CN101671362B - Process for preparing N-(phosphonomethyl) iminodiacetic acid by hydroxyacetonitrile continuous method - Google Patents
Process for preparing N-(phosphonomethyl) iminodiacetic acid by hydroxyacetonitrile continuous method Download PDFInfo
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Abstract
The invention discloses a process for preparing N-(phosphonomethyl) iminodiacetic acid by a hydroxyacetonitrile continuous method; in the method, hydroxyacetonitrile and ammonia which are used as raw materials are ammonolyzed, hydrolyzed with alkalis and condensed to obtain the N-(phosphonomethyl) iminodiacetic acid. The process is characterized in that iminodiacetonitrile is synthesized under the action of a polymerization inhibitor and a pH buffering agent in the ammonolysis step, wherein the amount of the polymerization inhibitor is 0.06-2.5% of the mass of the hydroxyacetonitrile, and the amount of the buffering agent is 1-50% of the weight of the hydroxyacetonitrile. The process has the characteristics that the iminodiacetonitrile prepared from the hydroxyacetonitrile and the ammonia does not need to be crystallized for separation and can be directly hydrolyzed with alkalis to produce iminodiacetic acid disodium salts, and the iminodiacetic acid disodium salt solution is directly used for synthesizing the N-(phosphonomethyl) iminodiacetic acid; and the prepared N-(phosphonomethyl) iminodiacetic acid has the advantages of high purity and yield.
Description
Technical field
The present invention provides the technology of a kind of pmida98 preparation, and adopting hydroxyacetonitrile and ammonia is initial feed, passes through ammonia and separates, and alkaline hydrolysis obtains purity greater than 98% pmida98 product behind the condensation step.
Background technology
Pmida98 mainly is to form with iminodiethanoic acid and phosphorous acid or phosphorus trichloride, formaldehyde condensation under certain conditions in industry.Traditional synthesis technique can be divided into several kinds:
1, this method of prussic acid method all has harsh requirement to equipment and security, and the synthetic natural gas source place of production that receives of prussic acid restricts, and promoted extension is limited.And a large amount of cyanide wastewater is arranged, and bad processing is handled with the method for burning, and power consumption is serious.
2, chloroactic acid method Mono Chloro Acetic Acid and sodium hydroxide reaction sound field sodium chloroacetate is again with Hydrazine Hydrate 80 reaction, salt acidifying again under the effect of Sodium Nitrite; Generate the Iminodiacetate hydrochlorate; Be dissolved in the hot water through crystallization, filtration, washing, obtaining iminodiethanoic acid, recrystallize, separation, purifying, the dry product that gets with the alkali neutralization; Remove synthetic pmida98 again, this method has been eliminated owing to trivial step basically.
3, this method of diethanolamine method is main raw material with the diethylolamine, and in the presence of catalyzer and sodium hydroxide, deamination under the condition of HTHP generates Iminodiacetic acid sodium salt, synthetic then pmida98.This method requires high to equipment, catalyzer, the also easy inactivation of catalyzer, and raw material diethylolamine price is unstable, and three wastes difficult treatment.
With the hydroxyacetonitrile is that raw material is separated through ammonia, alkaline hydrolysis, and steps such as condensation are synthesized pmida98; Report is also arranged both at home and abroad, and CN101092430A is through the synthetic pmida98 of the method for treating different things alike, but that this method is separated in the process side reaction at ammonia is more; Can generate a large amount of tar polymer simultaneously; Have a strong impact on alkaline hydrolysis, the condensation reaction of back, the yield of pmida98 is low, and purity is lower.US5187301 separates at ammonia and has same problem in the process.
The inventor has selected suitable stopper and consumption thereof to overcome this problem through a large amount of experiment screenings and optimization, and the yield of the pmida98 that makes greatly improves, and the pmida98 that obtains can reach more than 98% with conventional purification purity.
Summary of the invention
The purpose of this invention is to provide a kind of is raw material with hydroxyacetonitrile and ammoniacal liquor, the preparation technology of the pmida98 of serialization production high purity, high yield.
