CN105315303A - Glufosinate-ammonium separating and purifying method - Google Patents
Glufosinate-ammonium separating and purifying method Download PDFInfo
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- CN105315303A CN105315303A CN201510285941.9A CN201510285941A CN105315303A CN 105315303 A CN105315303 A CN 105315303A CN 201510285941 A CN201510285941 A CN 201510285941A CN 105315303 A CN105315303 A CN 105315303A
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- careless ammonium
- ammonium phosphine
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Abstract
The invention discloses a glufosinate-ammonium separating and purifying method. The method includes the steps of conducting ammoniation on a glufosinate-ammonium acidolysis solution or solid glufosinate-ammonium hydrochloride, conducting drying to obtain a glufosinate-ammonium crude product A, adding the glufosinate-ammonium crude product A to alcohol, conducting filtering to obtain a glufosinate-ammonium crude product B, adding the glufosinate-ammonium crude product B to phosphate ester, conducting filtering to obtain filtrate, washing a filter cake through phosphate ester, combining filtrate with washing liquid to obtain a glufosinate-ammonium crude product C, adding the glufosinate-ammonium crude product C to water to be extracted, and taking a water layer which can be directly used as a glufosinate-ammonium aqueous solution or obtaining high-purity glufosinate-ammonium active compounds after the water layer is spray-dried. The method is simple in step, the content of chloride impurities in the obtained glufosinate-ammonium aqueous solution or glufosinate-ammonium active compounds is extremely low, basically no organic impurities exist, the purity of the separated glufosinate-ammonium active compounds can reach 98% or higher, and the recovery rate of glufosinate-ammonium reaches up to 98% or higher. Compared with the traditional process, the method has the higher advantages of cost, safety, environmental friendliness and quality and has extremely-high social value and economic value.
Description
Technical field
The present invention relates to a kind of separation purification method of careless ammonium phosphine.
Technical background
Grass ammonium phosphine has another name called careless fourth phosphine, and we generally refer to careless ammonium phosphine ammonium salt by usually said careless ammonium phosphine.The chemical formula of grass ammonium phosphine ammonium salt is: C
5h
15n
2o
4p, structural formula is:
.Grass ammonium phosphine is developed in Hirst company (now belonging to Bayer A.G) by Germany in 1978 at first, and be developed so far from careless ammonium phosphine, research relevant to careless ammonium phosphine in the world is never interrupted.At present, the research patent that disclosed careless ammonium phosphine preparation is relevant is both at home and abroad various, such as US6359162B1, EP0009022A1, CN102399239A, CN102372738A, CN101747367A, CN103374030A, CN103588812A etc., wherein most is representational is US6359162B1, EP0009022A1.At present, the main synthesis technique of careless ammonium phosphine has: Si Chuike-Marian Zielinski synthesis method.Reaction equation is as follows:
Although the synthetic method of current research to careless ammonium phosphine has carried out detailed elaboration, but not describing in detail the separation of careless ammonium phosphine and purifying, is only simply mention once with the form of hydrolysis, alcohol recrystallization.And current careless ammonium phosphine synthesis technique is mostly same or similar with operational path above, all need to use strecker reaction in the synthesis of careless ammonium phosphine, and inevitably use ammonium chloride and sodium cyanide in strecker reaction, a large amount of sodium-chlor and chloride leach is had in acid hydrolysis solution in process intermediates acidolysis being formed careless ammonium phosphonium salt hydrochlorate, in addition careless ammonium phosphine acid hydrolysis solution medium-height grass ammonium phosphine exists with the form of careless ammonium phosphonium salt hydrochlorate, and the solubleness of careless ammonium phosphonium salt hydrochlorate in water is very large, therefore, after after acidolysis, alcohol analyses the separation purification method of ammonium or acidolysis again, the ammoniumization separation purification method that alcohol is analysed again can not obtain the higher careless ammonium phosphine of purity, the rate of recovery of grass ammonium phosphine is not high yet.
Patent CN102268037A discloses a kind of purifying process of careless ammonium phosphine, and provide a kind of feasible careless ammonium phosphine purification process, the method is as follows: careless ammonium phosphonium salt hydrochlorate is added alcohol R by (1)
1carry out esterification in OH, cool after reacting completely, filter, filtrate is removed solvent and is obtained careless ammonium phosphine esterified prod; (2) careless ammonium phosphine esterified prod step (1) obtained joins in aqueous hydrochloric acid the reaction that is hydrolyzed, and aftertreatment obtains careless ammonium phosphonium salt hydrochlorate; (3) careless ammonium phosphonium salt hydrochlorate step (2) obtained joins alcohol R
2in OH, pass into oxyethane, after reacting completely, obtain careless ammonium phosphonic acids; (4) step (3) is obtained careless ammonium phosphonic acids and join R
3in OH, pass into ammonia, react completely and obtain careless ammonium phosphine.The method can obtain purer Glufosinate-ammonium, makes the Glufosinate-ammonium preparing higher degree become possibility, has great positive effect.But this technical process is loaded down with trivial details, need to use the inflammable and explosive raw material of this height of oxyethane, reacting ethylene oxide also can produce the chloroethanol by product of severe toxicity, and security risk is very large, and oxyethane is expensive, adds cost; Use multiple alcohols repeatedly alcohol analyse, solvent consumption is large.
