CN101085783B - Method for hydrolyzing glyphosate acid - Google Patents
Method for hydrolyzing glyphosate acid Download PDFInfo
- Publication number
- CN101085783B CN101085783B CN2007100494425A CN200710049442A CN101085783B CN 101085783 B CN101085783 B CN 101085783B CN 2007100494425 A CN2007100494425 A CN 2007100494425A CN 200710049442 A CN200710049442 A CN 200710049442A CN 101085783 B CN101085783 B CN 101085783B
- Authority
- CN
- China
- Prior art keywords
- hydrolysis
- reactor
- glyphosphonic
- acid
- precursor compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention relates to a method for hydrolyzing glyphosate. It comprises following steps: mixing prosoma of glyphosate with chlorhydric acid solution, feeding the mixture according to required amount into autoclave, heating for hydrolysis; or feeding the mixture, heating not more than 100 Deg. C, and dropping said mixture into autoclave until meets the required amount, heating again for hydrolysis. The method is characterized by shortened hydrolysis time, increased utilizing rate of autoclave and heat, increased yeild and decreased energy consumption. It aslo solves the damage to autoclave caused by stop- and- go heating in traditional method.
Description
Technical field
The present invention relates to the hydrolysis reaction working method in a kind of glyphosate acid production process.
Background technology
Glyphosphonic acid is widely used at present a kind of weedicide.Since the mid-1970s commercialization in last century, because its remarkable herbicidal performance, range of application constantly enlarges.
The suitability for industrialized production of glyphosphonic acid is at present mainly by two kinds of methods: a kind of is the IDA method that all waits company generally to adopt as U.S. Meng Shan, is starting raw material production with the diethanolamine; Another kind method is as the disclosed alkyl esterification method of document DEOLSNO.P2942898.6, 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 midbody compound glyphosate dimethyl phthalate, then through hydrochloric acid hydrolysis, can generate and obtain glyphosphonic acid (III) or its hydrochloride, removal of solvent under reduced pressure and excessive hydrochloric acid are separated out the glyphosphonic acid crystallization.Reaction process is as follows:
It all is to carry out in reactor that industrial production is hydrolyzed with hydrochloric acid to the triethylamine salt (II) of midbody compound glyphosate dimethyl phthalate.At present, this hydrolysis reaction operation all is that elder generation is with the synthetic liquid of the triethylamine salt (II) of the glyphosate dimethyl phthalate of the precursor compound of glyphosphonic acid usually, and concentration is the hydrochloric acid soln in molar ratio 1 more than 30%: (2-4) inject simultaneously respectively in the reactor and mix, and then be warming up to gradually under 120 ℃ of required conditions of hydrolysis, carry out and finish hydrolysis reaction.Because intermediate (II) is an exothermic process with mixing of hydrochloric acid two materials, reactor after hydrolysis reaction is finished has very high temperature again, therefore carry out the next batch hydrolysis reaction after hydrolysis reaction is finished when feeding intake, must be earlier to reactor be cooled to be lower than 40 ℃ after, could inject two kinds of hydrolysis materials of next batch, obviously reduce otherwise the glyphosate yield can take place, the material phenomenon can take place significantly 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 at every turn before newly feeding intake, not only cause the significant wastage of the energy, and, bleed off in vain because the circulating water cooled water quality inferiority causes a large amount of steam valve water to be utilized effectively.Simultaneously also prolonged the reaction times greatly, reactor also is vulnerable to damage in this frequent cold and hot cataclysm process, directly two kinds of materials is injected reactor and mixes, 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, along with the carrying out of heating up and reacting, 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.