The objective of the invention is to realize through following measure:
A kind of hydroxyacetonitrile continuous processing prepares the technology of pmida98; Adopting hydroxyacetonitrile and ammonia is initial feed, separates alkaline hydrolysis through ammonia; Obtain pmida98 behind the condensation step; Its characteristic is separated at ammonia and is added stopper and pH buffer reagent in the step, and the add-on of stopper is the 0.06%-2.5% of hydroxyacetonitrile quality, and the add-on of pH buffer reagent is the 1%-50% of hydroxyacetonitrile weight.
Described stopper is a Resorcinol, toluhydroquinone, N nitrosodiphenyl amine or benzoquinones, preferable methyl quinhydrones; PH value buffer reagent is ammonium chloride, ammonium sulfate or ammonium phosphate, preferred ammonium chloride.
Separate at ammonia that the mol ratio of hydroxyacetonitrile and ammoniacal liquor is 1 in the step: 0.3-0.8, the pH value of hydroxyacetonitrile solution is controlled at 3-6.After the ammonia that after ammonolysis reaction is accomplished, obtains is separated and added the stablizer aluminum oxide in the liquid, after adding acid for adjusting pH value again and being 2-5, be cooled to 40-70 ℃.Wherein, the consumption of stablizer aluminum oxide is the 0.05%-4% of hydroxyacetonitrile.
Used acid can be hydrochloric acid, sulfuric acid or phosphoric acid.
Ammonia drips in hot alkaline solution after separating liquid acid adjustment cooling, and the dropping time is at 20-60min; The temperature of described hot alkaline solution is 60-90 ℃, and concentration is 15-50%.
Described alkaline solution can be sodium hydroxide or potassium hydroxide solution, preferred sodium hydroxide solution.The mol ratio of alkali and hydroxyacetonitrile is 1.0-1.6: 1.
In the aforesaid method, after ammonia is separated liquid and in heat alkali liquid, dropwised, be warmed up to 90-110 ℃, insulation 1.5-4h.With the alkali solution liquid cooling, add hydrochloric acid and phosphorous acid respectively, the control rate of addition maintains the temperature at below 95 ℃, is warming up to 105-140 ℃ behind reinforced the finishing and drips formaldehyde, and insulation 1-4h obtains pmida98 suspension-s, and crystallisation by cooling gets pmida98.
In the aforesaid method, the mol ratio of hydroxyacetonitrile and phosphorous acid is 2: 0.5-1.7, the mol ratio of hydroxyacetonitrile and formaldehyde is 2: 0.6-1.6, the mol ratio of hydroxyacetonitrile and hydrochloric acid is 1: 0.1-0.5.
The step that the present invention adopts specifically can be carried out according to following method:
1), hydroxyacetonitrile, pH buffer reagent and stopper are mixed, stir and be warming up to 70-100 ℃, preferred 90 ℃, dropping ammonia, the rate of addition of control ammoniacal liquor makes the pH value of hydroxyacetonitrile mixed solution at 3-6.The dropping time dropwises at 20min, is warming up to 101-110 ℃, and preferred 105 ℃, insulation reaction 10-30min, preferred 18min; Wherein, the add-on of stopper is the 0.06%-2.5% of hydroxyacetonitrile quality, preferred 0.5%-1%; The add-on of pH buffer reagent is the 1%-50% of hydroxyacetonitrile quality, preferred 1-20%.
2), add the stablizer aluminum oxide and separate in the liquid in the ammonia that step 1) obtains, and add acid for adjusting pH value in 2-5, preferred 3, be cooled to 40-70 ℃, preferred 50 ℃.Wherein the consumption of stablizer aluminum oxide is the 0.05%-4% of hydroxyacetonitrile amount, preferred 1.5%-2%.Used acid is hydrochloric acid, sulfuric acid or phosphoric acid.
