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The preparation method of glyphosate

A technology of glyphosate and chloromethylphosphonic acid, which is applied in the chemical industry, can solve the problems of low production cost, large amount of waste water, and difficulty in recycling, and achieve the effects of improving yield and quality, reducing material loss and reducing production cost.

Inactive Publication Date: 2016-06-08
CHONGQING UNISPLENDOUR CHEM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This method has the following problems: 1) Glyphosate is prepared by oxidation of diglyphosate, and the cost of using chlorine dioxide, hydrogen peroxide and other oxidants is relatively high. Although the air oxidation method is efficient, it has high requirements for equipment and catalysts, especially the metal ions of the catalyst 2) With iminodiacetonitrile as the starting material, the production cost of glyphosate is relatively low, but nearly 10 tons of waste liquid will be generated for every ton of glyphosate produced, and these waste liquids are biochemically treated More difficult; using iminodiacetic acid as a starting material can greatly reduce the discharge of waste liquid, but still faces the problem of preparing glyphosate from the above-mentioned oxidation of diglyphosate
This method has the following problems: 1) The catalyst triethylamine is expensive, highly toxic, and difficult to recycle; 2) The solvent methanol will react to form methylal during the depolymerization process of paraformaldehyde, and every ton of glyphosate produced Phosphine produces about 0.45 tons of methylal; during the hydrochloric acid hydrolysis process, monochloromethane is also produced as a by-product, which is difficult to recover; 3) about 5.2 tons of mother liquor is produced per ton of glyphosate production, and the amount of waste water is large, and biochemical treatment is difficult. Residual glyphosate is difficult to recycle
This method has the following problems: 1) the reaction of phosphorus trichloride and paraformaldehyde needs to be carried out under high temperature and high pressure conditions, and the requirements for equipment are relatively high; 2) the molar ratio of phosphorus trichloride and paraformaldehyde is 1.5: 1. The yield of chloromethylphosphonic acid is only 80%; 3) The molar ratio of chloromethylphosphonic acid to glycine is 1:1. Since the reaction between the two belongs to the SN2 nucleophilic substitution reaction, there is a by-product of hydroxymethylphosphine acid and N,N-bis(phosphonomethyl)glycine, resulting in a low yield of glyphosate, only 40% (calculated as formaldehyde)
The process uses the catalyst aluminum trichloride, changes the molar ratio of phosphorus trichloride and paraformaldehyde to make paraformaldehyde excessive, and the whole process is completed under normal pressure conditions, which overcomes the need for high-pressure conditions in the aforementioned chloromethylphosphonic acid method However, the problem of low yield of glyphosate is still not solved

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Example 1. Preparation of monosodium chloromethylphosphonic acid

[0025] Quickly add 278 grams (2 moles) of newly distilled phosphorus trichloride and 180 grams (6 moles) of paraformaldehyde into the reaction vessel, and slowly increase the temperature from room temperature to 80°C within 1.5 hours. After the paraformaldehyde is completely dissolved, the temperature is increased Incubate the reaction at 100°C for 8 hours, then cool the reaction solution to room temperature, add 11.2 g of anhydrous aluminum trichloride, slowly increase the temperature from room temperature to 180°C within 2 hours, keep the temperature for 4 hours, and then distill the by-product dichloride Methane, dichloromethyl ether and excess formaldehyde, the residue is cooled to room temperature, add 200 mL of water, hydrolyze at 70°C for 2 hours until the solid is completely dissolved, filter to remove a small amount of insoluble black residue, decolor the filtrate with activated carbon, and adjust t...

Embodiment 2

[0029] Example 2. Preparation of disodium aminomethylphosphonic acid

[0030] Add 621 grams of chloromethylphosphonic acid monosodium salt aqueous solution prepared in Example 1 (the mass percentage of chloromethylphosphonic acid monosodium salt is 45.68%, 1.89 moles) into the reaction kettle, and then add liquid ammonia (18.66) Mol), heat to 80°C, keep the temperature in the kettle at 1.5MPa and keep the reaction for 6 hours, monitor the reaction progress by high performance liquid chromatography, and stop when the residual amount of chloromethylphosphonic acid monosodium salt is less than 0.3% In the reaction, the residual ammonia gas in the system is eliminated to obtain 750 grams of an aqueous solution of disodium aminomethylphosphonic acid, in which the mass percentage of disodium aminomethylphosphonic acid is 36.64%, and the yield is 95%. The obtained aminomethylphosphonic acid disodium salt aqueous solution does not need to be purified, and can be directly used as a raw ma...

Embodiment 3

[0031] Example 3. Preparation of disodium aminomethylphosphonic acid

[0032] Add 621 grams of chloromethylphosphonic acid monosodium salt aqueous solution prepared in Example 1 (the mass percentage of chloromethylphosphonic acid monosodium salt is 45.68%, 1.89 moles) into the reaction kettle, and then add ammonia (18.66 moles) ), the temperature is raised to 80℃, and the reaction is kept for 6 hours under the condition of 1.5MPa in the kettle. The reaction progress is monitored by high performance liquid chromatography, and the reaction is stopped when the residual amount of chloromethylphosphonic acid monosodium salt is less than 0.3% , Exclude the residual ammonia in the system to obtain 750 grams of aminomethylphosphonic acid disodium salt aqueous solution, in which the mass percentage of aminomethylphosphonic acid disodium salt is 36.64%, and the yield is 95%. The obtained aminomethylphosphonic acid disodium salt aqueous solution does not need to be purified, and can be dire...

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PUM

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Abstract

The invention discloses a preparation method of glyphosate, which is prepared by reacting disodium salt of aminomethylphosphonic acid and chloroacetate in water; the method avoids the existing iminodiacetic acid method, dialkyl phosphonite The defects in the production of glyphosate by ester method and chloromethyl phosphonic acid method have the characteristics of cleanness, environmental protection and high efficiency. The yield and quality of glyphosate have been significantly improved. It can be recycled, reducing waste liquid discharge, reducing material loss, greatly reducing production costs, and good economic benefits.

Description

Technical field [0001] The invention belongs to the field of chemical engineering and relates to a method for synthesizing organic compounds. Background technique [0002] Glyphosate, whose chemical name is N-(phosphonomethyl)glycine, is a herbicide that has been widely used. Since its commercialization in the mid-1970s, its application range has continued to expand due to its excellent weeding performance. [0003] There are many literature reports on the methods of synthesizing glyphosate, such as iminodiacetic acid method, dialkyl phosphonite method, chloromethyl phosphonic acid method, phosphorous acid method, etc. However, the main methods for realizing industrialization at present are mainly The aminodiacetic acid method and the dialkyl phosphite method. [0004] The iminodiacetic acid method uses iminodiacetic acid or alkali metal salt of iminodiacetic acid as the starting material, and reacts with formaldehyde and phosphorous acid to prepare diglycphos; or takes iminodiacet...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/38
Inventor 吴传隆郑道敏丁永良姚如杰朱丽利王用贵秦岭杨帆任星宇陈宏杨
Owner CHONGQING UNISPLENDOUR CHEM
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