Patent CN103819503A discloses a kind of purifying process of careless ammonium phosphine, comprising: careless ammonium phosphonium salt hydrochlorate is joined alcohol R by (1)
1in OH, add R
2nH
2carry out aminating reaction, regulate pH value to 7.0-14.0, cooled and filtered, filtrate is removed solvent and is obtained careless ammonium phosphine ammonium salt and a small amount of organic impurity; (2) careless ammonium phosphine ammonium salt step (1) obtained is dissolved in suitable quantity of water, passes into CO
2be neutralized to pH value 2.0-5.0, add appropriate alcohol R
3oH, careless ammonium phosphonic acids Precipitation, centrifuging obtains careless ammonium phosphonic acids, wherein containing a small amount of bicarbonate of ammonia or organic amine carbonate; (3) careless ammonium phosphonic acids filter cake heating, drying step (2) obtained, bicarbonate of ammonia or organic amine carbonate decomposes, volatilization, thus obtain highly purified careless ammonium phosphonic acids.The method step (2) uses acid more weak CO
2cemented out by careless ammonium phosphonic acids stronger than it for acidity, this step rate of recovery is low, and products therefrom purity is low, and technology difficulty is large, not easily realizes; In addition, in the process isolating careless ammonium phosphonic acids, not only create the by-product ammonium chloride (amine) that should produce, also additionally create bicarbonate of ammonia or organic amine carbonate by-product.
Patent CN104059102A discloses the method for a kind of organic bases depickling legal system for high-purity careless ammonium phosphine, and careless ammonium phosphonium salt hydrochlorate for raw material, is dissolved into alcohol R with careless ammonium phosphonium salt hydrochlorate by it
1in OH, hot filtering inorganic salt and mechanical impurity; Filtrate adds organic bases R through partial concentration
2r
3r
4n carries out depickling reaction, cooledly leaches careless ammonium phosphine free alkali; Grass ammonium phosphine crude free base adds alcohol R
1in OH, pass into ammonia, namely cold filtration obtains careless ammonium phosphine product; The crystalline mother solution of free alkali first reclaims alcoholic solvent, then adds inorganic base aqueous solution neutralization, separates upper strata organic bases and directly overlap and react for depickling.The method is at use alcohol R
1when the hot filtering inorganic salt of OH and mechanical impurity, alcohol R
1oH can cause the rate of recovery on the low side with careless ammonium phosphonium salt hydrochlorate partial esterification.This patent uses alkalescence to be weaker than organic bases R
2r
3r
4the ammonia of N is by the R in careless ammonium phosphine free alkali
2r
3r
4n cements out, and runs counter to the basic principles of chemistry of highly basic weak base, and thus technology difficulty is large, is difficult to realize.
Summary of the invention
For the deficiency that prior art exists, the invention provides a kind of separation purification method of careless ammonium phosphine, the method is by means such as the adjustment of purification sequence, the uses of phosphoric acid ester, can be good at the Impurity removal in careless ammonium phosphine, and technique is simple, efficiently, safety, is applicable to industrial applications.
In the present invention, term grass ammonium phosphine refer to all: 2-amino-4-[hydroxyl (methyl) phosphono] butyric acid ammonium,
Structural formula is as shown in the formula shown in II.Grass ammonium phosphonium salt hydrochlorate refer to all: hydrochloric acid 2-amino-4-[hydroxyl (methyl) phosphono] butyric acid, structural formula is as shown in the formula shown in III.
In the present invention, in hydrochloric acid, being hydrolyzed with cyanamide derivative the careless ammonium phosphine acid hydrolysis solution (be called for short careless ammonium phosphine acid hydrolysis solution, lower with) containing careless ammonium phosphonium salt hydrochlorate formed is raw material, or with the not high careless ammonium phosphine HCl, solid of purity for raw material.Grass ammonium phosphine acid hydrolysis solution is the intermediates that Si Chuike-Marian Zielinski synthesis method synthesizes careless ammonium phosphine, and be hydrolyzed in hydrochloric acid by the cyanamide derivative described in formula I and form, hydrolysis reaction formula is as follows, and in formula I, R is hydrogen or ethyl.Grass ammonium phosphine HCl, solid is the careless ammonium phosphine hydrochloride, crude drying of careless ammonium phosphine acid hydrolysis solution directly obtained afterwards or the purity still undesirable careless ammonium phosphonium salt hydrochlorate obtained through certain process by careless ammonium phosphine acid hydrolysis solution.
In careless ammonium phosphine acid hydrolysis solution of the present invention, main component is careless ammonium phosphonium salt hydrochlorate, chloride inorganic salt (being mainly sodium-chlor and ammonium chloride), organic impurity (being mainly phosphorous organic impurity) and hydrochloric acid, its medium-height grass ammonium phosphonium salt hydrochlorate in careless ammonium phosphine content for 13 ~ 15wt%, chloride inorganic salt content is 15 ~ 18wt%, organic impurity content is 3 ~ 5wt%, and content of hydrochloric acid is 8 ~ 10wt%.Other compositions are mainly water.
