CN1362414A - Prepn of high-purity acephate powder (1) - Google Patents
Prepn of high-purity acephate powder (1) Download PDFInfo
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- CN1362414A CN1362414A CN 02113934 CN02113934A CN1362414A CN 1362414 A CN1362414 A CN 1362414A CN 02113934 CN02113934 CN 02113934 CN 02113934 A CN02113934 A CN 02113934A CN 1362414 A CN1362414 A CN 1362414A
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- former powder
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- acephate
- dimethyl thiophosphoryl
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Abstract
The preparation method of high-purity acephate raw powder includes the folloinwg steps: making O,O-dimethyl thiophosphorylamide undergo the processes of isomerization and acetylation or making O,S-dimethyl thiophosphorylamide undergo the process of acetylation, making the acephate dcrude undergo the processes of neutralization, extraction, precipitation, crystalization, washing, solid-liquid separation and drying so as to obtain the acephate raw powder. Its yield rate and product purity are high.
Description
Technical field:
The present invention relates to the preparation method of the former powder of a kind of high-purity acetyl acephatemet
Background technology:
Acephate, formal name used at school O, S-dimethyl-N-ethanoyl thio-phosphamide claims N-acetylaminohydroxyphenylarsonic acid O again, S-dimethyl phosphoric acid ester, molecular structure is
Pure product are white crystal, and fusing point 92-93 ℃ is a kind of agricultural chemicals of high-efficiency low-toxicity.
By O; the O-dimethyl thiophosphoryl amide is through isomerization and acetylize; or by O, the general content of acephate crude oil that S-dimethyl thiophosphoryl amide crude oil makes through acetylize must could obtain the former powder of desirable acephate through separating to purify at 30-70% (mass percent).Japanese Patent JP-B48-34583 has reported the former powder separating and extracting method of a kind of acephate: at first use chloroform extraction acephate crude oil, wash with salt solution then, carry out condensing crystal again.Japanese Patent JP-A64-75494 reported method is: at first use in the alkali aqueous solution and acephate crude oil, extract with ethylene dichloride or chloroform then, concentrate and recrystallization again.United States Patent (USP) 5,616,769 have also reported a kind of two-phase (water and organic phase) recrystallization method.Chinese patent 1238340 reported and a kind ofly at first acephate crude oil carried out crystallization, and after the isolation of crystalline, neutralization or washing crystalline mother solution, extraction acephate, the crystallization of extraction phase precipitation, coarse crystal are refining etc., and process gets the former powder of high-purity acetyl acephatemet.Chinese patent 1277201 reported and a kind ofly at first acephate crude oil carried out crystallization, after the isolation of crystalline, and the impurity in the extractive crystallization mother liquor, the process such as refining of secondary crystal, coarse crystal gets the former powder of high-purity acetyl acephatemet.Except that Chinese patent 1238340 and 1277201, all exist the former powder yield of acephate little in above-mentioned these methods, and contain the big problem of mother liquor yield of acephate.In addition, except that Chinese patent 1277201, all need processing to contain organophosphorus and other organic waste water in a large number, and the consumption of organic extractant is generally all bigger.
Summary of the invention:
The object of the present invention is to provide the preparation method of a kind of yield height, purity height, the former powder of low, the free of contamination high-purity acetyl acephatemet of cost
The objective of the invention is to realize in the following way: the preparation method of the former powder of a kind of high-purity acetyl acephatemet: by O; O-dimethyl thiophosphoryl amide or O; the S-dimethyl thiophosphoryl amide is a raw material; with O; isomerization of O-dimethyl thiophosphoryl amide and acetylize or with O; the acetylize of S-dimethyl thiophosphoryl amide, preparation acephate crude oil prepares the former powder of acephate with acephate crude oil by neutralization, extraction, precipitation, crystallization, washing, solid-liquid separation, drying process then.
O; O-dimethyl thiophosphoryl amide and methyl-sulfate carry out isomerization reaction; O; O-dimethyl thiophosphoryl amide and methyl-sulfate mass ratio are 0.02-0.1: 1; 30-90 ℃ of isomerization reaction temperature; reaction times is 2-10 hour; generate O; the S-dimethyl thiophosphoryl amide, then at O, the S-dimethyl thiophosphoryl amide directly adds aceticanhydride to carry out acetylization reaction and makes acephate crude oil; aceticanhydride and O; the mass ratio of S-dimethyl thiophosphoryl amide is 0.5-1.0: 1, and 30-90 ℃ of acetylization reaction temperature, time 2-10 hour.
