CN103044486A - Method for preparing glyphosate by directly oxidizing pmida - Google Patents
Method for preparing glyphosate by directly oxidizing pmida Download PDFInfo
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- CN103044486A CN103044486A CN2013100002337A CN201310000233A CN103044486A CN 103044486 A CN103044486 A CN 103044486A CN 2013100002337 A CN2013100002337 A CN 2013100002337A CN 201310000233 A CN201310000233 A CN 201310000233A CN 103044486 A CN103044486 A CN 103044486A
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Abstract
The invention discloses a method for preparing glyphosate by directly oxidizing pmida. The method comprises the steps that pmida and deionized water are mixed uniformly and added to a high-pressure reaction kettle; gas containing molecular oxygen serves as an oxidant at reaction temperature and pressure; pmida is directly oxidized through ultraviolet-visible light radiation; and glyphosate is prepared. Glyphosate prepared by the method has very high yield and purity, and no catalyst or promotor is required to be added in a preparation process, so that preparation and recovery costs of the catalyst are saved; the problem of catalyst and product separation is avoided; by-products are fewer; and the technology is simple.
Description
Technical field
The present invention relates to a kind of preparation method of glyphosate, be specifically related to gas take molecule-containing keto as oxygenant, the method for direct oxidation preparing glyphosate from N-phosphonomethyl aminodiacetic acid under the condition that ultraviolet-visible light exists.
Background technology
Glyphosate, chemical name N-phosphoryl methyl glycine is a kind of low toxicity, efficient, wide spectrum, eco-friendly steriland herbicide, since 19 century 70s come out, has been global most widely used agricultural chemicals just always.Glyphosate generally is to produce by the oxidation pmida98, mainly contains at present two kinds of production process routes.A kind of is the hydrogen peroxide oxidation route: make catalyzer with tungstate, molybdate, with hydrogen peroxide pmida98 is oxidized to oxynitrides first, with metal or metal-salt it is reduced to the former powder of glyphosate again.This route need use a large amount of hydrogen peroxide, has greatly improved raw materials cost, and oxidizing temperature be difficult to control, cause separation difficulty because containing a large amount of metal-salts in the reaction mother liquor, the yield of glyphosate and purity are all not high.
Another kind is to make oxygenant with air or oxygen, with the catalytic oxidation of carbon compositing catalyst.China Patent Publication No. CN 101045735, open day on October 3rd, 2007, the name of innovation and creation is called the method for preparing glyphosate by PMIDA of catalytic oxidizing by gas containing molecular oxygen, this application case discloses with gac as catalyzer, the method for preparing glyphosate by PMIDA catalytic oxidation under oxygen rich gas.Although the concentration of the method reactant is higher, the yield of glyphosate is also more satisfactory, and its shortcoming is that the reaction times is long, and efficient is low, and the adding of gac and gac have both increased cost with separating of product and also made process complications.U.S. Patent Publication No. US 3950402, open day on April 13rd, 1976, the name of innovation and creation is called Process for producing N-Phosphonomethyl Glycine, this application case discloses and precious metal (Pd, Pt, Rh) has been loaded on the gac method of preparing glyphosate by PMIDA catalytic oxidation under oxygen.Glyphosate yield and purity that this method obtains are all higher, also greatly reduce the content of by product formaldehyde, shortcoming is that precious metal is expensive and be easy to leaching loss, catalyzer preparation and regenerative process complexity, and the adding of catalyzer has greatly improved production cost and technical difficulty.China Patent Publication No. CN 101386627A, open day on March 18th, 2009, the name of innovation and creation is called the method for preparing glyphosate by PMIDA catalytic oxidation, this application case discloses the method for coming preparing glyphosate by PMIDA catalytic oxidation with the catalyzer of activated carbon supported carrying transition metal or its salt, this method reaction conditions is gentle, product yield is high, shortcoming is to have added nitric acid in the oxygenant, bring inconvenience to industrial production, and increased the technological process of catalyzer and product separation, so that operational path is complicated, production cost improves.
As known from the above, existing glyphosate preparation technology or long reaction time, by product formaldehyde is many, the glyphosate yield is low; Need to add catalyzer, cost height, catalyzer and product separation difficulty, low, the complicated operation of product purity.Therefore, it is significant to address the above problem to develop a kind of new glyphosate preparation method.
