CN1328283C - Method of producing ammonium glyphosate - Google Patents
Method of producing ammonium glyphosate Download PDFInfo
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- CN1328283C CN1328283C CNB2004100693529A CN200410069352A CN1328283C CN 1328283 C CN1328283 C CN 1328283C CN B2004100693529 A CNB2004100693529 A CN B2004100693529A CN 200410069352 A CN200410069352 A CN 200410069352A CN 1328283 C CN1328283 C CN 1328283C
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- glyphosate
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- ammonium salt
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Abstract
The present invention discloses a method for producing a glyphosate ammonium salt. The method for producing a glyphosate ammonium salt is characterized in that solid glyphosate acid and ammonia water are used as raw materials; the solid glyphosate acid is in a fixed phase, and the ammonia water is in a flowable phase; the ammonia water flows through the solid glyphosate acid and reacts, and the water in the flowable phase carries reaction products of glyphosate acid ammonium salt with large water solubility away in time; a glyphosate acid ammonium salt with high purity and high activity is continuously prepared. The method for producing a glyphosate ammonium salt has the advantages of high purity of the products of glyphosate acid ammonium salt, high reaction efficiency, high stability and activity of the products of glyphosate acid ammonium salt, simple production technology, little equipment investment, low production cost, large-scale and continuous production in industry, little pollution and low energy consumption.
Description
Technical field
The present invention relates to a kind of method of producing ammonium glyphosate.
Background technology
Glyphosate (chemical name: N-(phosphonomethyl) glycine, its structural formula is suc as formula shown in the I) has efficiently, does not have advantages such as residual in low toxicity and the soil as weedicide, has become the maximum and the fastest steriland herbicide of rate of growth of sales volume in the world at present.But because the solubleness of glyphosate in water is lower, 25 ℃ of per down 100 gram water can only dissolve glyphosphonic acid 1.2 grams, and general terms of settlement is to be made into salt soluble powder, emulsion or aqua.Advantages such as compare with glyphosate emulsion or aqua, it is long that glyphosate salt soluble powder product has validity period, and the transport and storage cost is low and easy to use.The glyphosate salt mainly contains sodium salt, sylvite and ammonium salt.Sodium salt has more water absorbability than ammonium salt, sylvite production cost height.Ammonium salt mainly contains glyphosphonic acid ammonium carbamate (its structural formula is suc as formula shown in the II), glyphosphonic acid isopropyl ammonium salt (its structural formula is shown in formula III) and ammonium glyphosate (its structural formula is suc as formula shown in the IV).Because the degradation production of ammonium glyphosate is the ammonia that plant can absorb, have low toxicity and advantages of environment protection, and the degradation production of ammonium carbamate and isopropyl ammonium salt ionic ammonium glyphosate is respectively high toxicity and methylamine and Isopropylamine with carcinogenesis, so ammonium glyphosate is used more extensive.
At present, there have been many patents to relate to synthetic method by glyphosphonic acid synthesizing glyphosate acid ammonium salt.Disclosedly mainly contain two classes about synthetic technology patent by glyphosphonic acid synthesizing glyphosate acid ammonium salt, the Patent publish of the first kind with the gas-solid reaction method of glyphosphonic acid and anhydrous ammonia gas prepared in reaction ammonium glyphosate, relevant patent has CN1068008; IL118576; KR257283; ZA9604774; AU704518; HU9802088; NZ306043; CA2221299; EP0832086; US5633397; WO9640697 and AU5419596.With patent CN1068008 is example, and the shortcoming of this gas-solid reaction method is that the solid product that is deposited on the reactor wall can influence in time removing of reaction heat; It is improper that ammonia adds speed control, easily forms the dirt plug of ingress.In addition, the solid ammonium salt that generates at the glyphosphonic acid solid surface can hinder the reaction of solid interior glyphosphonic acid and anhydrous ammonia gas.Can strike off precipitated solid product on the wall continuously so must install in reactor, strict control ammonia adds speed and makes raw material particulate glyphosate acid granularity as far as possible little.The patented technology of second class is to react the synthesizing glyphosate acid ammonium salt with ammonia soln and glyphosphonic acid, and relevant patent has CN1192743; CN1365254; CA2444608; EP1381278; US2002173423; WO02085122; US6734142; GR3036355T; IL118577; KR266126; ZA9604775; HU9802333; NZ307310; CA2221298; AU694877; EP0845000; US5716903; US5614468; WO9640696 and AU5662096 etc.With CN1192743 is example, this patent is reacted with glyphosphonic acid and 29% ammoniacal liquor, in order to control the water-content in the reaction system, need timing sampling analysis moisture content, strict control ammoniacal liquor adding speed and