CN106518920A - Synthetic method of glyphosate - Google Patents
Synthetic method of glyphosate Download PDFInfo
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- CN106518920A CN106518920A CN201610930633.1A CN201610930633A CN106518920A CN 106518920 A CN106518920 A CN 106518920A CN 201610930633 A CN201610930633 A CN 201610930633A CN 106518920 A CN106518920 A CN 106518920A
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- glyphosate
- glycine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
Abstract
The invention discloses a synthetic method of glyphosate. According to the method, formaldehyde, phosphorus trichloride, glycine and an oxidizing agent are used as main raw materials. the method comprises the following steps: firstly letting formaldehyde react with glycine in water to generate dihydroxymethyl glycine; dropwise adding phosphorus trichloride into an aqueous solution of dihydroxymethyl glycine to generate N-hydroxymethyl glyphosate and hydrogen chloride; reducing pressure to remove hydrogen chloride, carrying out catalytic oxidation on the N-hydroxymethyl glyphosate in the aqueous solution by the use of a catalyst and an oxidizing agent to obtain glyphosate and formic acid, further oxidizing the generated formic acid by the use of the oxidizing agent to obtain carbon dioxide and water; and finally separating glyphosate from the reaction system by a cooling crystallization mode and carrying out recrystallization so as to obtain a glyphosate raw medicine. The synthetic method has a simple process and is easy to operate. No triethylamine catalyst is used, and cost is low. The obtained product has high yield and high purity, can be used as a herbicide in the farming and forestry industry, and has a good application prospect.
Description
Technical field
The present invention relates to a kind of synthetic method of glyphosate, and in particular to a kind of to be closed with formaldehyde, glycine and phosphorus trichloride
Into N- methylol glyphosates, the then method of catalysis oxidation N- methylol glyphosate synthesis glyphosate.
Background technology
Glyphosate, English name Glyphosate, also known as：Glyphosate, agriculture reach (Roundup), careless dry phosphine, phosphine sweet acid, N- (phosphines
Sulfonylmethyl) amion acetic acid, sterling is non-volatile white solid, CAS accession number 1071-83-6, molecular formula C3H8NO5P, point
Son amount 169.07, insoluble in organic solvent, the solubility in water is 1.2% (when 25 DEG C).Glyphosate is to person poultry toxicity
It is low, the oral LD of rat acute50For 4320 mgs/kg, the percutaneous LD of rabbit50>7940 mgs/kg, to fish low toxicity, for people
The situation that class is wrongly taken, glyphosate typically just may produce vomiting and throat's pain phenomenon after oral administration in 15 minutes, in addition then
Stomachache and symptom of diarrhea may be produced, symptom is generally more apparent more than 100 milliliters in dose.Glyphosate belongs to the non-choosing of interior suction after bud
Selecting property high-efficiency broad spectrum steriland herbicide, by the leaf diameter surface wax coat for dissolving weeds, drug effect quickly enters plant conduction
System generation effect, the main enolpyruvyl shikimene phosphate synthase suppressed in plant body, so as to suppress shikimene to benzene
The conversion of alanine, cruel propylhomoserin and tryptophan, synthesizes protein and is interfered, make weeds exhausted dead, with wide spectrum, low
Poison, noresidue, Uptake and translocation and it is excellent go out natural disposition the features such as.
The sixties in 20th century, screening has synthesized glyphosate for U.S. Meng Shan all (Monsanto) chemical companies, due to the product
Perennial deep-rootedness difficulty can be killed to cut weeds, low toxicity, noresidue, do not accumulated in animal and aquatic organism, with microorganism after burying
Degraded, does not result in the excellent characteristics such as the pollution of soil and underground water, therefore causes the extensive of world agriculture circle once coming out
Concern.At present, process for synthesizing glyphosate has various, and more conventional production technology mainly has two：One be with hydrogen cyanide or
IDA route of the diethanol amine for raw material；Another is the domestic glycine method with glycine as initiation material for generally adopting.It is sweet
Sour method method produces the principal synthetic routes of glyphosate：With methyl alcohol as solvent, triethylamine is catalyst, adds formaldehyde and sweet ammonia
Acid carries out hydroxymethylation, and being subsequently adding dialkyl phosphite carries out condensation reaction, eventually passes acidic hydrolysis and obtains final product grass
Sweet phosphine.This technique is catalyst using triethylamine, and usage amount is greatly, expensive, and needs to add in a large number when triethylamine is reclaimed
Liquid caustic soda, there is high cost, the shortcomings of wastewater flow rate is big.