The present invention with careless ammonium phosphine acid hydrolysis solution for raw material, or with the not high careless ammonium phosphine HCl, solid of purity for raw material, adopt the technique of first ammonium, careless ammonium phosphonium salt hydrochlorate in careless ammonium phosphine acid hydrolysis solution or careless ammonium phosphine HCl, solid is converted into careless ammonium phosphine, effectively prevent in later separation step the generation of esterification side reaction when adding alcoholic solvent, improve the rate of recovery of careless ammonium phosphine; Then careless ammonium phosphine crude product alcohol is dissolved, make phosphorous dissolve organic contaminants in alcohol, achieve preliminary removal of impurities; Then the careless ammonium phosphine crude product phosphoric acid ester after alcohol is molten extracts, grass ammonium phosphine is dissolved in phosphoric acid ester, and chloride inorganic salt with the isolated in form of precipitation out, achieve being separated of careless ammonium phosphine and inorganic salt, separating effect is than using the effective of alcohol, and the extraction of careless ammonium phosphine is also more complete; Add water in the most backward phosphoric acid ester extraction phase careless ammonium phosphine to be separated from phosphoric acid ester, obtain the careless ammonium phosphine water layer that purity is high, reclaim simple, careless ammonium phosphine water layer directly can be processed into the careless ammonium phosphine aqua of all size, also spray-driedly can obtain highly purified Glufosinate-ammonium.
The concrete technical scheme of the present invention is as follows:
A separation purification method for careless ammonium phosphine, with solid grass ammonium phosphonium salt hydrochlorate or containing the careless ammonium phosphine acid hydrolysis solution of careless ammonium phosphonium salt hydrochlorate for raw material, separation and purification comprises the following steps:
(1) careless ammonium phosphine acid hydrolysis solution or solid grass ammonium phosphonium salt hydrochlorate and ammonia or ammoniacal liquor are reacted, make careless ammonium phosphonium salt hydrochlorate be converted into careless ammonium phosphine, drying obtains careless ammonium phosphine crude product A;
(2) careless ammonium phosphine crude product A is added in alcohol, careless ammonium phosphine crude product A is fully dissolved, then cross leaching filter cake, obtain careless ammonium phosphine crude product B;
(3) careless ammonium phosphine crude product B is added in phosphoric acid ester, careless ammonium phosphine crude product B is fully dissolved, then cross leaching filtrate, and use phosphoric acid ester washing leaching cake, filtrate and washings are merged, is designated as careless ammonium phosphine crude product C;
(4) add water careless ammonium phosphine crude product C extraction, stratification, and water intaking layer, containing highly purified careless ammonium phosphine in gained water layer.
In above-mentioned steps (1), react with ammonia or ammoniacal liquor again after solid grass ammonium phosphonium salt hydrochlorate water dissolution.Grass ammonium phosphine acid hydrolysis solution or solid grass ammonium phosphonium salt hydrochlorate and ammoniacal liquor or ammonia gas react make careless ammonium phosphonium salt hydrochlorate be converted into careless ammonium phosphine, reaction gained solution is designated as careless ammonium phosphine ammonium liquid, and when this step mainly prevents step (2) from using alcoholic solvent to be separated organic impurity, grass ammonium phosphonium salt hydrochlorate and alcoholic solvent generation esterification cause the rate of recovery to decline.
In above-mentioned steps (1), the consumption of ammonia or ammoniacal liquor meets careless ammonium phosphonium salt hydrochlorate and is all converted into careless ammonium phosphine, and the consumption of general ammonia or ammoniacal liquor can meet the demands to system pH when 6-10.Consider and energy-conservationly subtract useless, preferably use ammonia, when using ammoniacal liquor, the mass concentration of ammoniacal liquor can be 5% ~ 25%, preferably 18% ~ 25%.
In above-mentioned steps (1), obtain careless ammonium phosphine crude product A preferably by spray-dired mode is dry.The crude product obtained after drying is more conducive to adopting subsequent step (2) to be separated organic impurity.
In above-mentioned steps (2), the main purpose that grass ammonium phosphine crude product A adds alcohol is by adding alcoholic solvent by the dissolve organic contaminants in careless ammonium phosphine crude product A in alcoholic solvent, filtering gained filtrate is the alcoholic solution of organic impurity, and filter cake is mainly the mixture of muriate and careless ammonium phosphine.
In above-mentioned steps (2), described alcohol is the alcohol of C1-C4, such as methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol or the trimethyl carbinol, is preferably methyl alcohol or ethanol.
In above-mentioned steps (2), the consumption of alcohol all has impact to products obtained therefrom purity and yield, and consumption is too low well can not dissolve organic impurity, and consumption can dissolve the careless ammonium phosphine of part too much.In the present invention, the consumption of alcohol is 1-10 times of careless ammonium phosphine crude product A weight, is preferably 2 ~ 4 times.