O, the S-dimethyl thiophosphoryl amide, content is more than 70%; under the acylation catalyst effect, carry out acetylization reaction with aceticanhydride and make acephate crude oil, aceticanhydride and O, the mass ratio of S-dimethyl thiophosphoryl amide crude oil is 0.5-1.0: 1; 30-90 ℃ of acetylization reaction temperature, time 2-10 hour.
Acylation catalyst is the vitriol oil or methyl-sulfate or strongly-acid ion-exchange resin or solid super-strong acid.
With in the basic solution and acephate crude oil, neutral temperature is less than 25-55 ℃.
Basic solution is ammoniacal liquor or sodium carbonate solution or sodium hydroxide solution.
With the acephate in the organic solvent extraction neutralizer, extracting phase (water) reclaims ammonium acetate or acetic acid after treatment, and extraction phase (oil phase) carries out crystallization again behind precipitation recovery part solvent.
The organic solvent of extraction usefulness is carbonic ether, aliphatic carboxylic acid esters,, aliphatic ketone, aromatic hydrocarbons, aliphatic hydrocarbon, naphthenic hydrocarbon, halohydrocarbon or by the mixture of two or more (containing two kinds) above-mentioned these materials preparations.
Extraction phase behind the precipitation carries out primary crystallization, temperature is-10-20 ℃, time is 0.5-60 hour, use solvent wash then, isolate crystal and mother liquor, the crystal drying makes the former powder of high-purity acetyl acephatemet, mother liquor can be used to prepare missible oil after treatment, for obtaining the former powder of more acephate, then will carry out secondary crystal behind this mother liquor precipitation, temperature is-30-10 ℃, time is 0.5-60 hour, uses solvent wash, isolates crystal and mother liquor, the crystal drying promptly gets the former powder of high-purity acetyl acephatemet, and mother liquor can be prepared missible oil after treatment.
The solvent that is used to wash is for being carbonic ether, aliphatic carboxylic acid esters,, aliphatic ketone, aromatic hydrocarbons, aliphatic hydrocarbon, naphthenic hydrocarbon, halohydrocarbon or by the mixture of two or more (containing two kinds) above-mentioned these materials preparations.
Adopt the former powder rate of recovery of invention preparation acephate height, the purity height, therefore the recyclable utilization of employed extraction liquid has reduced production cost, does not also have discharging of waste liquid, and environment is not polluted.
The present invention will be further described according to embodiment below:
Embodiment 1:
Example 1: at the O of 945kg, add the 56.7kg methyl-sulfate in the O-dimethyl thiophosphoryl amide, carry out isomerization reaction and get 75.3% O, the S-dimethyl thiophosphoryl amide, add the 700kg mass concentration again and be 98% aceticanhydride, reacted 3 hours down at 55 ℃, get the acephate crude oil of content 56.4%.This acephate crude oil is neutralized to pH value 6.5-7.0 with 25% ammoniacal liquor, with 4500kg extraction agent extraction neutralizer, get 1600kg extracting phase (water) and 5680kg extraction phase (oil phase), the treated recovery acetic acid of water 420-450kg, put into crystallization kettle that band stirs behind the oil phase vacuum precipitation and be cooled to-5 ℃-0 ℃ and carry out primary crystallization, with solvent wash after separate, dry must 609kg content be 97.6% the former powder of acephate.Put into the crystallization kettle that band stirs behind the mother liquor precipitation to be cooled to-20--10 ℃ carries out secondary crystal, with solvent wash after separate, dry must 232kg content be 97.3% the former powder of high-purity acetyl acephatemet, and 400kg content is 20.5% secondary mother liquid.
