CN103554182A - Method for preparing glyphosate - Google Patents
Method for preparing glyphosate Download PDFInfo
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- CN103554182A CN103554182A CN201310604361.2A CN201310604361A CN103554182A CN 103554182 A CN103554182 A CN 103554182A CN 201310604361 A CN201310604361 A CN 201310604361A CN 103554182 A CN103554182 A CN 103554182A
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- glyphosate
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Abstract
The invention discloses a method for preparing glyphosate. The method comprises the following steps: with a chloromethyl-phosphonic acid sodium salt and a glycinate as raw materials and sodium iodide or polyethylene imine as a catalyst, reacting the components in water to prepare the glyphosate. The method overcomes the defects of such existing glyphosate production methods as an iminodiacetic acid method, a dialkyl phosphate method and a phosphorous acid method; the method has the advantages of being clean, environmental-friendly and efficient, the yield and quality of the glyphosate are greatly improved, and the crystallization mother liquor of the glyphosate can be circularly used after a desalting treatment to reduce the liquid waste emission and reduce the material consumption, so that the production cost is greatly reduced and the economic benefit is good.
Description
Technical field
The invention belongs to chemical field, relate to a kind of synthetic method of organic compound.
Background technology
Glyphosate, chemical name is N-((phosphonomethyl)) glycine, is widely used a kind of weedicide at present.Since the commercialization of eighties of last century the mid-1970s, due to its remarkable herbicidal performance, range of application constantly expands.
The method bibliographical information of synthesizing glyphosate has multiple, as iminodiacetic acid (salt) acid system, phosphonous acid dialkyl method, chloromethyl phosphonic acid method, phosphorous test etc., but really realize at present industrialized method, is mainly iminodiacetic acid (salt) acid system and dialkyl phosphite method.
Iminodiacetic acid (salt) acid system is that to take iminodiethanoic acid or iminodiacetic acid (salt) acid alkali metal salt be starting raw material, reacts and makes pmida98 with formaldehyde and phosphorous acid; Or take iminodiacetonitrile as starting raw material, through hydrolysis, obtain iminodiethanoic acid, then react and make pmida98 with formaldehyde and phosphorous acid; Last pmida98 oxidation makes glyphosate.There is following problem in the method: 1) by pmida98 oxidation, prepares glyphosate, adopt the oxidant cost such as dioxide peroxide, hydrogen peroxide higher, though adopt air oxidation process efficient to equipment and catalyzer require highly, especially the recovery of the metal ion of catalyzer is more difficult; 2) take iminodiacetonitrile as starting raw material, the production cost of glyphosate is lower, but 1 ton of glyphosate of every production will produce the waste liquid of nearly 10 tons, and these waste liquid biochemical treatments are more difficult; Take iminodiethanoic acid as starting raw material, can greatly reduce the discharge of waste liquid, but still face the problem that glyphosate is prepared in above-mentioned pmida98 oxidation.
Phosphonous acid dialkyl method is to take glycine as starting raw material, at triethylamine, be to react the triethylamine salt that makes methylol glycine under catalyzer, the methyl alcohol condition that is solvent with paraformaldehyde, through condensation reaction, make again the triethylamine salt of glyphosphonic acid dialkyl with phosphonous acid dialkyl, finally by hydrochloric acid hydrolysis, make glyphosate.There is following problem in the method: 1) catalyst of triethylamine is expensive, and toxicity is larger, and recycling also has certain difficulty; 2) solvent methanol can reaction generate methylal in paraformaldehyde solution collecting process, produces glyphosate per ton and approximately produces 0.45 ton of methylal; Also can by-product monochloro methane in hydrochloric acid hydrolysis process, be difficult to reclaim; 3) produce glyphosate per ton and approximately produce 5.2 tons of mother liquors, wastewater flow rate is large, and biochemical treatment difficulty is large, and in mother liquor, residual glyphosate is difficult to reclaim.Patent CN102875595A discloses usings mineral alkali and replaces triethylamine as catalyzer, to prepare the method for glyphosate, comparing existing triethylamine technology toxicity reduces, and the salt of mineral alkali and Formation of glycine more easily reacts with alkyl phosphite, can simplify reaction and post-processing step, Reaction time shorten, but the method does not still solve the other problem of above-mentioned phosphonous acid dialkyl method.