In above-mentioned steps (2), adjustment temperature of reaction can accelerate the dissolving of careless ammonium phosphine crude product A, improves purifying speed.General, added after in alcohol by careless ammonium phosphine crude product A, control temperature is 40 ~ 100 DEG C, and filters at this temperature.Preferably, added after in alcohol by careless ammonium phosphine crude product A, control temperature is 60 ~ 80 DEG C, and filters at this temperature, in this temperature range, both can reduce solvent usage quantity by dissolving organic impurity as much as possible, and can avoid potential side reaction again as far as possible.
In above-mentioned steps (3), use phosphoric acid ester is extraction solvent, to be dissolved in by the careless ammonium phosphine in careless ammonium phosphine crude product B in phosphoric acid ester thus to realize being separated with chloride inorganic salt.Selecting of phosphoric acid ester extraction agent of the present invention, makes to be separated careless ammonium phosphine from careless ammonium phosphine and muriatic mixture and is realized fast and efficiently, overcome separation method complicated operation now, yield is low wait not enough.
In above-mentioned steps (3), phosphoric acid ester has the structural formula of following formula IV, and in formula, X is-OH ,-CH
3,-C
2h
5,-OR
1or-OR
2, R
1be the alkyl or phenyl of 1 ~ 8 carbon atom, R
2it is the alkyl or phenyl of 1 ~ 8 carbon atom.In formula IV, R
1, R
2can be the same or different, but usually get R
1=R
2.
。
Preferably, phosphoric acid ester is trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, trioctyl phosphate, methyl-phosphoric acid dimethyl ester, ethyl phosphonic acid diethyl ester, methyl acid phosphate dibutylester, methyl acid phosphate dioctyl ester, and when adopting these phosphoric acid ester, separating effect is better.
In above-mentioned steps (3), the consumption of phosphoric acid ester also has impact to products obtained therefrom purity and yield, and consumption is too low well can not dissolve careless ammonium phosphine, and consumption can make cost raise too much.In the present invention, the consumption dissolving phosphoric acid ester during careless ammonium phosphine crude product B is 1 ~ 9 times of careless ammonium phosphine crude product B weight, preferably 2 ~ 4 times.
In above-mentioned steps (3), during washing leaching cake, the amount of phosphoric acid ester used is 1 times of careless ammonium phosphine crude product B.
In above-mentioned steps (3), careless ammonium phosphine crude product B adds after in phosphoric acid ester, and adjustment temperature of reaction can accelerate the dissolving of careless ammonium phosphine crude product B, improves purifying speed.General, added after in phosphoric acid ester by careless ammonium phosphine crude product B, control temperature is 30 ~ 120 DEG C, and filters at this temperature.Preferably, added after in phosphoric acid ester by careless ammonium phosphine crude product B, control temperature is 80 ~ 100 DEG C, and filters at this temperature, in this temperature range, both can accelerate dissolution rate, the adverse effects such as the polymerization of the phosphoric acid ester that high temperature can be avoided again to cause.
In above-mentioned steps (4), according to the characteristic that careless ammonium phosphine is soluble in water, use water the careless ammonium phosphine be dissolved in phosphoric acid ester can be stripped out, high purity grass ammonium phosphine is dissolved in water.The careless ammonium phosphine water layer impurity obtained is few, and careless ammonium phosphine purity is high, meets the demands, and directly can make the aqua of various concentration, also can directly obtain highly purified Glufosinate-ammonium by drying modes such as spraying dry.The consumption of water is generally 0.3 ~ 3 times of the weight of careless ammonium phosphine crude product B, and be preferably 0.3 ~ 1.5 times, so both careless ammonium phosphine can be extracted from crude product C, additionally reduce the use of water, cost is low.
In above-mentioned steps (4), careless ammonium phosphine crude product C adds a certain amount of water, is fully uniformly mixed, and leave standstill and separatory, oil reservoir is phosphoric acid ester, and water layer is careless ammonium phosphine solution.
In above-mentioned steps (4), careless ammonium phosphine crude product C is uniformly mixed with water at 20 ~ 80 DEG C, and leaves standstill separatory at this temperature.Preferably, be uniformly mixed with water at 40 ~ 60 DEG C, and leave standstill separatory at this temperature.
Major advantage of the present invention is as follows:
1. the present invention adopts the purification sequence that first ammoniumization is separated again, and operational path is novel, and selection phosphoric acid ester is extraction solvent, is avoided the generation of side reaction, simplify purifying process, improve the rate of recovery and the purity of careless ammonium phosphine by the cooperation of purification step and extraction solvent.
2. raw material sources of the present invention are wide, both can be careless ammonium phosphine acid hydrolysis solution also can be solid grass ammonium phosphonium salt hydrochlorate, careless ammonium phosphine after phosphoric acid ester extraction is easy to reclaim, the careless ammonium phosphine aqua of all size directly can be processed into after adding Water Sproading, also highly purified Glufosinate-ammonium can spray-driedly be obtained, simple and easy to do.
3. the present invention neither needs to use highly inflammable and explosive oxyethane, does not also need to use organic acid or organic bases, and more can not produce the chloroethanol by product of severe toxicity, security risk is low, more environmental protection.The present invention uses cheap ammoniacal liquor or ammonia as the de-acidying agent of careless ammonium phosphonium salt hydrochlorate, has obvious economic benefit compared with adopting the technique of oxyethane, organic acid or organic bases separating-purifying grass ammonium phosphine.