Example 2:
At 880kg content is 75% O, adds 616kg content in the S-dimethyl thiophosphoryl amide and be 98% aceticanhydride and 8.8kg content and be 98% sulfuric acid, 55 ℃ of reactions 3 hours down, 1504.8kg content be the acephate crude oil of 55-57%.Add the 500kg solvent in this crude oil, be neutralized to pH value 6.5-7.0 with ammoniacal liquor then, filter the ammonium acetate crystal that neutralization produces, filtrate is taked the continuous extraction mode, gets 3959.8kg content and be 21.2% liquid.The crystallization kettle of putting into the band stirring behind the vacuum precipitation is cooled to-5 ℃-0 ℃ and carries out primary crystallization, separate 657.5kg coarse crystal and 853.6kg mother liquor, this mother liquor is put into the crystallization kettle that band stirs and is cooled to-20 ℃--10 ℃ are carried out secondary crystal, separate the secondary crystal mother liquor of 281.6kg coarse crystal and 245.2kg content 30.5%.The acephate coarse crystal that primary crystallization and secondary crystal obtained is dissolved in the 1056.5kg organic solvent, be cooled to terminal temperature-15-10 ℃ gradually at 0.5-30 hour, through separate, dry 736.7kg content is 98.0% the former powder of high-purity acetyl acephatemet.Refinement mother liquor can recycle or dispose after treatment missible oil.
Claims (10)
1, the preparation method of the former powder of a kind of high-purity acetyl acephatemet; by O; O-dimethyl thiophosphoryl amide or O; the S-dimethyl thiophosphoryl amide is a raw material; it is characterized in that: with O, isomerization of O-dimethyl thiophosphoryl amide and acetylize or with O, the acetylize of S-dimethyl thiophosphoryl amide; preparation acephate crude oil prepares the former powder of acephate with acephate crude oil by neutralization, extraction, precipitation, crystallization, washing, solid-liquid separation, drying process then.
2; the preparation method of the former powder of high-purity acetyl acephatemet according to claim 1; it is characterized in that: O; O-dimethyl thiophosphoryl amide and methyl-sulfate carry out isomerization reaction; O; O-dimethyl thiophosphoryl amide and methyl-sulfate mass ratio are 0.02-0.1: 1; 30-90 ℃ of isomerization reaction temperature; reaction times is 2-10 hour, generates O, the S-dimethyl thiophosphoryl amide; then at O; the S-dimethyl thiophosphoryl amide directly adds aceticanhydride to carry out acetylization reaction and makes acephate crude oil, and aceticanhydride and O, the mass ratio of S-dimethyl thiophosphoryl amide are 0.5-1.0: 1; 30-90 ℃ of acetylization reaction temperature, time 2-10 hour.
3, the preparation method of the former powder of high-purity acetyl acephatemet according to claim 1; it is characterized in that: O; the S-dimethyl thiophosphoryl amide; content is more than 70%; under the acylation catalyst effect, carry out acetylization reaction with aceticanhydride and make acephate crude oil, aceticanhydride and O, the mass ratio of S-dimethyl thiophosphoryl amide crude oil is 0.5-1.0: 1; 30-90 ℃ of acetylization reaction temperature, time 2-10 hour.
4, the preparation method of the former powder of high-purity acetyl acephatemet according to claim 3 is characterized in that: acylation catalyst is the vitriol oil or methyl-sulfate or strongly-acid ion-exchange resin or solid super-strong acid.
5, the preparation method of the former powder of high-purity acetyl acephatemet according to claim 1 is characterized in that: use in the basic solution and acephate crude oil, neutral temperature is less than 25-55 ℃.
6, the preparation method of the former powder of high-purity acetyl acephatemet according to claim 5 is characterized in that: basic solution is ammoniacal liquor or sodium carbonate solution or sodium hydroxide solution.
7, the preparation method of the former powder of high-purity acetyl acephatemet according to claim 1, it is characterized in that: with the acephate in the organic solvent extraction neutralizer, extracting phase (water) reclaims ammonium acetate or acetic acid after treatment, and extraction phase (oil phase) carries out crystallization again behind precipitation recovery part solvent.
8, the preparation method of the former powder of high-purity acetyl acephatemet according to claim 7 is characterized in that: the organic solvent of extraction usefulness is carbonic ether, aliphatic carboxylic acid esters,, aliphatic ketone, aromatic hydrocarbons, aliphatic hydrocarbon, naphthenic hydrocarbon, halohydrocarbon or by the mixture of two or more (containing two kinds) above-mentioned these materials preparations.