3), step 2) 40-70 ℃ ammonia obtaining separates drop and goes in the hot alkaline solution, the dropping time is 20-60min, preferred 45min is warming up to 90-110 ℃ then, preferred 103 ℃, insulation 1.5-4.0h, preferred 2.5h.Wherein, alkali lye can be sodium hydroxide or potassium hydroxide solution, preferred sodium hydroxide solution, and the mol ratio of alkali and hydroxyacetonitrile is 1.0-1.6: 1, the temperature of preferred 1.3: 1 hot alkaline solutions is 60-90 ℃, concentration is 15-50%, preferred 30%.
4), with alkali solution liquid cooling, add respectively and drip phosphorous acid and hydrochloric acid soln in the alkali solution liquid that step 3) obtains, drip formaldehyde then; Time length is 20-50min, preferred 25min, insulation reaction 1-4h; Preferred 2h gets pmida98 suspension-s, and crystallisation by cooling gets pmida98; Wherein, the mol ratio of hydroxyacetonitrile and phosphorous acid is 2: 0.5-1.7, preferred 2: 1.2-1.4; The mol ratio of hydroxyacetonitrile and hydrochloric acid is 1: 0.1-0.5, preferred 1: 0.3; The mol ratio of hydroxyacetonitrile and formaldehyde is 2: 0.6-1.6, preferred 2: 1.3-1.4.
The pH value of above-mentioned raw materials hydroxyacetonitrile before adding ammoniacal liquor is 2-5.
It is main raw material that the present invention adopts hydroxyacetonitrile and ammoniacal liquor, under the effect of stopper and pH buffer reagent, generates the NSC 263496 hot soln, and the ammonia used water that generates in the process absorbs, and it is capable of circulation in ammonolysis reaction to be made into certain density ammoniacal liquor liquid.In addition, separate in the step synthesizing iminodiacetic acid (salt) nitrile under the effect of stopper and pH buffer reagent at ammonia; Without the NSC 263496 Crystallization Separation, in the NSC 263496 hot soln, add the stablizer aluminum oxide, adjust pH is at 2-5; Be cooled to 40-70 ℃, be added drop-wise to then in the sodium hydroxide solution of heat, get the Iminodiacetic acid sodium salt salts solution behind the alkaline hydrolysis; Without the Crystallization Separation of iminodiethanoic acid, directly use Iminodiacetic acid sodium salt salts solution and phosphorous acid, formaldehyde condensation equally, make pmida98 bullion suspension-s; Through conventional crystallization, separate then, wash, filter excessively the pmida98 product.The characteristics of this step are: use hydroxyacetonitrile and ammonia need not pass through Crystallization Separation as the NSC 263496 of initial feed preparation; Directly alkaline hydrolysis generates Iminodiacetic acid sodium salt salt, and directly with the synthetic pmida98 of this sodium salt solution, method is simple; The pmida98 purity that makes is high, and yield is high.
Experimental data scope of the present invention is carried out fully the optimum experimental condition that by product is few for reaction.Described " % " is the quality percentage composition.
The present invention and existing technology relatively beneficial effect are: the ammonia of hydroxyacetonitrile is separated part and has been added stopper and pH buffer reagent ammonium sulfate or ammonium chlorides such as toluhydroquinone, N nitrosodiphenyl amine, benzoquinones; Through adding stopper; Thereby the polymerization between the blocking-up itrile group, thus make reaction be tending towards the gentle generation that reduces other side reactions through pH buffer reagent and stablizer, help the generation of alkaline hydrolysis and condensation reaction; The yield and the purity of pmida98 are greatly improved: make the transformation efficiency of hydroxyacetonitrile improve 8%-10%; By product and polymkeric substance reduce 10-15%, and all more than 85%, the purity of pmida98 is brought up to more than 98% to the yield of hydroxyacetonitrile.And step is simple, and cost reduces, and is suitable for industrial mass production.
