CN104262394B - The environment friendly clean producing method of a kind of preparing glyphosate from N-phosphonomethyl aminodiacetic acid and device - Google Patents
The environment friendly clean producing method of a kind of preparing glyphosate from N-phosphonomethyl aminodiacetic acid and device Download PDFInfo
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Abstract
The invention discloses environment friendly clean producing method and the device of a kind of preparing glyphosate from N-phosphonomethyl aminodiacetic acid；Production method comprises the following steps: 1) with hydrogen peroxide, air or oxygen rich gas as oxidant, and activated carbon is catalyst, in water, PMIDA is oxidized to glyphosate；2) add alkali, obtain the mixture of glyphosate salt solution and activated carbon；3) solid-liquid separation, solid is activated carbon, and filtrate is glyphosate salt solution；4) glyphosate salt solution entrance bipolar membrane electrodialysis device being carried out bipolar membrane electrodialysis process, salt room controls pH=2.0 ~ 3.0 and obtains glyphosate solution, and alkali room obtains aqueous slkali；Process units includes oxidation reaction apparatus, equipment for separating liquid from solid, bipolar membrane electrodialysis device and crystallization apparatus.Present invention, avoiding the shortcoming generating by-product methyl glyphosate, it also avoid and repeatedly heat and cool down the high energy consumption caused, use bipolar membrane electrodialysis technology that glyphosate salt is converted into glyphosate, it is not necessary to acid adding is neutralized, three-waste free pollution simultaneously.
Description
Technical field
The present invention relates to the production technical field of glyphosate, be specifically related to environment friendly clean producing method and the device of a kind of preparing glyphosate from N-phosphonomethyl aminodiacetic acid.
Background technology
Glyphosate (N-((phosphonomethyl))-glycine) be a kind of efficiently, wide spectrum, low toxicity, the organophosphorus herbicide of safety, perennial deep root malignant weed is prevented highly effective, is widely used at aspects such as agriculture, woods, gardening.Due to the continuous expansion of whole world genetically modified crops cultivated area, and the recovery of Global Agriculture particularly developing country agricultural and modernization, the demand growth of glyphosate is rapid, it has also become the pesticide species that sales volume is maximum in the world and growth rate is the fastest.
At present, the method producing glyphosate is a lot, mainly has glycine method and iminodiacetic acid (salt) acid system etc..Glycine method realizes industrialized production for 1986, and the yield of China is bigger.IDA method is developed and realizes industrialized production in the later stage nineties in last century, and the method uses Iminodiacetonitrile 1,1'-Imidodiacetonitrile or diethanolamine to produce iminodiacetic acid, be then condensed with formaldehyde and phosphorous acid to PMIDA, reoxidize and obtain glyphosate.In prior art, the method utilizing PMIDA oxidation preparation is a lot, mainly has hydrogen peroxide activated carbon method oxidizing process, air activated carbon oxidation process, oxygen rich gas activated carbon oxidation process, transiting metal oxidation method and electrolytic oxidation etc..
The method that US3950402 discloses and makees catalyst on activated carbon with noble-metal-supported, dioxygen oxidation draws glyphosate.Owing to using special catalyst, therefore reaction yield is higher, and typically up to 95-96%, but precious metal catalyst oxidizing process catalyst preparation cost is high, and catalyst is not easily recycled, the more difficult control of course of reaction.
US3969398 discloses with activated carbon as catalyst, uses the method that the molecule sweet phosphine of oxygen bis oxide prepares glyphosate.The feature of the method is low cost, and reaction yield is higher.
CN101045735A discloses with active carbon with high specific surface area as catalyst, utilizes oxygen rich gas to carry out aoxidizing the reaction drawing glyphosate for oxidant.This method solve and carry out, with low concentration PMIDA saturated solution, the shortcoming reacted, energy consumption is high, reduce production cost, use the method that glyphosate is dissolved then filtered while hot isolating active charcoal by hot conditions, the shortcoming of the method is that the formaldehyde in reaction mother liquor easily reacts generation methyl glyphosate with glyphosate, reduces the quality of reaction yield and product.
