CN101709064A - Process for synthesizing glyphosate - Google Patents
Process for synthesizing glyphosate Download PDFInfo
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- CN101709064A CN101709064A CN200910185462A CN200910185462A CN101709064A CN 101709064 A CN101709064 A CN 101709064A CN 200910185462 A CN200910185462 A CN 200910185462A CN 200910185462 A CN200910185462 A CN 200910185462A CN 101709064 A CN101709064 A CN 101709064A
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Abstract
The invention discloses a process for synthesizing glyphosate, comprising the steps of: firstly, hydrolyzing iminodiacetonitrile to generate iminodisodium salt, generating iminomonosodium salt by the iminodisodium salt, and continuously acidifying the iminomonosodium salt to obtain iminodiacetic acid; secondly, reacting the iminodiacetic acid with formaldehyde and phosphorous acid to prepare N-Phosphonomethyl iminodiacetic acid (PMIDA), mixing the PMIDA with water and sodium tungstate, and adding hydrogen peroxide for reacting; and thirdly, adding stabilizer and ferrous sulfate water to reaction liquid for reacting to obtain finished product of glyphosate. The invention has simple process and can realize large-scale production; in addition, the synthesized glyphosate has high yield and purity.
Description
Technical field
The present invention relates to the synthetic field of industry, specifically is process for synthesizing glyphosate.
Background technology
Glyphosate, formal name used at school N-((phosphonomethyl)) glycine, N-((phosphonomethyl)) Padil is a kind of organophosphorus herbicide, and pure product are non-volatile white solid, and proportion is 0.5, fusing about about 230 ℃ greatly, and follow decomposition.Solubleness in the time of 25 ℃ in water is 1.2%, is insoluble to common organic solvents, and its isopropyl amine salt is dissolved in water fully.Not flammable, do not explode, storage at normal temperature is stable.Centering charcoal steel, galvanized sheet iron have corrosive nature.
Summary of the invention
The invention provides a kind of process for synthesizing glyphosate, its synthesis technique is simple, and is easy to operate, and product yield and purity height.
Technical scheme of the present invention is:
Process for synthesizing glyphosate is characterized in that: may further comprise the steps:
(1), iminodiethanoic acid is synthetic: the adding weight part is that ammoniacal liquor and the weight part of 1.8-2.0 are the alkali aqueous solution of 2.0-2.3 in reactor, adding total weight parts again is the 45-55% of the iminodiacetonitrile amount of 0.7-0.8, continue to drip remaining iminodiacetonitrile then, be warming up to 100-105 ℃ after dripping, hydrolysis generates the imino-diacetic sodium salt, produced simultaneously ammonia condensing reflux is to reactor, and ammonia tail gas water absorbs into ammoniacal liquor; After ammonia has taken off, to react feed liquid vacuum suction acidolysis still, being cooled to and slowly dripping weight part after 80 ℃ of temperature is the concentrated hydrochloric acid of 1.7-1.8, generate imino-one sodium salt, drip hydrochloric acid and add gac again, filter out active breeze then, filtrate is to crystallization kettle, continue to drip 31% concentrated hydrochloric acid of 0.7-0.8 weight part, cooling is discharged to suction filtration then simultaneously, is the iminodiethanoic acid filter cake behind the centrifuge dripping, filtrate enters concentration kettle, squeezes into the crystallization kettle recycled after dehydration back suction filtration is removed sodium-chlor;
(2), pmida98 is synthetic: with the iminodiethanoic acid that makes, concentrated hydrochloric acid that weight part is 1.2-1.4, phosphorous acid that weight part is 0.6-0.7, water that weight part is 0.5-1.5 add contract and still in, temperature rising reflux, evenly dripping weight part is the formaldehyde of 0.2-0.4, and 105 ℃-110 ℃ of controlled temperature refluxed 2.5 hours, heat up then after the depickling, cooling is separated out the pmida98 crystal, is discharged to suction filtration, centrifuge dripping obtains wet product pmida98, and filtrate is squeezed into to contracting and still is applied mechanically;
(3), glyphosate is synthetic: adding weight part in stills for air blowing is the water of 1.3-1.5, the wet product pmida98 that makes, weight part is the sodium wolframate of 0.005-0.007, slowly heat up, when temperature in the kettle rises to 56-58 ℃, drip weight part and be 0.8-1.2 hydrogen peroxide, drip slowly evenly, 56-58 ℃ of temperature in the kettle control drips and finishes, and continues insulation reaction in this temperature range, reaction solution becomes clarification gradually, be discharged to reduction kettle, being cooled to after 30 ℃ of the certain temperatures beginning, slowly to drip weight part be the ferrous sulfate of 0.04-0.05, control reaction temperature＜40 ℃, reaction times is 2-3 hour; After dropping finishes, continue to stir, cooling, centrifugal then, centrifugal gained filter cake carries out drying, gets glyphosate.