The principle of glyphosphonic acid method for hydrolysis of the present invention, remain the precursor compound (II) of above-mentioned glyphosphonic acid is mixed afterwards (as the mol ratio 1 of routine: the 2-4 mixed) with hydrochloric acid soln (concentration of using as routine is the hydrochloric acid soln 30% or more), in reactor, under heating condition, be hydrolyzed, but in its specific operation process, be after earlier the precursor compound (II) of this glyphosphonic acid and two kinds of materials of hydrochloric acid soln being mixed with the synthetic liquid of nitration mixture in another other container unit, pressing the given load amount of reactor hydrolysis reaction again injects in the reactor, can heat up, and can be warming up to the reaction that is hydrolyzed under the required temperature condition of hydrolysis reaction rapidly.Said this prepared the independent container unit of the synthetic liquid of nitration mixture in advance, can directly be the reinforced high-level storage groove of use commonly used, also can select other appropriate containers preparation after, squeeze into the high-level storage groove that feeds in raw material with pump again and feed in raw material.
Because to the batch mixes of the precursor compound of glyphosate acid (normally being present in form in the synthetic liquid) and hydrochloric acid soln is to carry out in other independent container such as reservoir, rather than directly in reactor, carry out, heat release when therefore it mixes does not have too many influence, and also be easy to control, also can not be subjected to the influence of temperature of reaction kettle, also just need not to feed intake again after the reactor cooling earlier, but can directly inject the mixture for preparing by the hydrolysis requirement in the reactor, thereby avoided energy dissipation that reactor is lowered the temperature repeatedly and caused, and, also can shorten required total time of hydrolytic process greatly simultaneously to the infringement that reactor brings.On the other hand, the preparation nitration mixture synthesizes liquid in another independent container in advance, not only is easy to guarantee the accuracy of mixing of materials metering, more can effectively solve the wrong problem that feeds intake.
In the mixing and the improved basis of feeding mode to the hydrolysis material in the said hydrolyzed process, at synthetic liquid after the lifting capacity mode is injected reactor routinely with nitration mixture, can also adopt earlier reaction mass to be warming up to rapidly and be up to 100 ℃, and under the condition that is not higher than this temperature, continuation is injected the synthetic liquid of nitration mixture to drip the mode secondary in reactor, end when volume of material reaches the given load amount to still, continue to be warming up to 120 ℃ then and carry out and finish hydrolysis reaction.Increasing in the intensification hydrolytic process that this is reinforced for the second time, is can reduce this situation gradually at inventory in the still in the intensification hydrolytic process to propose, and also is only just can be achieved adopting on the above-mentioned basis of preparing the synthetic liquid of nitration mixture in advance of the present invention.Because this reinforced employing for the second time is that " dropping " mode feeds intake, therefore neither can produce obvious variation and influence normally carrying out of hydrolysis reaction the still interior reaction temperature, material in the still is replenished, avoid occurring in the still energy dissipation that excessive clearance spaces causes, improve the utilization ratio of reactor greatly, also can significantly improve output.Test shows, adopts this feeding mode production second time that drips mode, and feeding intake to produce than traditional way to increase by at least 50% charging capacity, also can corresponding increase output at least 50%.
In order to improve the hydrolysis temperature rise rate in early stage, avoid simultaneously on hydrolysis gas phase pipeline, adding a gas-liquid separation device towards the next harm of strip, guarantee normally carrying out of hydrolysis reaction.
Embodiment by the following examples 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
Synthetic liquid 1000 grams of nitration mixture that mixed in 1: 3.2 in molar ratio by the hydrochloric acid of the synthetic liquid of the precursor compound of glyphosphonic acid and 30% are added in the there-necked flask of 1000ml, be warmed up to 80 ℃, after part organic solvent and water are deviate from, be added dropwise to the synthetic liquid of 400 these nitration mixture of gram again, the dropping time was at 10-20 minute.Drip off and continue to be warmed up to 120 ℃, hydrolysis reaction is carried out fully.Detect solid glyphosate content and the glyphosate content in mother liquor, calculating in the glycine total recovery is 81.5%.
Embodiment 2
Synthetic liquid 1000 grams of nitration mixture with being mixed in 1: 3.3 in molar ratio by the hydrochloric acid of the synthetic liquid of the precursor compound of glyphosphonic acid and 32% add in the there-necked flask of 1000ml; Be warmed up to 90 ℃, after part organic solvent and water are deviate from, be added dropwise to the synthetic liquid of the same nitration mixture of 500 grams again, the dropping time was at 10-20 minute.Drip off and continue to be warmed up to 120 ℃, hydrolysis reaction is carried out fully.Detect solid glyphosate content and the glyphosate content in mother liquor, calculating in the glycine total recovery is 81.2%.