CN101508701A discloses a kind of method of dioxygen oxidation preparing glyphosate from N-phosphonomethyl aminodiacetic acid, water, PMIDA and activated carbon are put in stress reaction, heated and stirred becomes float, then pass to dioxygen oxidation, reaction terminates filtered while hot and removes activated carbon, filtrate decompression rectification concentrates, and crystallisation by cooling, is filtrated to get glyphosate products.
CN101337978A discloses with activated carbon as catalyst, oxygen rich gas as oxidant, the method that PMIDA is oxidized to glyphosate.After oxidation reaction terminates, reactant liquor cooled down, be filtrated to get the mixture of glyphosate and activated carbon, then this mixture mix with water, heat and make glyphosate dissolve then filtered while hot removing activated carbon, filtrate crystallisation by cooling, be filtrated to get glyphosate products.The method, by glyphosate and the mother solution containing formaldehyde first separate reheating molten isolating active charcoal, avoids the side reaction that glyphosate occurs with formaldehyde to a certain extent, but separation process still needs to carry out under high temperature again, and heating for multiple times cooling, and energy consumption is higher.
CN101531677A discloses the preparation method of a kind of glyphosate.PMIDA and catalyst activity charcoal are mixed in aqueous media, oxidation reaction is carried out with oxygen, reaction is lowered the temperature after terminating, solid-liquid separation obtains the filter cake containing glyphosate crystals and activated carbon, filter cake joins in glyphosate saturated solution, isolating active charcoal and glyphosate solution after heating for dissolving, glyphosate solution cooling, crystallization, isolated glyphosate products and filtrate, filtrate is applied mechanically as glyphosate saturated solution.
CN10169867A discloses a kind of method of preparing glyphosate by PMIDA catalytic oxidation, by PMIDA, water, activated carbon, promoter mix and blend, it is passed through dioxygen oxidation, reaction cools down, after terminating, the filter cake obtaining glyphosate and activated carbon, filter cake adds water and filters isolating active charcoal after thermosol, filtrate crystallisation by cooling, filters to obtain glyphosate products.
In sum, glyphosate is prepared in PMIDA activated carbon catalysis oxidation, and activated carbon and the separation method of glyphosate mainly have a following two: 1) react the direct filtered while hot that heats up after terminating, isolated mother solution and activated carbon, mother solution crystallisation by cooling, solid-liquid separation obtains glyphosate products；The major defect of the method is containing a certain amount of formaldehyde in reaction mother liquor, at high temperature easily reacts generation methyl glyphosate with glyphosate, reduces quality and the yield of glyphosate；2) reaction terminates rear crystallisation by cooling, isolated glyphosate and the mixture of activated carbon, by this mixture with in the saturated solution joining water or glyphosate, heating makes glyphosate all dissolve, then filtered while hot obtains activated carbon and glyphosate solution, solution crystallisation by cooling, isolated glyphosate products；Although this method can avoid the generation of by-product methyl glyphosate to a certain extent, but complex operation, repeatedly heat and cool down, energy consumption is high.
Summary of the invention
In view of this, it is an object of the invention to provide environment friendly clean producing method and the device of a kind of preparing glyphosate from N-phosphonomethyl aminodiacetic acid, do not produce by-product, quality and the yield of glyphosate products can be improved, and can reduce energy consumption and production costs.
For reaching above-mentioned purpose, the present invention provides following technical scheme:
The invention discloses the environment friendly clean producing method of a kind of preparing glyphosate from N-phosphonomethyl aminodiacetic acid, comprise the following steps:
1) with hydrogen peroxide, air or oxygen rich gas as oxidant, activated carbon is catalyst, in water, PMIDA is oxidized to glyphosate；
2) reaction system of step 1) is lowered the temperature, add alkali, obtain the mixture of glyphosate salt solution and activated carbon；
3) by step 2) mixture of gained carries out solid-liquid separation, and solid is activated carbon, and filtrate is glyphosate salt solution；
4) the glyphosate salt solution of step 3) gained being entered bipolar membrane electrodialysis device and carry out bipolar membrane electrodialysis process, salt room controls pH=2.0 ~ 3.0 and obtains glyphosate solution, and alkali room obtains aqueous slkali.