Summary of the invention
The present invention has overcome the prior art defective, and the method for the simple direct oxidation preparing glyphosate from N-phosphonomethyl aminodiacetic acid of a kind of technique is provided.The method is take the gas of molecule-containing keto as oxygenant, direct oxidation preparing glyphosate from N-phosphonomethyl aminodiacetic acid under the ultraviolet-visible rayed, need not to add any catalyzer or promotor, and with low cost, product yield and purity are all higher, low, the simple to operate facility of by product formaldehyde content.
Technical problem to be solved by this invention, can solve by the following technical programs:
A kind of method of direct oxidation preparing glyphosate from N-phosphonomethyl aminodiacetic acid may further comprise the steps:
(1) join in the autoclave after pmida98 and deionized water are mixed, the mass ratio of pmida98 and deionized water is (1 ~ 2): (5 ~ 100).The ultraviolet-visible light light source is housed in the autoclave, can makes things convenient for and accurately regulate the wavelength of light source.System is warming up to 30 ~ 80 ℃, and pressure rises to 0.1 ~ 0.7MPa, and the maintenance stirring velocity is 400 ~ 1000r/min, passes into nitrogen simultaneously in autoclave, to drain air wherein; After temperature and pressure all reaches and is stabilized in required temperature of reaction and pressure, nitrogen is switched to gas take molecule-containing keto as oxygenant, regulate the ultraviolet-visible optical wavelength and shine reactant, reactant is carried out the direct oxidation reaction, the reaction times is 1 ~ 2h.
(2) the reacted reaction solution of step (1) is heated, recrystallization obtains the former powder of glyphosate.
The wavelength region of employed ultraviolet-visible light is 220 ~ 695nm in the described step (1), and preferable range is 238 ~ 630nm;
Reaction pressure in the described step (1) is 0.1 ~ 0.7MPa, preferred 0.2 ~ 0.6MPa;
Temperature of reaction is 30 ~ 80 ℃ in the described step (1), preferred 40 ~ 70 ℃;
The gas of the molecule-containing keto in the described step (1) is air or oxygen;
Need not add any catalyzer or promotor in the reaction in the described step (1).
Compared with prior art, the present invention adopts the ultraviolet-visible rayed to carry out the pmida98 direct oxidation to prepare glyphosate, need not add catalyzer or promotor, the yield of glyphosate and purity are all very high, yield is greater than 96%, and purity is greater than 97%, and greatly reduces the content of formaldehyde.Technical scheme provided by the invention had both been saved the cost of catalyzer preparation, recovery, had also avoided the problem of catalyzer and product separation, and by-product is few, and technique is extremely simple.Do not introduce the material that environment is had harm in the reaction in addition, belong to the friendly process process fully.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.
Embodiment 1
Mixing solutions with 0.1kg pmida98 (purity is 98%) and 9.9kg deionized water, add and be equipped with in the autoclave of ultraviolet-visible radiant, low whipping speed is the temperature and pressure that raises under the condition of 400r/min, and passes into nitrogen to drain the air in the reactant; When temperature of reaction reaches and be stabilized in 40 ℃, reaction pressure reaches and be stabilized in 0.6MPa, the adjusting optical wavelength is 341nm, it is that the air of 300ml/min carries out direct oxidation reaction to reactant that nitrogen is switched to flow, reaction times is 1.0h, reaction end post-heating reaction solution carries out recrystallization and obtains glyphosate, the yield of glyphosate is 96.1%, and the purity of glyphosate is 97.2%, and formaldehyde content is lower.
Embodiment 2
Mixing solutions with 1.5kg pmida98 (purity is 98%) and 8.5kg deionized water, add and be equipped with in the autoclave of ultraviolet-visible radiant, low whipping speed is the temperature and pressure that raises under the condition of 800r/min, and passes into nitrogen to drain the air in the reactant; When temperature of reaction reaches and be stabilized in 50 ℃, reaction pressure reaches and be stabilized in 0.4MPa, the adjusting optical wavelength is 434nm, it is that the air of 600ml/min carries out direct oxidation reaction to reactant that nitrogen is switched to flow, reaction times is 1.6h, reaction end post-heating reaction solution carries out recrystallization and obtains glyphosate, the yield of glyphosate is 97.2%, and the purity of glyphosate is 97.0%, and formaldehyde content is lower.
