CN101463044A - Mechanochemical synthesis of ammonium glyphosate preparation - Google Patents
Mechanochemical synthesis of ammonium glyphosate preparation Download PDFInfo
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- CN101463044A CN101463044A CNA2008102498618A CN200810249861A CN101463044A CN 101463044 A CN101463044 A CN 101463044A CN A2008102498618 A CNA2008102498618 A CN A2008102498618A CN 200810249861 A CN200810249861 A CN 200810249861A CN 101463044 A CN101463044 A CN 101463044A
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Abstract
The invention provides a mechanochemical synthesis method of a glyphosate ammonium preparation. The mechanochemical synthesis method is characterized by comprising the following steps: putting glyphosate acid and ammonium carbonate with an equivalent proportion or an excessive proportion into grinding equipment for a grinding reaction; adding an auxiliary agent or a filling material during or after the reaction, wherein, the weight ratio of the glyphosate acid, the auxiliary agent and the filling material is 100:0-50:0-100; thus obtaining the glyphosate ammonium preparation. The mechanochemical synthesis method avoids the steps of adding the solvent, post-processing steps of the solvent and the like, has simpler process, and can achieve the purposes of reducing the energy consumption and improving the production efficiency.
Description
Technical field
The present invention relates to weedicide and the synthetic method thereof used on a kind of agricultural, relate in particular to the Mechanochemical synthesis of ammonium glyphosate preparation.
Technical background
Mechanochemical reaction is to utilize the reactant powder temperature and pressure that the high strength impact moment produces in grinding (as by ball milling etc.) process, causes local, inhomogeneous reaction.Issue a kind of method of biochemical reaction in other words in the effect of mechanical energy.Owing to there is not the intervention of solvent molecule, the microenvironment of reaction is different from conventional solution system, and the reactive site molecular arrangement is orderly, the reaction preference height, because concentration of reactants can reach 100%, reaction efficiency is improved significantly.Because the development of nanometer material science, mechanochemistry comes into one's own as a kind of new synthesizing mean.In recent years, mechanochemical reaction is not because easy handling relates to the use of solvent and traditional chemical engineering unit operation usually and compares, and process is simple, has begun to be used to gradually organic synthetic and decomposition.Because it meets the theory of Green Chemistry, the research of this respect receives increasing concern at home and abroad.
Glyphosate is a kind of agricultural chemicals of volume of production and marketing maximum, is wide spectrum, efficient, low toxicity and the steriland herbicide splendid with Environmental compatibility, be widely used in crop broadcast before and receive the no-tillage weeding in back.Because the glyphosate ortho acid is insoluble in water, can give full play to its drug effect after must being translated into salt, make the form of ammonium salt usually and use.
As everyone knows, the most frequently used method of synthesizing glyphosate is with behind glyphosate and the ammoniacal liquor reaction salify, makes ammonium glyphosate through operations such as concentrated, drying, pulverizing or granulations again.Perhaps add auxiliary agent, make solid preparation (mixture).CN 1503627 promptly is typical example.Similarly also have CN 1394483, CN 101172985, CN 1724547, CN 1192743, CN1365254, CN 1365252 all to adopt glyphosphonic acid and ammoniacal liquor to carry out the prepared in reaction ammonium glyphosate.CN 1462582 is a raw material with ammonium glyphosate and auxiliary agent, is equipped with the glyphosate mixture according to a conventional method.Similarly also have CN 1181881, CN 1394482 (pulvis or granule etc.).
The former powder of CN 1340508 usefulness glyphosphonic acids is made solvent and ammonia gas react with methyl alcohol, cooling crystallization method synthesizing glyphosate acid ammonium.This method adopts solvent to react and crystallization, will inevitably be because of needing increase on the energy consumption that solvent recuperation brings and the risk on the safety.
The preparation method of CN 1260349 ammonium glyphosates is: with the glyphosphonic acid is raw material, reacts with liquefied ammonia in autoclave pressure, then via the gas pressure relief slot granulation.The operation of band pressure is its disadvantage.
Also have the CN 1192742 for preparing the ammonium glyphosate method by gas-solid reaction, and gas-solid liquid phase reaction and solvent extraction prepare the CN 1445234 of ammonium glyphosate.