Chloromethyl phosphonic acid method is that paraformaldehyde is reacted to generation chloromethyl phosphonic dichloride with excessive phosphorus trichloride, then hydrolysis generation chloromethyl phosphonic acid, and the latter and glycine reactant make glyphosate.There is following problem in the method: 1) reaction needed of phosphorus trichloride and paraformaldehyde is carried out under high temperature, condition of high voltage, to having relatively high expectations of equipment; 2) mol ratio of phosphorus trichloride and paraformaldehyde is 1.5:1, causes the yield of chloromethyl phosphonic acid to only have 80%; 3) mol ratio of chloromethyl phosphonic acid and glycine is 1:1, because the two reaction belongs to S
n2 nucleophilic substitution reactions, have by product hydroxymethyl phosphonic acid and N, and N-bis-(phosphonomethyl) glycine (increasing sweet phosphine) generates, and causes the yield of glyphosate on the low side, and only 40%(is in formaldehyde).Patent CN100360546C discloses the technique that one kettle way is prepared chloromethyl phosphonic acid one sodium salt, that to take phosphorus trichloride and excessive paraformaldehyde be raw material, aluminum trichloride (anhydrous) is catalyzer, synthetic chloromethyl phosphonic dichloride under normal pressure catalysis, and hydrolysis obtains chloromethyl phosphonic acid, regulator solution pH value makes catalyst precipitation chloromethyl phosphonic acid is transformed into chloromethyl phosphonic acid one sodium salt simultaneously, filter evaporation concentration, crystallisation by cooling, obtain chloromethyl phosphonic acid one sodium salt crude product, after recrystallization, productive rate can reach 80%.This technique has been used catalyzer aluminum chloride, the mol ratio that has changed phosphorus trichloride and paraformaldehyde makes paraformaldehyde excessive, whole process completes under condition of normal pressure, has overcome the defect that aforementioned chloromethyl phosphonic acid method needs condition of high voltage, but still does not solve glyphosate productive rate problem on the low side.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of new method of preparing glyphosate, avoid existing iminodiacetic acid (salt) acid system, phosphonous acid dialkyl method, chloromethyl phosphonic acid method to produce the defect that glyphosate exists, clean, environmental protection, efficient, improve yield and the quality of glyphosate, Recycling Mother Solution is applied mechanically, and reduces discharging of waste liquid and material loss, reduces production costs.
After deliberation, the invention provides following technical scheme:
The method of preparing glyphosate, is that to take chloromethyl phosphonic acid one sodium salt and glycinate be raw material, and sodium iodide or polymine are catalyzer, and in water, glyphosate is prepared in reaction.
Raw material chloromethyl phosphonic acid one sodium salt can obtain from commercial channel, also can be synthetic voluntarily according to literature method; Both can be crude product, can be also the sterling after recrystallization.
Raw material glycinate can for Sodium glycocollate, glycine potassium, Calcium glycinate, glycine barium etc. any, be preferably Sodium glycocollate.It can obtain from commercial channel, also can be synthetic voluntarily according to literature method; Both can be crude product, can be also the sterling after recrystallization.
Because glycinate is excessive, contribute to reduce the generation of by product, the mol ratio of chloromethyl phosphonic acid one sodium salt and glycinate is preferably 1:5-10, more preferably 1:9-10.
In reaction, add a certain amount of catalyzer to be conducive to the generation of glyphosate, reduce by product.The consumption of catalyzer is preferably the 0.4%-2% of chloromethyl phosphonic acid one sodium salt and glycinate gross weight.
