CN101786735A - Film treatment method of glyphosate mother liquor - Google Patents
Film treatment method of glyphosate mother liquor Download PDFInfo
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- CN101786735A CN101786735A CN 201010109701 CN201010109701A CN101786735A CN 101786735 A CN101786735 A CN 101786735A CN 201010109701 CN201010109701 CN 201010109701 CN 201010109701 A CN201010109701 A CN 201010109701A CN 101786735 A CN101786735 A CN 101786735A
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Abstract
The invention relates to a film treatment method of a mother liquor obtained by synthesizing glyphosate by using an alkyl ester method. The method comprises the following steps of: adding acid to regulate the pH value to 1-5 aiming at an alkali mother liquor after adding alkali to a glyphosate mother liquor and recovering triethylamine; then removing visible particle impurities through a cloth bag filter and(or) an active carbon filter; entering a first-stage film for treating to separate out a first-stage concentrated liquid and a first-stage dilute liquid; adding partial water to the concentrated liquid to dilute and then entering a second-stage film for separating out a second-stage concentrated liquid and a second-stage dilute liquid; adding water to the second-stage concentrated liquid to dilute and then passing through a third-stage film for separating out a third-stage concentrated liquid and a third-stage dilute liquid; mixing the dilute liquids of the first stage, the second stage and the third stage and then treating an obtained mixed liquid through a fourth-stage film for separating out a fourth-stage concentrated liquid and a fourth-stage dilute liquid; and applying the fourth-stage concentrated liquid to the inlet of the first-stage film. The invention realizes the effective separation of salts and organic matters in the glyphosate mother liquor under a room temperature condition and lays a foundation for next resource utilization.
Description
Technical field
The present invention relates to the membrane processing method of glyphosate mother solution.
Technical background
Glyphosate is a kind of application natural disposition post-emergence herbicide that goes out very widely, and along with the continuous expansion that transgenic technology is used, glyphosate output increases rapidly, becomes most important kind in the weedicide.At present, the main synthetic method of domestic glyphosate is an alkyl esterification method, but in preparation process, can produce the glyphosate mother solution of a large amount of high content of salt.At present, the treatment process of glyphosate mother solution normally through after concentrating the most salt of removal, is mixed with 10% sodium glyphosate aqua.Too much can cause soil bad dispersibility, soil property viscous but 10% sodium glyphosate aqua uses, become soda soil, cause crop failure and downgrade, therefore country forbade the production of 10% sodium glyphosate aqua in 2010.Like this, just caused the sodium glyphosate mother liquor very difficult, because go back the method for the effective processing high density of none sodium salt waste water at present.
Chinese patent CN101058586A has introduced a kind of glyphosate mother solution membrane processing method, mainly is with glyphosate mother solution pH regulator to 2～11, reaches 2～5% through glyphosate content in ultrafiltration, nanofiltration and three grades of films processing of the reverse osmosis membrane back concentrated solution then.The aqua of concentrated solution preparation 10% ammonium glyphosate, sodium salt, sylvite, isopropyl amine salt after concentrating.See through in the liquid at last and contain a large amount of salt, glyphosate content＜0.1% can be used as high density salt solution and uses, as the chlor-alkali water.But this patent does not illustrate the salts contg in the concentrated solution, and concentrated solution can only be prepared glyphosate 10% aqua; Have only the glyphosate content's index in the light liquid, do not have other impurity indexs, the existence of other impurity, the range of application of the light liquid of the very big influence of meeting.Application number provides a kind of method of glyphosate mother solution preparation 30～70% effective constituent glyphosate formulations for 200910100214.5 patent of invention.But this method do not mention film and handle to adopt what film to handle, and in the smart mother liquor saltiness higher be 2%.Crucial is, the glyphosate mother solution amount is very big, all is used to prepare 30% and above preparation, and market capacity is limited, can't consume.
Summary of the invention
The present invention adopts membrane processing method in order to solve above-mentioned difficulties, realized separating of organism and inorganic salt in the glyphosate mother solution to greatest extent, lays a good foundation for the effective constituent in the glyphosate mother solution all is widely used.