CN 1589628 and CN 1504093 preparation methods roughly are: the former powder of glyphosphonic acid, bicarbonate of ammonia, Secondary ammonium phosphate, alkyl polyglycoside are made glyphosate ammonium salt solid preparation through granulation after mixing again.Though whole process does not relate to solvent yet, owing to be simple mixing, glyphosphonic acid does not react with bicarbonate of ammonia as yet, and therefore when storing especially in enormous quantities the storage, having reacts emits the potentially dangerous of great amount of carbon dioxide.There is hidden danger in the stability aspect.
In a word, the method for synthesizing glyphosate ammonium salt is a lot, but not appearing in the newspapers with mechanochemical reaction synthesizing glyphosate ammonium salt.
Summary of the invention
The purpose of this invention is to provide a kind of can overcome above-mentioned defective, glyphosphonic acid and ammonium carbonate salts reaction thoroughly, the Mechanochemical synthesis of the simple ammonium glyphosate preparation of technology.
A kind of Mechanochemical synthesis of ammonium glyphosate preparation, it is characterized in that: glyphosphonic acid and ammonium carbonate salts are dropped in the grinding plant in equivalent or excessive ratio carry out griding reaction, in the process of reaction or after the reaction end, add auxiliary agent and filler, wherein the weight ratio that feeds intake of glyphosphonic acid and auxiliary agent, filler is 100:0～50:0～100, promptly gets ammonium glyphosate preparation.
For realizing goal of the invention, the Mechanochemical synthesis of described ammonium glyphosate preparation, ammonium carbonate salts are the mixture of bicarbonate of ammonia or volatile salt or both arbitrary proportions.
For realizing goal of the invention, the Mechanochemical synthesis of described ammonium glyphosate preparation, ammonium carbonate salts are the mixture of bicarbonate of ammonia or volatile salt or both arbitrary proportions, in the time of grinding, feed ammonia.
For realizing goal of the invention, the Mechanochemical synthesis of described ammonium glyphosate preparation, the glyphosate acid wet product that glyphosphonic acid dry product that the glyphosphonic acid employing has been dried or centrifuge dripping obtain.
For realizing goal of the invention, the Mechanochemical synthesis of described ammonium glyphosate preparation, auxiliary agent is the mixture of a kind of tensio-active agent and defoamer, the perhaps mixture of kinds of surface promoting agent and defoamer, defoamer is the defoamer of the commercially available non-cationic of routine, and the weight ratio that feeds intake of glyphosphonic acid, auxiliary agent, filler optimization is 100:5～25:15～40.
For realizing goal of the invention, the Mechanochemical synthesis of described ammonium glyphosate preparation, the part by weight of tensio-active agent and defoamer are 1:0.0005～0.05, and the part by weight of optimization is 1:0.01～0.03.
For realizing goal of the invention, the Mechanochemical synthesis of described ammonium glyphosate preparation, tensio-active agent comprise following three classes:
(1) nonionogenic tenside: alkyl-glucoside, castor oil polyoxyethylene ether, Span Soxylat A 25-7, alkyl polyoxyethylene ether, aliphatic acid polyethenoxy, polyoxyethylene alkylphenol ether and alkylamine Soxylat A 25-7, and corresponding ethylene oxide/propylene oxide multipolymer;
(2) anion surfactant: soap, alkyl-sulphate, hydrocarbyl sulfonate and alkyl polyoxyethylene vitriol;
(3) above-mentioned surfactant mixtures.
For realizing goal of the invention, the Mechanochemical synthesis of described ammonium glyphosate preparation, filler adopts the chemical fertilizer of nitrogenous phosphorus potassium, comprise: a kind of or any several mixture of ammonium sulfate, ammonium chloride, urea, phosphorus ammonium, vitriolate of tartar, excessive bicarbonate of ammonia or volatile salt also can be considered to a kind of filler.
Be the realization goal of the invention, the Mechanochemical synthesis of described ammonium glyphosate preparation, grinding plant adopts planetary ball mill or tubular ball mill or kneader, and the mode of grinding can be that intermittent type also can be a continous way.