The selection of material feed way also has certain effect to reducing the generation of by product.Preferably, the inventive method is to add catalyzer in the glycinate aqueous solution, then drips chloromethyl phosphonic acid one sodium-salt aqueous solution, and 60-100 ℃ of insulation reaction, makes glyphosate.Preferred, be to add catalyzer in the glycinate aqueous solution, be warming up to 60-100 ℃, drip chloromethyl phosphonic acid one sodium-salt aqueous solution, control time for adding is 8-12 hour, after dropwising, 60-100 ℃ of insulation reaction 8-16 hour, makes glyphosate.Best, be to add catalyzer in the glycinate aqueous solution, be warming up to 80-90 ℃, drip chloromethyl phosphonic acid one sodium-salt aqueous solution, control time for adding is 8-10 hour, after dropwising, 80-90 ℃ of insulation reaction 12 hours, makes glyphosate.
Chloromethyl phosphonic acid one sodium salt and the concentration of glycinate in water are the keys that affects glyphosate yield.Preferably, the concentration of chloromethyl phosphonic acid one sodium-salt aqueous solution is 35%-60%, and the concentration of glycinate is 30%-60%.
Preferably, described chloromethyl phosphonic acid one sodium-salt aqueous solution adopts following methods to make: phosphorus trichloride is reacted to 6-10 hour with paraformaldehyde in 80-100 ℃, be cooled to 10-30 ℃, add catalyzer aluminum trichloride (anhydrous), in 2 hours, be slowly warming up to again 160-180 ℃, insulation reaction 2-4 hour, steam by product methylene dichloride, dichlormethyl ether and unnecessary formaldehyde, resistates adds water and is hydrolyzed to obtain chloromethyl phosphonic acid, hydrolyzed solution filters, filtrate activated carbon decolorizing, by sodium hydrate regulator solution pH value, make catalyzer change aluminum hydroxide precipitation completely into again, filter, collect filtrate, obtain chloromethyl phosphonic acid one sodium-salt aqueous solution, the mol ratio of phosphorus trichloride and paraformaldehyde is 1:2-4, and the add-on of catalyzer is the 1-3% of phosphorus trichloride and paraformaldehyde gross weight.
Preferably, the described glycinate aqueous solution adopts following methods to make: glycine is water-soluble, add aqueous sodium hydroxide solution, and stirring reaction, obtains the Sodium glycocollate aqueous solution, and the mol ratio of glycine and sodium hydroxide is 1:1.
Preferably, after chloromethyl phosphonic acid one sodium salt finishes with reacting of glycinate, by reaction solution with inorganic acid for adjusting pH to 1-2, be cooled to 0-30 ℃, crystallization, suction filtration, filtration cakes torrefaction, obtains glyphosate; Filtrate regulates pH to 10-11 with mineral alkali, condensing crystal desalination, and residue Recycling Mother Solution is to next batch glyphosate production.
Preferred, after chloromethyl phosphonic acid one sodium salt finishes with reacting of glycinate, reaction solution is added to activated carbon decolorizing, to filter, filtrate to 1-2, is cooled to 0-10 ℃ with salt acid for adjusting pH, crystallization, suction filtration, filtration cakes torrefaction, obtains glyphosate; Filtrate regulates pH to 10-11 with sodium hydroxide, and condensing crystal is removed sodium-chlor, and residue Recycling Mother Solution is applied mechanically to next batch glyphosate production.
Because residue contains catalyzer and excessive glycine in mother liquor, its recycled during to next batch glyphosate production, can, according to the content of catalyzer in mother liquor and glycine, added to appropriate catalyzer and glycinate raw material.
Beneficial effect of the present invention is: the invention provides and a kind ofly take chloromethyl phosphonic acid one sodium salt and glycinate and prepare the novel process of glyphosate as raw material, avoided existing iminodiacetic acid (salt) acid system, phosphonous acid dialkyl method and phosphorous test to produce the defect that glyphosate exists, there is clean, environmental protection, feature efficiently, yield and the quality of glyphosate are significantly increased, mother liquor after glyphosate crystallization is capable of circulation applying mechanically after desalination is processed, reduce discharging of waste liquid, reduce material loss, production cost declines to a great extent, good in economic efficiency.
Embodiment
In order to make object of the present invention, technical scheme and beneficial effect clearer, below the preferred embodiments of the present invention are described in detail.