employing are warmed wind exsiccant form and are removed the water that generates in the dereaction; In order to reduce the oxidation of warm air, also need to add the antioxidant S-WAT in the reaction process to glyphosphonic acid.Obviously the shortcoming of this production technique is comparatively complicated and the power consumption height.In addition, the method (number of patent application 99119971.5, publication number CN1260349) that on November 8th, 1999, Zhejiang Xinan Chemical Industry Group Co.Ltd applied for feeding liquefied ammonia and glyphosphonic acid prepared in reaction ammonium glyphosate in autoclave pressure.This reaction is for thermopositive reaction, obviously in time removes investment that reaction heat, huge ammonia recovery system and reaction under high pressure bring and reaches hidden danger greatly and make this technology be difficult to large-scale commercial production.On August 31st, 2000, the said firm applied for the method (number of patent application 00125934.2, publication number CN1340508A) of (methyl alcohol, ethanol, sherwood oil, toluene, dimethylbenzene or naphthenic hydrocarbon) ammonia and glyphosphonic acid prepared in reaction ammonium glyphosate in organic solvent again.Obviously, these lower boilings, adding inflammable or poisonous organic solvent not only can make production cost of products increase considerably in the reaction system, and can bring such as unsafe factors such as pollution and fire.On September 5th, 2002, Zhejiang Xinan Chemical Industry Group Co.Ltd applied for making earlier glyphosphonic acid again, water and ammonia gas react, and then the patented technology (number of patent application 02141788.1) of adding organic solvent such as methyl alcohol, ethanol or methylal, similarly patent also has WO2004022570.Obviously, such technology still can make production cost of products increase considerably, and also can bring the shortcoming such as unsafe factors such as pollution and fire simultaneously.The CN1394482 patent application discloses glyphosate technicals and ammonia react, and adds the method that natural matter auxiliary agent salify prepares ammonium glyphosate, but the adding of natural matter auxiliary agent not only can make production cost improve, and the purification step of product is increased.
The same with most of organic reactions, the reaction of glyphosphonic acid and ammonia also is a kind of balanced reaction, aforesaid method all adopts the method that improves raw material ammonia concentration to promote the direction of reacting towards generating ammonium glyphosate to carry out, carrying out along with reaction, the concentration of glyphosphonic acid and ammonia has all reduced, and speed of response reduces; And still having the glyphosphonic acid and the ammonia of part not to react completely after the reaction end, reaction efficiency is low.For example, be to have adopted the method for anhydrous ammonia gas (the pure ammonia of high density) to promote to react the method for carrying out in the gas-solid reaction method with glyphosphonic acid and anhydrous ammonia gas prepared in reaction ammonium glyphosate in the patent of the first kind towards the direction that generates ammonium glyphosate; Perhaps, in autoclave pressure, feed the method (number of patent application is 00125934.2, and publication number is CN1340508) of liquefied ammonia (the pure ammonia of high density) and glyphosphonic acid prepared in reaction ammonium glyphosate; The method of in the patented technology of second class, reacting etc. with bigger ammoniacal liquor of concentration (29% ammoniacal liquor) and glyphosphonic acid.
Summary of the invention
The purpose of this invention is to provide a kind of high-efficiency and continuous, technology and simply produce the method for ammonium glyphosate.
The method of production ammonium glyphosate provided by the present invention is to be raw material with solid glyphosate acid and ammoniacal liquor, is stationary phase with solid glyphosate acid, is moving phase with ammoniacal liquor, and it is sour and react to make ammoniacal liquor flow through solid glyphosate, obtains ammonium glyphosate.
For the ease of storage and transportation, the described ammonium glyphosate that obtains can also be prepared as the ammonium glyphosate solid through steps such as dehydration and crystallizations.
In order to improve reaction efficiency and the high temperature oxidation that prevents glyphosphonic acid, and temperature of reaction system is maintained below 60 ℃, the concentration of volume percent of described ammoniacal liquor should be between 5-20%, its flow through solid glyphosate acid time or and should be controlled between 10 minutes-1.5 hours duration of contact of solid glyphosate acid, preferably between 40 minutes-70 minutes, and make the high ammoniacal liquor of concentration have slower flow velocity as far as possible.When solid glyphosate acid reduces, can add at any time, make the pack height of glyphosphonic acid in reaction tower enough high, to guarantee sufficiently long duration of contact of ammoniacal liquor and glyphosphonic acid, ammonia all in the moving phase can both total overall reaction be fallen in the exit, and building-up reactions can be carried out continuously.