Further, described step 2) in, described alkali is sodium hydroxide, potassium hydroxide or ammonia, and alkali is 1 ~ 3:1 with the mol ratio of glyphosate.
Further, in described step 3), isolated activated carbon hot wash Posterior circle is applied to step 1), and cleaning mixture is integrated with in filtrate.
Further, in described step 4), it is to be passed through glyphosate salt solution in salt room that bipolar membrane electrodialysis processes, and is passed through water or dilute aqueous slkali, negative electrode and anode are passed through unidirectional current in alkali room.
Further, in described step 4), the temperature that bipolar membrane electrodialysis processes is 40 ~ 50 DEG C.
Further, in described step 4), alkali room obtains caustic solution circulation and is applied to step 2).
Further, the step isolating glyphosate from glyphosate solution is also included: by crystallisation by cooling after glyphosate solution crystallisation by cooling or concentration, crystal solution filters, and obtains glyphosate after filter cake washing, drying；Glyphosate mother solution recycled after crystallization is to glyphosate crystal or the dilution that is applied to glyphosate salt solution.
The invention also discloses the environment-protecting clean process units of a kind of preparing glyphosate from N-phosphonomethyl aminodiacetic acid for said method, including oxidation reaction apparatus, equipment for separating liquid from solid, bipolar membrane electrodialysis device and crystallization apparatus, the material outlet of described oxidation reaction apparatus is connected with the material inlet of equipment for separating liquid from solid, the filtrate (liquid of described equipment for separating liquid from solid is connected with the salt room of bipolar membrane electrodialysis device, the solid outlet of equipment for separating liquid from solid is connected with oxidation reaction apparatus, the alkali room of described bipolar membrane electrodialysis device is connected with oxidation reaction apparatus, the salt room of bipolar membrane electrodialysis device is connected with crystallization apparatus.
Further, described oxidation reaction apparatus is stainless steel pressure reactor.
Further, described bipolar membrane electrodialysis device side and other side are respectively equipped with the cathode chamber (I) of built-in negative electrode and are provided with the anode chamber (II) of built-in anode, film pair it is provided with between cathode chamber and anode chamber, one film forms by a spaced Bipolar Membrane (BP) and a cation exchange membrane (C), described film is positioned at cathode direction to Bipolar Membrane with the anode that the relative position of cation exchange membrane is Bipolar Membrane, the negative electrode of Bipolar Membrane is positioned at anode direction, a cation exchange membrane it is provided with between two Bipolar Membrane, described film constitutes alkali room (III) to cathode direction and the anode membrane of Bipolar Membrane, anode membrane and Bipolar Membrane anode direction constitute salt room (IV).
The beneficial effects of the present invention is:
1) present invention lowers the temperature after oxidation reaction terminates and adds alkali in reactant liquor, glyphosate is changed into glyphosate salt to improve its dissolubility, then can isolated glyphosate salt solution and activated carbon at low temperatures, avoid the formaldehyde at high temperature mother solution and easily react the shortcoming of generation by-product methyl glyphosate with glyphosate, it also avoid and repeatedly heat and cool down the high energy consumption caused.
2) use bipolar membrane electrodialysis technology that glyphosate salt is converted into glyphosate, reclaim the alkali of correspondence simultaneously, it is neutralized without acid adding, thus completely eliminate traditional salt molten method by-product sulfate or the shortcoming of hydrochlorate, three-waste free pollution, reducing the processing cost of brine waste, and good product quality, yield is high.
Accompanying drawing explanation
In order to make the purpose of the present invention, technical scheme and beneficial effect clearer, the present invention provides drawings described below to illustrate:
Fig. 1 is environment-protecting clean process units and the process chart of the preparing glyphosate from N-phosphonomethyl aminodiacetic acid of the embodiment of the present invention 1；
Fig. 2 is bipolar membrane electrodialysis device and process chart in the embodiment of the present invention 1.
Detailed description of the invention
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.