4. the inventive method is simple, and in gained grass ammonium phosphine aqua or Glufosinate-ammonium, the content of chloride impurity is extremely low, and substantially without organic impurity, the purity of separating obtained Glufosinate-ammonium can reach more than 98%, and the rate of recovery of careless ammonium phosphine is up to more than 98%.Present method has larger cost advantage, safety and environmental protection advantage and quality-advantage than traditional technique, has high social value and economic worth.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.It is to be understood that following explanation is only to explain the present invention, its content is not limited.If no special instructions, the concentration of ammoniacal liquor used is mass percentage concentration.Grass ammonium phosphine content all adopts high effective liquid chromatography for measuring.
Main component and the content of careless ammonium phosphine acid hydrolysis solution used in following embodiment are: careless ammonium phosphine meter content amounted to by careless ammonium phosphonium salt hydrochlorate is 13.98%, sodium-chlor and ammonium chloride total content are 15.28%, organic impurity content is 3.76%, and content of hydrochloric acid is 9.43%, and all the other are water.
Solid grass ammonium phosphonium salt hydrochlorate used in following embodiment adopts alcohol to analyse the solid phase prod of gained above-mentioned careless ammonium phosphine acid hydrolysis solution.
embodiment 1
Take 500g grass ammonium phosphine acid hydrolysis solution (amounting to careless ammonium phosphine content is 13.98%) in 1000ml four-hole boiling flask, drip the ammoniacal liquor of 182.8g18% wherein to PH=6.07, obtain ammonium liquid 682.7g, ammonium liquid is carried out spraying dry, obtains careless ammonium phosphine crude product A185.3g (moisture 0.7%).Proceeded in 500ml four-hole bottle by careless ammonium phosphine crude product A, add 185.3g propyl carbinol and then stir down and be warming up to 100 DEG C, filtered while hot after insulation 1h, dries to obtain careless ammonium phosphine crude product B165.1g by filtration gained filter cake.Careless ammonium phosphine crude product B is proceeded in 1000ml four-hole bottle, add 330.2g trimethyl phosphite 99 and then under stirring, be warming up to 80 DEG C, filter at this temperature and use 165.1g trimethyl phosphite 99 washing leaching cake after insulation 1h, obtain careless ammonium phosphine crude product C(and filtrate and washings) 429.2g.Under room temperature, in careless ammonium phosphine crude product C, add 247.6g water and be warming up to 60 DEG C and stir 30min, then leave standstill insulation 3h and make it layering, water-yielding stratum is divided to obtain careless ammonium phosphine aqueous solution 316.6g, recording its medium-height grass ammonium phosphine content is 21.70%, obtain the Glufosinate-ammonium 69.6g that content is 98.7% after spray-dried, the careless ammonium phosphine rate of recovery is 98.29%.
embodiment 2
Take 500g grass ammonium phosphine acid hydrolysis solution (amounting to careless ammonium phosphine content is 13.98%) in 1000ml four-hole boiling flask, be added dropwise to the ammoniacal liquor of 205.4g18% wherein to PH=8.13, obtain ammonium liquid 705.4g, ammonium liquid is carried out spraying dry, obtains careless ammonium phosphine crude product A185.2g (moisture 0.6%).Proceeded in 3000ml four-hole bottle by careless ammonium phosphine crude product A, add 1852g propyl alcohol and then stir down and be warming up to 40 DEG C, filtered while hot after insulation 1h, dries to obtain careless ammonium phosphine crude product B164.7g by filtration gained filter cake.Careless ammonium phosphine crude product B is proceeded in 2000ml four-hole bottle, add 1154.3g tributyl phosphate and then under stirring, be warming up to 50 DEG C, filter at this temperature and use 164.7g tributyl phosphate washing leaching cake after insulation 1h, obtain careless ammonium phosphine crude product C(and filtrate and washings) 1252.9g.Under room temperature, in careless ammonium phosphine crude product C, add 148.4g water and be warming up to 60 DEG C and stir 30min, then leave standstill insulation 3h and make it layering, water-yielding stratum is divided to obtain careless ammonium phosphine aqueous solution 217.2g, recording its medium-height grass ammonium phosphine content is 31.67%, obtain the Glufosinate-ammonium 69.9g that content is 98.4% after spray-dried, the careless ammonium phosphine rate of recovery is 98.44%.
embodiment 3
Take 500g grass ammonium phosphine acid hydrolysis solution (amounting to careless ammonium phosphine content is 13.98%) in 1000ml four-hole boiling flask, be added dropwise to the ammoniacal liquor of 193.8g18% wherein to PH=7.01, obtain ammonium liquid 693.8g, ammonium liquid is carried out spraying dry, obtains careless ammonium phosphine crude product A185.4g (moisture 0.3%).Proceeded in 2000ml four-hole bottle by careless ammonium phosphine crude product A, add 741.6g Virahol and then stir down and be warming up to 60 DEG C, filtered while hot after insulation 1h, dries to obtain careless ammonium phosphine crude product B164.9g by filtration gained filter cake.Careless ammonium phosphine crude product B is proceeded in 500ml four-hole bottle, add 164.9g trioctyl phosphate and then under stirring, be warming up to 100 DEG C, filter at this temperature and use 164.9g trioctyl phosphate washing leaching cake after insulation 1h, obtain careless ammonium phosphine crude product C(and filtrate and washings) 263.7g.In careless ammonium phosphine crude product C, 494.7g water is added and temperature control to 20 DEG C stirring 30min under room temperature, then leave standstill insulation 3h and make it layering, water-yielding stratum is divided to obtain careless ammonium phosphine aqueous solution 563.3g, recording its medium-height grass ammonium phosphine content is 12.24%, obtain the Glufosinate-ammonium 69.8g that content is 98.8% after spray-dried, the careless ammonium phosphine rate of recovery is 98.61%.
