CN1340508A - Process for synthesizing ammonium glyphosphonate - Google Patents
Process for synthesizing ammonium glyphosphonate Download PDFInfo
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- CN1340508A CN1340508A CN 00125934 CN00125934A CN1340508A CN 1340508 A CN1340508 A CN 1340508A CN 00125934 CN00125934 CN 00125934 CN 00125934 A CN00125934 A CN 00125934A CN 1340508 A CN1340508 A CN 1340508A
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- glyphosphonate
- ammonium
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- glyphosate
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Abstract
A process for synthesizing ammonium glyphosphonate includes adding alcohol, ether, arylhydrocarbone and alkylhydrocarbon or organic solvent-water mixture to reactor, adding glyphosate and ammonia gas, reaction at 10-50 deg.c for 2-8 hr, then cooling to 15-20 deg.C, taking the precipitated crystal, and drying to obtain ammonium glyphosphonate; returning mother liquid to the system for reusing it 6-15 times, and distilling the last mother liquid to obtain ammonium glyphosphonate. Its advantages include simple process, high quality and high yield.
Description
The present invention relates to the preparation of the preparation of glyphosate salt, particularly ammonium glyphosate.
Glyphosate is the organophosphorus bud rear defence grass agent of a kind of efficient, wide spectrum, low toxicity, interior suction, safety.Because of it has good interior suction conductive performance, very effective to preventing and kill off of multiple dark root malignant weed, farming, woods, herd, aspect such as garden has a extensive future.This product is one of pesticide species of present maximum tonnage in the world.
10% gyphosate solution is arranged, 41% glyphosate isopropyl amine salt aqua, preparations such as 62% glyphosate isopropyl amine salt aqua and 30% soluble glyphosate pulvis in the anti-careless agent of present domestic glyphosate class.Along with domestic and international glyphosate products scale constantly enlarges, quality improves constantly, and competition is growing more intense, and the glyphosate formulation product development turns to high-content, pollution-freeization direction to develop.By glyphosate synthesizing glyphosate ammonium salt, be processed into the soluble powder product, have advantages such as drug effect height, the transport and storage cost is low, easy to use, environmental pollution is few.
Application number 96196134.1, the application for a patent for invention prospectus of publication number CN1192743A have disclosed the method with glyphosphonic acid and the aqua ammonia aqueous solution (ammoniacal liquor) prepared in reaction ammonium glyphosate.Because ammoniacal liquor contains big water gaging, so this method technology is complicated, palpus successive drying in the whole process that ammoniacal liquor adds, to keep suitable water content, and need strict control ammoniacal liquor to add speed, it is fast to drive away moisture content speed ratio introducing moisture content speed in the assurance system, need timing sampling assay determination water content thus, and product also needs drying treatment.
Application number 96196133.3, the application for a patent for invention prospectus of publication number CH1192742A has disclosed the method with glyphosphonic acid and anhydrous ammonia gas prepared in reaction ammonium glyphosate, this method need adopt " cleaning-type automatically " reactor, require set " thruster " maintenance precise measure in the reactor, can strike off sedimentary product on the wall continuously, otherwise on wall, form the solid lining, can influence reaction heat and remove.And want strict control ammonia to add speed, guarantee that ammonia and glyphosphonic acid are incorporated in the reactor in complete homodisperse mode, ammonia enter the mouth improper easy formation inlet the dirt plug and generate and gather blocks of solid, product must be dried pulverizing.
Adopt glyphosate and liquefied ammonia prepared in reaction ammonium glyphosate by No. 99119971.5 patent applications that the applicant proposes, require to be reflected in the autoclave pressure to carry out.
The objective of the invention is to provides a kind of technology simple for overcoming above-mentioned defective, constant product quality, yield height, the process for synthesizing ammonium glyphosphonate that can react under lower pressure.
Process for synthesizing ammonium glyphosphonate of the present invention, its special character be in reactor, add organic solvent, glyphosate and ammonia in 10～50 ℃ the reaction 2～8 hours after, make the reaction solution cooling take out the crystallisate of wherein separating out, this crystallisate drying gets the product ammonium glyphosate.
The mother liquor that takes out behind the crystallisate contains solvent and a small amount of ammonium glyphosate, and this mother liquor can return to be made solvent and continue batch reaction down, replenishes an amount of solvent simultaneously to supply the deficiency of solvent due to the partial mother liquid loss.
Described mother liquor can return as solvent cycle and apply mechanically 6～15 batches, and the last batch of mother liquor is handled through distillation, takes out ammonium glyphosate wherein.
Solvent of the present invention is alcohol, ether, aromatic hydrocarbons, alkane or the water-content organic solvent-water mixed liquid less than 25% (W/W).
Described solvent is preferably methyl alcohol, ethanol, sherwood oil, toluene, dimethylbenzene or hexanaphthene.