The content of the invention
The mesh of the present invention is to provide a kind of synthetic method of glyphosate, and the method is improved to traditional glycine method,
With formaldehyde, phosphorus trichloride, glycine, oxidant as primary raw material, Jing chemical reactions generate glyphosate, process is simple, operation letter
Just, methyl alcohol and triethylamine, low cost are not required to.
Glyphosate synthesis method of the present invention, concrete technical scheme are as follows：
A kind of synthetic method of glyphosate, the method are comprised the following steps：
（1）Formaldehyde and glycine are reacted in aqueous, dihydroxymethyl glycine is generated；
（2）To step（1）Mixture in phosphorus trichloride is added dropwise, reacted dihydroxymethyl glycine and phosphorus trichloride, it is raw
Into N- methylol glyphosates；
（3）By step（2）In the glyphosate of methylol containing N- solution decompression depickling, as far as possible elimination reaction generate hydrogen chloride, take off
After acid, be dissolved in water residue, then plus alkaline matter adjustment pH value of solution；
（4）After adjustment pH, catalyst and oxidant are added in solution, the N- methylols glyphosate in solution is sweet for grass
Phosphine；
（5）After oxidation, by step（4）Mixture post-processed, obtain glyphosate.
Further, above-mentioned steps（1）In, the formaldehyde can be formalin or paraformaldehyde.The solvent of reaction
Water can be added in the form of single water, it is also possible to introduced from raw material, such as when formaldehyde is formalin, formalin
Solution can bring the more water of system into, can also be that raw material is introduced and is individually added into while the mode for carrying out is added.Water is used as molten
Agent is used, and its consumption may be referred to conventional amount used of the prior art, and those skilled in the art are according to disclosed in prior art
Content is easily selected.
Further, above-mentioned steps（1）In, formaldehyde is 1.8～2.2 with the mol ratio of glycine：1, preferably 1.9～
2.1：1, when formaldehyde is paraformaldehyde, its molal quantity presses monomer CH2The molal quantity meter of O.Formaldehyde and glycine can be 10
Reacted at～50 DEG C.
Further, above-mentioned steps（2）In, phosphorus trichloride is 0.8～1.2 with the mol ratio of glycine：1, preferably 0.9
～1.1：1.
Further, above-mentioned steps（2）In, reaction temperature is -10～50 DEG C.
Further, above-mentioned steps（3）In, being warming up to 50～80 DEG C carries out decompression depickling, and depickling pressure can select-
0.05～-0.1MPa.Hydrogen chloride after removing is absorbed with water, used as by-product hydrochloric acid.
Further, above-mentioned steps（3）In, after depickling, be dissolved in water residue, and the addition of water is about glycine weight
4～8 times.
Further, above-mentioned steps（3）In, the alkaline matter be liquid caustic soda, solid sodium hydroxide, solid potassium hydroxide,
Sodium hydrate aqueous solution or potassium hydroxide aqueous solution.The pH of solution is adjusted to 0.5～3.0, is preferably adjusted to 1.0～2.0.
Step of the present invention（4）In, the synthesis of glyphosate is realized by oxidation, with prior art in obtain grass by hydrolysis sweet
The thinking of phosphine is different greatly.Oxidation used catalyst is activated carbon, or the mixture of activated carbon and sodium tungstate.Oxidation used
Agent is hydrogen peroxide, air, oxygen rich gas or oxygen.Wherein, oxygen rich gas refers to oxygen content more than content of oxygen in air
But the not mixed gas of purity oxygen, such as oxygen-enriched air.
Further, above-mentioned steps（4）In, catalyst is 0.05～0.20 with the weight ratio of glycine:1.Work as oxidant
For hydrogen peroxide when, the mol ratio of hydrogen peroxide and glycine is 1.0～1.3:1, when oxidant is air, oxygen rich gas or oxygen
When, oxidant is continually fed in oxidizing process, keeps reaction system pressure for 0.2～1.0MPa, preferably 0.4～
0.6MPa。
Further, above-mentioned steps（4）In, the temperature of oxidation reaction is 50～130 DEG C.Middle control point is carried out in oxidizing process
Analysis, until N- methylol glyphosates conversion ratio is reaction end more than 99.5%.