embodiment 4
Take 500g grass ammonium phosphine acid hydrolysis solution (amounting to careless ammonium phosphine content is 13.98%) in 1000ml four-hole boiling flask, be added dropwise to the ammoniacal liquor of 150.7g25% wherein to PH=9.04, obtain ammonium liquid 650.7g, ammonium liquid is carried out spraying dry, obtains careless ammonium phosphine crude product A185.8g (moisture 0.9%).Proceeded in 1000ml four-hole bottle by careless ammonium phosphine crude product A, add 371.6g ethanol and then stir down and be warming up to 80 DEG C, filtered while hot after insulation 1h, dries to obtain careless ammonium phosphine crude product B165.0g by filtration gained filter cake.Careless ammonium phosphine crude product B is proceeded in 2000ml four-hole bottle, add 1485g methyl-phosphoric acid dimethyl ester and then under stirring, be warming up to 30 DEG C, filter at this temperature and use 165g methyl-phosphoric acid dimethyl ester washing leaching cake after insulation 1h, obtain careless ammonium phosphine crude product C(and filtrate and washings) 1583.9g.Under room temperature, in careless ammonium phosphine crude product C, add 49.5g water and be warming up to 80 DEG C and stir 30min, then leave standstill insulation 3h and make it layering, water-yielding stratum is divided to obtain careless ammonium phosphine aqueous solution 119.6g, recording its medium-height grass ammonium phosphine content is 57.34%, obtain the Glufosinate-ammonium 69.9g that content is 98.1% after spray-dried, the careless ammonium phosphine rate of recovery is 98.12%.
embodiment 5
Take 500g grass ammonium phosphine acid hydrolysis solution (amounting to careless ammonium phosphine content is 13.98%) in 1000ml four-hole boiling flask, be added dropwise to the ammoniacal liquor of 165.8g25% wherein to PH=10.17, obtain ammonium liquid 665.8g, ammonium liquid is carried out spraying dry, obtains careless ammonium phosphine crude product A185.6g (moisture 0.6%).Proceeded in 2000ml four-hole bottle by careless ammonium phosphine crude product A, add 1299.2g methyl alcohol and then stir down and be warming up to 50 DEG C, filtered while hot after insulation 1h, dries to obtain careless ammonium phosphine crude product B164.7g by filtration gained filter cake.Careless ammonium phosphine crude product B is proceeded in 1000ml four-hole bottle, add 658.8g ethyl phosphonic acid diethyl ester and then under stirring, be warming up to 70 DEG C, filter at this temperature and use 164.7g ethyl phosphonic acid diethyl ester washing leaching cake after insulation 1h, obtain careless ammonium phosphine crude product C(and filtrate and washings) 757.6g.Under room temperature, in careless ammonium phosphine crude product C, add 329.4g water and be warming up to 40 DEG C and stir 30min, then leave standstill insulation 3h and make it layering, water-yielding stratum is divided to obtain careless ammonium phosphine aqueous solution 399.3g, recording its medium-height grass ammonium phosphine content is 17.25%, obtain the Glufosinate-ammonium 69.6g that content is 98.9% after spray-dried, the careless ammonium phosphine rate of recovery is 98.56%.
embodiment 6
Take 500g grass ammonium phosphine acid hydrolysis solution (amounting to careless ammonium phosphine content is 13.98%) in 1000ml four-hole boiling flask, pass into 41.4g ammonia wherein to PH=10.17, obtain ammonium liquid 541.4g, ammonium liquid is carried out spraying dry, obtains careless ammonium phosphine crude product A185.5g (moisture 0.9%).Proceeded in 2000ml four-hole bottle by careless ammonium phosphine crude product A, add 1299.2g ethanol and then stir down and be warming up to 50 DEG C, filtered while hot after insulation 1h, dries to obtain careless ammonium phosphine crude product B164.6g by filtration gained filter cake.Careless ammonium phosphine crude product B is proceeded in 1000ml four-hole bottle, add 658.4g triphenylphosphate and then under stirring, be warming up to 120 DEG C, filter at this temperature and use 164.6g triphenylphosphate washing leaching cake after insulation 1h, obtain careless ammonium phosphine crude product C(and filtrate and washings) 757.8g.Under room temperature, in careless ammonium phosphine crude product C, add 246.9g water and be warming up to 60 DEG C and stir 30min, then leave standstill insulation 3h and make it layering, water-yielding stratum is divided to obtain careless ammonium phosphine aqueous solution 316.9g, recording its medium-height grass ammonium phosphine content is 21.69%, obtain the Glufosinate-ammonium 70.0g that content is 98.2% after spray-dried, the careless ammonium phosphine rate of recovery is 98.32%.