The preferred temperature of reaction of the present invention is 20～40 ℃, and the reaction times is 2.5～4 hours.
Reaction solution can be cooled to 15～20 ℃ after the present invention's reaction, take out crystallisate wherein.
The crystallisate that is taken out, available pallet baker, revolution double cone dryer or ebullated bed baker are carried out dry, and the solvent of removing is recycling after condensation is reclaimed.
The present invention is owing to be to react synthesizing glyphosate acid ammonium with glyphosate and ammonia in organic solvent, reaction can be carried out under normal temperature, normal pressure or 0-0.5MPa pressure, so reaction process is simple, easy and simple to handle, running cost is low, show that through test, mensuration product yield of the present invention can reach more than 97%; The present invention has product separation, the dry characteristics that are easy to simultaneously.
Specify synthesis technique of the present invention with embodiment below.
Embodiment 1 gets the former powder of 170g glyphosate (purity 95%), drop in the 1000ml four-hole boiling flask, in wherein injecting 500ml methyl alcohol, it is 1～2 times ammonia of glyphosate that whipped state feeds mole number down, control reaction temperature is about 25 ℃, and stirring reaction made reaction solution be cooled to 20 ℃ after 3 hours, suction filtration takes out the crystallisate that folds, and this crystallisate drying gets the product ammonium glyphosate.
Embodiment 2 processs of the test and equipment add 100g water with example 1 before the reaction in addition in system.
Embodiment 3 processs of the test and equipment replace methyl alcohol to make solvent with example 1 with industrial alcohol.
Embodiment 4 processs of the test and equipment replace methyl alcohol to make solvent with example 1 with sherwood oil (90 ℃ of boiling points).
Embodiment 5 processs of the test and equipment replace the methyl alcohol solvent with example 1 with toluene.
Embodiment 6 processs of the test and equipment replace the methyl alcohol solvent with example 1 with dimethylbenzene.
Embodiment 7 processs of the test and equipment replace methyl alcohol to make solvent with example 1 with hexanaphthene.
Embodiment 8 returns down batch reaction with the mother liquor that reclaims with solvent on example 1 basis.
Embodiment 9 processes and equipment are with example 8, and mother liquor returns recycle and is no less than 5 times, replenish an amount of methyl alcohol to solvent at every turn when utilizing and reach 500ml.
Following table provides above embodiment product purity (weight percentage) and yield, and yield is in glyphosate (purity 95%).
| Embodiment | Ammonium glyphosate (%) | Yield (%) |
| ????1 | ?????94.65 | ?????98.0 |
| ????2 | ?????94.76 | ?????97.8 |
| ????3 | ?????94.54 | ?????97.5 |
| ????4 | ?????94.76 | ?????98.0 |
| ????5 | ?????95.0 | ?????98.5 |
| ????6 | ?????94.43 | ?????98.3 |
| ????7 | ?????94.62 | ?????98.1 |
| ????8 | ?????94.62 | ?????97.9 |
| ????9 | ?????94.55 | ?????98.1 |
Embodiment 10 processes and equipment are with example 1～example 9 any examples, and temperature of reaction changes 10 ℃ into, and the reaction times changes 10 hours into.
Embodiment 11 processes and equipment are with example 1～example 9 any examples, and temperature of reaction changes 15 ℃ into, and the reaction times changes 8 hours into.
Embodiment 12 processes and equipment are with example 1～example 9 any examples, and temperature of reaction changes 20 ℃ into, and the reaction times changes 5 hours into.
Embodiment 13 processes and equipment are with example 1～example 9 any examples, and temperature of reaction changes 30 ℃ into, and the reaction times changes 3 hours into.
Embodiment 14 processes and equipment are with example 1～example 9 any examples, and temperature of reaction changes 35 ℃ into, and the reaction times changes 2.5 hours into.
Embodiment 15 processes and equipment are with example 1～example 9 any examples, and temperature of reaction changes 40 ℃ into, and the reaction times changes 2.5 hours into.
Embodiment 16 processes and equipment are with example 1～example 9 any examples, and temperature of reaction changes 50 ℃ into, and the reaction times changes 2 hours into.
Embodiment 17 processes and equipment add water 50g with example 1～example 9 any examples in the reacting precursor system in addition, and temperature of reaction is any temperature in 20～40 ℃, and the reaction times is any time in 2～8 hours.
Show constant product quality of the present invention, embodiment 10～17 product purities and yield and example 1～example 9 basic identical after tested.
Claims (7)
1, process for synthesizing ammonium glyphosphonate is characterized in that adding organic solvent, glyphosate and ammonia and after 2～8 hours, makes the reaction solution cooling take out the crystallisate of wherein separating out in 10～50 ℃ of reactions in reactor, this crystallisate drying gets the product ammonium glyphosate.