By synthesizing glyphosate by catalytic oxidation, after catalysis oxidation, gained reactant liquor is containing glyphosate to the inventive method
Reactant liquor, by post-processing to the reactant liquor, you can obtain glyphosate finished product.Step of the present invention（5）Last handling process
Comprise the following steps：
A. by step（4）Mixture cooling crystallization, filter, gained precipitation and filtrate it is stand-by；
B. precipitation obtained by step a is added to the water, is warming up to dissolving, then filters to isolate solid catalyst, that what is isolated consolidates
Step is entered after body catalyst hot wash（4）Recycled, will filter gained filtrate and cleaning solution obtained by washing catalyst
Merge, it is stand-by；
C. by the filtrate of step b and cleaning solution cooling crystallization, filter, obtain glyphosate wet product and glyphosate mother solution, gained glyphosate
The process of wet product drying, obtains glyphosate products, and gained glyphosate mother solution enters step b as water circulation set used by dissolution precipitation
With；
D., after the glyphosate mother solution recycled 5～8 times of step c, the mother liquor of recycled is mixed with the filtrate of step a,
Adjustment pH to 7.0-8.5, carries out burning disposal after then concentrating, obtains byproduct steam and pyrophosphate.
In above-mentioned steps a and c, cooling crystallization is carried out at 0～30 DEG C, preferably carry out cooling crystallization at 0～15 DEG C.
In above-mentioned steps b, after precipitation is added to the water, 85～95 DEG C of dissolvings are warming up to, 85～90 DEG C of dissolvings are preferably warming up to.
Glyphosate products obtained by above-mentioned steps c are dry white crystals, using glyphosate technicals national standard《GB
12686-2004 glyphosate technicals》Described method is analyzed chemical examination, measures glyphosate content for 95～98%.
Formaldehyde and glycine are first reacted generation dihydroxymethyl glycine in water by the present invention【Molecular formula（HOCH2）2NCH2COOH】, phosphorus trichloride is added dropwise in dihydroxymethyl glycine solution then and generates N- methylol glyphosates【Molecular formula
(HO)2P(O)CH2N(CH2OH)CH2COOH】And hydrogen chloride；Catalyst and oxidant are used after removed under reduced pressure hydrogen chloride by N- hydroxyls
Methyl glyphosate is catalytically oxidized to glyphosate and formic acid in aqueous, and the formic acid of generation is oxidized agent and is further oxidized to dioxy
Change carbon and water；Because glyphosate is compared with solubility very little under low temperature, finally by the way of cooling crystallization by glyphosate from reactant
Separate in system and recrystallized, obtain glyphosate technicals.Synthetic method craft of the present invention is simple, easily operated, does not make
With Triethylamine catalyst, low cost, products obtained therefrom yield are higher, and purity is high, can be used as herbicide in agriculture and forestry, with good
Application prospect.
Description of the drawings
Fig. 1 is the process chart of glyphosate synthesis method of the present invention.
