CN1133638C - Method of extracting high-purity acephate from acephate raw oil - Google Patents
Method of extracting high-purity acephate from acephate raw oil Download PDFInfo
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- CN1133638C CN1133638C CNB991154258A CN99115425A CN1133638C CN 1133638 C CN1133638 C CN 1133638C CN B991154258 A CNB991154258 A CN B991154258A CN 99115425 A CN99115425 A CN 99115425A CN 1133638 C CN1133638 C CN 1133638C
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Abstract
The present invention discloses a method for extracting orthene raw powder with high purity from orthene crude oil, which mainly comprises the processes containing orthene crude oil crystallization, crystallization separation, impurity extraction in crystallization mother liquid, extraction residual phase crystallization and the recrystallization of orthene raw powder coarse crystals. The method for extracting orthene raw powder with high purity from orthene crude oil has the characteristics of high recovery rate, high purity, low cost, no drain of waste water containing organic phosphor and no environment pollution.
Description
The present invention relates to a kind of method of from acephate crude oil, extracting the former powder of high-purity acetyl acephatemet.
Acephate, formal name used at school O, S-two bases-N-ethanoyl thio-phosphamide claim N-acetylaminohydroxyphenylarsonic acid O again, S-dimethyl phosphoric acid fat, molecular structure is
Pure product are white crystal, and molten some 92-93 ℃ is a kind of agricultural chemicals of high-efficiency low-toxicity.
Acephate crude oil generally is to be raw material with acephatemet (O, S-dimethyl thiophosphoryl amide) crude oil and aceticanhydride, carries out acetylizad reaction product under catalyst action; Or with O, O-dimethyl thiophosphoryl amide (isomer of acephatemet) and aceticanhydride are raw material, carry out acetylize and isomerized reaction product under catalyst action.Acephate content is generally 30-65% (mass percent) in such acephate crude oil, must could obtain the former powder of desirable acephate through separating to purify.
This century, the seventies Japanese Patent JP-B48-34583 disclosed 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.The eighties Japanese Patent JP-A64-75494 disclosed method is: at first use in the alkali aqueous solution and acephate crude oil, extract with ethylene dichloride or chloroform the present then, concentrate and recrystallization again.Mainly there are following three problems in these two kinds of methods:
(1). almost (JP-B48-34583 is with using brine treatment behind the chloroform extraction acephate crude oil to the acephate that reaction is obtained with the water chance all; JP-A64-75494 directly uses in the alkali aqueous solution and acephate crude oil), and acephate decomposes in the aqueous solution (particularly at alkaline aqueous solution) easily, so the acephate loss may be bigger in the sepn process, causes total separation yield rate on the low side.
(2). water can't recycle in sepn process, thereby produces a large amount of organophosphorus waste water, causes environmental pollution pressure.In the time of discharge of wastewater, also may bring the emission loss of organic solvent and acephate, further increase separation costs.
(3). the ratio of separating the former powder of acephate that obtains is not high, and the acephate mother liquor of corresponding generation larger proportion.Because the missible oil with the mother liquor preparation is impure more, so general stability is very poor.
The object of the present invention is to provide a kind of rate of recovery height, cost is low, purity is high extracts the method for the former powder of high-purity acetyl acephatemet from acephate crude oil.
The present invention is achieved in that the method for extracting the former powder of high-purity acetyl acephatemet from acephate crude oil: its process is:
1. acephate crude oil is carried out crystallization, Tc is-10-35 ℃, and crystallization time is 0.5-30 hour, separate then, the former powder coarse crystal of acephate;
2. carry out the impurity extraction with the mother liquor of organic extractant after to acephate crude oil Crystallization Separation;
3. extracting phase is carried out crystallization, Tc is-30-30 ℃, and the time is 0.5-30 hour, fractional crystallization, the former powder coarse crystal of acephate;
4. with organic solvent the former powder coarse crystal of acephate is carried out recrystallization, get the former powder of highly purified acephate.
Organic extractant is: aromatic hydrocarbons, aliphatic hydrocarbon, halohydrocarbon, naphthenic hydrocarbon or by the mixture of two or more (containing two kinds) these materials preparations.Organic solvent is: carbonic ether, aliphatic carboxylic acid esters,, fatty alcohol, aliphatic ketone or by the mixture of two or more (containing two kinds) these materials preparations.Carbonic ether is the carbonic ether that contains the C1-C4 alkyl.Aliphatics carboxylic ester ester is a C2-C12 carboxylic acid C2-C8 ester.Fatty alcohol is the C1-C8 fatty alcohol.Aliphatic ketone is the C3-C8 aliphatic ketone.