Embodiment
1
The environment-protecting clean process units of the preparing glyphosate from N-phosphonomethyl aminodiacetic acid of the present embodiment and technological process are as shown in Figure 1, process units includes oxidation reaction apparatus, equipment for separating liquid from solid, bipolar membrane electrodialysis device and crystallization apparatus, the material outlet of described oxidation reaction apparatus is connected with the material inlet of equipment for separating liquid from solid, the filtrate (liquid of described equipment for separating liquid from solid is connected with the salt room of bipolar membrane electrodialysis device, the solid outlet of equipment for separating liquid from solid is connected with oxidation reaction apparatus, the alkali room of described bipolar membrane electrodialysis device is connected with oxidation reaction apparatus, the salt room of bipolar membrane electrodialysis device is connected with crystallization apparatus；Described oxidation reaction apparatus is stainless steel pressure reactor；Production method comprises the following steps:
1) PMIDA is oxidized to glyphosate: add PMIDA 500g (1.67mol), water 1100g, activated carbon 100g, stirring in stainless steel pressure reactor, and temperature controls, for 50-55 DEG C, to be passed through air, and Stress control is 0.5MPa, and flow-control is 10m3/ h.kmol, the concentration of on-line monitoring air vent oxygen, oxygen concentration first reduces and then increases, when oxygen concentration increases more than 10% for 10 minutes, and reaction terminates；
2) preparation of sodium glyphosate: cooling reactant liquor, to room temperature, adds 30% sodium hydroxide solution 224g, obtains the mixture of sodium glyphosate solution and activated carbon；
3) solid-liquid separation: be filtered to remove activated carbon, activated carbon twice Posterior circle of 50mL hot wash is applied to step 1), and cleaning mixture is integrated with in filtrate, obtains sodium glyphosate solution；
4) preparation of glyphosate: above-mentioned sodium glyphosate solution enters bipolar membrane electrodialysis device and carries out bipolar membrane electrodialysis process；Bipolar membrane electrodialysis device and technological process are as shown in Figure 2, bipolar membrane electrodialysis device side and other side are respectively equipped with the cathode chamber (I) of built-in negative electrode and are provided with the anode chamber (II) of built-in anode, film pair it is provided with between cathode chamber and anode chamber, one film forms by a spaced Bipolar Membrane (BP) and a cation exchange membrane (C), described film is positioned at cathode direction to Bipolar Membrane with the anode that the relative position of cation exchange membrane is Bipolar Membrane, the negative electrode of Bipolar Membrane is positioned at anode direction, a cation exchange membrane it is provided with between two Bipolar Membrane, described film constitutes alkali room (III) to cathode direction and the anode membrane of Bipolar Membrane, anode membrane and Bipolar Membrane anode direction constitute salt room (IV)；Sodium glyphosate solution it is passed through in salt room, alkali room is passed through the sodium hydroxide solution that mass fraction is 2%, negative electrode and anode are passed through unidirectional current, the temperature that bipolar membrane electrodialysis processes controls to be 40 ~ 50 DEG C (if the temperature that bipolar membrane electrodialysis processes is relatively low, glyphosate can separate out blocking membrane module in a large number)；It is electrodialysis terminal that pH in salt room controls 2.0, analyzes the glyphosate in salt room, and its yield is more than 95%, and the sodium hydroxide mass fraction in alkali room is 8.4%, is concentrated to give the sodium hydroxide solution of 30%, recycled to step 2)；
5) glyphosate products is separated: being passed through by the glyphosate solution in salt room and being concentrated into mass fraction is 25%, is subsequently cooled to 5 DEG C of crystallizations, and sucking filtration obtains glyphosate wet product, drying, obtains the glyphosate 268.7g of content 98.2%, yield 93.5%.Glyphosate mother solution recycled after crystallization uses the dilution of sodium glyphosate to glyphosate crystal or set.