2, process for synthesizing ammonium glyphosphonate as claimed in claim 1, the mother liquor that it is characterized in that taking out crystallisate return to be made solvent and continues following batch of described reaction.
3, process for synthesizing ammonium glyphosphonate as claimed in claim 2 is characterized in that mother liquor returns as solvent cycle to apply mechanically 6～15 batches that the last batch of mother liquor is handled through distillation, takes out ammonium glyphosate wherein.
4,, it is characterized in that described solvent is alcohol, ether, aromatic hydrocarbons, alkane or the water-content organic solvent-water mixed liquid less than 25% (W/W) as claim 1,2 or 3 described process for synthesizing ammonium glyphosphonate.
5,, it is characterized in that described solvent is methyl alcohol, ethanol, sherwood oil, toluene, dimethylbenzene or hexanaphthene as claim 1,2 or 3 described process for synthesizing ammonium glyphosphonate.
6, process for synthesizing ammonium glyphosphonate as claimed in claim 4 is characterized in that temperature of reaction is 20～40 ℃, and the reaction times is 2.5～4 hours.
7, process for synthesizing ammonium glyphosphonate as claimed in claim 6 is characterized in that making reaction solution be cooled to 15～20 ℃ after the reaction, takes out crystallisate wherein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001259342A CN1165541C (en) | 2000-08-31 | 2000-08-31 | Process for synthesizing ammonium glyphosphonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001259342A CN1165541C (en) | 2000-08-31 | 2000-08-31 | Process for synthesizing ammonium glyphosphonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1340508A true CN1340508A (en) | 2002-03-20 |
| CN1165541C CN1165541C (en) | 2004-09-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001259342A Expired - Lifetime CN1165541C (en) | 2000-08-31 | 2000-08-31 | Process for synthesizing ammonium glyphosphonate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004022570A1 (en) * | 2002-09-05 | 2004-03-18 | Zhejiang Xinan Chemical Industrial Group Co. Ltd. | Preparation of solid ammonium glyphosate using organic solvent in extraction |
| CN1308335C (en) * | 2004-04-09 | 2007-04-04 | 浙江新安化工集团股份有限公司 | Recovering and utilizing method of glyphosate neutralizing mother liquid |
| CN101947434A (en) * | 2010-09-10 | 2011-01-19 | 北京化工大学 | Lamellar zirconium glyphosate using as lead-ion absorbing material |
| WO2015062286A1 (en) * | 2013-10-30 | 2015-05-07 | Rotam Agrochem International Company Limited | Process for preparation of herbicidal carboxylic acid salts |
| US9221853B2 (en) | 2009-12-09 | 2015-12-29 | Zhejiang Wynca Chemical Industry Group Co., Ltd. | Glyphosate dimethylamine salt crystal, preparation method and use thereof |
-
2000
- 2000-08-31 CN CNB001259342A patent/CN1165541C/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004022570A1 (en) * | 2002-09-05 | 2004-03-18 | Zhejiang Xinan Chemical Industrial Group Co. Ltd. | Preparation of solid ammonium glyphosate using organic solvent in extraction |
| US7435847B2 (en) | 2002-09-05 | 2008-10-14 | Zhejiang Xin' | Preparation of solid ammonium glyphosate using organic solvent in extraction |
| AU2003261610B2 (en) * | 2002-09-05 | 2009-06-25 | Zhejiang Xinan Chemical Industrial Group Co. Ltd. | Preparation of solid ammonium glyphosate using organic solvent in extraction |
| CN1308335C (en) * | 2004-04-09 | 2007-04-04 | 浙江新安化工集团股份有限公司 | Recovering and utilizing method of glyphosate neutralizing mother liquid |
| US9221853B2 (en) | 2009-12-09 | 2015-12-29 | Zhejiang Wynca Chemical Industry Group Co., Ltd. | Glyphosate dimethylamine salt crystal, preparation method and use thereof |
| CN101947434A (en) * | 2010-09-10 | 2011-01-19 | 北京化工大学 | Lamellar zirconium glyphosate using as lead-ion absorbing material |
| CN101947434B (en) * | 2010-09-10 | 2012-10-31 | 北京化工大学 | Lamellar zirconium glyphosate using as lead-ion absorbing material |
| WO2015062286A1 (en) * | 2013-10-30 | 2015-05-07 | Rotam Agrochem International Company Limited | Process for preparation of herbicidal carboxylic acid salts |
| CN105705481A (en) * | 2013-10-30 | 2016-06-22 | 龙灯农业化工国际有限公司 | Process for preparation of hrrbicidal carboxylic acid salts |
| US10011552B2 (en) | 2013-10-30 | 2018-07-03 | Rotam Agrochem International Company Limited | Process for preparation of herbicidal carboxylic acid salts |
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| Publication number | Publication date |
|---|---|
| CN1165541C (en) | 2004-09-08 |
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Granted publication date: 20040908 |