CN1165541C - Process for synthesizing ammonium glyphosphonate - Google Patents
Process for synthesizing ammonium glyphosphonate Download PDFInfo
- Publication number
- CN1165541C CN1165541C CNB001259342A CN00125934A CN1165541C CN 1165541 C CN1165541 C CN 1165541C CN B001259342 A CNB001259342 A CN B001259342A CN 00125934 A CN00125934 A CN 00125934A CN 1165541 C CN1165541 C CN 1165541C
- Authority
- CN
- China
- Prior art keywords
- glyphosphonate
- ammonium
- reaction
- glyphosate
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- 230000008569 process Effects 0.000 title claims description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 19
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005562 Glyphosate Substances 0.000 claims abstract description 15
- 229940097068 glyphosate Drugs 0.000 claims abstract description 15
- 239000012452 mother liquor Substances 0.000 claims abstract description 10
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- PDYXIVPKOMYDOK-UHFFFAOYSA-N Glyphosate-monoammonium Chemical compound [NH4+].OC(=O)CNCP(O)([O-])=O PDYXIVPKOMYDOK-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 239000002178 crystalline material Substances 0.000 abstract 3
- 239000004009 herbicide Substances 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- ZEKANFGSDXODPD-UHFFFAOYSA-N glyphosate-isopropylammonium Chemical compound CC(C)N.OC(=O)CNCP(O)(O)=O ZEKANFGSDXODPD-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 244000144980 herd Species 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000003211 malignant effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
The present invention relates to a technique for synthesizing ammonium glyphosphonate. Solvents of alcohol, ether, aromatic hydrocarbon and alkane or organic solvent-water mixed liquor with the water content less than 25%(W/W) is added in a reactor, glyphosate and ammonia are added to react for 2 to 8 hours at the temperature of 10 to 50 DEG C, the reaction liquor is cooled to 15-20 DEG C, and the precipitated crystalline material is taken out. The crystalline material is dried, and thus, the product of ammonium glyphosphonate is prepared. The mother liquor of the crystalline material is taken out to return back to the reactor and serve as solvent to go on the next batch of reaction, and is circularly used for 6 to 15 times, the final batch of mother liquid is distilled, and the ammonium glyphosphonate is taken out. The present invention is used for producing water-solubility glyphosate herbicides, the technique is simple, and the product has stable 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 CH 1192742A 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 CN1340508A (en) | 2002-03-20 |
| CN1165541C true CN1165541C (en) | 2004-09-08 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001259342A Expired - Lifetime CN1165541C (en) | 2000-08-31 | 2000-08-31 | Process for synthesizing ammonium glyphosphonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1165541C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1244587C (en) * | 2002-09-05 | 2006-03-08 | 浙江新安化工集团股份有限公司 | Gas-liquid-solid three phase reactions and solvent exraction for preparing ammonia glyphosate acid |
| 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 |
| CN101723973B (en) | 2009-12-09 | 2012-09-26 | 浙江新安化工集团股份有限公司 | Method for preparing glyphosate dimethylamine salt solid |
| CN101947434B (en) * | 2010-09-10 | 2012-10-31 | 北京化工大学 | Layered zirconium glyphosate as lead ion adsorption material |
| GB2519787B (en) | 2013-10-30 | 2018-08-29 | Rotam Agrochem Int Co Ltd | Process for the preparation of herbicidal carboxylic acid salts |
-
2000
- 2000-08-31 CN CNB001259342A patent/CN1165541C/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| CN1340508A (en) | 2002-03-20 |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
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Granted publication date: 20040908 |