Embodiment 3
The synthetic liquid of nitration mixture that was mixed in 1: 3.2 in molar ratio by the hydrochloric acid of the synthetic liquid of the precursor compound of glyphosphonic acid and 30% is squeezed in the 6300KL hydrolysis kettle for 6200 kilograms, got in the header tank for 2200 kilograms.The synthetic liquid of nitration mixture in the hydrolysis kettle is warmed up to 80 ℃, after part organic solvent and water are deviate from, the synthetic drop of the nitration mixture in the header tank is added in the hydrolysis kettle, drips time 1-2 hour, and dropping temperature is no more than 80 ℃.Material is warmed up to 120 ℃ in the continuation time still, and hydrolysis reaction is carried out fully.Detect solid glyphosate content and the glyphosate content in mother liquor, calculating in the glycine total recovery is 80.8%.
Embodiment 4
The synthetic liquid of nitration mixture that was mixed in 1: 3.2 in molar ratio by the hydrochloric acid of the synthetic liquid of the precursor compound of glyphosphonic acid and 30% is squeezed in the 6300KL hydrolysis kettle for 6200 kilograms, got in the header tank for 3000 kilograms.The synthetic liquid of nitration mixture in the hydrolysis kettle is warmed up to 80 ℃, after part organic solvent and water are deviate from, the synthetic drop of the nitration mixture in the header tank is added in the hydrolysis kettle, drips time 1-2 hour, and dropping temperature is no more than 90 ℃.Material is warmed up to 120 ℃ in the continuation time still, and hydrolysis reaction is carried out fully.Detect solid glyphosate content and the glyphosate content in mother liquor, calculating in the glycine total recovery is 80.8%.
Claims (2)
1. the method for hydrolysis of glyphosphonic acid, the precursor compound of glyphosphonic acid is hydrolyzed under heating condition in reactor with hydrochloric acid soln, it is characterized in that earlier the precursor compound of glyphosphonic acid and hydrochloric acid soln are mixed with in another container unit after nitration mixture synthesizes liquid, lifting capacity is injected in the reactor in accordance with regulations, be warming up to the reaction that is hydrolyzed under the hydrolysis temperature condition, and after it is characterized in that injecting in the reactor the synthetic liquid of nitration mixture, be warming up to earlier≤100 ℃, and under this temperature, continue in reactor, to inject the synthetic liquid of nitration mixture to drip the mode secondary, end when volume of material reaches the given load amount to still, continuing then heats up finishes hydrolysis reaction, the precursor compound of wherein said glyphosphonic acid is the triethylamine salt of glyphosphonic acid dimethyl ester, and glyphosphonic acid precursor compound and hydrochloric acid soln in molar ratio 1: 2-1: 4 mix.