Specific embodiment
The synthetic method of glyphosate of the present invention is with formaldehyde, phosphorus trichloride, glycine, oxidant as primary raw material, concrete to wrap
Include following steps：
（1）, add formaldehyde and water in reaction vessel, add glycine, stir to dissolving, generate dihydroxymethyl glycine；
（2）, phosphorus trichloride is added dropwise in reaction vessel, stir, make dihydroxymethyl glycine generate N- hydroxyls with phosphorus trichloride reaction
Methyl glyphosate and hydrogen chloride；
（3）, decompression depickling, the hydrogen chloride in elimination reaction thing as far as possible, hydrogen chloride is only absorbed by the water, so as to by-product hydrochloric acid；
（4）, in reaction vessel, add water, stirring and dissolving, plus alkaline matter to adjust pH；
（5）, in reaction vessel add catalyst and oxidant, oxidative synthesis glyphosate, oxidizing process to carry out middle control analysis, directly
Reaction end is more than 99.5% to N- methylol glyphosates conversion ratio；
（6）, by step（5）Reaction system be cooled to 0～30 DEG C (preferably 0～15 DEG C), stirring, crystallisation by cooling, it is isolated
Solid mixture；
（7）, by step（6）The solid mixture of gained is added in water or glyphosate mother solution, is heated to 85～95 DEG C (preferably 85
～90 DEG C) dissolve, filter to isolate activated carbon while hot, the activated carbon hot wash Posterior circle isolated is applied to step（5）,
Cleaning solution is integrated with filtrate；
（8）, by step（7）The filtrate of gained is cooled to 0～30 DEG C (preferably 0～15 DEG C), stirring, crystallisation by cooling, separates grass
Sweet phosphine wet product and glyphosate mother solution, the glyphosate mother solution for obtaining enter step（7）Recycled；
（9）, by step（8）The glyphosate wet product for obtaining is drying to obtain glyphosate finished product；
（10）, glyphosate mother solution Jing after time, accessory substance can be accumulated, and when mother liquid recycle 5～8 times, mother is applied mechanically in merging
Liquid and step（6）Filtrate, adjust pH to 7.0～8.5, after concentration, centralized burning is processed, byproduct steam and pyrophosphate.
In above-mentioned synthetic method, the formaldehyde added in reaction vessel is preferably formalin or paraformaldehyde；Plus
1.8～2.2 times for glycine of the molal quantity of the formaldehyde for entering, preferably the 1.9～2.1 of glycine molal quantity times；Reaction temperature
For 10～50 DEG C, such as 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, preferably 40-50 DEG C, the reaction time is 1-2h.
In above-mentioned synthetic method, the molal quantity of the phosphorus trichloride added in reaction vessel is the 0.8～1.2 of glycine
Times, preferably the 0.9～1.1 of glycine molal quantity times；Phosphorus trichloride is added in the form of being added dropwise, temperature control during dropwise addition
At -10～10 DEG C, time for adding is 1.5-2h, after completion of dropping, first at 0～30 DEG C（It is preferred that 0-10 DEG C）Reaction 1-1.5h, so
30-50 DEG C is warming up to again afterwards（It is preferred that 40-50 DEG C）Reaction 2-3h.
In above-mentioned synthetic method, decompression depickling temperature is 50～80 DEG C, and pressure is -0.05～-0.1MPa.Decompression depickling can
With the hydrogen chloride tried one's best in elimination reaction thing, the hydrogen chloride of removing is only absorbed by the water, and so as to by-product hydrochloric acid, step can be reduced after depickling
Suddenly（4）Caustic dosage, reduce reaction system in salt generation, reduce production cost.
In above-mentioned synthetic method, step（4）In, add alkaline matter adjust pH value be 0.5～3.0, such as 0.5,1.0,
2.0th, 3.0, preferably 1.0～2.0；The alkaline matter of addition is preferably liquid caustic soda, solid sodium hydroxide, solid potassium hydroxide, hydrogen
Aqueous solution of sodium oxide or potassium hydroxide aqueous solution.
In above-mentioned synthetic method, step（4）In, the oxidant is hydrogen peroxide, air, oxygen rich gas or purity oxygen.Institute
Catalyst is stated for activated carbon, or for activated carbon and the mixture of sodium tungstate.The consumption of catalyst is：Catalyst and glycine
Weight ratio is 0.05～0.20:1.Oxidation reaction is carried out at 50～130 DEG C, such as 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C,
100℃、120℃、130℃.When oxidant is hydrogen peroxide, oxidant hydrogen peroxide is 1.0～1.3 with the mol ratio of glycine:
1, oxidant hydrogen peroxide is added by the way of being added dropwise, and time for adding is 1-1.5h, is further continued for reaction 2-4h basic after dripping
Reaction end can be reached；When oxidant is air, oxygen rich gas or purity oxygen, oxidant is continually fed under agitation, is kept
Reaction system 0.2～1.0MPa of pressure, preferably 0.4～0.6MPa, are passed through oxidant always until reaction end.
The representative embodiments of several present invention are set forth below, these embodiments are only given to be explained further
Technical scheme is illustrated, limitation of the invention can not be interpreted as, without departing from the spirit and scope of the present invention
On the basis of, many conversion can be carried out to the present invention.In these embodiments, unless stated otherwise, all of percentage is all
Refer to mass percent.