Described process for synthesizing glyphosate is characterized in that: may further comprise the steps:
(1), iminodiethanoic acid is synthetic: add weight part and be 1.87 ammoniacal liquor and weight part in reactor and be 2.166 alkali aqueous solution, add weight part again and be the 45%-55% of 0.702 iminodiacetonitrile amount, continue remaining dropping iminodiacetonitrile, be warmed up to 100-105 ℃ after dripping, hydrolysis generates the imino-diacetic sodium salt, produced simultaneously ammonia condensing reflux is to reactor, and ammonia tail gas water absorbs into ammoniacal liquor; After ammonia has taken off, will react feed liquid vacuum suction acidolysis still, be cooled to≤slowly to drip weight part after 80 ℃ and be 1.704 mass concentration be 31% hydrochloric acid, generate imino-one sodium salt, drip hydrochloric acid and add gac again, filter out active breeze then, filtrate is to crystallization kettle, continue to drip the concentrated hydrochloric acid of 0.8 weight part, cooling is discharged to suction filtration simultaneously, is the iminodiethanoic acid filter cake behind the centrifuge dripping, filtrate enters concentration kettle, squeezes into the crystallization kettle recycled after dehydration back suction filtration is removed sodium-chlor;
(2), pmida98 is synthetic: with iminodiethanoic acid, the weight part that makes be 1.272 mass concentration be 31% hydrochloric acid, weight part be 0.65 phosphorous acid, weight part be 0.958 water add contract and still in, heat up, by contracting and the still condenser refluxes; Evenly drip weight part then and be 0.259 formaldehyde, 105 ℃-110 ℃ of controlled temperature refluxed 2.5 hours, and after the intensification depickling, cooling is separated out the pmida98 crystal, is discharged to suction filtration, and the solid centrifuge dripping obtains wet product pmida98, and filtrate is squeezed into to contracting and still is applied mechanically;
(3), glyphosate is synthetic: the adding weight part is 1.345 water in stills for air blowing, the pmida98 that makes, weight part are 0.006 sodium wolframate, slowly heat up, when temperature in the kettle rises to 57 ℃, dripping weight part and be 0.977 mass concentration is 27.5% hydrogen peroxide, 57 ℃ of temperature in the kettle controls, drip and finish, continuation is insulation reaction in this temperature range, reaction solution becomes clarification gradually, is discharged to reduction kettle, and being cooled to beginning behind certain temperature＜30 ℃, slowly to drip weight part be 0.045 ferrous sulfate, control reaction temperature＜40 ℃, the reaction times is 2-3 hour; After the dropping end, continue to stir, cooling, centrifugal then, centrifugal gained filter cake carries out drying, gets glyphosate, and filtrate concentrates, and gets gyphosate solution.
Synthesis technique of the present invention is simple, can realize scale operation, and the productive rate of synthetic glyphosate and purity height.
