CN103554182B - Prepare the method for glyphosate - Google Patents
Prepare the method for glyphosate Download PDFInfo
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- CN103554182B CN103554182B CN201310604361.2A CN201310604361A CN103554182B CN 103554182 B CN103554182 B CN 103554182B CN 201310604361 A CN201310604361 A CN 201310604361A CN 103554182 B CN103554182 B CN 103554182B
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Abstract
The invention discloses a kind of method of preparing glyphosate, is that sodium iodide or polymine are catalyst taking chloromethyl phosphonic acid one sodium salt and glycinate as raw material, and in water, glyphosate is prepared in reaction. The method has 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.
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 herbicide at present. From upperSince the commercialization in mid-term of individual century 70, 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 phosphineAcid system, phosphorous test etc. are mainly iminodiacetic acid (salt) acid system and dialkyl phosphite but really realize at present industrialized methodMethod.
Iminodiacetic acid (salt) acid system is as initiation material, with formaldehyde and sub-phosphorus taking iminodiacetic acid or iminodiacetic acid (salt) acid alkali metal saltAcid reaction makes PMIDA; Or taking iminodiacetonitrile as initiation material, obtain iminodiacetic acid through hydrolysis, then with formaldehydeReaction makes PMIDA with phosphorous acid; Last PMIDA oxidation makes glyphosate. There is following problem in the method: 1) by PMIDAGlyphosate is prepared in oxidation, adopts the oxidant cost such as chlorine dioxide, hydrogen peroxide higher, although adopt air oxidation process efficient rightRequiring of equipment and catalyst is high, and especially the recovery of the metal ion of catalyst is more difficult; 2) taking iminodiacetonitrile as initial formerMaterial, 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 liquids are rawChange processing more difficult; Taking iminodiacetic acid as initiation material, can greatly reduce the discharge of waste liquid, but still face above-mentioned twoThe problem of glyphosate is prepared in sweet phosphine oxidation.
Phosphonous acid dialkyl method is taking glycine as initiation material, is that catalyst, methyl alcohol are solvent with paraformaldehyde at triethylamineCondition under reaction make the triethylamine salt of methylol glycine, then make glyphosate with phosphonous acid dialkyl through condensation reactionThe triethylamine salt of dialkyl, makes glyphosate finally by hydrochloric acid hydrolysis. There is following problem in the method: 1) catalyst of triethylamineExpensive, toxicity is larger, and recycling also has certain difficulty; 2) solvent methanol can reaction in paraformaldehyde solution collecting processGenerate dimethoxym ethane, produce glyphosate per ton and approximately produce 0.45 ton of dimethoxym ethane; Also can by-product monochloro methane in hydrochloric acid hydrolysis process, difficultyTo 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 residual in mother liquorGlyphosate be difficult to reclaim. Patent CN102875595A discloses using inorganic base and has replaced triethylamine to prepare glyphosate as catalystMethod, compares existing triethylamine technology toxicity and reduce, and the salt of inorganic base and Formation of glycine is more easily and phosphorous acid alkylEster reaction, can simplify reaction and post-processing step, Reaction time shorten, but the method does not still solve above-mentioned phosphonous acid dioxaneThe other problem that base ester method exists.