In following embodiments, glyphosate content is measured in such a way：Glyphosate sample is dissolved in after water, 15 DEG C with
On acid medium in generate nitroso glyphosate with natrium nitrosum effect, nitroso glyphosate has absorption maximum at 242nm
Peak, by mensuration absorbance quantitative analysis glyphosate, calculates mass fraction.
Embodiment 1
98% paraformaldehyde 12g is added in 500ml four-hole bottles, adds 20g water, heating for dissolving to be warming up to 30 DEG C, add
98.5% glycine 15g, stirs to dissolving, 41 DEG C of insulation reactions 1 hour.
- 10 DEG C are cooled to, 27.5g phosphorus trichlorides are slowly added dropwise, 1.5 hours completion of dropping, in 0 DEG C of insulation reaction 1 hour,
It is warming up to 50 DEG C to react 2 hours.
80 DEG C of decompression depicklings 1.5 hours, the as far as possible chlorination in elimination reaction thing are to slowly warm up under the negative pressure of -0.1MPa
Hydrogen, hydrogen chloride are only absorbed by the water, so as to by-product hydrochloric acid.
After depickling, 60g water, stirring and dissolving, liquid feeding adjusting PH with base=2.0, addition 2g activated carbons and 0.2g are added in four-hole bottle
Sodium tungstate, is warming up in the case where being stirred continuously under 68 DEG C, normal pressure and starts 30% hydrogen peroxide 27g, 1 hour completion of dropping, insulation 4 is added dropwise
Hour, oxidizing process carries out middle control analysis, until N- methylol glyphosates conversion ratio is oxidation reaction terminal more than 99.5%,
Detect that test paper whitening color, insulation terminate with starch potassium iodide paper.
35 DEG C are cooled to, the new 15% copperas solution 5g for preparing are added dropwise, are added dropwise 1 hour, be incubated 2 hours, removed excessive
Hydrogen peroxide, be subsequently cooled to 5 DEG C, crystallize 3h, isolated solid mixture, filtrate concentration after burning disposal.
The solid mixture for filtering gained is added in the 2000ml four-hole bottles for filling 1000g glyphosate mother solutions, is heated to
85～95 DEG C (preferably 85～90 DEG C) dissolve, filter to isolate activated carbon while hot, follow after the activated carbon hot wash isolated
Ring set is used, and cleaning solution is integrated with filtrate.10 hours, crystallisation by cooling will be stirred at 1 DEG C of the filtrate of gained, separate glyphosate wet product
And glyphosate mother solution, the glyphosate mother solution for obtaining applied mechanically for lower batch.The glyphosate wet product for obtaining is dried glyphosate is obtained
29.6g, content 97.14%, yield 87.63%.
Still contain 0.5%～3% glyphosate in glyphosate mother solution Jing after 5～8 times are applied mechanically, adjust pH=7.0～8.5, collect after concentration
Middle burning disposal, byproduct steam and pyrophosphate.
Embodiment 2
37% formalin 65g is added toward 500ml four-hole bottles, 98.5% glycine 30g is added, is warming up to 35 DEG C, stir to
Dissolving, 45 DEG C of insulation reactions 1 hour.
- 8 DEG C are cooled to, 55g phosphorus trichlorides are slowly added dropwise, 1.5 hours completion of dropping, in 2 DEG C of insulation reactions 1 hour, rise
Temperature is reacted 2 hours to 45 DEG C.
60 DEG C of decompression depicklings 3 hours, the as far as possible chlorination in elimination reaction thing are to slowly warm up under the negative pressure of -0.1MPa
Hydrogen, hydrogen chloride are only absorbed by the water, so as to by-product hydrochloric acid.
After depickling, 120g water, the above-mentioned distillation substrate of stirring and dissolving, hydro-oxidation potassium water are added in 1000ml high pressure zirconium kettles
Solution adjusts pH=2.0, adds 4g activated carbons, is warming up in the case where being stirred continuously under 68 DEG C, normal pressure and starts 30% hydrogen peroxide is added dropwise
54g, 1 hour completion of dropping are warming up to 130 DEG C of insulation reactions 4 hours, and N- methylol glyphosates conversion ratio is more than 99.5%, reaches
Reaction end.