The preparation of embodiment 1, chloromethyl phosphonic acid one sodium salt
In reaction vessel, add rapidly 278 grams of new steaming phosphorus trichlorides (2 moles) and 180 grams of paraformaldehydes (6 moles), in 1.5 hours, by room temperature, be slowly warming up to 80 ℃, after paraformaldehyde dissolves completely, be warming up to 100 ℃ of insulation reaction 8 hours, again reaction solution is cooled to room temperature, add 11.2 grams of aluminum trichloride (anhydrous)s, in 2 hours, by room temperature, be slowly warming up to 180 ℃, insulation reaction 4 hours, by product methylene dichloride is removed in redistillation, dichlormethyl ether and unnecessary formaldehyde, resistates is cooled to room temperature, add water 200mL, 70 ℃ of hydrolysis are dissolved to solid for 2 hours completely, remove by filter a small amount of insoluble black residue, filtrate activated carbon decolorizing, with sodium hydroxide, regulate pH to 10 again, there is aluminum hydroxide precipitation to generate, filter, obtain 621 grams of filtrates (being chloromethyl phosphonic acid one sodium-salt aqueous solution), wherein the quality percentage composition of chloromethyl phosphonic acid one sodium salt is 45.68%.
Gained chloromethyl phosphonic acid one sodium-salt aqueous solution, without purifying, can directly carry out subsequent reactions as raw material.In embodiment 8-13, adopt this chloromethyl phosphonic acid one sodium-salt aqueous solution.
Also gained chloromethyl phosphonic acid one sodium-salt aqueous solution evaporation concentration can be cooled to 0 ℃, crystallization, suction filtration, dry, obtain 319.6 grams of chloromethyl phosphonic acid one sodium salt crude products, yield counts 89% with phosphorus trichloride, and purity is 85%.Again water-soluble chloromethyl phosphonic acid one sodium-salt aqueous solution that makes of this crude product is carried out to subsequent reactions.
The ethanol-water mixed solvent that can be also 4:1 by volume ratio by above-mentioned chloromethyl phosphonic acid one sodium salt crude product carries out recrystallization, filters, dry, obtains 252.7 grams of chloromethyl phosphonic acid one sodium salt sterlings, and yield counts 82% with phosphorus trichloride, and purity is 99%.Water-soluble chloromethyl phosphonic acid one sodium-salt aqueous solution that makes of this sterling is carried out to subsequent reactions.
The preparation of embodiment 2, Sodium glycocollate
In reactor, add 1400 grams, 1399 grams of glycine (18.66 moles) and water, more slowly add 1866 grams of 40% (w/w) aqueous sodium hydroxide solutions (18.66 moles), stirring reaction, makes the Sodium glycocollate aqueous solution.The gained Sodium glycocollate aqueous solution, without purifying, can directly carry out subsequent reactions as raw material.
The preparation of embodiment 3, Sodium glycocollate
In reactor, add 800 grams, 714 grams of glycine (9.33 moles) and water, more slowly add 933 grams of 40% (w/w) aqueous sodium hydroxide solutions (9.33 moles), stirring reaction, makes the Sodium glycocollate aqueous solution.The gained Sodium glycocollate aqueous solution, without purifying, can directly carry out subsequent reactions as raw material.
The preparation of embodiment 4, Sodium glycocollate
In reactor, add 500 grams, 285.6 grams of glycine (3.73 moles) and water, more slowly add 373.2 grams of 40% (w/w) aqueous sodium hydroxide solutions (3.73 moles), stirring reaction, makes the Sodium glycocollate aqueous solution.The gained Sodium glycocollate aqueous solution, without purifying, can directly carry out subsequent reactions as raw material.
The preparation of embodiment 5, Sodium glycocollate
In reactor, add 500 grams, 267 grams of glycine (3.56 moles) and water, more slowly add 356 grams of 40% (w/w) aqueous sodium hydroxide solutions (3.56 moles), stirring reaction, makes the Sodium glycocollate aqueous solution.The gained Sodium glycocollate aqueous solution, without purifying, can directly carry out subsequent reactions as raw material.