The present invention is owing to carry out crystallization treatment to acephate crude oil; again the acephate in the mother liquor is carried out separating treatment behind the separating most acephate; can significantly reduce acephate like this and contact the loss of decomposing and causing with water; do not produce the waste water that contains organophosphorus; the protection environment; can improve the rate of recovery and the purity of acephate, reduce the production cost of acephate.
Below in conjunction with embodiment the present invention is described in further detail:
Because acephate is met the water ratio and is easier to decompose, so the present invention at first carries out crystallization treatment to acephate crude oil, carries out other separating treatment behind the separating most acephate again, can significantly reduce loss like this.The crude oil crystallization can be stirred or not have in the crystallization kettle of stirring and carry out at band, and the crystallization initial temperature is 10-50 ℃, and terminal temperature is-10-10 ℃, rate of temperature fall is 1-12 ℃/hour.
Generally also contain the acephate of 20-40% in the mother liquor that produces after the crystallization of acephate crude oil, other composition mainly is O, O-dimethyl-N-ethanoyl thio-phosphamide, O, O, impurity such as O-trimethylammonium thio-phosphamide, acetic acid.Though these impurity can adopt the rectification under vacuum method, because acephate is met thermolysis easily, so lose acephate unavoidably.The present invention adopts extracting process to remove impurity.Extraction agent can be the mixture of aromatic hydrocarbons, aliphatic hydrocarbon, halohydrocarbon, naphthenic hydrocarbon or two or more (containing two kinds) these materials, and the consumption of extraction agent changes between 1-20 part.Extraction process can adopt intermittently, continuous or semi-continuous mode is operated.Extraction temperature generally is controlled at 30-50 ℃ according to different variation of all kinds of and consumption of extraction agent.Extraction phase can pass through agent of rectificating method separating and extracting and impurity.
Through acephate concentration in the extracting phase after the extraction only is 40-55%, so can carry out the extracting phase crystallization.Extracting phase crystallization condition and crude oil crystallization are basic identical, and only crystallization terminal temperature difference is generally less than-10 ℃.
Acephate content is generally 75-90% in the acephate coarse crystal after crystallization of acephate crude oil and the extracting phase crystallization, also needs the further refining former powder of acephate that could obtain higher degree.Refining is the method that adopts the organic solvent recrystallization.The organic solvent that is used for recrystallization can be the mixture of carbonic ether, aliphatic carboxylic acid esters,, fatty alcohol, aliphatic ketone or two or more (containing two kinds) these materials.Carbonic ether preferably contains the carbonic ether of C1-C4 alkyl, as methylcarbonate, diethyl carbonate, carbonic acid dipropyl fat; The aliphatic carboxylic acid esters, is C2-C12 carboxylic acid C2-C8 ester preferably, as butyl butyrate, isoamyl butyrate, octyl acetate; Fatty alcohol is the C1-C8 fatty alcohol preferably, as ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, primary isoamyl alcohol, hexanol, octanol; Aliphatic ketone is the C3-C8 aliphatic ketone preferably, as methylethylketone, the positive acetone of methyl, mibk.The consumption of organic solvent is crystal yield and the purity that enables to reach higher according to all kinds of differences of used solvent and different, and in every part of acephate, the consumption of organic solvent is generally 0.2-10 part.At first the acephate coarse crystal is dissolved in organic solvent, crystallisation by cooling then in (the too high meeting of temperature causes the acetate acephatemet to decompose) below 60 ℃.Tc is-10-12 ℃.Isolate behind the crystal through the former powder of the acephate that suitably is drying to obtain hope.Refinement mother liquor can circulate as next batch purified solvent, also can reclaim solvent through precipitation, remainingly gets back to crystallization in a collection of extracting phase, or disposes missible oil.
The present invention does not make the water or the aqueous solution in sepn process, so just do not have the discharge of wastewater problem.Therefore, the present invention has not only realized cleaning production basically, and has significantly reduced decomposition loss and because the acephate that discharge of wastewater caused and the emission loss of extraction agent of acephate.
The preparation of acephate crude oil: in 1000Kg purity is 75% methamidophos from crude oil, add the 10Kg weight concentration respectively and be 98% sulfuric acid and 700Kg weight concentration and be 98% aceticanhydride, reacted 3 hours down at 50 ℃, getting content is the acephate crude oil of 54-55%.