Chloromethyl phosphonic acid method is paraformaldehyde to be reacted with excessive phosphorus trichloride generate chloromethyl phosphonic dichloride, then hydrolysis generates chlorineMethylphosphonic acid, the latter and glycine reactant make glyphosate. There is following problem in the method: 1) phosphorus trichloride and paraformaldehydeReaction needed 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 is1.5:1, causes the yield of chloromethyl phosphonic acid to only have 80%; 3) mol ratio of chloromethyl phosphonic acid and glycine is 1:1, due to the twoReaction belongs to SN2 nucleophilic substitutions, have accessory substance hydroxymethyl phosphonic acid and N, and N-bis-(phosphonomethyl) glycine (increasing sweet phosphine) is rawBecome, cause the yield of glyphosate on the low side, only 40%(is in formaldehyde). Patent CN100360546C discloses one kettle way and has prepared chlorineThe technique of methylphosphonic acid one sodium salt, is that aluminum trichloride (anhydrous) is catalyst taking phosphorus trichloride and excessive paraformaldehyde as raw material,Synthetic chloromethyl phosphonic dichloride under normal pressure catalysis, hydrolysis obtains chloromethyl phosphonic acid, and regulator solution pH value makes catalyst precipitation simultaneouslyChloromethyl phosphonic acid is transformed into chloromethyl phosphonic acid one sodium salt, filters, evaporation and concentration, crystallisation by cooling, obtains chloromethyl phosphonic acid one sodium saltCrude product, after recrystallization, productive rate can reach 80%. This technique has been used catalyst alchlor, has changed phosphorus trichloride and paraformaldehydeMol ratio make paraformaldehyde excessive, whole process completes under condition of normal pressure, having overcome aforementioned chloromethyl phosphonic acid method needs high pressureThe defect of condition, but still do 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 are produced the defect that glyphosate exists, and clean, environmental protection, efficient, improvesThe yield of glyphosate and quality, 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:
Preparing the method for glyphosate, is that sodium iodide or polymine are taking chloromethyl phosphonic acid one sodium salt and glycinate as raw materialCatalyst, 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 beCrude product can be also the sterling after recrystallization.
Raw material glycinate can be Sodium Glycinate, glycine potassium, calcium glycine, glycine barium etc. any, be preferably sweet ammoniaAcid sodium. It can obtain from commercial channel, also can be synthetic voluntarily according to literature method; Both can be crude product, can be also heavySterling after crystallization.
Contribute to reduce the generation of accessory substance because glycinate is excessive, the mol ratio of chloromethyl phosphonic acid one sodium salt and glycinate is excellentElect 1:5-10 as, more preferably 1:9-10.
In reaction, add a certain amount of catalyst to be conducive to the generation of glyphosate, reduce accessory substance. The consumption of catalyst is preferably chlorineThe 0.4%-2% of methylphosphonic acid one sodium salt and glycinate gross weight.
The selection of material feed way also has certain effect to the generation that reduces accessory substance. Preferably, the inventive method is to sweet ammoniaIn acid salt aqueous solution, add catalyst, then drip chloromethyl phosphonic acid one sodium-salt aqueous solution, 60-100 DEG C of insulation reaction, makes grass sweetPhosphine. Preferred, be to add catalyst in the glycinate aqueous solution, be warming up to 60-100 DEG C, drip chloromethyl phosphonic acid one sodiumSaline solution, control time for adding is 8-12 hour, after dropwising, 60-100 DEG C of insulation reaction 8-16 hour, makes grass sweetPhosphine. Best, be to add catalyst in the glycinate aqueous solution, be warming up to 80-90 DEG C, drip chloromethyl phosphonic acid one natrium brineSolution, control time for adding is 8-10 hour, after dropwising, 80-90 DEG C 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, chloromethylThe concentration of phosphonic acids 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: by phosphorus trichloride and paraformaldehyde in80-100 DEG C of reaction 6-10 hour, is cooled to 10-30 DEG C, adds catalyst aluminum trichloride (anhydrous), more slowly rises in 2 hoursTemperature is to 160-180 DEG C, and insulation reaction 2-4 hour, steams accessory substance carrene, dichlormethyl ether and unnecessary formaldehyde, residueAdd water and be hydrolyzed to obtain chloromethyl phosphonic acid, hydrolyzate filters, filtrate activated carbon decolorizing, then make by sodium hydrate regulator solution pH valueCatalyst changes aluminum hydroxide precipitation completely into, filters, and collects filtrate, obtains chloromethyl phosphonic acid one sodium-salt aqueous solution; Phosphorus trichlorideWith the mol ratio of paraformaldehyde be 1:2-4, the addition of catalyst 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, and add NaOH water-solubleLiquid, stirring reaction, obtains the Sodium Glycinate aqueous solution, and the mol ratio of glycine and NaOH is 1:1.