Reactant liquor is moved in 1000ml four-hole bottles, 5 DEG C are cooled to, 3h is crystallized, isolated solid mixture, filtrate are dense
Burning disposal after contracting.
The solid mixture for filtering gained is added in the 3000ml four-hole bottles for filling 2000g glyphosate mother solutions, is heated
85～95 DEG C (preferably 85～90 DEG C) dissolve, filter to isolate activated carbon while hot, follow after the activated carbon hot wash isolated
Ring set is used, and cleaning solution is integrated with filtrate.10 hours, crystallisation by cooling will be stirred at 1 DEG C of the filtrate of gained, separate glyphosate wet product
And glyphosate mother solution, under the glyphosate mother solution for obtaining, batch is applied mechanically.The glyphosate wet product for obtaining is dried glyphosate is obtained
58.8g, content 97.03%, yield 87.12%.
Still contain 0.5%～3% glyphosate in glyphosate mother solution Jing after 5～8 times are applied mechanically, adjust pH=7.0～8.5, collect after concentration
Middle burning disposal, byproduct steam and pyrophosphate.
Embodiment 3
37% formalin 65g is added in 500ml four-hole bottles, 98.5% glycine 30g is added, is warming up to 40 DEG C, stir to
Dissolving, insulation reaction 1 hour.
- 8 DEG C are cooled to, 55g phosphorus trichlorides are slowly added dropwise, 1.5 hours completion of dropping, in 10 DEG C of insulation reactions 1 hour, rise
Temperature is reacted 2 hours to 50 DEG C.
70 DEG C of decompression depicklings 2.5 hours, the as far as possible chlorination in elimination reaction thing are to slowly warm up under the negative pressure of -0.1MPa
Hydrogen, hydrogen chloride are only absorbed by the water, so as to by-product hydrochloric acid.
After depickling, the addition 120g water in 1000ml high pressure zirconium kettles, the above-mentioned distillation substrate of stirring and dissolving, liquid feeding adjusting PH with base=
1.0,4g activated carbons are added, and 55-70 DEG C are warming up in the case where being stirred continuously, are passed through oxygen-enriched air（Oxygen volume content 90%）, keep
In kettle, pressure is reacted 6 hours in 0.4-0.6MP, reaches reaction end.
After oxidation reaction is finished, reactant liquor is moved in 1000ml four-hole bottles, is cooled to 5 DEG C, is crystallized 3 hours, isolated
Solid mixture, burning disposal after filtrate concentration.
The solid mixture for filtering gained is added in the 3000ml four-hole bottles for filling 2000g glyphosate mother solutions, is heated to
85～95 DEG C (preferably 85～90 DEG C) dissolve, filter to isolate activated carbon while hot, follow after the activated carbon hot wash isolated
Ring set is used, and cleaning solution is integrated with filtrate.10 hours, crystallisation by cooling will be stirred at 1 DEG C of the filtrate of gained, separate glyphosate wet product
And glyphosate mother solution, under the glyphosate mother solution for obtaining, batch is applied mechanically.The glyphosate wet product for obtaining is dried glyphosate is obtained
59.5g, content 97.94%, yield 88.07%.
Still contain 0.5%～3% glyphosate in glyphosate mother solution Jing after 5～8 times are applied mechanically, adjust pH=7.0～8.5, collect after concentration
Middle burning disposal, byproduct steam and pyrophosphate.
Comparative example
37% formalin 65g is added in 500ml four-hole bottles, 98.5% glycine 30g is added, is warming up to 40 DEG C, stir to
Dissolving, insulation reaction 1 hour.
- 8 DEG C are cooled to, 55g phosphorus trichlorides are slowly added dropwise, 1.5 hours completion of dropping, in 0 DEG C of insulation reaction 1 hour, rise
Temperature is reacted 2 hours to 45 DEG C.