Comparative example
1
1) PMIDA is oxidized to glyphosate: add PMIDA 500g (1.67mol), water 1100g, activated carbon 100g, stirring in stainless steel pressure reactor, and temperature controls, for 50-55 DEG C, to be passed through air, and Stress control is 0.5MPa, and flow-control is 10m3/ h.kmol, the concentration of on-line monitoring air vent oxygen, oxygen concentration first reduces and then increases, when oxygen concentration increases more than 10% for 10 minutes, and reaction terminates；
2) preparation of sodium glyphosate: cooling reactant liquor, to room temperature, adds 30% sodium hydroxide solution 224g, obtains the mixture of sodium glyphosate solution and activated carbon；
3) solid-liquid separation: be filtered to remove activated carbon, activated carbon twice Posterior circle of 50mL hot wash is applied to step 1), and cleaning mixture is integrated with in filtrate, obtains sodium glyphosate solution；
4) preparation of glyphosate: the sodium glyphosate solution hydrochloric acid of step 3) gained is regulated pH=2.1-2.3, is subsequently cooled to 5 DEG C of crystallizations, filters, and washing is dried to obtain glyphosate 258.0g, content 95.8%, yield 87.5%.
Comparative example
2
1) sweet phosphine is oxidized to glyphosate: add PMIDA 500g (1.67mol), water 1100g, activated carbon 100g, stirring in stainless steel pressure reactor, and temperature controls, for 50-55 DEG C, to be passed through air, and Stress control is 0.5MPa, and flow-control is 10m3/ h.kmol, the concentration of on-line monitoring air vent oxygen, oxygen concentration first reduces and then increases, when oxygen concentration increases more than 10% for 10 minutes, and reaction terminates；
2) solid-liquid separation: cooling reactant liquor, to room temperature, filters, obtains the mixture of glyphosate and activated carbon；
3) preparation of glyphosate: by step 2) solid mixture that obtains and 4000L water, mixing, it is stirred and heated to 80 DEG C of abundant dissolvings, filtered while hot, filtrate is with 200mL hot wash twice, cleaning mixture and filtrate merging are cooled to 3-5 DEG C, filter, washing, be dried to obtain glyphosate 252.0g, content 97.1%, yield 86.7%.
Finally illustrate is, preferred embodiment above is only in order to illustrate technical scheme and unrestricted, although the present invention being described in detail by above preferred embodiment, but skilled artisan would appreciate that, in the form and details it can be made various change, without departing from claims of the present invention limited range.
Claims (9)
1. the environment friendly clean producing method of a preparing glyphosate from N-phosphonomethyl aminodiacetic acid, it is characterised in that: comprise the following steps:
1) with hydrogen peroxide, air or oxygen rich gas as oxidant, activated carbon is catalyst, in water, PMIDA is oxidized to glyphosate；
2) reaction system of step 1) is lowered the temperature, add alkali, obtain the mixture of glyphosate salt solution and activated carbon；
3) by step 2) mixture of gained carries out solid-liquid separation, and solid is activated carbon, and filtrate is glyphosate salt solution；
4) the glyphosate salt solution of step 3) gained being entered bipolar membrane electrodialysis device and carry out bipolar membrane electrodialysis process, the temperature that bipolar membrane electrodialysis processes is 40 ~ 50 DEG C, and salt room controls pH=2.0 ~ 3.0 and obtains glyphosate solution, and alkali room obtains aqueous slkali.
2. according to the environment friendly clean producing method of the preparing glyphosate from N-phosphonomethyl aminodiacetic acid described in claim 1, it is characterised in that: described step 2) in, described alkali is sodium hydroxide, potassium hydroxide or ammonia, and alkali is 1 ~ 3:1 with the mol ratio of glyphosate.
3. according to the environment friendly clean producing method of the preparing glyphosate from N-phosphonomethyl aminodiacetic acid described in claim 1, it is characterised in that: in described step 3), isolated activated carbon hot wash Posterior circle is applied to step 1), and cleaning mixture is integrated with in filtrate.
4. according to the environment friendly clean producing method of the preparing glyphosate from N-phosphonomethyl aminodiacetic acid described in claim 1, it is characterized in that: in described step 4), it is to be passed through glyphosate salt solution in salt room that bipolar membrane electrodialysis processes, and is passed through water or dilute aqueous slkali, negative electrode and anode are passed through unidirectional current in alkali room.
5. according to the environment friendly clean producing method of the preparing glyphosate from N-phosphonomethyl aminodiacetic acid described in claim 1, it is characterised in that: in described step 4), alkali room obtains caustic solution circulation and is applied to step 2).
