acid sodium salt, is 11.4%, and as triclopyroxyacetic acid potassium salt, is 12.2%.

[0019] Example 1: 60% glyphosate ammonium salt·triclopyroxyacetic acid sodium salt soluble powder

[0020] Add triclopyroxyacetic acid technical and 33% sodium hydroxide solution to a kneader. The mass ratio of triclopyroxyacetic acid to 33% sodium hydroxide solution is 1:0.5. Start the agitator to mix the materials. After mixing for 2 hours, unload the material, pack it in bags, store it for 3 days, take it out, dry it and crush it to obtain sodium triclopyroxyacetic acid salt with an acid content of 87.6%.

[0021] The 60% glyphosate ammonium salt·triclopyroxyacetic acid sodium salt soluble powder comprises the following components: glyphosate ammonium salt 56.5%, triclopyroxyacetic acid sodium salt 11.4%, naphthalene sulfonate formaldehyde condensate sodium salt 3%, alkyl naphthalene sulfonate sodium salt 3%, isomeric dodecyl alcohol polyoxyethylene ether 1%, alkyl glycoside 5%, 2-phosphonobutane-1,2,4-tricarboxylic acid 10%, and ammonium sulfate to 100%. After weighing according to the specified amounts, triclopyroxyacetic acid salt and filler are added to a mixer and mixed for 30 minutes. Then, the adjuvants and glyphosate salt are added and mixed for another 30 minutes. Finally, the mixture is pulverized in a pulverizer to prepare the 60% glyphosate ammonium salt·triclopyroxyacetic acid sodium salt soluble powder.

[0022] Comparative Example 1: 60% Glyphosate Ammonium Salt·Triclopyr Sodium Salt Soluble Powder

[0023] The 60% glyphosate ammonium salt·triclopyroxyacetic acid sodium salt soluble powder of Comparative Example 1 was formulated based on Example 1 by subtracting 2-phosphonobutane-1,2,4-tricarboxylic acid, which has the effect of resisting hard water, while the other conditions remained unchanged.

[0024] Add triclopyroxyacetic acid technical and 33% sodium hydroxide solution to a kneader. The mass ratio of triclopyroxyacetic acid to 33% sodium hydroxide solution is 1:0.5. Start the agitator to mix the materials. After mixing for 2 hours, unload the material, pack it in bags, store it for 3 days, take it out, dry it and crush it to obtain sodium triclopyroxyacetic acid salt with an acid content of 87.6%.

[0025] The 60% glyphosate ammonium salt·triclopyroxyacetic acid sodium salt soluble powder comprises the following components: 56.5% glyphosate ammonium salt, 11.4% triclopyroxyacetic acid sodium salt, 3% naphthalene sulfonate formaldehyde condensate sodium salt, 3% alkyl naphthalene sulfonate sodium salt, 1% isomeric dodecyl alcohol polyoxyethylene ether, 5% alkyl glycoside, and ammonium sulfate to 100%. After weighing according to the measured amount, triclopyroxyacetic acid salt and filler are added to a mixer and mixed for 30 minutes. Then, the adjuvants and glyphosate salt are added and mixed for another 30 minutes. Finally, the mixture is pulverized in a pulverizer to prepare the 60% glyphosate ammonium salt·triclopyroxyacetic acid sodium salt soluble powder.

[0026] Example 2: 60% glyphosate ammonium salt·triclopyroxyacetic acid potassium salt soluble powder

[0027] Add triclopyroxyacetic acid technical, 48% potassium hydroxide solution, and pure water to a kneader. The mass ratio of triclopyroxyacetic acid: 48% potassium hydroxide solution: pure water is 1:0.47:0.1. Start the agitator to mix the materials. After mixing for 2 hours, unload the material, pack it in bags, store it for 3 days, take it out, dry it, and crush it to obtain potassium triclopyroxyacetic acid salt with an acid content of 82.0%.

[0028] The 60% glyphosate ammonium salt·triclopyroxyacetic acid potassium salt soluble powder comprises the following components: glyphosate ammonium salt 56.8%, triclopyroxyacetic acid potassium salt 12.2%, naphthalenesulfonate formaldehyde condensate sodium salt 2%, alkyl naphthalenesulfonate sodium salt 3%, isomeric dodecyl alcohol polyoxyethylene ether 1%, alkyl glycoside 5%, diethylenetriaminepentaacetic acid pentasodium salt 5%, and potassium chloride to make up the difference. After weighing according to the measured amount, triclopyroxyacetic acid salt and filler are added to a mixer and mixed for 30 minutes. Then, the adjuvants and glyphosate salt are added and mixed for another 30 minutes. Finally, the mixture is pulverized in a pulverizer to prepare the 60% glyphosate ammonium salt·triclopyroxyacetic acid sodium salt soluble powder.