Preferably, after chloromethyl phosphonic acid one sodium salt finishes with reacting of glycinate, by reactant liquor with inorganic acid for adjusting pH extremely1-2, is cooled to 0-30 DEG C, crystallization, and suction filtration, filtration cakes torrefaction, obtains glyphosate; Filtrate regulates pH to 10-11 with inorganic base,Condensing crystallizing desalination, residue Recycling Mother Solution is to next group glyphosate production.
Preferred, after chloromethyl phosphonic acid one sodium salt finishes with reacting of glycinate, reactant liquor is added to activated carbon decolorizing,Filter, filtrate to 1-2, is cooled to 0-10 DEG C with salt acid for adjusting pH, crystallization, and suction filtration, filtration cakes torrefaction, obtains glyphosate; FiltrateWith NaOH adjusting pH to 10-11, condensing crystallizing is removed sodium chloride, and residue Recycling Mother Solution is applied mechanically to next group glyphosate productionIn.
Because residue contains catalyst and excessive glycine in mother liquor, by its recycled during to next group glyphosate production,Can be according to the content of catalyst in mother liquor and glycine, add appropriate catalyst and glycinate raw material.
Beneficial effect of the present invention is: the invention provides and a kind of prepare taking chloromethyl phosphonic acid one sodium salt and glycinate as raw materialThe new technology of glyphosate, has avoided existing iminodiacetic acid (salt) acid system, phosphonous acid dialkyl method and phosphorous test to produce glyphosateThe defect existing, has clean, environmental protection, feature efficiently, and yield and the quality of glyphosate are significantly increased, glyphosate crystallizationAfter mother liquor through desalination process after capable of circulation applying mechanically, reduce discharging of waste liquid, reduce material loss, production cost declines to a great extent, warpHelp profitable.
Detailed description of the invention
In order to make object of the present invention, technical scheme and beneficial effect clearer, below the preferred embodiments of the present invention are carried outDetailed description.
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, be slowly warming up to 80 DEG C by room temperature, after paraformaldehyde dissolves completely, be warming up to 100 DEG C of insulation reaction 8 hours,Again reactant liquor is cooled to room temperature, adds 11.2 grams of aluminum trichloride (anhydrous)s, in 2 hours, be slowly warming up to 180 DEG C by room temperature,Insulation reaction 4 hours, accessory substance carrene, dichlormethyl ether and unnecessary formaldehyde are removed in redistillation, and residue is cooled to room temperature,The 200mL that adds water, 70 DEG C of hydrolysis 2 hours to solid dissolves completely, removes by filter a small amount of insoluble black residue, and filtrate is with activeCarbon decoloring, then with NaOH adjusting pH to 10, have aluminum hydroxide precipitation to generate, filter, obtaining filtrate (is chloromethyl phosphonic acidOne sodium-salt aqueous solution) 621 grams, 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 8-13Adopt this chloromethyl phosphonic acid one sodium-salt aqueous solution.
Also can, by gained chloromethyl phosphonic acid one sodium-salt aqueous solution evaporation and concentration, be cooled to 0 DEG C, crystallization, suction filtration, dry, obtain319.6 grams of chloromethyl phosphonic acid one sodium salt crude products, yield counts 89% with phosphorus trichloride, and purity is 85%. Again this crude product is dissolved inWater makes chloromethyl phosphonic acid one sodium-salt aqueous solution and carries out subsequent reactions.
Also above-mentioned chloromethyl phosphonic acid one sodium salt crude product can be recrystallized with the ethanol-water mixed solvent that volume ratio is 4:1, filter,Dry, obtain 252.7 grams of chloromethyl phosphonic acid one sodium salt sterlings, yield counts 82% with phosphorus trichloride, and purity is 99%. ShouldWater-soluble chloromethyl phosphonic acid one sodium-salt aqueous solution that makes of sterling carries out subsequent reactions.