Embodiment
Process for synthesizing glyphosate:
(1), iminodiethanoic acid is synthetic: add weight part and be 1.87 ammoniacal liquor and weight part in reactor and be 2.166 alkali aqueous solution, add weight part again and be 0.702 iminodiacetonitrile amount 45%-55%, continue remaining dropping iminodiacetonitrile, drip 100-105 ℃ of back intensification, hydrolysis generates the imino-diacetic sodium salt, produced simultaneously ammonia condensing reflux is to reactor, and ammonia tail gas water absorbs into ammoniacal liquor; After ammonia has taken off, will react feed liquid vacuum suction acidolysis still, being cooled to after 80 ℃ and slowly dripping weight part is that 1.704 mass concentration is 31% hydrochloric acid, generate imino-one sodium salt, drip hydrochloric acid and add gac again, filter out active breeze then, filtrate is to crystallization kettle, continue to drip 31% hydrochloric acid of 0.8 weight part, cooling is discharged to suction filtration simultaneously, is the iminodiethanoic acid filter cake behind the centrifuge dripping, filtrate enters concentration kettle, squeezes into the crystallization kettle recycled after dehydration back suction filtration is removed sodium-chlor;
(2), pmida98 is synthetic: with iminodiethanoic acid, the weight part that makes be 1.272 mass concentration be 31% hydrochloric acid, weight part be 0.65 phosphorous acid, weight part be 0.958 water add contract and still in, heat up, by contracting and the still condenser refluxes; Evenly drip weight part then and be 0.259 formaldehyde, controlled temperature 107-110 ℃, refluxed 2.5 hours, after the intensification depickling, cooling is separated out the pmida98 crystal, is discharged to suction filtration, and the solid centrifuge dripping obtains wet product pmida98, and filtrate is squeezed into to contracting and still is applied mechanically;
(3), glyphosate is synthetic: the adding weight part is 1.345 water in stills for air blowing, the pmida98 that makes, weight part is 0.006 sodium wolframate, slowly heat up, when temperature in the kettle rises to 57 ℃, dripping weight part and be 0.977 mass concentration is 27.5% hydrogen peroxide, 57 ℃ of temperature in the kettle controls, drip and finish, continue insulation reaction in this temperature range, reaction solution becomes clarification gradually, be discharged to reduction kettle, be cooled to place stablizer behind certain temperature＜30 ℃, begin slowly to drip weight part then and be 0.045 ferrous sulfate, control reaction temperature＜40 ℃, reaction times is 2-3 hour; After the dropping end, continue to stir, cooling, centrifugal then, centrifugal gained filter cake carries out drying, gets glyphosate, and filtrate concentrates, and gets gyphosate solution.
Claims (2)
1. process for synthesizing glyphosate is characterized in that: may further comprise the steps:
(1), iminodiethanoic acid is synthetic: the adding weight part is that ammoniacal liquor and the weight part of 1.8-2.0 are the alkali aqueous solution of 2.0-2.3 in reactor, adding total weight parts again is the 45-55% of the iminodiacetonitrile amount of 0.7-0.8, continue to drip remaining iminodiacetonitrile then, be warming up to 100-105 ℃ after dripping, hydrolysis generates the imino-diacetic sodium salt, produced simultaneously ammonia condensing reflux is to reactor, and ammonia tail gas water absorbs into ammoniacal liquor; After ammonia has taken off, to react feed liquid vacuum suction acidolysis still, being cooled to and slowly dripping weight part after 80 ℃ of temperature is the concentrated hydrochloric acid of 1.7-1.8, generate imino-one sodium salt, drip hydrochloric acid and add gac again, filter out active breeze then, filtrate is to crystallization kettle, continue to drip 31% concentrated hydrochloric acid of 0.7-0.8 weight part, cooling is discharged to suction filtration then simultaneously, is the iminodiethanoic acid filter cake behind the centrifuge dripping, filtrate enters concentration kettle, squeezes into the crystallization kettle recycled after dehydration back suction filtration is removed sodium-chlor;
(2), pmida98 is synthetic: with the iminodiethanoic acid that makes, concentrated hydrochloric acid that weight part is 1.2-1.4, phosphorous acid that weight part is 0.6-0.7, water that weight part is 0.5-1.5 add contract and still in, temperature rising reflux, evenly dripping weight part is the formaldehyde of 0.2-0.4, and 105 ℃-110 ℃ of controlled temperature refluxed 2.5 hours, heat up then after the depickling, cooling is separated out the pmida98 crystal, is discharged to suction filtration, centrifuge dripping obtains wet product pmida98, and filtrate is squeezed into to contracting and still is applied mechanically;
(3), glyphosate is synthetic: adding weight part in stills for air blowing is the water of 1.3-1.5, the wet product pmida98 that makes, weight part is the sodium wolframate of 0.005-0.007, slowly heat up, when temperature in the kettle rises to 56-58 ℃, drip weight part and be 0.8-1.2 hydrogen peroxide, drip slowly evenly, 56-58 ℃ of temperature in the kettle control drips and finishes, and continues insulation reaction in this temperature range, reaction solution becomes clarification gradually, be discharged to reduction kettle, being cooled to after 30 ℃ of the certain temperatures beginning, slowly to drip weight part be the ferrous sulfate of 0.04-0.05, control reaction temperature＜40 ℃, reaction times is 2-3 hour; After dropping finishes, continue to stir, cooling, centrifugal then, centrifugal gained filter cake carries out drying, gets glyphosate.