The preparation of embodiment 6, Sodium glycocollate
In reactor, add 400 grams, 251 grams of glycine (3.28 moles) and water, more slowly add 328 grams of 40% (w/w) aqueous sodium hydroxide solutions (3.28 moles), stirring reaction, makes the Sodium glycocollate aqueous solution.The gained Sodium glycocollate aqueous solution, without purifying, can directly carry out subsequent reactions as raw material.
The preparation of embodiment 7, glyphosate
In the Sodium glycocollate aqueous solution making to embodiment 2, add 8.4 grams of sodium iodides, be warming up to 80 ℃, (chloromethyl phosphonic acid one sodium salt content is 45.68% slowly to drip 621 grams of chloromethyl phosphonic acid one sodium-salt aqueous solutions that embodiment 1 makes, 1.89 mole), controlling rate of addition makes time for adding at least more than 8 hours, after dropwising, be warming up to 90 ℃ of insulation reaction 12 hours, gained reaction solution adds activated carbon decolorizing, filter, filtrate regulates pH to 1 with concentrated hydrochloric acid, be cooled to 5 ℃, crystallization, suction filtration, filter cake is dried, obtain 302.4 grams of glyphosates, yield is 93%, purity is 97%, filtrate is that mother liquor regulates pH to 10 with sodium hydroxide, concentrated, cooling, and precipitated sodium chloride crystallization, filters, and filtrate cycle is applied mechanically to next batch glyphosate production.
The preparation of embodiment 8, glyphosate
In the Sodium glycocollate aqueous solution making to embodiment 3, add embodiment 7 to remove 3 grams of residue mother liquor after sodium-chlor and sodium iodides, be warming up to 80 ℃, (chloromethyl phosphonic acid one sodium salt content is 45.68% slowly to drip 621 grams of chloromethyl phosphonic acid one sodium-salt aqueous solutions that embodiment 1 makes, 1.89 mole), controlling rate of addition makes time for adding at least more than 8 hours, after dropwising, be warming up to 90 ℃ of insulation reaction 12 hours, gained reaction solution adds activated carbon decolorizing, filter, filtrate regulates pH to 1 with concentrated hydrochloric acid, be cooled to 5 ℃, crystallization, suction filtration, filter cake is dried, obtain 305.6 grams of glyphosates, yield is 94%, purity is 97%, filtrate is that mother liquor regulates pH to 10 with sodium hydroxide, concentrated, cooling, and precipitated sodium chloride crystallization, filters, and filtrate cycle is applied mechanically to next batch glyphosate production.
The preparation of embodiment 9, glyphosate
In the Sodium glycocollate aqueous solution making to embodiment 4, add embodiment 8 to remove 2 grams of residue mother liquor after sodium-chlor and sodium iodides, be warming up to 80 ℃, (chloromethyl phosphonic acid one sodium salt content is 45.68% slowly to drip 621 grams of chloromethyl phosphonic acid one sodium-salt aqueous solutions that embodiment 1 makes, 1.89 mole), controlling rate of addition makes time for adding at least more than 8 hours, after dropwising, be warming up to 90 ℃ of insulation reaction 12 hours, gained reaction solution adds activated carbon decolorizing, filter, filtrate regulates pH to 1 with concentrated hydrochloric acid, be cooled to 5 ℃, crystallization, suction filtration, filter cake is dried, obtain 308.9 grams of glyphosates, yield is 95%, purity is 97%, filtrate is that mother liquor regulates pH to 10 with sodium hydroxide, concentrated, cooling, and precipitated sodium chloride crystallization, filters, and filtrate cycle is applied mechanically to next batch glyphosate production.
