CN101343288A - Hydrolyzation method in glyphosate acid preparation process - Google Patents
Hydrolyzation method in glyphosate acid preparation process Download PDFInfo
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- CN101343288A CN101343288A CNA2008100459229A CN200810045922A CN101343288A CN 101343288 A CN101343288 A CN 101343288A CN A2008100459229 A CNA2008100459229 A CN A2008100459229A CN 200810045922 A CN200810045922 A CN 200810045922A CN 101343288 A CN101343288 A CN 101343288A
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- hydrolysis
- acid
- hydrochloric acid
- glyphosate
- preparation process
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Abstract
Disclosed is a hydrolysis method in the preparation process of glyphosate acid, comprising: taking formaldehyde or paraform paraformaldehyde, triethylamine, glycine and methyl phosphite compounds as raw materials to generate a precursor of glyphosate acid through the condensation reaction, then obtaining the glyphosate acid or hydrochloric acid salt thereof through hydrolysis with hydrochloric acid under the heating condition. After the condensation reaction, a reaction mixture containing a glyphosate acid precursor compound and a hydrochloric acid solution with concentration equal or greater than 30 percent which are present in a mass ratio of (2.1-2.6):1 are mixed in the conveying and running process to a hydrolysis device, then the reaction mixture is rapidly heated to a temperature less than or equal to 105 DEG C and fed into the hydrolysis device for hydrolysis. The method can reduce the hydrolysis time by about one half and increase the output by 50 to 150 percent compared with the current single-batch hydrolysis mode.
Description
Technical field
The present invention relates to a kind of hydrolysis reaction method in weedicide glyphosate acid production process.
Background technology
Glyphosphonic acid is the weedicide of present a kind of superior performance of using.
Disclosed alkyl esterification method is one of its preparation method among the document DEOLSNO.P2942898.6, adopt be with Paraformaldehyde 96 (or formaldehyde) in containing the methanol solvate of triethylamine after the heating for dissolving, add glycine and dimethylphosphite (or trimethyl phosphite) more respectively and carry out condensation reaction, generate the triethylamine salt (II) of target product glyphosphonic acid (or its hydrochloride) precursor body compound glyphosate dimethyl phthalate (III), through hydrochloric acid hydrolysis under heating condition, obtain targeted product glyphosphonic acid (III) or its hydrochloride then.Removal of solvent under reduced pressure and excessive hydrochloric acid are promptly separated out the glyphosphonic acid crystallization.Reaction process is as follows:
NH
2CH
2COOH+(CH
2O)
n+N(C
2H
5)
3→HOCH
2NHCH
2COOH·N(C
2H
5)
3
(I)
(HO)
2POCH
2NHCH
2COOH+N(C
2H
5)
3·HCl+CH
3Cl
(III)
On the industrial production triethylamine salt (II) of this precursor compound glyphosate dimethyl phthalate being hydrolyzed with hydrochloric acid at present is to carry out in reactor, usually all be the hydrochloric acid soln the 30% or more earlier synthetic liquid of the triethylamine salt (II) of this precursor compound glyphosate dimethyl phthalate and hydrolysis used in molar ratio 1: (2-4) inject mixing in the reactor respectively simultaneously, and then be warming up to gradually under 120 ℃ of required conditions of hydrolysis, carry out and finish hydrolysis reaction.Because precursor compound is an exothermic process with mixing of hydrochloric acid, reactor after hydrolysis reaction is finished has very high temperature again, therefore carry out the next batch hydrolysis reaction after batch hydrolysis reaction is finished before when feeding intake, must be earlier to reactor be cooled to be lower than 40 ℃ after, could inject two kinds of hydrolysis materials of following batch, otherwise the glyphosate yield obviously reduces, and the material phenomenon easily takes place to dash simultaneously.After lifting capacity feeds intake in accordance with regulations, also must slowly heat up gradually,, the synthetic liquid of nitration mixture be lost to avoid generation towards the material problem.All need to be in the reactor cooling of the condition of high temperature before newly feeding intake at every turn, not only cause the significant wastage of the energy, and because cooling circulating water quality difference causes a large amount of steam valve water to be utilized effectively is bled off in vain, also prolonged the reaction times greatly simultaneously.Reactor also is vulnerable to damage in this frequent cold and hot cataclysm process, directly two kinds of materials are injected reactor and mix, the also normal inaccurate even material problem of miscarrying of batching that easily takes place.On the other hand, though being the given load amounts by reactor, two kinds of hydrolysis materials that injected feed intake, but because material in the reaction system and solvent etc. all are volatile components, carrying out along with intensification and hydrolysis reaction, inventory in the still can reduce gradually, top clearance spaces in the reactor is constantly increased, caused the invalid heating ratio also thereupon increase of heating jacket, cause the upper heat and lower cold phenomenon of reactor these clearance spaces.By present feeding mode production, this problem ubiquity but can't solve.This is not only the another factor that increases energy dissipation, and has reduced the reactor utilization ratio, has influenced production efficiency and output.