2. process for synthesizing glyphosate according to claim 1 is characterized in that: may further comprise the steps:
(1), iminodiethanoic acid is synthetic: add weight part and be 1.87 ammoniacal liquor and weight part in reactor and be 2.166 alkali aqueous solution, add weight part again and be the 45%-55% of 0.702 iminodiacetonitrile amount, continue remaining dropping iminodiacetonitrile, be warmed up to 100-105 ℃ after dripping, hydrolysis generates the imino-diacetic sodium salt, produced simultaneously ammonia condensing reflux is to reactor, and ammonia tail gas water absorbs into ammoniacal liquor; After ammonia has taken off, will react feed liquid vacuum suction acidolysis still, be cooled to≤slowly to drip weight part after 80 ℃ and be 1.704 mass concentration be 31% hydrochloric acid, generate imino-one sodium salt, drip hydrochloric acid and add gac again, filter out active breeze then, filtrate is to crystallization kettle, continue to drip the concentrated hydrochloric acid of 0.8 weight part, cooling is discharged to suction filtration simultaneously, is the iminodiethanoic acid filter cake behind the centrifuge dripping, filtrate enters concentration kettle, squeezes into the crystallization kettle recycled after dehydration back suction filtration is removed sodium-chlor;
(2), pmida98 is synthetic: with iminodiethanoic acid, the weight part that makes be 1.272 mass concentration be 31% hydrochloric acid, weight part be 0.65 phosphorous acid, weight part be 0.958 water add contract and still in, heat up, by contracting and the still condenser refluxes; Evenly drip weight part then and be 0.259 formaldehyde, 105 ℃-110 ℃ of controlled temperature refluxed 2.5 hours, and after the intensification depickling, cooling is separated out the pmida98 crystal, is discharged to suction filtration, and the solid centrifuge dripping obtains wet product pmida98, and filtrate is squeezed into to contracting and still is applied mechanically;
(3), glyphosate is synthetic: the adding weight part is 1.345 water in stills for air blowing, the pmida98 that makes, weight part are 0.006 sodium wolframate, slowly heat up, when temperature in the kettle rises to 57 ℃, dripping weight part and be 0.977 mass concentration is 27.5% hydrogen peroxide, 57 ℃ of temperature in the kettle controls, drip and finish, continuation is insulation reaction in this temperature range, reaction solution becomes clarification gradually, is discharged to reduction kettle, and being cooled to beginning behind certain temperature＜30 ℃, slowly to drip weight part be 0.045 ferrous sulfate, control reaction temperature＜40 ℃, the reaction times is 2-3 hour; After the dropping end, continue to stir, cooling, centrifugal then, centrifugal gained filter cake carries out drying, gets glyphosate, and filtrate concentrates, and gets gyphosate solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN200910185462A CN101709064A (en) | 2009-11-13 | 2009-11-13 | Process for synthesizing glyphosate |
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| CN200910185462A CN101709064A (en) | 2009-11-13 | 2009-11-13 | Process for synthesizing glyphosate |
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| CN101709064A true CN101709064A (en) | 2010-05-19 |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891764A (en) * | 2010-06-30 | 2010-11-24 | 湖北汇达科技发展有限公司 | Method for preparing N-phosphonomethyliminodiacetic acid |
| CN102343210A (en) * | 2011-09-28 | 2012-02-08 | 临海市利民化工有限公司 | Method for comprehensively recycling SO2 in waste ammonia gas and flue gas generated by thiophene acetic acid |