The preparation of embodiment 10, glyphosate
In the Sodium glycocollate aqueous solution making to embodiment 5, add embodiment 9 to remove 2 grams of residue mother liquor after sodium-chlor and sodium iodides, be warming up to 80 ℃, (chloromethyl phosphonic acid one sodium salt content is 45.68% slowly to drip 601 grams of chloromethyl phosphonic acid one sodium-salt aqueous solutions that embodiment 1 makes, 1.83 mole), controlling rate of addition makes time for adding at least more than 8 hours, after dropwising, be warming up to 90 ℃ of insulation reaction 12 hours, gained reaction solution adds activated carbon decolorizing, filter, filtrate regulates pH to 1 with concentrated hydrochloric acid, be cooled to 5 ℃, crystallization, suction filtration, filter cake is dried, obtain 294.6 grams of glyphosates, yield is 95%, purity is 97%, filtrate is that mother liquor regulates pH to 10 with sodium hydroxide, concentrated, cooling, and precipitated sodium chloride crystallization, filters, and filtrate cycle is applied mechanically to next batch glyphosate production.
The preparation of embodiment 11, glyphosate
In the Sodium glycocollate aqueous solution making to embodiment 6, add embodiment 10 to remove 2 grams of residue mother liquor after sodium-chlor and sodium iodides, be warming up to 80 ℃, (chloromethyl phosphonic acid one sodium salt content is 45.68% slowly to drip 554 grams of chloromethyl phosphonic acid one sodium-salt aqueous solutions that embodiment 1 makes, 1.69 mole), controlling rate of addition makes time for adding at least more than 8 hours, after dropwising, be warming up to 90 ℃ of insulation reaction 12 hours, gained reaction solution adds activated carbon decolorizing, filter, filtrate regulates pH to 1 with concentrated hydrochloric acid, be cooled to 5 ℃, crystallization, suction filtration, filter cake is dried, obtain 271.5 grams of glyphosates, yield is 95%, purity is 97%, filtrate is that mother liquor regulates pH to 10 with sodium hydroxide, concentrated, cooling, and precipitated sodium chloride crystallization, filters, and filtrate cycle is applied mechanically to next batch glyphosate production.
The preparation of embodiment 12, glyphosate
In the Sodium glycocollate aqueous solution making to embodiment 2, add 33.6 grams of polymines, be warming up to 80 ℃, (chloromethyl phosphonic acid one sodium salt content is 45.68% slowly to drip 621 grams of chloromethyl phosphonic acid one sodium-salt aqueous solutions that embodiment 1 makes, 1.89 mole), controlling rate of addition makes time for adding at least more than 8 hours, after dropwising, be warming up to 90 ℃ of insulation reaction 12 hours, gained reaction solution adds activated carbon decolorizing, filter, filtrate regulates pH to 1 with concentrated hydrochloric acid, be cooled to 5 ℃, crystallization, suction filtration, filter cake is dried, obtain 305.6 grams of glyphosates, yield is 94%, purity is 97%, filtrate is that mother liquor regulates pH to 10 with sodium hydroxide, concentrated, cooling, and precipitated sodium chloride crystallization, filters, and filtrate cycle is applied mechanically to next batch glyphosate production.
Finally explanation is, above preferred embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is described in detail by above preferred embodiment, but those skilled in the art are to be understood that, can to it, make various changes in the form and details, and not depart from the claims in the present invention book limited range.
Claims (10)
1. the method for preparing glyphosate, is characterized in that, take chloromethyl phosphonic acid one sodium salt and glycinate is raw material, and sodium iodide or polymine are catalyzer, and in water, glyphosate is prepared in reaction.
2. the method for preparing glyphosate as claimed in claim 1, is characterized in that, described glycinate is Sodium glycocollate.
3. the method for preparing glyphosate as claimed in claim 1, is characterized in that, the mol ratio of described chloromethyl phosphonic acid one sodium salt and glycinate is 1:5-10, and the consumption of catalyzer is the 0.4%-2% of chloromethyl phosphonic acid one sodium salt and glycinate gross weight.
4. the method for preparing glyphosate as described in claims 1 to 3 any one, is characterized in that, in the glycinate aqueous solution, adds catalyzer, then drips chloromethyl phosphonic acid one sodium-salt aqueous solution, and 60-100 ℃ of insulation reaction, makes glyphosate.
5. the method for preparing glyphosate as claimed in claim 4, it is characterized in that, in the glycinate aqueous solution, add catalyzer, be warming up to 60-100 ℃, drip chloromethyl phosphonic acid one sodium-salt aqueous solution, control time for adding is 8-12 hour, after dropwising, 60-100 ℃ of insulation reaction 8-16 hour, makes glyphosate.