Summary of the invention
At above-mentioned situation, the present invention will provide a kind of method for hydrolysis of improved glyphosphonic acid, to solve the problem that traditional hydrolysis method exists in the present glyphosphonic acid industrial production.
Method for hydrolysis in the glyphosate acid preparation process of the present invention, primary process is to be raw material after condensation reaction generates the precursor of glyphosate acid with formaldehyde or Paraformaldehyde 96, triethylamine, glycine and methyl phosphite compounds equally, is hydrolyzed under heating condition to obtain glyphosphonic acid or its hydrochloride with hydrochloric acid.Wherein, contain the reaction mixture of glyphosphonic acid precursor compound and 〉=30% hydrochloric acid soln (2.1～2.6) after the condensation reaction: 1 mass ratio is mixing (be called and add sour condensated liquid) in the conveying operational process of hydrolysis device, be heated to rapidly then≤105 ℃, particularly preferably be rapidly be heated to≤90 ℃ and send into hydrolysis device and be hydrolyzed.
Test shows; aforesaid method of the present invention is by just shortening mixing and heat-up time of the reaction mixture that contains the glyphosphonic acid precursor compound and hydrochloric acid soln; make the reaction mixture that contains the glyphosphonic acid precursor compound rapidly under the protection of enough acid, can significantly reduce the generation of side reaction.Therefore, above-mentioned said mixing, the online mode that hydrochloric acid soln is added with employing in the line of pipes of the reaction mixture that contains the glyphosphonic acid precursor compound is mixed into good, can make it can obtain fully in moment, mix uniformly.
To the above-mentioned heating that adds sour condensated liquid, equally also be to finish rapidly to good with fast as far as possible speed.Realize that said rapid heating can have multiple mode, for example can be by to the heating of transport pipe, or adopt tower heating, and adopt mode such as film heating, can reach and make mixture be heated to the purpose of said temperature rapidly, and then it is sent into hydrolysis device be hydrolyzed.Serve as preferred to adopt the film type of heating especially wherein, except that realizing that " moment " is heated to the said temperature, also more help removing this and add low-boiling point material (as methylal, methyl alcohol, methyl chloride, HCL etc.) in the sour condensated liquid, make the smaller volume that adds sour condensated liquid, help improving the hydrolysis conversion of glyphosate.
Above-mentioned said film type of heating, can adopt relevant device currently reported and/or that use, also can adopt as the mode among the embodiment that can be for reference, be provided with a sprinkling at the center of hydrolysis kettle or get rid of the throwing structure, by this sprinkling or get rid of and throw structure and this is added sour condensated liquid spray or get rid of and throw by on the still inwall of design temperature heating and be heated to said temperature rapidly, reaction then is hydrolyzed in hydrolysis kettle.According to the needs of hydrolysis reaction, the material that is heated to said temperature rapidly can also be sent into the reaction that is hydrolyzed simultaneously in some hydrolysis devices simultaneously.
If adding sour condensated liquid and can not in time send in the hydrolysis kettle for some reason and be hydrolyzed in the said process, then this adds sour condensated liquid and should lower the temperature and store, particularly to store for good being lower than under 40 ℃ of conditions, to reduce generation, help improving the transformation efficiency of glyphosate as by products such as methylglycine, amine methyl acid phosphates.
Be appreciated that by foregoing, method for hydrolysis of the present invention can adopt automatic control mode to make condensation reaction thing and hydrochloric acid in required ratio on-line mixing homogenizing by mixing tank, and after temperature required, be hydrolyzed by rapid even instantaneously heating, therefore operations such as preparation process and hydrolysis reaction are carried out continuously, guaranteed the continuity of production operation, help enhancing productivity, all the more so in the time of particularly in a plurality of equipment, being hydrolyzed reaction simultaneously.Test shows, the hydrolysis that method for hydrolysis of the present invention can generally be wanted original technology 8-10 hour reduces to only needed to finish in 4-5 hour, it is about 1/2 that hydrolysis time can reduce, if under the situation about being hydrolyzed simultaneously in a plurality of hydrolysis kettles, hydrolysis rate also can further increase.On the other hand, because the minimizing of W-response time, side reaction also reduces to some extent, and glyphosate yield and former opaque amount increase.Therefore, adopt aforesaid method of the present invention, the output of the comparable existing single still hydrolysis process of hydrolysis output approximately improves 50-150%.
Embodiment below in conjunction with embodiment is described in further detail foregoing of the present invention again.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.Do not breaking away under the above-mentioned technological thought situation of the present invention, various replacements or change according to ordinary skill knowledge and customary means are made all should comprise within the scope of the invention.