9, the preparation method of the former powder of high-purity acetyl acephatemet according to claim 7, it is characterized in that: the extraction phase behind the precipitation carries out primary crystallization, temperature is-10-20 ℃, time is 0.5-60 hour, use solvent wash then, isolate crystal and mother liquor, the crystal drying makes the former powder of high-purity acetyl acephatemet, and mother liquor can be used to prepare missible oil, secondary crystal more after treatment, temperature is-30-10 ℃, time is 0.5-60 hour, uses solvent wash, isolates crystal and mother liquor, the crystal drying promptly gets the former powder of high-purity acetyl acephatemet, and mother liquor can be prepared missible oil after treatment.
10, the preparation method of the former powder of high-purity acetyl acephatemet according to claim 1 is characterized in that: the solvent that is used to wash is for being carbonic ether, aliphatic carboxylic acid esters,, aliphatic ketone, aromatic hydrocarbons, aliphatic hydrocarbon, naphthenic hydrocarbon, halohydrocarbon or by the mixture of two or more (containing two kinds) above-mentioned these materials preparations.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021139342A CN1176929C (en) | 2002-01-28 | 2002-01-28 | Prepn of high-purity acephate powder (1) |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021139342A CN1176929C (en) | 2002-01-28 | 2002-01-28 | Prepn of high-purity acephate powder (1) |
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| CN1362414A true CN1362414A (en) | 2002-08-07 |
| CN1176929C CN1176929C (en) | 2004-11-24 |
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| CNB021139342A Expired - Fee Related CN1176929C (en) | 2002-01-28 | 2002-01-28 | Prepn of high-purity acephate powder (1) |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100439376C (en) * | 2006-10-13 | 2008-12-03 | 清华大学 | Method and apparatus for separating acetyl methamidophos from neutral solution |
| CN1931864B (en) * | 2005-09-18 | 2010-05-05 | 李坚 | Preparation of high content methamidophos and acetyl methamidophos product |
| CN101816843A (en) * | 2010-04-14 | 2010-09-01 | 清华大学 | Device and method for extracting acephate from neutralization solution |
| CN106496061A (en) * | 2016-10-20 | 2017-03-15 | 湘潭大学 | A kind of method of acetyl spermine in extract and separate acylation reaction liquid |
| CN112592368A (en) * | 2020-12-10 | 2021-04-02 | 安道麦股份有限公司 | Method for synthesizing acephate |
| CN112979698A (en) * | 2021-02-24 | 2021-06-18 | 湖南沅江赤蜂农化有限公司 | Synthesis method of acephate |
| WO2022180555A1 (en) * | 2021-02-25 | 2022-09-01 | Upl Limited | A process for production of acephate |
-
2002
- 2002-01-28 CN CNB021139342A patent/CN1176929C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1931864B (en) * | 2005-09-18 | 2010-05-05 | 李坚 | Preparation of high content methamidophos and acetyl methamidophos product |
| CN100439376C (en) * | 2006-10-13 | 2008-12-03 | 清华大学 | Method and apparatus for separating acetyl methamidophos from neutral solution |
| CN101816843A (en) * | 2010-04-14 | 2010-09-01 | 清华大学 | Device and method for extracting acephate from neutralization solution |
| CN101816843B (en) * | 2010-04-14 | 2012-02-08 | 清华大学 | Device and method for extracting acephate from neutralization solution |
| CN106496061A (en) * | 2016-10-20 | 2017-03-15 | 湘潭大学 | A kind of method of acetyl spermine in extract and separate acylation reaction liquid |
| CN106496061B (en) * | 2016-10-20 | 2018-06-05 | 湘潭大学 | A kind of method of acetyl spermine in extract and separate acylation reaction liquid |
| CN112592368A (en) * | 2020-12-10 | 2021-04-02 | 安道麦股份有限公司 | Method for synthesizing acephate |
| CN112979698A (en) * | 2021-02-24 | 2021-06-18 | 湖南沅江赤蜂农化有限公司 | Synthesis method of acephate |
| WO2022180555A1 (en) * | 2021-02-25 | 2022-09-01 | Upl Limited | A process for production of acephate |
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|---|---|
| CN1176929C (en) | 2004-11-24 |
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