Embodiment
Embodiment 1:
In 274g concentration is to add the 0.96g toluhydroquinone in 51% the hydroxyacetonitrile solution, and 27.4g ammonium chloride is warming up to 90 ℃ under stirring condition, drips concentration and be 26% ammoniacal liquor 86.3g; The control rate of addition, the pH value that makes hydroxyacetonitrile solution is 4.5, and 20min dropwises, and is warming up to 102 ℃; The insulation 20min, filtered while hot, to filtrating in add stablizer aluminum oxide 2.2g, and with the hydrochloric acid adjust pH in 3; Filter, be cooled to 50 ℃, the concentration that splashes into 416g70 ℃ is in 30% the sodium hydroxide solution, and begins to discharge ammonia; The ammonia water absorbs, and the temperature of keeping sodium hydroxide solution system when dripping is at 75-80 ℃, and 30min dropwises, and is warming up to 102 ℃; Insulation 2h generates to there being ammonia, finishes reaction cooled to 40 ℃, the Iminodiacetic acid sodium salt salts solution; The hydrochloric acid that in this Iminodiacetic acid sodium salt salts solution, adds 73g36% slowly adds phosphorous acid 127.9g down at holding temperature 50-80 ℃, is warming up to 105 ℃ then, drips the formaldehyde of 134.9g37%; The dropping time is 4h, at 110 ℃ of following insulation reaction 2h, finishes reaction, gets pmida98 suspension-s; Cooling, crystallization, mistake filter pmida98 product 238.8g, purity 98.1%, and the calculating pmida98 is 87.5% to the yield of hydroxyacetonitrile, the hydroxyacetonitrile transformation efficiency is 92%.
Embodiment 2:
In 140g concentration is to add the 0.45gN-nitrosodiphenylamine in 51% the hydroxyacetonitrile solution, ammonium chloride, and the add-on of ammonium chloride is 1% of a hydroxyacetonitrile quality, under stirring condition, is warming up to 90 ℃; By the mol ratio of hydroxyacetonitrile and ammoniacal liquor is that to drip concentration at 1: 0.8 be 26% ammoniacal liquor, the control rate of addition, and the pH value that makes hydroxyacetonitrile solution is 5, and 25min dropwises; Be warming up to 105 ℃, insulation 20min, filtered while hot adds stablizer aluminum oxide 1.2g in filtrating; And with the hydrochloric acid adjust pH in 5, be cooled to 50 ℃, the concentration that splashes into 210g60 ℃ is in 25% the sodium hydroxide solution, and begins to discharge ammonia; The ammonia water absorbs, and the temperature of keeping sodium hydroxide solution system when dripping is at 75-80 ℃, and 35min dropwises, and is warming up to 104 ℃; Insulation 2.5h finishes reaction cooled to 50 ℃, the Iminodiacetic acid sodium salt salts solution, in this Iminodiacetic acid sodium salt salts solution, add the hydrochloric acid of 32g36%; Slowly add phosphorous acid 63.9g down at holding temperature 50-80 ℃, be warming up to 110 ℃ then, drip the formaldehyde of 67.1g37%, the dropping time is 4h; At 110 ℃ of following insulation reaction 2.5h, finish reaction, pmida98 suspension-s, cooling, crystallization, cross and filter pmida98 product 120.9g; Purity 98.5%, the calculating pmida98 is 89.2% to the yield of hydroxyacetonitrile, the hydroxyacetonitrile transformation efficiency is 93%.