Embodiment 3
Mixing solutions with 1.5kg pmida98 (purity is 98%) and 8.5kg deionized water, add and be equipped with in the autoclave of ultraviolet-visible radiant, low whipping speed is the temperature and pressure that raises under the condition of 800r/min, and passes into nitrogen to drain the air in the reactant; When temperature of reaction reaches and be stabilized in 70 ℃, reaction pressure reaches and be stabilized in 0.3MPa, the adjusting optical wavelength is 238nm, it is that the air of 700ml/min carries out direct oxidation reaction to reactant that nitrogen is switched to flow, reaction times is 1.1h, reaction end post-heating reaction solution carries out recrystallization and obtains glyphosate, the yield of glyphosate is 97.5%, and the purity of glyphosate is 97.3%, and formaldehyde content is lower.
Embodiment 4
Mixing solutions with 1.5kg pmida98 (purity is 98%) and 8.5kg deionized water, add and be equipped with in the autoclave of ultraviolet-visible radiant, low whipping speed is the temperature and pressure that raises under the condition of 600r/min, and passes into nitrogen to drain the air in the reactant; When temperature of reaction reaches and be stabilized in 55 ℃, reaction pressure reaches and be stabilized in 0.6MPa, the adjusting optical wavelength is 426nm, it is that the oxygen of 40ml/min carries out direct oxidation reaction to reactant that nitrogen is switched to flow, reaction times is 1.7h, reaction end post-heating reaction solution carries out recrystallization and obtains glyphosate, the yield of glyphosate is 97.4%, and the purity of glyphosate is 96.8%, and formaldehyde content is lower.
Embodiment 5
Mixing solutions with 2.5kg pmida98 (purity is 98%) and 7.5kg deionized water, add and be equipped with in the autoclave of ultraviolet-visible radiant, low whipping speed is the temperature and pressure that raises under the condition of 600r/min, and passes into nitrogen to drain the air in the reactant; When temperature of reaction reaches and be stabilized in 70 ℃, reaction pressure reaches and be stabilized in 0.2MPa, the adjusting optical wavelength is 572nm, it is that the oxygen of 90ml/min carries out direct oxidation reaction to reactant that nitrogen is switched to flow, reaction times is 1.8h, reaction end post-heating reaction solution carries out recrystallization and obtains glyphosate, the yield of glyphosate is 99.0%, and the purity of glyphosate is 97.4%, and formaldehyde content is lower.
Embodiment 6
Mixing solutions with 2.5kg pmida98 (purity is 98%) and 7.5kg deionized water, add and be equipped with in the autoclave of ultraviolet-visible radiant, low whipping speed is the temperature and pressure that raises under the condition of 800r/min, and passes into nitrogen to drain the air in the reactant; When temperature of reaction reaches and be stabilized in 50 ℃, reaction pressure reaches and be stabilized in 0.4MPa, the adjusting optical wavelength is 630nm, it is that the air of 600ml/min carries out direct oxidation reaction to reactant that nitrogen is switched to flow, reaction times is 1.9h, reaction end post-heating reaction solution carries out recrystallization and obtains glyphosate, the yield of glyphosate is 98.3%, and the purity of glyphosate is 96.7%, and formaldehyde content is lower.
Embodiment 7
Mixing solutions with 4.0kg pmida98 (purity is 98%) and 6.0kg deionized water, add and be equipped with in the autoclave of ultraviolet-visible radiant, low whipping speed is the temperature and pressure that raises under the condition of 1000r/min, and passes into nitrogen to drain the air in the reactant; When temperature of reaction reaches and be stabilized in 60 ℃, reaction pressure reaches and be stabilized in 0.5MPa, the adjusting optical wavelength is 486nm, it is that the oxygen of 120ml/min carries out direct oxidation reaction to reactant that nitrogen is switched to flow, reaction times is 2.0h, reaction end post-heating reaction solution carries out recrystallization and obtains glyphosate, the yield of glyphosate is 98.6%, and the purity of glyphosate is 97.0%, and formaldehyde content is lower.