The method that the present invention produces ammonium glyphosate has following advantage: 1) product ammonium glyphosate purity salt height: when mobile ammoniacal liquor of the present invention touches the solid glyphosate acid that is fixed in the reaction tower, promptly react and generate water miscible ammonium glyphosate, the ammonium glyphosate that is generated is dissolved in the water of reaction system, is taken away by water; When ammoniacal liquor flow near the reaction tower bottom, ammonia all in the ammoniacal liquor reacted completely with glyphosphonic acid, and what the reaction tower lower end flowed out is highly purified ammonium glyphosate salt brine solution substantially; And reaction raw materials is not introduced the unclassified stores that can influence product purity except ammoniacal liquor, glyphosphonic acid; 2) reaction efficiency height: although in the moving phase of the present invention the concentration of ammonia in process of flowing along with the reaction carrying out reduce gradually, but the water-soluble big ammonium glyphosate that generates can in time be taken away by water, so when the pack height of glyphosphonic acid in reaction tower is enough big or during sufficiently long duration of contact (10 minutes～1.5 hours) of ammonia in the moving phase and glyphosphonic acid, amino molecule in the system in the entire reaction tower all always with the solid glyphosate acid-respons of high density, react more complete; 3) product ammonium glyphosate salt-stable and active high: the solubleness of glyphosphonic acid per 100 gram water under 25 ℃ are 1.2 grams, it is exactly glyphosphonic acid that unique in the gained ammonium glyphosate product salt of the present invention, content is approximately 1% impurity, and the herbicidal active component of ammonium glyphosate product salt is exactly a glyphosphonic acid, make and reach 92% by product active ingredient height of the present invention; 4) production technique is simple, facility investment is little, product cost is low: the used reaction tower of the present invention is simple in structure, do not need devices such as high pressure, stirring, reaction product does not need complicated post-processing steps such as separation, adopts equipment such as existing conventional column still, prilling tower promptly can obtain the high-purity solid finished product; 5) production method of the present invention can be used for industrial large scale continuous prod; 6) pollute little, energy consumption is low: reaction raw materials ammonia can be all and the glyphosphonic acid generation ammonium glyphosate that reacts in reaction process, the water that fractionation by distillation is come out does not contain ammonia, can be directly used in the dilution of commercially available strong aqua, whole process of production can be accomplished zero release.
Description of drawings
Fig. 1 is the process flow sheet of continuous production ammonium glyphosate
Embodiment
Embodiment 1, production ammonium glyphosate
The technical process of continuous production ammonium glyphosate as shown in Figure 1,1 is reaction tower among the figure; 2 is column still; 3 is prilling tower.Reaction tower 1 bottom is provided with sieve plate 4 and sieve plate 5, is used for fixing solid glyphosate acid and intercepts and captures the solid glyphosate acid that may run off; Its top also has the charging opening 6 of solid glyphosate acid, is used for replenishing glyphosphonic acid to reaction tower 1; Ammoniacal liquor enters from the top of reaction tower 1 and sprays in the solid glyphosate acid, and flows through solid glyphosate acid.Reaction tower 1 lower end effluent liquid is the ammonium glyphosate salt brine solution.This ammonium glyphosate salt brine solution can take out by the check valve 7 below reaction tower 1, also can flow to continuously in the distillation tower 2, boils off the most of moisture of ammonium glyphosate salt brine solution according to the distillation method of routine, becomes the strong solution of ammonium glyphosate; This strong solution flows to continuously and carries out crystallization in the prilling tower 3 then, can obtain purity up to 98.8% ammonium glyphosate solid phase prod.
Highly be that 1.8 rice diameters are that to insert in 15 centimetres the reaction tower 1 highly be 1.5 meters solid glyphosate acid, adding concentration expressed in percentage by volume from top amount with 8.8 milliliters/second then is 5% ammoniacal liquor, when the glyphosphonic acid solid reduces to 1.2 meters, in time add glyphosphonic acid solid to 1.5 meter.This moment, ammoniacal liquor flow through the time of solid glyphosate acid or be 40-50 minute the duration of contact of ammoniacal liquor and solid glyphosate acid, and the temperature in the reaction tower 1 can maintain 30-50 ℃.Effluent liquid enters and carries out distillation and crystallization in distillation tower 2 and the prilling tower 3 according to a conventional method, obtains purity and be 98.8% ammonium glyphosate solid phase prod.