Embodiment 3:
In 420g concentration is 51% hydroxyacetonitrile solution, add benzoquinones, add-on be hydroxyacetonitrile consumption 1%, 41.4g ammonium phosphate, add-on is 50% of a hydroxyacetonitrile; Under stirring condition, being warming up to 92 ℃, is that to drip concentration at 1: 0.3 be 26% ammoniacal liquor by the mol ratio of hydroxyacetonitrile and ammoniacal liquor, the control rate of addition, and the pH value that makes hydroxyacetonitrile solution is 5; 35min dropwises, and is warming up to 101 ℃, insulation 18min, filtered while hot; In filtrating, add stablizer aluminum oxide 3.6g, and with the hydrochloric acid adjust pH in 4, be cooled to 50 ℃, the concentration that splashes into 630g75 ℃ is in 50% the sodium hydroxide solution; And begin to discharge ammonia, and the ammonia water absorbs, and the temperature of keeping sodium hydroxide solution system when dripping is at 75-80 ℃, and 40min dropwises; Be warming up to 110 ℃, insulation 1.5h finishes reaction cooled to 60 ℃, the Iminodiacetic acid sodium salt salts solution; The hydrochloric acid that in this Iminodiacetic acid sodium salt salts solution, adds 100g36% slowly adds phosphorous acid 192g down at holding temperature 50-80 ℃, is warming up to 110 ℃ then; Mol ratio by hydroxyacetonitrile and formaldehyde is the formaldehyde of dropping 37% in 1: 0.7, and the dropping time is 3.5h, at 110 ℃ of following insulation reaction 2.5h; Finish reaction, pmida98 suspension-s, cooling, crystallization, cross and filter pmida98 product 362.1g; Purity 98.8%, the calculating pmida98 is 88.6% to the yield of hydroxyacetonitrile, the hydroxyacetonitrile transformation efficiency is 92.6%.
Embodiment 4:
In 850g concentration is 51% hydroxyacetonitrile solution, add Resorcinol, add-on is 2% of a hydroxyacetonitrile, ammonium chloride, and add-on is 30% of a hydroxyacetonitrile; Under stirring condition, be warming up to 90 ℃, dropping concentration is 26% ammoniacal liquor 260g, the control rate of addition, and the pH value that makes hydroxyacetonitrile solution is 4; 20min dropwises, and is warming up to 105 ℃, insulation 20min, filtered while hot; In filtrating, add stablizer aluminum oxide 7.5g, and with the hydrochloric acid adjust pH in 3, be cooled to 50 ℃, the concentration that splashes into 1265g90 ℃ is in 15% the potassium hydroxide solution; And begin to discharge ammonia, and the ammonia water absorbs, and the temperature of keeping sodium hydroxide solution system when dripping is at 75-80 ℃, and 60min dropwises; Be warming up to 90 ℃, insulation 4h finishes reaction cooled to 70 ℃, the Iminodiacetic acid sodium salt salts solution; The hydrochloric acid that in this Iminodiacetic acid sodium salt salts solution, adds 205g36%, the mol ratio by hydroxyacetonitrile and phosphorous acid under holding temperature 50-80 ℃ is 1: 0.6 slowly adding phosphorous acid, is warming up to 140 ℃ then; Mol ratio by hydroxyacetonitrile and formaldehyde is the formaldehyde of dropping 37% in 1: 0.8, and the dropping time is 4h, at 110 ℃ of following insulation reaction 2.0h; Finish reaction, pmida98 suspension-s, cooling, crystallization, cross and filter pmida98 product 741.2g; Purity 98.3%, the calculating pmida98 is 90.1% to the yield of hydroxyacetonitrile, the hydroxyacetonitrile transformation efficiency is 94%.
Claims (9)
1. a hydroxyacetonitrile continuous processing prepares the technology of pmida98; Adopting hydroxyacetonitrile and ammonia is raw material, separates alkaline hydrolysis through ammonia; Obtain pmida98 behind the condensation step; It is characterized in that separating adding stopper and pH buffer reagent in the step at ammonia, the add-on of stopper is the 0.06%-2.5% of hydroxyacetonitrile quality, and the add-on of pH buffer reagent is the 1%-50% of hydroxyacetonitrile weight; Described stopper is a toluhydroquinone, N nitrosodiphenyl amine or benzoquinones; The ammonia that after ammonolysis reaction is accomplished, obtains adds acid for adjusting pH value 2-5 after separating and adding the stablizer aluminum oxide in the liquid, is cooled to 40-70 ℃ again; Wherein, the consumption of stablizer aluminum oxide is the 0.05%-4% of hydroxyacetonitrile.
2. hydroxyacetonitrile continuous processing as claimed in claim 1 prepares the technology of pmida98, it is characterized in that pH value buffer reagent is ammonium chloride, ammonium sulfate or ammonium phosphate.