The present invention compared with prior art saves the links such as aftertreatment of adding solvent and solvent, and technology is simpler, can realize cutting down the consumption of energy the purpose of enhancing productivity.
Embodiment
Under classify several embodiments of the present invention as, but the present invention is not limited to these embodiment.Directly obtain the ammonium glyphosate granule after the repressed moulding of glyphosate pulvis.Also can be by conventional means, add extrusion molding granulation after the suitable quantity of water, dry ammonium glyphosate granule.
Embodiment 1
169 parts of glyphosphonic acids and 79 parts of bicarbonate of ammonia and 8 parts of AGP (alkyl-glucoside), 50 parts of ammonium sulfate and 0.1 part of defoamer put in the mill ground 5-20 minute fast, promptly get the ammonium glyphosate salt powder.
Embodiment 2
169 parts of glyphosphonic acids and 79 parts of bicarbonate of ammonia and 18 parts of AGP, 60 parts of urea, 20 parts of ammonium chlorides and 0.2 part of defoamer put in the mill ground 5-20 minute fast, promptly get the ammonium glyphosate salt powder.
Embodiment 3
169 parts of glyphosphonic acids and 79 parts of bicarbonate of ammonia and 16 parts of alkylamine Soxylat A 25-7s, 80 parts of ammonium sulfate and 0.4 part of defoamer put in the mill ground 5-20 minute fast, promptly get the ammonium glyphosate salt powder.
Embodiment 4
169 parts of glyphosphonic acids and 48 parts of volatile salts and 4 parts of AGP, 10 parts of alkylamine Soxylat A 25-7s, 20 parts of ammonium sulfate, 60 parts of ammonium chlorides and 0.2 part of defoamer put in the mill ground 5-20 minute fast, promptly get the ammonium glyphosate salt powder.
Embodiment 5
169 parts of glyphosphonic acids and 79 parts of bicarbonate of ammonia and 6 parts of AGP, 2 parts of OP-10 (a kind of polyoxyethylene alkylphenol ether), 10 parts of ammonium sulfate, 50 parts of ammonium chlorides and 0.2 part of defoamer put in the mill ground 5-20 minute fast, promptly get the ammonium glyphosate salt powder.
Embodiment 6
169 parts of wet product in (being converted into 100%) glyphosphonic acid workshop and 48 parts of volatile salts and 8 parts of AGP, 15 parts of ammonium sulfate, 50 parts of diammonium phosphate and 0.2 part of defoamer are put in the mill quick grinding 5-20 minute, feed 2 parts of ammonias when grinding, the complete ammonium glyphosate mistura salina that promptly gets of reaction.
Embodiment 7
169 parts of wet product in (being converted into 100%) glyphosphonic acid workshop and 85 parts of bicarbonate of ammonia and 30 parts of AGP, 150 parts of ammonium sulfate and 0.5 part of defoamer are put in the mill quick grinding 5-20 minute, promptly get the ammonium glyphosate mistura salina.
Embodiment 8
169 parts of wet product in (being converted into 100%) glyphosphonic acid workshop and 90 parts of bicarbonate of ammonia and 20 parts of AGP, 40 parts of vitriolate of tartar, 80 parts of ammonium sulfate and 0.4 part of defoamer are put in the mill quick grinding 5-20 minute, promptly get the ammonium glyphosate mistura salina.
Embodiment 9
169 parts of glyphosphonic acids and 79 parts of bicarbonate of ammonia and 4 parts of sodium oleates, 4 parts of AGP, 4 parts of K-12 (a kind of alkyl-sulphate), 40 parts of urea, 20 parts of ammonium chlorides and 0.2 part of defoamer put in the mill ground 5-20 minute fast, promptly get the ammonium glyphosate salt powder.
Embodiment 10
169 parts of glyphosphonic acids and 53 parts of volatile salts and 4 parts of AES ammonium salts (a kind of alkyl polyoxyethylene vitriol), 4 parts of AGP, 4 parts of sodium alkyl benzene sulfonates (a kind of hydrocarbyl sulfonate), 40 parts of urea, 20 parts of ammonium chlorides and 0.2 part of defoamer are put in the mill and ground 5-20 minute fast, promptly get the ammonium glyphosate salt powder.