Production Flow Chart is with embodiment 1.It highly is being 1.8 meters, diameter is that to insert in 15 centimetres the reaction tower 1 highly be 1.5 meters solid glyphosate acid, adding concentration from top amount with 6.3 milliliters/second then is 20% ammoniacal liquor, when the glyphosphonic acid solid reduces to 1.2 meters, in time adds glyphosphonic acid solid to 1.5 meter.The time that this moment, ammoniacal liquor flow through solid glyphosate acid is 56-70 minute, and the temperature in the reaction tower 1 can maintain 45-60 ℃ automatically.Effluent liquid enters and carries out distillation and crystallization in distillation tower 2 and the prilling tower 3 according to a conventional method, obtains purity and be 98.8% ammonium glyphosate solid phase prod.
Claims (5)
1, a kind of method of producing ammonium glyphosate, with solid glyphosate acid and ammoniacal liquor is raw material, it is characterized in that: being to be stationary phase with the solid glyphosate acid that is fixed in the reaction tower, is moving phase with ammoniacal liquor, make ammoniacal liquor flow through solid glyphosate acid and react, obtain ammonium glyphosate.
2, method according to claim 1 is characterized in that: the concentration expressed in percentage by volume of described ammoniacal liquor is 5-20%.
3, method according to claim 1 and 2 is characterized in that: the described reaction product ammonium glyphosate that obtains can also obtain high purity, highly active ammonium glyphosate solid phase prod through dehydration and crystallisation step.
4, method according to claim 1 and 2 is characterized in that: described ammoniacal liquor flows through the time of solid glyphosate acid or be 10 minutes-1.5 hours the duration of contact of ammoniacal liquor and solid glyphosate acid.
5, method according to claim 4 is characterized in that: be 40 minutes-70 minutes described duration of contact.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100693529A CN1328283C (en) | 2004-07-19 | 2004-07-19 | Method of producing ammonium glyphosate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100693529A CN1328283C (en) | 2004-07-19 | 2004-07-19 | Method of producing ammonium glyphosate |
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| CN1724547A CN1724547A (en) | 2006-01-25 |
| CN1328283C true CN1328283C (en) | 2007-07-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2004100693529A Expired - Fee Related CN1328283C (en) | 2004-07-19 | 2004-07-19 | Method of producing ammonium glyphosate |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100389116C (en) * | 2006-06-12 | 2008-05-21 | 江苏好收成韦恩农药化工有限公司 | Method for producing glyphosate monovalent salt using glyphosate bivalent, trivalent salt |
| CN101172985B (en) * | 2006-10-31 | 2011-04-20 | 浙江新安化工集团股份有限公司 | Improved process for producing glyphosate acid ammonium salt |
| CN105732707A (en) * | 2016-03-19 | 2016-07-06 | 安徽东至广信农化有限公司 | Technique for continuously producing glyphosate isopropylamine salt |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5614468A (en) * | 1995-06-07 | 1997-03-25 | Monsanto Company | Preparation of ammonium glyphosate using aqueous ammonium hydroxide in a liquid-solid reaction system |
| CN1260349A (en) * | 1999-11-08 | 2000-07-19 | 浙江新安化工集团股份有限公司 | Preparation method for ammonium glyphosphonate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5614468A (en) * | 1995-06-07 | 1997-03-25 | Monsanto Company | Preparation of ammonium glyphosate using aqueous ammonium hydroxide in a liquid-solid reaction system |
| US5716903A (en) * | 1995-06-07 | 1998-02-10 | Monsanto Company | Preparation of ammonium glyphosate using aqueous ammonium hydroxide in a liquid-solid reaction system |
| CN1192743A (en) * | 1995-06-07 | 1998-09-09 | 孟山都公司 | Prepn. of ammonium glyphosate using aqueous ammonium hydroxide in liquid-solid reaction system |
| CN1260349A (en) * | 1999-11-08 | 2000-07-19 | 浙江新安化工集团股份有限公司 | Preparation method for ammonium glyphosphonate |
Non-Patent Citations (1)
| Title |
|---|
| 草甘膦胺盐的合成及可溶性粒剂（粉剂）的制备 周曙光等，浙江化工，第34卷 2003 * |
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