2. the method for hydrolysis of glyphosphonic acid according to claim 1 is characterized in that adding a gas-liquid separation device on hydrolysis gas phase pipeline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100494425A CN101085783B (en) | 2007-07-04 | 2007-07-04 | Method for hydrolyzing glyphosate acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100494425A CN101085783B (en) | 2007-07-04 | 2007-07-04 | Method for hydrolyzing glyphosate acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101085783A CN101085783A (en) | 2007-12-12 |
| CN101085783B true CN101085783B (en) | 2011-09-14 |
Family
ID=38936973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100494425A Active CN101085783B (en) | 2007-07-04 | 2007-07-04 | Method for hydrolyzing glyphosate acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101085783B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632469B (en) * | 2016-12-06 | 2019-06-04 | 湖北泰盛化工有限公司 | A kind of hydrogen chloride acidolysis process and device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1161042A (en) * | 1994-07-01 | 1997-10-01 | 孟山都公司 | Process for preparing N-phosphonomethylamino carboxylic acids |
| CN1340507A (en) * | 2000-08-31 | 2002-03-20 | 浙江新安化工集团股份有限公司 | Process for preparing glyphosate |
| CN1939927A (en) * | 2006-09-19 | 2007-04-04 | 浙江新安化工集团股份有限公司 | Continuous synthesis of glyphosate by dimethyl ester |
-
2007
- 2007-07-04 CN CN2007100494425A patent/CN101085783B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1161042A (en) * | 1994-07-01 | 1997-10-01 | 孟山都公司 | Process for preparing N-phosphonomethylamino carboxylic acids |
| CN1340507A (en) * | 2000-08-31 | 2002-03-20 | 浙江新安化工集团股份有限公司 | Process for preparing glyphosate |
| CN1939927A (en) * | 2006-09-19 | 2007-04-04 | 浙江新安化工集团股份有限公司 | Continuous synthesis of glyphosate by dimethyl ester |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101085783A (en) | 2007-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100443490C (en) | Process for preparing glyphosate | |
| CN103894170A (en) | Solid base catalyst and method for preparing biodiesel by use of solid base catalyst | |
| CN101914218A (en) | Powdered composite calcium zinc stabilizing agent and preparation method thereof | |
| CN102516035B (en) | Preparation method of bisphenol F | |
| CN101684064B (en) | Environment-friendly process for producing dihydromyrcenol by using dihydromyrcene hydration reaction | |
| CN102408396B (en) | Method for preparing versatate glycidyl | |
| CN101265166B (en) | Method for producing monopentaerythritol, bipentaerythritol and tripentaerythritol | |
| CN101085783B (en) | Method for hydrolyzing glyphosate acid | |
| CN102320982B (en) | Method for producing o-nitroaniline by multiple series-connected kettles | |
| CN101928202A (en) | Production method of high-purity 3-chloro-1, 2-propanediol | |
| CN100448907C (en) | Phenolic resin and its production process | |
| CN102311388B (en) | Industrialized production method of 3,4-dimethylpyrazole and phosphate thereof | |
| CN101089005A (en) | Prepn process of cyclic phosphonate compound | |
| CN100343226C (en) | Trihydroxymethyl aminomethane synthesis method | |
| CN101704842A (en) | Process for preparing glyphosate by using glycine | |
| CN101643437A (en) | Preparation and application of oximide acetic acid and salts thereof | |
| CN103012475B (en) | A kind of preparation method of glyphosate | |
| CN103145562B (en) | N-ethyl aniline preparation method | |
| CN104230706A (en) | Preparation method of pentaerythritol oleate | |
| CN107141432A (en) | A kind of production method of phenolic resin | |
| CN103721749B (en) | Avoid composite catalyst and the application thereof of fouling in production of biodiesel | |
| CN101875673B (en) | Method for synthesizing glyphosate | |
| CN104876804B (en) | A kind of preparation method of high 4,4 ' content of isomer Bisphenol F | |
| CN103044644B (en) | High-strength environmentally-friendly furan resin for casting and preparation method thereof | |
| CN103387519B (en) | Preparation method for 4-hydroxybenzyl cyanide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: FUHUA TONGDA PESTICIDE SCIENCE AND TECHNOLOGY CO. Free format text: FORMER OWNER: SICHUAN LESHAN FUHUA AGRICULTURAL SCIENCE INVESTMENT GROUP CO., LTD. Effective date: 20080815 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20080815 Address after: Sichuan city of Leshan province Wutongqiao District Bridge Town Post encoding: 614800 Applicant after: Sichuan Leshan Fuhua Tongda Pesticide Technology Co.,Ltd. Address before: Sichuan city of Leshan province Wutongqiao District Bridge Town Post encoding: 614800 Applicant before: Sichuan Leshan Fuhua Agricultural Science Investment Group Co.,Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 614803 Jinsu Town, Wutongqiao District, Leshan City, Sichuan Province Patentee after: Fuhua Tongda Chemical Co.,Ltd. Address before: Wutongqiao District Qiao Gou Zhen 614800 Sichuan city of Leshan Province Patentee before: Sichuan Leshan Fuhua Tongda Pesticide Technology Co.,Ltd. |