embodiment 7
Take 100g grass ammonium phosphonium salt hydrochlorate (content 83.33%, amounting to careless ammonium phosphine content is 75.86%, chloride content 15.39%, all the other are organic impurity) in 500ml four-hole boiling flask, be added dropwise to the ammoniacal liquor of 76.0g18% wherein to PH=7.21, obtain ammonium liquid 176.0g, ammonium liquid is carried out spraying dry, obtains careless ammonium phosphine crude product A113.2g (moisture 0.4%).Proceeded in 1000ml four-hole bottle by careless ammonium phosphine crude product A, add 452.8g isopropylcarbinol and then stir down and be warming up to 60 DEG C, filtered while hot after insulation 1h, dries to obtain careless ammonium phosphine crude product B111.9g by filtration gained filter cake.Careless ammonium phosphine crude product B is proceeded in 1000ml four-hole bottle, add 447.6g methyl acid phosphate dioctyl ester and then under stirring, be warming up to 60 DEG C, filter at this temperature and use 111.9g methyl acid phosphate dioctyl ester washing leaching cake after insulation 1h, obtain careless ammonium phosphine crude product C(and filtrate and washings) 627.4g.In careless ammonium phosphine crude product C, 100.7g water is added and temperature control to 50 DEG C stirring 30min under room temperature, then leave standstill insulation 3h and make it layering, water-yielding stratum is divided to obtain careless ammonium phosphine aqueous solution 176.7g, recording its medium-height grass ammonium phosphine content is 42.45%, obtain the Glufosinate-ammonium 75.7g that content is 99.1% after spray-dried, the careless ammonium phosphine rate of recovery is 98.87%.
embodiment 8
Take 500g grass ammonium phosphine acid hydrolysis solution (amounting to careless ammonium phosphine content is 13.98%) in 1000ml four-hole boiling flask, be added dropwise to the ammoniacal liquor of 164.3g25% wherein to PH=9.97, obtain ammonium liquid 664.3g, ammonium liquid is carried out spraying dry, obtains careless ammonium phosphine crude product A186.2g (moisture 1.0%).Proceeded in 2000ml four-hole bottle by careless ammonium phosphine crude product A, add the 744.8g trimethyl carbinol and then stir down and be warming up to 80 DEG C, filtered while hot after insulation 1h, dries to obtain careless ammonium phosphine crude product B165.2g by filtration gained filter cake.Careless ammonium phosphine crude product B is proceeded in 1000ml four-hole bottle, add 495.6g dibutyl phosphate and then under stirring, be warming up to 90 DEG C, filter at this temperature and use 165.2g dibutyl phosphate washing leaching cake after insulation 1h, obtain careless ammonium phosphine crude product C(and filtrate and washings) 595.6g.Under room temperature, in careless ammonium phosphine crude product C, add 247.8g water and be warming up to 60 DEG C and stir 30min, then leave standstill insulation 3h and make it layering, water-yielding stratum is divided to obtain careless ammonium phosphine aqueous solution 317.7g, recording its medium-height grass ammonium phosphine content is 21.76%, obtain the Glufosinate-ammonium 70.4g that content is 98.2% after spray-dried, the careless ammonium phosphine rate of recovery is 98.90%.
embodiment 9
Take 100g grass ammonium phosphonium salt hydrochlorate (content 83.33%, amounting to careless ammonium phosphine content is 75.86%, chloride content 15.39%, all the other are organic impurity) in 500ml four-hole boiling flask, be added dropwise to the ammoniacal liquor of 54.7g25% wherein to PH=7.16, obtain ammonium liquid 154.6g, ammonium liquid is carried out spraying dry, obtains careless ammonium phosphine crude product A113.6g (moisture 0.8%).Proceeded in 1000ml four-hole bottle by careless ammonium phosphine crude product A, add 340.8g ethanol and then stir down and be warming up to 60 DEG C, filtered while hot after insulation 1h, dries to obtain careless ammonium phosphine crude product B111.5g by filtration gained filter cake.Careless ammonium phosphine crude product B is proceeded in 1000ml four-hole bottle, add 334.5g dioctylphosphoric acid ester and then under stirring, be warming up to 80 DEG C, filter at this temperature and use 111.5g dioctylphosphoric acid ester washing leaching cake after insulation 1h, obtain careless ammonium phosphine crude product C(and filtrate and washings) 513.1g.In careless ammonium phosphine crude product C, 167.3g water is added and temperature control to 50 DEG C stirring 30min under room temperature, then leave standstill insulation 3h and make it layering, water-yielding stratum is divided to obtain careless ammonium phosphine aqueous solution 244.6g, recording its medium-height grass ammonium phosphine content is 30.50%, obtain the Glufosinate-ammonium 75.4g that content is 98.9% after spray-dried, the careless ammonium phosphine rate of recovery is 98.36%.