6. according to the environment friendly clean producing method of the preparing glyphosate from N-phosphonomethyl aminodiacetic acid described in claim 1, it is characterized in that: also include isolating the step of glyphosate from glyphosate solution: by crystallisation by cooling after glyphosate solution crystallisation by cooling or concentration, crystal solution filters, and obtains glyphosate after filter cake washing, drying；Glyphosate mother solution recycled after crystallization is to glyphosate crystal or the dilution that is applied to glyphosate salt solution.
7. the environment-protecting clean process units for the preparing glyphosate from N-phosphonomethyl aminodiacetic acid of method described in claim 1 to 6 any one, it is characterized in that: include oxidation reaction apparatus, equipment for separating liquid from solid, bipolar membrane electrodialysis device and crystallization apparatus, the material outlet of described oxidation reaction apparatus is connected with the material inlet of equipment for separating liquid from solid, the filtrate (liquid of described equipment for separating liquid from solid is connected with the salt room of bipolar membrane electrodialysis device, the solid outlet of equipment for separating liquid from solid is connected with oxidation reaction apparatus, the alkali room of described bipolar membrane electrodialysis device is connected with oxidation reaction apparatus, the salt room of bipolar membrane electrodialysis device is connected with crystallization apparatus.
The environment-protecting clean process units of preparing glyphosate from N-phosphonomethyl aminodiacetic acid the most according to claim 7, it is characterised in that: described oxidation reaction apparatus is stainless steel pressure reactor.
The environment-protecting clean process units of preparing glyphosate from N-phosphonomethyl aminodiacetic acid the most according to claim 7, it is characterized in that: described bipolar membrane electrodialysis device side and other side are respectively equipped with the cathode chamber (I) of built-in negative electrode and are provided with the anode chamber (II) of built-in anode, film pair it is provided with between cathode chamber and anode chamber, one film forms by a spaced Bipolar Membrane (BP) and a cation exchange membrane (C), described film is positioned at cathode direction to Bipolar Membrane with the anode that the relative position of cation exchange membrane is Bipolar Membrane, the negative electrode of Bipolar Membrane is positioned at anode direction, a cation exchange membrane it is provided with between two Bipolar Membrane, described film constitutes alkali room (III) to cathode direction and the anode membrane of Bipolar Membrane, anode membrane and Bipolar Membrane anode direction constitute salt room (IV).
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104621178B (en) * | 2015-02-10 | 2016-10-12 | 重庆紫光化工股份有限公司 | A kind of glyphosate pesticide active compound and preparation method thereof |
| CN105154911A (en) * | 2015-08-25 | 2015-12-16 | 杭州蓝然环境技术有限公司 | Technology for producing EDTA through bipolar membrane method |
| CN105541903A (en) * | 2015-12-14 | 2016-05-04 | 浙江新安化工集团股份有限公司 | Preparation method of glufosinate-ammonium |
| CN105669742B (en) * | 2016-01-14 | 2018-06-08 | 江苏七洲绿色化工股份有限公司 | A kind of purification process of glufosinate-ammonium |
| CN105541905B (en) * | 2016-01-14 | 2018-05-01 | 江苏七洲绿色化工股份有限公司 | A kind of purification process of glufosinate-ammonium |
| CN105541904B (en) * | 2016-01-14 | 2018-11-13 | 江苏七洲绿色化工股份有限公司 | A kind of purification process of glufosinate-ammonium |
| CN105541907B (en) * | 2016-01-14 | 2018-05-11 | 江苏七洲绿色化工股份有限公司 | A kind of purification process of glufosinate-ammonium |
| CN105541906B (en) * | 2016-01-14 | 2018-05-11 | 江苏七洲绿色化工股份有限公司 | A kind of purification process of glufosinate-ammonium |