30% hydrochloric acid solution 60g after reaction, is added in reactant liquor, is stirred, 110 is gradually heating to 4 hours
DEG C, then keep 110 DEG C of back flow reactions 4h.After reaction, 80 DEG C of decompression depicklings, the as far as possible chlorination in elimination reaction thing are cooled to
Hydrogen, after depickling plus adjusting PH with base=1.0, is cooled to 5 DEG C, stirs 3 hours, separates out without crystal.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of synthetic method of glyphosate, is characterized in that comprising the following steps：
（1）Formaldehyde and glycine are reacted in aqueous, dihydroxymethyl glycine is generated；
（2）To step（1）Mixture in phosphorus trichloride is added dropwise, reacted dihydroxymethyl glycine and phosphorus trichloride, it is raw
Into N- methylol glyphosates；
（3）By step（2）In the glyphosate of methylol containing N- solution decompression depickling, as far as possible elimination reaction generate hydrogen chloride, take off
After acid, be dissolved in water residue, then plus alkaline matter adjustment pH value of solution；
（4）After adjustment pH, catalyst and oxidant are added in solution, the N- methylols glyphosate in solution is sweet for grass
Phosphine；
（5）After oxidation, by step（4）Mixture post-processed, obtain glyphosate.
2. synthetic method according to claim 1, is characterized in that：Step（4）In, the catalyst is activated carbon, or
It is the mixture of activated carbon and sodium tungstate；The oxidant is hydrogen peroxide, air, oxygen rich gas or oxygen.
3. synthetic method according to claim 1 and 2, is characterized in that：Step（1）In, aqueous solvent by raw material introduce or/and
It is individually added into.
4. synthetic method according to claim 1 and 2, is characterized in that：Step（1）In, the formaldehyde includes that formaldehyde is water-soluble
Liquid or paraformaldehyde.
5. synthetic method according to claim 1 and 2, is characterized in that：In step (1), the mol ratio of formaldehyde and glycine
For 1.8～2.2：1, preferably 1.9～2.1：1；In step (2), phosphorus trichloride is 0.8～1.2 with the mol ratio of glycine：1,
Preferably 0.9～1.1：1；In step (4), catalyst is 0.05～0.20 with the weight ratio of glycine:1, when oxidant is double
During oxygen water, hydrogen peroxide is 1.0～1.3 with the mol ratio of glycine:1, when oxidant is air, oxygen rich gas or oxygen, oxygen
Agent is continually fed in oxidizing process, keeps reaction system pressure to be 0.2～1.0Mpa, preferably 0.4～0.6MPa.
6. synthetic method according to claim 1 and 2, is characterized in that：Step（1）In, reaction temperature is 10～50 DEG C；Step
Suddenly（2）In, reaction temperature is -10～50 DEG C；Step（3）In, decompression depickling temperature is 50～80 DEG C；Step（4）In, reaction temperature
Spend for 50～130 DEG C.
7. synthetic method according to claim 1 and 2, is characterized in that：Step（3）In, pH to 0.5-3.0 is adjusted, preferably
To 1.0～2.0.
8. synthetic method according to claim 1 and 2, is characterized in that：Step（3）In, the alkaline matter is liquid caustic soda, consolidates
Body NaOH, solid potassium hydroxide, sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
9. synthetic method according to claim 1 and 2, is characterized in that：Step（4）Mixture carry out according to the following steps after
Process：
A. by step（4）Mixture cooling crystallization, filter, gained precipitation and filtrate it is stand-by；
B. precipitation obtained by step a is added to the water, is warming up to dissolving, then filters to isolate solid catalyst, that what is isolated consolidates
Step is entered after body catalyst hot wash（4）Recycled, will filter gained filtrate and cleaning solution obtained by washing catalyst
Merge, it is stand-by；
C. by the filtrate of step b and cleaning solution cooling crystallization, filter, obtain glyphosate wet product and glyphosate mother solution, gained glyphosate
The process of wet product drying, obtains glyphosate products, and gained glyphosate mother solution enters step b as water circulation set used by dissolution precipitation
With；
D., after the glyphosate mother solution recycled 5～8 times of step c, the mother liquor of recycled is mixed with the filtrate of step a,
Adjustment pH to 7.0-8.5, carries out burning disposal after then concentrating, obtains byproduct steam and pyrophosphate.
10. synthetic method according to claim 9, is characterized in that：In step a and c, cooling crystallization is carried out at 0～30 DEG C,
It is preferred that carrying out cooling crystallization at 0～15 DEG C；In step b, after precipitation is added to the water, 85～95 DEG C of dissolvings are warming up to, it is preferred to heat up
Dissolve to 85～90 DEG C.
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