6. the method for preparing glyphosate as claimed in claim 4, is characterized in that, the mass percentage concentration of described chloromethyl phosphonic acid one sodium-salt aqueous solution is 35%-60%, and the mass percentage concentration of the glycinate aqueous solution is 30%-60%.
7. the method for preparing glyphosate as claimed in claim 4, it is characterized in that, described chloromethyl phosphonic acid one sodium-salt aqueous solution adopts following methods to make: phosphorus trichloride is reacted to 6-10 hour with paraformaldehyde in 80-100 ℃, be cooled to 10-30 ℃, add catalyzer aluminum trichloride (anhydrous), in 2 hours, be slowly warming up to again 160-180 ℃, insulation reaction 2-4 hour, steam by product methylene dichloride, dichlormethyl ether and unnecessary formaldehyde, resistates adds water and is hydrolyzed to obtain chloromethyl phosphonic acid, hydrolyzed solution filters, filtrate activated carbon decolorizing, by sodium hydrate regulator solution pH value, make catalyzer change aluminum hydroxide precipitation completely into again, filter, collect filtrate, obtain chloromethyl phosphonic acid one sodium-salt aqueous solution, the mol ratio of phosphorus trichloride and paraformaldehyde is 1:2-4, and the add-on of catalyzer is the 1-3% of phosphorus trichloride and paraformaldehyde gross weight.
8. the method for preparing glyphosate as claimed in claim 4, is characterized in that, the described glycinate aqueous solution adopts following methods to make: glycine is water-soluble, add aqueous sodium hydroxide solution, stirring reaction, obtains the Sodium glycocollate aqueous solution, and the mol ratio of glycine and sodium hydroxide is 1:1.
9. the method for preparing glyphosate as claimed in claim 1, is characterized in that, after chloromethyl phosphonic acid one sodium salt finishes with reacting of glycinate, by reaction solution with inorganic acid for adjusting pH to 1-2, be cooled to 0-30 ℃, crystallization, suction filtration, filtration cakes torrefaction, obtains glyphosate; Filtrate regulates pH to 10-11 with mineral alkali, condensing crystal desalination, and residue Recycling Mother Solution is applied mechanically to next batch glyphosate production.
10. the preparation method of glyphosate as claimed in claim 9, it is characterized in that, after chloromethyl phosphonic acid one sodium salt finishes with reacting of glycinate, reaction solution is added to activated carbon decolorizing, filter, filtrate uses salt acid for adjusting pH to 1-2, be cooled to 0-10 ℃, crystallization, suction filtration, filtration cakes torrefaction, obtains glyphosate; Filtrate regulates pH to 10-11 with sodium hydroxide, and condensing crystal is removed sodium-chlor, and residue Recycling Mother Solution is applied mechanically to next batch glyphosate production.
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| CN111234162A (en) * | 2020-03-19 | 2020-06-05 | 嘉兴学院 | Side chain grafted glyphosate degradable polyurethane and preparation method and application thereof |
| CN113072580A (en) * | 2021-04-19 | 2021-07-06 | 浙江新安化工集团股份有限公司 | Method for recovering glyphosate from glyphosate acid mother liquor by glycine method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1634941A (en) * | 2004-10-20 | 2005-07-06 | 西南师范大学 | Process for one-pot preparation of chloromethyl monosodium phosphonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1634941A (en) * | 2004-10-20 | 2005-07-06 | 西南师范大学 | Process for one-pot preparation of chloromethyl monosodium phosphonate |
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| 陈优生: "《有机化学》", 29 February 2012 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234162A (en) * | 2020-03-19 | 2020-06-05 | 嘉兴学院 | Side chain grafted glyphosate degradable polyurethane and preparation method and application thereof |
| CN113072580A (en) * | 2021-04-19 | 2021-07-06 | 浙江新安化工集团股份有限公司 | Method for recovering glyphosate from glyphosate acid mother liquor by glycine method |
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