3. hydroxyacetonitrile continuous processing as claimed in claim 1 prepares the technology of pmida98, it is characterized in that separating at ammonia that the mol ratio of hydroxyacetonitrile and ammoniacal liquor is 1 in the step: 0.3-0.8; The pH value of hydroxyacetonitrile solution is controlled at 3-6.
4. hydroxyacetonitrile continuous processing as claimed in claim 1 prepares the technology of pmida98, it is characterized in that used acid is hydrochloric acid, sulfuric acid or phosphoric acid.
5. continuous processing as claimed in claim 1 prepares the technology of pmida98, it is characterized in that the ammonia after the cooling is separated drop to be added in the hot alkaline solution, and the dropping time is at 20-60min; The temperature of described hot alkaline solution is 60-90 ℃, and concentration is 15-50%.
6. hydroxyacetonitrile continuous processing as claimed in claim 5 prepares the technology of pmida98, and the mol ratio that it is characterized in that alkali and hydroxyacetonitrile is 1.0-1.6: 1.
7. hydroxyacetonitrile continuous processing as claimed in claim 5 prepares the technology of pmida98, it is characterized in that ammonia is separated liquid and in heat alkali liquid, dropwised after, be warmed up to 90-110 ℃, insulation 1.5-4h.
8. hydroxyacetonitrile continuous processing as claimed in claim 7 prepares the technology of pmida98, it is characterized in that the alkali solution liquid cooling is added hydrochloric acid and phosphorous acid respectively; The control rate of addition; Maintain the temperature at below 95 ℃, be warming up to 105-140 ℃ behind reinforced the finishing and drip formaldehyde, insulation 1-4h; Obtain pmida98 suspension-s, crystallisation by cooling gets pmida98.
9. hydroxyacetonitrile continuous processing as claimed in claim 8 prepares pmida98 technology; The mol ratio that it is characterized in that hydroxyacetonitrile and phosphorous acid is 2: 0.5-1.7; The mol ratio of hydroxyacetonitrile and formaldehyde is 2: 0.6-1.6, the mol ratio of hydroxyacetonitrile and hydrochloric acid is 1: 0.1-0.5.
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| CN103497355B (en) * | 2013-09-03 | 2015-11-04 | 臧洪瑞 | Aminated compounds linking agent and the application in hydrogel preparation method thereof |
| CN106883264A (en) * | 2017-04-24 | 2017-06-23 | 威海韩孚生化药业有限公司 | A kind of preparation method of PMIDA |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1609112A (en) * | 2004-05-12 | 2005-04-27 | 江苏好收成韦恩农药化工有限公司 | Production process of N-phosphono methyl imido diacetic acid |
| CN1830953A (en) * | 2006-03-30 | 2006-09-13 | 重庆紫光化工有限责任公司 | Process for preparing iminodiacetonitrile |
| CN101050191A (en) * | 2007-05-15 | 2007-10-10 | 四川省天然气化工研究院 | Method for preparing diethylacetonitrile in imino group |
| CN101092430A (en) * | 2006-06-23 | 2007-12-26 | 北京清华紫光英力化工技术有限责任公司 | Clean production method for preparing glyphosate through 'one pot method'by using hydroxyl acetonitrile as raw material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1609112A (en) * | 2004-05-12 | 2005-04-27 | 江苏好收成韦恩农药化工有限公司 | Production process of N-phosphono methyl imido diacetic acid |
| CN1830953A (en) * | 2006-03-30 | 2006-09-13 | 重庆紫光化工有限责任公司 | Process for preparing iminodiacetonitrile |
| CN101092430A (en) * | 2006-06-23 | 2007-12-26 | 北京清华紫光英力化工技术有限责任公司 | Clean production method for preparing glyphosate through 'one pot method'by using hydroxyl acetonitrile as raw material |
| CN101050191A (en) * | 2007-05-15 | 2007-10-10 | 四川省天然气化工研究院 | Method for preparing diethylacetonitrile in imino group |
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