The preparation of embodiment 2, Sodium Glycinate
In reactor, add 1400 grams, 1399 grams of glycine (18.66 moles) and water, more slowly add 40% (w/w) hydrogen-oxygenChange 1866 grams of sodium water solutions (18.66 moles), stirring reaction, makes the Sodium Glycinate aqueous solution. The gained Sodium Glycinate aqueous solution withoutNeed purifying, can directly carry out subsequent reactions as raw material.
The preparation of embodiment 3, Sodium Glycinate
In reactor, add 800 grams, 714 grams of glycine (9.33 moles) and water, more slowly add 40% (w/w) NaOH933 grams of the aqueous solution (9.33 moles), stirring reaction, makes the Sodium Glycinate aqueous solution. The gained Sodium Glycinate aqueous solution is without purifying,Can directly carry out subsequent reactions as raw material.
The preparation of embodiment 4, Sodium Glycinate
In reactor, add 500 grams, 285.6 grams of glycine (3.73 moles) and water, more slowly add 40% (w/w) hydroxide373.2 grams of sodium water solutions (3.73 moles), stirring reaction, makes the Sodium Glycinate aqueous solution. The gained Sodium Glycinate aqueous solution withoutPurifying, can directly carry out subsequent reactions as raw material.
The preparation of embodiment 5, Sodium Glycinate
In reactor, add 500 grams, 267 grams of glycine (3.56 moles) and water, more slowly add 40% (w/w) NaOH356 grams of the aqueous solution (3.56 moles), stirring reaction, makes the Sodium Glycinate aqueous solution. The gained Sodium Glycinate aqueous solution is without purifying,Can directly carry out subsequent reactions as raw material.
The preparation of embodiment 6, Sodium Glycinate
In reactor, add 400 grams, 251 grams of glycine (3.28 moles) and water, more slowly add 40% (w/w) NaOH328 grams of the aqueous solution (3.28 moles), stirring reaction, makes the Sodium Glycinate aqueous solution. The gained Sodium Glycinate aqueous solution is without purifying,Can directly carry out subsequent reactions as raw material.
The preparation of embodiment 7, glyphosate
In the Sodium Glycinate aqueous solution making to embodiment 2, add 8.4 grams of sodium iodides, be warming up to 80 DEG C, slowly drip embodiment1 621 grams of the chloromethyl phosphonic acid making one sodium-salt aqueous solutions (chloromethyl phosphonic acid one sodium salt content is 45.68%, 1.89 mole), controlRate of addition processed makes time for adding at least more than 8 hours, after dropwising, is warming up to 90 DEG C of insulation reaction 12 hours, instituteObtain reactant liquor and add activated carbon decolorizing, filter, filtrate regulates pH to 1 with concentrated hydrochloric acid, is cooled to 5 DEG C, crystallization, suction filtration, filterCake is dried, and obtains 302.4 grams of glyphosates, and yield is 93%, and purity is 97%; Filtrate is that mother liquor NaOH regulates pH extremely10, concentrated, cooling, precipitated sodium chloride crystallization, filters, and filtrate cycle is applied mechanically to next group glyphosate production.
The preparation of embodiment 8, glyphosate
In the Sodium Glycinate aqueous solution making to embodiment 3, add embodiment 7 to remove residue mother liquor and the sodium iodide 3 after sodium chlorideGram, be warming up to 80 DEG C, slowly drip 621 grams of (chloromethyl phosphonic acids one of chloromethyl phosphonic acid one sodium-salt aqueous solution that embodiment 1 makesSodium salt content is 45.68%, 1.89 mole), control rate of addition and make time for adding at least more than 8 hours, after dropwising,Be warming up to 90 DEG C of insulation reaction 12 hours, gained reactant liquor adds activated carbon decolorizing, filters, and filtrate regulates pH extremely with concentrated hydrochloric acid1, be cooled to 5 DEG C, crystallization, suction filtration, filter cake is dried, and obtains 305.6 grams of glyphosates, and yield is 94%, and purity is 97%; FilterLiquid is that mother liquor NaOH regulates pH to 10, concentrated, cooling, and precipitated sodium chloride crystallization, filters, filtrate cycle apply mechanically toIn next group glyphosate production.