Embodiment 11
169 parts of glyphosphonic acids and 79 parts of bicarbonate of ammonia and 4 parts of sodium oleates, 4 parts of peregals-20 (a kind of alkyl polyoxyethylene ether), 4 parts of alkylamine Soxylat A 25-7s, 40 parts of urea, 20 parts of ammonium chlorides and 0.4 part of defoamer are put in the mill ground 5-20 minute fast, promptly get the ammonium glyphosate salt powder.
Embodiment 12
169 parts of glyphosphonic acids and 79 parts of bicarbonate of ammonia and 2 parts of ammonium oleates, 4 parts of alkylamine Soxylat A 25-7s, 4 parts of AGP, 40 parts of urea, 20 parts of ammonium chlorides and 0.3 part of defoamer put in the mill ground 5-20 minute fast, promptly get the ammonium glyphosate salt powder.
Embodiment 13
169 parts of glyphosphonic acids, 40 parts of bicarbonate of ammonia and 25 parts of volatile salts and 4 parts of sodium oleates, 4 parts of alkylamine Soxylat A 25-7s, 4 parts of AGP, 40 parts of urea, 20 parts of ammonium chlorides and 0.3 part of defoamer put in the mill ground 5-20 minute fast, promptly get the ammonium glyphosate salt powder.
Embodiment 14
169 parts of glyphosphonic acids and 79 parts of bicarbonate of ammonia and 4 parts of AGP (alkyl-glucoside), 60 parts of ammonium sulfate and 0.004 part of defoamer put in the mill ground 5-20 minute fast, promptly get the ammonium glyphosate salt powder.
Embodiment 15
169 parts of glyphosphonic acids and 79 parts of bicarbonate of ammonia are put into quick the grinding 5-20 minute in the mill, promptly get ammonium glyphosate.
Embodiment 16
169 parts of glyphosphonic acids and 48 parts of volatile salts are put into quick the grinding 5-20 minute in the mill, promptly get ammonium glyphosate.
Claims (10)
1, a kind of Mechanochemical synthesis of ammonium glyphosate preparation, it is characterized in that: glyphosphonic acid and ammonium carbonate salts are dropped in the grinding plant in equivalent or excessive ratio carry out griding reaction, in the process of reaction or after the reaction end, add auxiliary agent and filler, wherein the weight ratio that feeds intake of glyphosphonic acid and auxiliary agent, filler is 100:0～50:0～100, promptly gets ammonium glyphosate preparation.
2, the Mechanochemical synthesis of ammonium glyphosate preparation as claimed in claim 1 is characterized in that: ammonium carbonate salts is the mixture of bicarbonate of ammonia or volatile salt or both arbitrary proportions.
3, the Mechanochemical synthesis of ammonium glyphosate preparation as claimed in claim 1 is characterized in that: ammonium carbonate salts is the mixture of bicarbonate of ammonia or volatile salt or both arbitrary proportions, in the time of grinding, feeds ammonia.
4, the Mechanochemical synthesis of ammonium glyphosate preparation as claimed in claim 1 is characterized in that: the glyphosate acid wet product that glyphosphonic acid dry product that the glyphosphonic acid employing has been dried or centrifuge dripping obtain.
5, the Mechanochemical synthesis of ammonium glyphosate preparation as claimed in claim 1, it is characterized in that: auxiliary agent is the mixture of a kind of tensio-active agent and defoamer, the perhaps mixture of kinds of surface promoting agent and defoamer, defoamer are the defoamer of conventional commercially available non-cationic.
6, the Mechanochemical synthesis of ammonium glyphosate preparation as claimed in claim 1 is characterized in that: the weight ratio that feeds intake of glyphosphonic acid, auxiliary agent, filler optimization is 100:5～25:15～40.
7, the Mechanochemical synthesis of ammonium glyphosate preparation as claimed in claim 5 is characterized in that: the part by weight of tensio-active agent and defoamer is 1:0.0005～0.05, and the part by weight of optimization is 1:0.01～0.03.