Embodiment
Embodiment 1
Be after raw material generates the precursor of glyphosate acid through condensation reaction with formaldehyde or Paraformaldehyde 96, triethylamine, glycine and methyl phosphite compounds in the usual way, the reaction mixture (being condensated liquid) that contains glyphosphonic acid precursor compound thing on-line mixing after enters 10 thin film heaters with 30% hydrochloric acid by mass ratio at 2.1: 1, moment collects in the hydrolysis kettle after being heated to 90 ℃, storage is full, 8000 liters of hydrolysis kettle volumes, 5 minutes times spent.Then, in hydrolysis kettle, continue to be heated to 118 ℃, 4 hours times spent.Insulation is 30 minutes under 118 ℃ of temperature, blowing, and crystallization obtains 1.3 tons in former powder through centrifugation, oven dry, yield 72% (yield of ordinary method production is no more than 71%).
Embodiment 2
By above-mentioned same usual manner synthetic after, condensated liquid and 31% hydrochloric acid on-line mixing after are entered 10 thin film heaters by mass ratio at 2.4: 1, collect in the hydrolysis kettle after the instantaneously heating to 87 ℃, store completely 8000 liters of hydrolysis kettle volumes, 5 minutes times spent; In hydrolysis kettle, continue to be heated to 117 ℃ then, 4 hours times spent; Insulation is 30 minutes under 117 ℃ of temperature, blowing, and crystallization obtains 1.355 tons in former powder, yield 75% through centrifugation, oven dry; Produce according to a conventional method, get 1.318 tons in former powder, yield 73%.
Embodiment 3
Same condensated liquid and 31% hydrochloric acid on-line mixing after are entered 10 thin film heaters by mass ratio at 2.6: 1, collect in the hydrolysis kettle after the instantaneously heating to 89 ℃, storage is full, 8000 liters of hydrolysis kettle volumes, 5 minutes times spent; In hydrolysis kettle, continue to be heated to 119 ℃ then, 4 hours times spent; Insulation is 30 minutes under 119 ℃ of temperature, blowing, and crystallization obtains 1.363 tons in former powder, yield 75.5% through centrifugation, oven dry; Produce according to a conventional method, get 1.32 tons in former powder, yield 73.2%.
Claims (4)
1. the method for hydrolysis in the glyphosate acid preparation process, with formaldehyde or Paraformaldehyde 96, triethylamine, glycine and methyl phosphite compounds are after raw material generates the precursor compound of glyphosate acid through condensation reaction, under heating condition, be hydrolyzed to obtain glyphosphonic acid or its hydrochloride with hydrochloric acid, the reaction mixture that it is characterized in that containing glyphosphonic acid precursor compound thing after the condensation reaction and 〉=30% hydrochloric acid soln are by (2.1～2.6): 1 mass ratio is heated to rapidly≤105 ℃ and send into hydrolysis device and be hydrolyzed after mixing in the conveying operational process of hydrolysis device.
2. the method for hydrolysis in the glyphosate acid preparation process as claimed in claim 1 is characterized in that the online mode mixing that said hydrochloric acid soln adds in the line of pipes of the reaction mixture that contains the glyphosphonic acid precursor compound.
3. the method for hydrolysis in the glyphosate acid preparation process as claimed in claim 1, after it is characterized in that the reaction mixture and mixed in hydrochloric acid of said glyphosphonic acid precursor compound, be heated to rapidly with the film type of heating and send into hydrolysis device again after the said temperature and be hydrolyzed.
4. as the method for hydrolysis in the described glyphosate acid preparation process of one of claim 1 to 3, it is characterized in that the reaction mixture of said glyphosphonic acid precursor compound and the mixture after the mixed in hydrochloric acid be heated to rapidly≤send into hydrolysis device after 90 ℃ the temperature to be hydrolyzed.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550158B (en) * | 2009-05-22 | 2011-10-19 | 四川省乐山市福华通达农药科技有限公司 | Production method for secondary acid hydrolysis of dimethyl ester glyphoate acid |
| CN101560224B (en) * | 2009-05-19 | 2012-02-01 | 四川省乐山市福华通达农药科技有限公司 | Hydrolysis process in process of preparing glyphosate by glycine method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU173170B (en) * | 1974-06-27 | 1979-03-28 | Chinoin Gyogyszer Es Vegyeszet | Process for producing n-phosphonomethyl-glycine |
| CH647528A5 (en) * | 1978-10-27 | 1985-01-31 | Bcap Biolog Chem Act Pat | PROCESS FOR THE PREPARATION OF N-phosphonomethylglycine. |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560224B (en) * | 2009-05-19 | 2012-02-01 | 四川省乐山市福华通达农药科技有限公司 | Hydrolysis process in process of preparing glyphosate by glycine method |
| CN101550158B (en) * | 2009-05-22 | 2011-10-19 | 四川省乐山市福华通达农药科技有限公司 | Production method for secondary acid hydrolysis of dimethyl ester glyphoate acid |
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Address after: 614803 Jinsu Town, Wutongqiao District, Leshan City, Sichuan Province Patentee after: Fuhua Tongda Chemical Co.,Ltd. Address before: 614800 Sichuan city of Leshan province Wutongqiao District Bridge Town Fuhua agricultural investment group Patentee before: Sichuan Leshan Fuhua Tongda Pesticide Technology Co.,Ltd. |