Film of the present invention is handled the method for glyphosate mother solution, may further comprise the steps: the alkali liquor that glyphosate is reclaimed behind the triethylamine adds acid for adjusting pH to 1～5, by cloth envelop collector and (or) activated charcoal filter removes and enters the one-level film behind the visible particle impurity and handle, and tells the light liquid of one-level dope and one-level.The one-level dope enters the secondary membrane sepn, tells the light liquid of secondary dope and secondary, and the secondary dope is divided into three grades of dopes and three grades of light liquid through three grades of films.Handle through the level Four film after one, two, three light liquid mixes, isolate the light liquid of level Four dope and level Four, the level Four dope is applied mechanically to the import of one-level film.
One-level dope and secondary dope can add and enter the secondary film more respectively after the portion water dilution and three grades of films carry out separating treatment.
Preferably, the one, two, three, four film is one or several in ultra-filtration membrane, nanofiltration membrane and the reverse osmosis membrane.
Preferably, nanofiltration membrane at different levels and reverse osmosis membrane are low-pressure membrane or high-pressure membrane, and working pressure is 1～10MPa.
Preferably, every grade of dope thin up amount is 0.5～2 times of every grade of dope amount.
After above-mentioned film processing, glyphosate content 〉=5% of three grades of dopes, salts contg≤1%.Glyphosate in the light liquid of level Four, increase in the mother liquors such as sweet phosphine, methyl glyphosate, aminomethyl phosphonic acid main organic content all≤0.1%; Salts contg 〉=10%; COD:2000～5000ppm; Total phosphorus :≤500ppm.
Preferably, add an amount of former powder of glyphosate, APG glyphosate auxiliary agent and ammonia or Isopropylamine or potassium hydroxide in three grades of dopes, be mixed with effective constituent and be 30～41% gyphosate solution.
Preferably, three grades of concentrated removals after the portion water branch of dopes process add an amount of ammonium glyphosate and APG glyphosate auxiliary agent is made 30～70% soluble powder or granule.
Wherein, three grades of dopes are regulated pH to 1～5, and the former powder of glyphosate of content 〉=50% is taken out in the cooling back.
Wherein, after three grades of dopes passed through the wherein whole glyphosate of oxidation removal, evaporation concentration was fallen wherein part moisture, carries out spraying drying and obtains powdery solid, is used to prepare composite fertilizer.Oxygenant comprises O
3, H
2O
2-O
3, ClO
2, oxygenant such as sodium chlorate, Fetion reagent.
After three grades of dope evaporation concentration are removed part moisture, having suitable viscosity, is good thickening material, adds in the composite fertilizer, help the granulation of composite fertilizer, and have weeding function, and be excellent function composite fertilizer.
Three grades of dopes are removed after the most of moisture through concentrating, and place in the High Temperature Furnaces Heating Apparatus and calcine, temperature 〉=1000 ℃.Residual ash after the calcining is used for the preparation of brick or cement.
The light liquid of level Four is through concentrating the high quality salt that takes out content 〉=98%.
The light liquid of level Four is through peroxidation, remove wherein organic matters after, can be used as the chlor-alkali water.Oxygenant comprises O
3, H
2O
2-O
3, ClO
2, oxygenant such as sodium chlorate, Fetion reagent.
Dope, light liquid simmer down to one are imitated or multiple-effect evaporation concentrates.
Description of drawings
Fig. 1 is the schema of the membrane processing method of glyphosate mother solution of the present invention;
Embodiment
Embodiment 1.
(1) alkyl esterification method glyphosate mother solution 1000kg, 30% hydrochloric acid of adding 142kg, pH transfers to 3.5, enters the one-level film after filtering through cloth envelop collector and handles one-level dope 450kg, the light liquid 692kg of one-level; The one-level dope enters the processing of secondary film, secondary dope 290kg, the light liquid 460kg of secondary after adding water 300kg; The secondary dope enters three grades of films processing, three grades of dope 167kg, three grades of light liquid 413kg after adding water 290kg.Enter the level Four film after one, two, three light liquid mixes and handle, obtain 21kg level Four dope and the light liquid of 1544kg level Four.The level Four dope is applied mechanically to next batch one-level film processing import.