8, the Mechanochemical synthesis of ammonium glyphosate preparation as claimed in claim 1 is characterized in that tensio-active agent comprises following three classes:
(1) nonionogenic tenside: alkyl-glucoside, castor oil polyoxyethylene ether, Span Soxylat A 25-7, alkyl polyoxyethylene ether, aliphatic acid polyethenoxy, polyoxyethylene alkylphenol ether and alkylamine Soxylat A 25-7, and corresponding ethylene oxide/propylene oxide multipolymer;
(2) anion surfactant: soap, alkyl-sulphate, hydrocarbyl sulfonate and alkyl polyoxyethylene vitriol;
(3) above-mentioned surfactant mixtures.
9, the Mechanochemical synthesis of ammonium glyphosate preparation as claimed in claim 1, it is characterized in that: filler adopts the chemical fertilizer of nitrogenous phosphorus potassium, comprise: a kind of or any several mixture of ammonium sulfate, ammonium chloride, urea, phosphorus ammonium, vitriolate of tartar, excessive bicarbonate of ammonia or volatile salt also can be considered to a kind of filler.
10, the Mechanochemical synthesis of ammonium glyphosate preparation as claimed in claim 1 is characterized in that: grinding plant adopts planetary ball mill or tubular ball mill or kneader, and the mode of grinding can be that intermittent type also can be a continous way.
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| CN2008102498618A CN101463044B (en) | 2008-12-27 | 2008-12-27 | Mechanochemical synthesis of ammonium glyphosate preparation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102640749A (en) * | 2012-04-11 | 2012-08-22 | 印海平 | Preparation method of ammonium salt granules |
| CN110818577A (en) * | 2019-11-07 | 2020-02-21 | 南京威尔生物化学有限公司 | Preparation method and application of glyphosate granule auxiliary agent with high drug effect |
| CN112221424A (en) * | 2020-10-14 | 2021-01-15 | 浙江新安化工集团股份有限公司 | System and method for continuously producing ammonium glyphosate granules |
| CN115594712A (en) * | 2022-10-08 | 2023-01-13 | 湖北泰盛化工有限公司（Cn） | Gas-solid heterogeneous glyphosate continuous ammoniation method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1225979C (en) * | 2002-12-04 | 2005-11-09 | 四川贝尔实业有限责任公司 | Solid soluble glyphosate formulation |
| CN1242676C (en) * | 2003-08-25 | 2006-02-22 | 四川迪美特生物科技有限公司 | Glyphosate ammonium salt solid preparation and its making method |
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2008
- 2008-12-27 CN CN2008102498618A patent/CN101463044B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102640749A (en) * | 2012-04-11 | 2012-08-22 | 印海平 | Preparation method of ammonium salt granules |
| CN110818577A (en) * | 2019-11-07 | 2020-02-21 | 南京威尔生物化学有限公司 | Preparation method and application of glyphosate granule auxiliary agent with high drug effect |
| CN112221424A (en) * | 2020-10-14 | 2021-01-15 | 浙江新安化工集团股份有限公司 | System and method for continuously producing ammonium glyphosate granules |
| CN112221424B (en) * | 2020-10-14 | 2022-04-15 | 浙江新安化工集团股份有限公司 | System and method for continuously producing ammonium glyphosate granules |
| CN115594712A (en) * | 2022-10-08 | 2023-01-13 | 湖北泰盛化工有限公司（Cn） | Gas-solid heterogeneous glyphosate continuous ammoniation method |
| CN115594712B (en) * | 2022-10-08 | 2023-12-19 | 湖北泰盛化工有限公司 | Method for continuously ammonifying gas-solid heterogeneous glyphosate |
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| CN101463044B (en) | 2011-01-26 |
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Application publication date: 20090624 Assignee: Hubei Taisheng Chemical Co.,Ltd. Assignor: Zhejiang jinfanda Biochemical Technology Co., Ltd.|Hangzhou Limited by Share Ltd tetrahedron Contract record no.: 2014990000388 Denomination of invention: Mechanochemical synthesis of ammonium glyphosate preparation Granted publication date: 20110126 License type: Common License Record date: 20140609 |
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