Embodiment 1: with 1710Kg acephate content is that 54.1% above-mentioned acephate crude oil is put in the crystallization kettle that stirs to band, it is that 82% former powder coarse crystal of acephate and 945Kg acephate content are 31.5% mother liquor that 4 hours uniform decrease in temperature to 5 ℃, centrifugation obtain 765Kg content.After mother liquor is used 400Kg extraction agent extracting impurities, 600Kg acephate content is 46.5% extracting phase, extracting phase is put into band stirred crystallization still, 4 hours uniform decrease in temperature are to-20 ℃, and it is that 83% coarse crystal and 370Kg acephate content are 23.8% mother liquor that centrifugation obtains 230Kg acephate content.Above-mentioned two subcrystalline coarse crystals are joined in the dissolution kettle, add 1200Kg benzene again, be heated to 48 ℃ of stirring and dissolving, put then to refining kettle, be cooled to-10 ℃ of crystallizations 5 hours.It is that 98.5% former powder of acephate and 1250Kg acephate content are 2% refinement mother liquor that centrifugation, drying obtain 805Kg content.
Embodiment 2: be 54.1% acephate crude oil with 1710Kg acephate content, put to the crystallization kettle of band stirring, it is that 83% coarse crystal and 950Kg acephate content are 31.7% mother liquor that 4 hours uniform decrease in temperature to 2 ℃, centrifugation obtain 760Kg acephate content.Mother liquor with 400Kg extraction agent extracting impurities after, 600Kg acephate content is 46.8% extracting phase.Extracting phase is put in the crystallization kettle that stirs to band, and 4 hours uniform decrease in temperature are to-20 ℃, and it is that 82.5% coarse crystal and 365Kg acephate content are 23.8% mother liquor that centrifugation obtains 235Kg acephate content.Two subcrystalline coarse crystals are joined in the dissolution kettle, add 1250Kg acephate content among the embodiment 1 again and be 2% refinement mother liquor, be heated to 48 ℃ of stirring and dissolving, put then to refining kettle, be cooled to-10 ℃ of crystallizations 5 hours.It is that 98.3% former powder of acephate and 1280Kg acephate content are 3.1% refinement mother liquor that centrifugation, drying obtain 828Kg content, and refinement mother liquor can reclaim solvent by the vacuum precipitation recycling 5-10 time.
Claims (7)
1. method of from acephate crude oil, extracting the former powder of high-purity acetyl acephatemet: it is characterized in that:
1. acephate crude oil is carried out crystallization, Tc is-10-35 ℃, and crystallization time is 0.5-30 hour, separate then, the former powder coarse crystal of acephate;
2. carry out the impurity extraction with the mother liquor of organic extractant after to acephate crude oil Crystallization Separation;
3. extracting phase is carried out crystallization, Tc is-30-30 ℃, and the time is 0.5-30 hour, fractional crystallization, the former powder coarse crystal of acephate;
4. with organic solvent the former powder coarse crystal of acephate is carried out recrystallization, get the former powder of highly purified acephate.
2. the method for extracting the former powder of high-purity acetyl acephatemet from acephate crude oil according to claim 1, it is characterized in that: organic extractant is: the mixture of aromatic hydrocarbons, aliphatic hydrocarbon, halohydrocarbon, naphthenic hydrocarbon or two or more these material preparations.
3. the method for extracting the former powder of high-purity acetyl acephatemet from acephate crude oil according to claim 1, it is characterized in that: organic solvent is: the mixture of carbonic ether, aliphatic carboxylic acid esters,, fatty alcohol, aliphatic ketone or two or more these material preparations.
4. the method for extracting the former powder of high-purity acetyl acephatemet from acephate crude oil according to claim 3, it is characterized in that: carbonic ether is the carbonic ether that contains the C1-C4 alkyl.
5. the method for extracting the former powder of high-purity acetyl acephatemet from acephate crude oil according to claim 3, it is characterized in that: aliphatics carboxylic ester ester is a C2-C12 carboxylic acid C2-C8 ester.
6. the method for extracting the former powder of high-purity acetyl acephatemet from acephate crude oil according to claim 3, it is characterized in that: fatty alcohol is the C1-C8 fatty alcohol.
7. the method for extracting the former powder of high-purity acetyl acephatemet from acephate crude oil according to claim 3, it is characterized in that: aliphatic ketone is the C3-C8 aliphatic ketone.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB991154258A CN1133638C (en) | 1999-06-11 | 1999-06-11 | Method of extracting high-purity acephate from acephate raw oil |
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| CNB991154258A CN1133638C (en) | 1999-06-11 | 1999-06-11 | Method of extracting high-purity acephate from acephate raw oil |
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| CN1277201A CN1277201A (en) | 2000-12-20 |
| CN1133638C true CN1133638C (en) | 2004-01-07 |
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| CNB991154258A Expired - Fee Related CN1133638C (en) | 1999-06-11 | 1999-06-11 | Method of extracting high-purity acephate from acephate raw oil |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN101816843B (en) * | 2010-04-14 | 2012-02-08 | 清华大学 | Device and method for extracting acephate from neutralization solution |
| CN105541604A (en) * | 2016-01-29 | 2016-05-04 | 湘潭大学 | Separation method for acetic acid in acylation reaction liquid |
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