The preparation of embodiment 9, glyphosate
In the Sodium Glycinate aqueous solution making to embodiment 4, add embodiment 8 to remove residue mother liquor and the sodium iodide 2 after sodium chlorideGram, be warming up to 80 DEG C, slowly drip 621 grams of (chloromethyl phosphonic acids one of chloromethyl phosphonic acid one sodium-salt aqueous solution that embodiment 1 makesSodium salt content is 45.68%, 1.89 mole), control rate of addition and make time for adding at least more than 8 hours, after dropwising,Be warming up to 90 DEG C of insulation reaction 12 hours, gained reactant liquor adds activated carbon decolorizing, filters, and filtrate regulates pH extremely with concentrated hydrochloric acid1, be cooled to 5 DEG C, crystallization, suction filtration, filter cake is dried, and obtains 308.9 grams of glyphosates, and yield is 95%, and purity is 97%; FilterLiquid is that mother liquor NaOH regulates pH to 10, concentrated, cooling, and precipitated sodium chloride crystallization, filters, filtrate cycle apply mechanically toIn next group glyphosate production.
The preparation of embodiment 10, glyphosate
In the Sodium Glycinate aqueous solution making to embodiment 5, add embodiment 9 to remove residue mother liquor and the sodium iodide 2 after sodium chlorideGram, be warming up to 80 DEG C, slowly drip 601 grams of (chloromethyl phosphonic acids one of chloromethyl phosphonic acid one sodium-salt aqueous solution that embodiment 1 makesSodium salt content is 45.68%, 1.83 mole), control rate of addition and make time for adding at least more than 8 hours, after dropwising,Be warming up to 90 DEG C of insulation reaction 12 hours, gained reactant liquor adds activated carbon decolorizing, filters, and filtrate regulates pH extremely with concentrated hydrochloric acid1, be cooled to 5 DEG C, crystallization, suction filtration, filter cake is dried, and obtains 294.6 grams of glyphosates, and yield is 95%, and purity is 97%; FilterLiquid is that mother liquor NaOH regulates pH to 10, concentrated, cooling, and precipitated sodium chloride crystallization, filters, filtrate cycle apply mechanically toIn next group glyphosate production.
The preparation of embodiment 11, glyphosate
In the Sodium Glycinate aqueous solution making to embodiment 6, add embodiment 10 to remove residue mother liquor and the sodium iodide 2 after sodium chlorideGram, be warming up to 80 DEG C, slowly drip 554 grams of (chloromethyl phosphonic acids one of chloromethyl phosphonic acid one sodium-salt aqueous solution that embodiment 1 makesSodium salt content is 45.68%, 1.69 mole), control rate of addition and make time for adding at least more than 8 hours, after dropwising,Be warming up to 90 DEG C of insulation reaction 12 hours, gained reactant liquor adds activated carbon decolorizing, filters, and filtrate regulates pH extremely with concentrated hydrochloric acid1, be cooled to 5 DEG C, crystallization, suction filtration, filter cake is dried, and obtains 271.5 grams of glyphosates, and yield is 95%, and purity is 97%; FilterLiquid is that mother liquor NaOH regulates pH to 10, concentrated, cooling, and precipitated sodium chloride crystallization, filters, filtrate cycle apply mechanically toIn next group glyphosate production.