Claims (6)
1. the method for a direct oxidation preparing glyphosate from N-phosphonomethyl aminodiacetic acid is characterized in that may further comprise the steps:
(1) after being mixed, pmida98 and deionized water join in the autoclave, the mass ratio of pmida98 and deionized water is (1 ~ 2): (5 ~ 100), the ultraviolet-visible light light source is housed in the autoclave, can make things convenient for and accurately regulate the wavelength of light source, system is warming up to 30 ~ 80 ℃, and pressure rises to 0.1 ~ 0.7MPa, and the maintenance stirring velocity is 400 ~ 1000r/min, simultaneously in autoclave, pass into nitrogen, to drain air wherein; After temperature and pressure all reaches and is stabilized in required temperature of reaction and pressure, nitrogen is switched to gas take molecule-containing keto as oxygenant, regulate the ultraviolet-visible optical wavelength and shine reactant, reactant is carried out the direct oxidation reaction, the reaction times is 1 ~ 2h;
(2) the reacted reaction solution of step (1) is heated, recrystallization obtains the former powder of glyphosate.
2. the method for described a kind of direct oxidation preparing glyphosate from N-phosphonomethyl aminodiacetic acid according to claim 1, the wavelength region that it is characterized in that ultraviolet-visible light is 220 ~ 695nm, preferable range is 238 ~ 630nm.
3. the method for described a kind of direct oxidation preparing glyphosate from N-phosphonomethyl aminodiacetic acid according to claim 1 is characterized in that reaction pressure is 0.1 ~ 0.7MPa, preferred 0.2 ~ 0.6MPa.
4. the method for described a kind of direct oxidation preparing glyphosate from N-phosphonomethyl aminodiacetic acid according to claim 1 is characterized in that temperature of reaction is 30 ~ 80 ℃, preferred 40 ~ 70 ℃.
5. the method for described a kind of direct oxidation preparing glyphosate from N-phosphonomethyl aminodiacetic acid according to claim 1, the gas that it is characterized in that molecule-containing keto is air or oxygen.
6. the method for described a kind of direct oxidation preparing glyphosate from N-phosphonomethyl aminodiacetic acid according to claim 1 is characterized in that need not adding any catalyzer or promotor in the reaction.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3950402A (en) * | 1972-05-31 | 1976-04-13 | Monsanto Company | Process for producing N-phosphonomethyl glycine |
| US3954848A (en) * | 1972-05-31 | 1976-05-04 | Monsanto Company | Process for producing N-phosphonomethyl glycine |
| CN102229621A (en) * | 2011-05-07 | 2011-11-02 | 安徽国星生物化学有限公司 | Method for preparing glyphosate by catalyzing and oxidizing glyphosine in the presence of ultraviolet light source |
| CN102241704A (en) * | 2011-05-07 | 2011-11-16 | 安徽国星生物化学有限公司 | Preparation method of glyphosate by catalytic oxidation of PMIDA (phosphonomethyl iminodiacetic acid) under microwave action |
| CN102690289A (en) * | 2012-06-26 | 2012-09-26 | 四川迪美特生物科技有限公司 | Method for preparing glyphosate |
-
2013
- 2013-01-02 CN CN2013100002337A patent/CN103044486A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3950402A (en) * | 1972-05-31 | 1976-04-13 | Monsanto Company | Process for producing N-phosphonomethyl glycine |
| US3954848A (en) * | 1972-05-31 | 1976-05-04 | Monsanto Company | Process for producing N-phosphonomethyl glycine |
| CN102229621A (en) * | 2011-05-07 | 2011-11-02 | 安徽国星生物化学有限公司 | Method for preparing glyphosate by catalyzing and oxidizing glyphosine in the presence of ultraviolet light source |
| CN102241704A (en) * | 2011-05-07 | 2011-11-16 | 安徽国星生物化学有限公司 | Preparation method of glyphosate by catalytic oxidation of PMIDA (phosphonomethyl iminodiacetic acid) under microwave action |
| CN102690289A (en) * | 2012-06-26 | 2012-09-26 | 四川迪美特生物科技有限公司 | Method for preparing glyphosate |
Non-Patent Citations (2)
| Title |
|---|
| 周曙光等: "草甘膦合成工艺的改进", 《精细化工》, vol. 26, no. 6, 15 June 2009 (2009-06-15), pages 605 - 608 * |
| 石峰等: "氧气氧化法制备草甘膦", 《合肥工业大学学报（自然科学版）》, vol. 31, no. 8, 28 August 2008 (2008-08-28), pages 1257 - 1259 * |
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Application publication date: 20130417 |