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| CN106518698A (en) * | 2016-09-20 | 2017-03-22 | 重庆紫光化工股份有限公司 | Environmental-protection clean production process for reducing ethylenediaminetetraacetic acid by-production inorganic acid sodium |
| CN106496266B (en) * | 2016-09-27 | 2018-08-17 | 江苏七洲绿色化工股份有限公司 | A kind of preparation method of glufosinate-ammonium |
| CN106496265B (en) * | 2016-09-27 | 2018-08-17 | 江苏七洲绿色化工股份有限公司 | A kind of synthetic method of glufosinate-ammonium |
| CN108148091B (en) * | 2016-12-02 | 2020-01-14 | 利尔化学股份有限公司 | Clean preparation method of glufosinate-ammonium |
| CN112358499A (en) * | 2020-11-12 | 2021-02-12 | 江苏春江润田农化有限公司 | Synthesis method of glufosinate-ammonium |
| CN114605470B (en) * | 2022-04-06 | 2023-08-04 | 中国林业科学研究院林产化学工业研究所 | Method for refining and decoloring glufosinate-ammonium stock solution |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3859183A (en) * | 1973-11-07 | 1975-01-07 | Monsanto Co | Process for producing n-phosphonomethyl glycine triesters |
| US4566956A (en) * | 1984-12-07 | 1986-01-28 | The Dow Chemical Company | Electrochemical conversion of soluble salts of insoluble acids to their acid form |
| US4832937A (en) * | 1988-09-28 | 1989-05-23 | The Dow Chemical Company | Regeneration of chelated polyvalent metal solutions by controlled potential electrolysis |
| DE10054993A1 (en) * | 1999-11-10 | 2001-05-17 | Basf Ag | Production of N-phosphonomethylglycine, useful as herbicide, comprises electrochemical oxidation of phosphonomethyliminodiacetic acid using anodically-polarized layer formed by deposition |
| CN104829648A (en) * | 2005-04-01 | 2015-08-12 | 孟山都技术公司 | Control of N-(phosphonomethyl) iminodiacetic acid conversion in manufacture of glyphosate |
| CN101195639B (en) * | 2007-08-02 | 2011-11-16 | 莫一平 | Method for processing mother solution of glyphosate |
| CN101591351A (en) * | 2008-05-28 | 2009-12-02 | 北京紫光英力化工技术有限公司 | The novel process of a kind of pmida98 or its salt glyphosate catalytic oxidation preparation and salt thereof |
| CN101298445A (en) * | 2008-06-17 | 2008-11-05 | 徐昌洪 | Method for directly preparing vitamin C with sodium gulonate |
| CN101748425B (en) * | 2008-12-05 | 2014-07-09 | 宜兴方晶科技有限公司 | Preparation method of stannous methanesulfonate |
| CN101525349A (en) * | 2009-04-10 | 2009-09-09 | 四川贝尔实业有限责任公司 | Method for preparing glyphosate by catalyzing and oxidizing N-phosphonomethyl iminodiacetic acid |
| CN101643408A (en) * | 2009-08-31 | 2010-02-10 | 厦门世达膜科技有限公司 | Production method of gulonic acid in production of vitamin C |
| CN102010431B (en) * | 2010-12-02 | 2012-08-01 | 胡建荣 | Ceftezole sodium compound and novel method thereof |
| CN102127110B (en) * | 2011-01-28 | 2012-11-21 | 杭州天创净水设备有限公司 | Method for separating and purifying glufosinate-ammonium solution |
| CN103374030B (en) * | 2012-04-13 | 2016-03-23 | 浙江新安化工集团股份有限公司 | A kind ofly prepare the careless method of ammonium phosphine and the preparation method of intermediate thereof |
| CN103396440B (en) * | 2013-08-23 | 2016-03-16 | 重庆紫光化工股份有限公司 | A kind of preparation method of careless ammonium phosphine |
| CN103664665A (en) * | 2013-12-13 | 2014-03-26 | 天津天成制药有限公司 | Solid sodium sarcosine preparation method |
-
2014
- 2014-09-16 CN CN201410469750.3A patent/CN104262394B/en not_active Expired - Fee Related
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Also Published As
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| CN104327115A (en) | 2015-02-04 |
| CN104262391A (en) | 2015-01-07 |
| CN104327115B (en) | 2016-08-24 |
| CN104262391B (en) | 2016-08-24 |
| CN104262393B (en) | 2017-01-11 |
| CN104313636B (en) | 2016-08-24 |
| CN104313636A (en) | 2015-01-28 |
| CN104262393A (en) | 2015-01-07 |
| CN104262394A (en) | 2015-01-07 |
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