Claims (10)
1. a separation purification method for careless ammonium phosphine, is characterized in that: in hydrochloric acid, be hydrolyzed the careless ammonium phosphine acid hydrolysis solution containing careless ammonium phosphonium salt hydrochlorate of formation for raw material with solid grass ammonium phosphonium salt hydrochlorate or with the cyanamide derivative described in formula I, in formula I, R is hydrogen or ethyl;
Comprise the following steps:
(1) careless ammonium phosphine acid hydrolysis solution or solid grass ammonium phosphonium salt hydrochlorate and ammonia or ammoniacal liquor are reacted, make careless ammonium phosphonium salt hydrochlorate be converted into careless ammonium phosphine, drying obtains careless ammonium phosphine crude product A;
(2) careless ammonium phosphine crude product A is added in alcohol, careless ammonium phosphine crude product A is fully dissolved, then cross leaching filter cake, obtain careless ammonium phosphine crude product B;
(3) careless ammonium phosphine crude product B is added in phosphoric acid ester, careless ammonium phosphine crude product B is fully dissolved, then cross leaching filtrate, and use phosphoric acid ester washing leaching cake, filtrate and washings are merged, is designated as careless ammonium phosphine crude product C;
(4) add water careless ammonium phosphine crude product C extraction, stratification, and water intaking layer, containing highly purified careless ammonium phosphine in gained water layer.
2. separation purification method according to claim 1, is characterized in that: the water layer in step (4) directly as careless ammonium phosphine aqua, or obtains high purity Glufosinate-ammonium after drying.
3. separation purification method according to claim 1, is characterized in that: in step (2), and described alcohol is methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol or the trimethyl carbinol, is preferably methyl alcohol or ethanol; In step (3), phosphoric acid ester has the structural formula of following formula IV, and in formula, X is-OH ,-CH
3,-C
2h
5,-OR
1or-OR
2, R
1be the alkyl or phenyl of 1 ~ 8 carbon atom, R
2it is the alkyl or phenyl of 1 ~ 8 carbon atom; Preferably, phosphoric acid ester is trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, trioctyl phosphate, methyl-phosphoric acid dimethyl ester, ethyl phosphonic acid diethyl ester, methyl acid phosphate dibutylester, methyl acid phosphate dioctyl ester;
。
4. the separation purification method according to claim 1 or 3, is characterized in that: in step (2), and the consumption of alcohol is 1-10 times of careless ammonium phosphine crude product A weight, is preferably 2 ~ 4 times; In step (3), the consumption dissolving phosphoric acid ester during careless ammonium phosphine crude product B is 1 ~ 9 times of careless ammonium phosphine crude product B weight, preferably 2 ~ 4 times.
5. the separation purification method according to claim 1,3 or 4, is characterized in that: in step (2), and careless ammonium phosphine crude product A adds after in alcohol, and control temperature is 40 ~ 100 DEG C, and filters at this temperature, is preferably 60 ~ 80 DEG C.
6. the separation purification method according to claim 1,3 or 4, is characterized in that: in step (3), and careless ammonium phosphine crude product B adds after in phosphoric acid ester, and control temperature is 30 ~ 120 DEG C, and filters at this temperature, is preferably 80 ~ 100 DEG C.
7. separation purification method according to claim 1, is characterized in that: in step (4), and the consumption of water is 0.3 ~ 3 times of the weight of careless ammonium phosphine crude product B, is preferably 0.3 ~ 1.5 times.
8. the separation purification method according to claim 1 or 7, is characterized in that: in step (4), and careless ammonium phosphine crude product C adds water to extract and carries out at 20 ~ 80 DEG C, preferably carries out at 40 ~ 60 DEG C.
9. separation purification method according to claim 1, it is characterized in that: be careless ammonium phosphonium salt hydrochlorate, chloride inorganic salt, organic impurity and hydrochloric acid containing main component in the careless ammonium phosphine acid hydrolysis solution of careless ammonium phosphonium salt hydrochlorate, its medium-height grass ammonium phosphonium salt hydrochlorate in careless ammonium phosphine content for 13 ~ 15wt%, chloride inorganic salt content is 15 ~ 18wt%, organic impurity content is 3 ~ 5wt%, and content of hydrochloric acid is 8 ~ 10wt%.
10. separation purification method according to claim 1, is characterized in that: in step (1), after solid grass ammonium phosphonium salt hydrochlorate water dissolution again with ammoniacal liquor or ammonia gas react; In step (1), obtain careless ammonium phosphine crude product A by spraying dry.
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| CN113234767A (en) * | 2021-05-13 | 2021-08-10 | 永农生物科学有限公司 | Method for producing solid L-glufosinate ammonium salt powder free of crystal water |
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| CN111574559A (en) * | 2020-04-30 | 2020-08-25 | 河北威远生物化工有限公司 | Post-treatment method of L-glufosinate-ammonium enzyme hydrolysate |
| CN113234767A (en) * | 2021-05-13 | 2021-08-10 | 永农生物科学有限公司 | Method for producing solid L-glufosinate ammonium salt powder free of crystal water |
| CN114163472A (en) * | 2021-11-27 | 2022-03-11 | 永农生物科学有限公司 | Method for synthesizing alpha-aminonitrile under alcohol solvent, and synthesis method and product of glufosinate-ammonium |
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