| CN102351587A (en) * | 2011-06-27 | 2012-02-15 | 西南大学 | Methods for producing high efficiency fertilizer by using iminodiacetonitrile and waste mother liquor thereof |
| CN102382136A (en) * | 2010-08-30 | 2012-03-21 | 张抱东 | Novel hydrogen peroxide oxidation process for glyphosate |
| CN102627666A (en) * | 2012-03-23 | 2012-08-08 | 江苏好收成韦恩农化股份有限公司 | Method for synthesis of N-(phosphonomethyl) iminodiacetic acid |
| CN102649799A (en) * | 2011-02-23 | 2012-08-29 | 重庆紫光化工股份有限公司 | Preparation method for glyphosate |
| CN102952159A (en) * | 2012-11-14 | 2013-03-06 | 江苏泰仓农化有限公司 | Process for preparing glyphosate intermediate N-Phosphonomethyl iminodiacetic acid by applying N-Phosphonomethyl iminodiacetic acid waste water |
| CN103232355A (en) * | 2013-04-25 | 2013-08-07 | 重庆紫光化工股份有限公司 | Environmentally-friendly clean production method of iminodiacetic acid |
| CN104098602A (en) * | 2014-07-08 | 2014-10-15 | 重庆紫光化工股份有限公司 | Energy-saving and clean production method of PMIDA |
| CN104447863A (en) * | 2014-12-09 | 2015-03-25 | 安徽工业大学 | Method for preparing N-(Phosphonomethyl)iminodiacetic acid |
| CN105693767A (en) * | 2016-03-19 | 2016-06-22 | 安徽东至广信农化有限公司 | Production technology of glyphosate |
| CN107501109A (en) * | 2017-07-17 | 2017-12-22 | 南通光荣化工有限公司 | A kind of iminodiacetic acid (salt) acid treating Preparation Method |
| CN107522738A (en) * | 2017-07-13 | 2017-12-29 | 安徽东至广信农化有限公司 | A kind of synthesis technique of glyphosate |
| CN108912168A (en) * | 2018-08-10 | 2018-11-30 | 泰兴市飞天化工有限公司 | A method of preparing pmida |
-
2009
- 2009-11-13 CN CN200910185462A patent/CN101709064A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891764A (en) * | 2010-06-30 | 2010-11-24 | 湖北汇达科技发展有限公司 | Method for preparing N-phosphonomethyliminodiacetic acid |
| CN102382136A (en) * | 2010-08-30 | 2012-03-21 | 张抱东 | Novel hydrogen peroxide oxidation process for glyphosate |
| CN102649799A (en) * | 2011-02-23 | 2012-08-29 | 重庆紫光化工股份有限公司 | Preparation method for glyphosate |
| CN102351587B (en) * | 2011-06-27 | 2014-06-11 | 西南大学 | Methods for producing high efficiency fertilizer by using iminodiacetonitrile and waste mother liquor thereof |
| CN102351587A (en) * | 2011-06-27 | 2012-02-15 | 西南大学 | Methods for producing high efficiency fertilizer by using iminodiacetonitrile and waste mother liquor thereof |
| CN102343210A (en) * | 2011-09-28 | 2012-02-08 | 临海市利民化工有限公司 | Method for comprehensively recycling SO2 in waste ammonia gas and flue gas generated by thiophene acetic acid |
| CN102627666A (en) * | 2012-03-23 | 2012-08-08 | 江苏好收成韦恩农化股份有限公司 | Method for synthesis of N-(phosphonomethyl) iminodiacetic acid |
| CN102952159A (en) * | 2012-11-14 | 2013-03-06 | 江苏泰仓农化有限公司 | Process for preparing glyphosate intermediate N-Phosphonomethyl iminodiacetic acid by applying N-Phosphonomethyl iminodiacetic acid waste water |
| CN103232355A (en) * | 2013-04-25 | 2013-08-07 | 重庆紫光化工股份有限公司 | Environmentally-friendly clean production method of iminodiacetic acid |
| CN104098602A (en) * | 2014-07-08 | 2014-10-15 | 重庆紫光化工股份有限公司 | Energy-saving and clean production method of PMIDA |
| CN104447863A (en) * | 2014-12-09 | 2015-03-25 | 安徽工业大学 | Method for preparing N-(Phosphonomethyl)iminodiacetic acid |
| CN105693767A (en) * | 2016-03-19 | 2016-06-22 | 安徽东至广信农化有限公司 | Production technology of glyphosate |
| CN107522738A (en) * | 2017-07-13 | 2017-12-29 | 安徽东至广信农化有限公司 | A kind of synthesis technique of glyphosate |
| CN107501109A (en) * | 2017-07-17 | 2017-12-22 | 南通光荣化工有限公司 | A kind of iminodiacetic acid (salt) acid treating Preparation Method |
| CN108912168A (en) * | 2018-08-10 | 2018-11-30 | 泰兴市飞天化工有限公司 | A method of preparing pmida |
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Application publication date: 20100519 |