[0029] Example 3: 60% glyphosate ammonium salt·triclopyroxyacetic acid potassium salt soluble powder

[0030] Add triclopyroxyacetic acid technical, 48% potassium hydroxide solution, and pure water to a kneader. The mass ratio of triclopyroxyacetic acid: 48% potassium hydroxide solution: pure water is 1:0.47:0.1. Start the agitator to mix the materials. After mixing for 2 hours, unload the material, pack it in bags, store it for 3 days, take it out, dry it, and crush it to obtain potassium triclopyroxyacetic acid salt with an acid content of 81.2%.

[0031] The 60% glyphosate ammonium salt·triclopyroxyacetic acid potassium salt soluble powder comprises the following components: glyphosate ammonium salt 56.6%, triclopyroxyacetic acid potassium salt 12.3%, naphthalene sulfonate formaldehyde condensate sodium salt 4%, alkyl naphthalene sulfonate sodium salt 3%, isomeric dodecyl alcohol polyoxyethylene ether 1%, alkyl glycoside 5%, 2-phosphonobutane-1,2,4-tricarboxylic acid 10%, and potassium chloride to make up the difference. After weighing according to the measured amount, triclopyroxyacetic acid salt and filler are added to a mixer and mixed for 30 minutes. Then, the adjuvants and glyphosate salt are added and mixed for another 30 minutes. Finally, the mixture is pulverized in a pulverizer to prepare the 60% glyphosate ammonium salt·triclopyroxyacetic acid sodium salt soluble powder.

[0032] Example 4

[0033] The samples prepared in Examples 1 to 3 were tested for relevant indicators, and the relevant index data are shown in Table 1.

[0034] As can be seen from the solubility and solution stability data in the table, compared with Comparative Example 1, after adding the anti-hard water agent 2-phosphonobutane-1,2,4-tricarboxylic acid, the residue at 5 min and 18 h was significantly reduced, that is, the amount of precipitation after dilution with water was significantly reduced, and the solution stability was improved.

[0035] Table 1 Main technical indicators of the 60% glyphosate-triclopyroxyacetic acid soluble powder of the present invention

[0036]

[0037]

[0038] Example 5

[0039] The samples prepared in Examples 1-3 and Comparative Example 1 were subjected to field efficacy tests on non-cultivated land. The main weeds were barnyard grass, fleabane, foxtail, crabgrass, goosegrass, and shrubs. The efficacy was investigated 15 and 30 days after application. Examples 1-3 showed good weed control efficacy, while Comparative Example 1 showed slightly lower efficacy. Table 2 shows the efficacy data of the samples from Examples 1-3 and Comparative Example 1.

[0040] Table 2. Herbicidal effect of the 60% glyphosate·triclopyroxyacetic acid soluble powder of the present invention.

[0041]

[0042] In summary, the 60% glyphosate·triclopyroxyacetic acid soluble powder prepared by this invention meets all quality control requirements, exhibits minimal precipitation after dilution, good solution stability, excellent performance, and good weed control efficacy. Furthermore, this preparation method reduces energy consumption and wastewater during production, making it more economical and environmentally friendly, simple to operate, and more conducive to large-scale production.

Claims

1. A method for preparing a glyphosate·triclopyroxyacetic acid soluble powder, characterized in that, The process includes the following steps: (1) Add triclopyroxyacetic acid, inorganic base and appropriate amount of water into a kneader, turn on the stirring, stir and mix evenly, unload the material, pile up the material, dry it, and obtain triclopyroxyacetic acid salt; the inorganic base is sodium hydroxide solution or potassium hydroxide solution. (2) Triclopyroxyacetic acid salt and filler are put into a mixer, mixed, and then the adjuvant and glyphosate salt are added and mixed. The mixture is then taken out and crushed to obtain glyphosate·triclopyroxyacetic acid soluble powder. The filler is one or a mixture of potassium chloride, sodium chloride, and ammonium sulfate; the amount of filler added is 20-30 wt% of the total raw material. The filler also contains pentasodium diethylenetriaminepentaacetate and / or 2-phosphonobutane-1,2,4-tricarboxylic acid, the amount of which is 5-50 wt% of the total filler. The additive is one or a mixture of sodium naphthalene sulfonate formaldehyde condensate, sodium alkyl naphthalene sulfonate, isomeric dodecyl alcohol polyoxyethylene ether, and alkyl glycoside, the amount of which is 10-15 wt% of the total raw material.

2. The method for preparing a glyphosate-triclopyroxyacetic acid soluble powder as described in claim 1, characterized in that, In step (1) above, the mixing time is 2-3 hours.

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