The preparation of embodiment 12, glyphosate
In the Sodium Glycinate aqueous solution making to embodiment 2, add 33.6 grams of polymines, be warming up to 80 DEG C, slowly drip realExecute 621 grams of chloromethyl phosphonic acid one sodium-salt aqueous solutions (chloromethyl phosphonic acid one sodium salt content is 45.68%, 1.89 mole) that example 1 makes,Control rate of addition and make time for adding at least more than 8 hours, after dropwising, be warming up to 90 DEG C of insulation reaction 12 hours,Gained reactant liquor adds activated carbon decolorizing, filters, and filtrate regulates pH to 1 with concentrated hydrochloric acid, is cooled to 5 DEG C, crystallization, and suction filtration,Filter cake is dried, and obtains 305.6 grams of glyphosates, and yield is 94%, and purity is 97%; Filtrate is that mother liquor NaOH regulates pH extremely10, concentrated, cooling, precipitated sodium chloride crystallization, filters, and filtrate cycle is applied mechanically to next group glyphosate production.
Finally explanation, above preferred embodiment is only unrestricted in order to technical scheme of the present invention to be described, although by above-mentionedPreferred embodiment is described in detail the present invention, but it will be appreciated by those skilled in the art that can be in form andIn details, it is made to various changes, and do not depart from the claims in the present invention book limited range.
Claims (9)
1. the method for preparing glyphosate, is characterized in that, in the glycinate aqueous solution, adds catalyst, then drips chloromethyl phosphonic acid one sodium-salt aqueous solution, and 60-100 DEG C of insulation reaction, makes glyphosate; Described catalyst is sodium iodide or polymine; The mol ratio of described chloromethyl phosphonic acid one sodium salt and glycinate is 1:5-10.
2. the method for preparing glyphosate as claimed in claim 1, is characterized in that, described glycinate is Sodium Glycinate.
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 catalyst is the 0.4%-2% of chloromethyl phosphonic acid one sodium salt and glycinate gross weight.
4. the method for preparing glyphosate as claimed in claim 1, it is characterized in that, in the glycinate aqueous solution, add catalyst, be warming up to 60-100 DEG C, drip chloromethyl phosphonic acid one sodium-salt aqueous solution, control time for adding is 8-12 hour, after dropwising, 60-100 DEG C of insulation reaction 8-16 hour, makes glyphosate.
5. the method for preparing glyphosate as claimed in claim 1, 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%.
6. the method for preparing glyphosate as claimed in claim 1, 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 DEG C, be cooled to 10-30 DEG C, add catalyst aluminum trichloride (anhydrous), in 2 hours, be slowly warming up to again 160-180 DEG C, insulation reaction 2-4 hour, steam accessory substance carrene, dichlormethyl ether and unnecessary formaldehyde, residue adds water and is hydrolyzed to obtain chloromethyl phosphonic acid, hydrolyzate filters, filtrate activated carbon decolorizing, make catalyst change aluminum hydroxide precipitation completely into by sodium hydrate regulator solution pH value 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 addition of catalyst is the 1-3% of phosphorus trichloride and paraformaldehyde gross weight.
7. the method for preparing glyphosate as claimed in claim 1, is characterized in that, the described glycinate aqueous solution adopts following methods to make: glycine is water-soluble, add sodium hydrate aqueous solution, stirring reaction, obtains the Sodium Glycinate aqueous solution, and the mol ratio of glycine and NaOH is 1:1.
8. 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 reactant liquor with inorganic acid for adjusting pH to 1-2, be cooled to 0-30 DEG C, crystallization, suction filtration, filtration cakes torrefaction, obtains glyphosate; Filtrate regulates pH to 10-11 with inorganic base, condensing crystallizing desalination, and residue Recycling Mother Solution is applied mechanically to next group glyphosate production.
9. the preparation method of glyphosate as claimed in claim 8, it is characterized in that, after chloromethyl phosphonic acid one sodium salt finishes with reacting of glycinate, reactant liquor is added to activated carbon decolorizing, filter, filtrate uses salt acid for adjusting pH to 1-2, be cooled to 0-10 DEG C, crystallization, suction filtration, filtration cakes torrefaction, obtains glyphosate; Filtrate regulates pH to 10-11 with NaOH, and condensing crystallizing is removed sodium chloride, and residue Recycling Mother Solution is applied mechanically to next group glyphosate production.
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