The glyphosate content of (2) three grades of dopes is 5.4%, salts contg is 0.8%.Glyphosate in the light liquid of level Four, increase in the mother liquors such as sweet phosphine, methyl glyphosate, aminomethyl phosphonic acid main organic content all≤0.1%; Salts contg is 11%; COD:3000ppm; Total phosphorus: 380ppm.
Add 24.6% the former powder of glyphosate in (3) three grades of dopes, logical ammonia to pH be about 7, add 10% APG glyphosate auxiliary agent, be mixed with 30% gyphosate solution.It is 99% high quality salt that the light liquid of level Four takes out content through three-effect evaporation and condensation, and cut enters environment-friendly disposal system.
Embodiment 2.
(1) alkyl esterification method glyphosate mother solution 1000kg, 30% hydrochloric acid of adding 155kg, pH transfers to 1.5, enters the one-level film after filtering through cloth envelop collector and handles one-level dope 420kg, the light liquid 735kg of one-level; The one-level dope enters the processing of secondary film, secondary dope 240kg, the light liquid 460kg of secondary after adding water 280kg; The secondary dope enters three grades of films processing, three grades of dope 155kg, three grades of light liquid 325kg after adding water 240kg.Enter the level Four film after one, two, three light liquid mixes and handle, obtain 23kg level Four dope and the light liquid of 1497kg level Four.The level Four dope is applied mechanically to next batch one-level film processing import.
The glyphosate content of (2) three grades of dopes is 5.9%, salts contg is 0.7%.Glyphosate in the light liquid of level Four, increase in the mother liquors such as sweet phosphine, methyl glyphosate, aminomethyl phosphonic acid main organic content all≤0.1%; Salts contg is 12%; COD:2500ppm; Total phosphorus: 320ppm.
Add 24.1% the former powder of glyphosate in (3) three grades of dopes, drip Isopropylamine to glyphosate and all dissolve, add 10% APG glyphosate auxiliary agent, be mixed with 30% gyphosate solution.The light liquid of level Four is 99% high quality salt through three-effect evaporation and condensation taking-up content.
Embodiment 3.
(1) alkyl esterification method glyphosate mother solution 1000kg, 30% hydrochloric acid of adding 150kg, pH transfers to 2.5, enters the one-level film after filtering through cloth envelop collector and handles one-level dope 440kg, the light liquid 710kg of one-level; The one-level dope enters the processing of secondary film, secondary dope 245kg, the light liquid 475kg of secondary after adding water 280kg; The secondary dope enters three grades of films processing, three grades of dope 165kg, three grades of light liquid 325kg after adding water 245kg.Enter the level Four film after one, two, three light liquid mixes and handle, obtain 20kg level Four dope and the light liquid of 1490kg level Four.The level Four dope is applied mechanically to next batch one-level film processing import.
The glyphosate content of (2) three grades of dopes is 5.6%, salts contg is 0.65%.Glyphosate in the light liquid of level Four, increase in the mother liquors such as sweet phosphine, methyl glyphosate, aminomethyl phosphonic acid main organic content all≤0.1%; Salts contg is 12%; COD:2300ppm; Total phosphorus: 330ppm.
(3) three grades of dopes are through H
2O
2-O
3After the oxidation, glyphosate all is decomposed, and behind concentrated removal 30～40% moisture, carries out spraying drying, generates powdery solid, is configured to composite fertilizer.
(4) three grades of dopes join in the composite fertilizer material after concentrating and removing 20～40% moisture, carry out granulation then.Through field experiment, not only help increasing the speed of growth of target plant, and can kill other vegetation.
(5) the light liquid of level Four is after the Fetion reagent oxidation, as the chlor-alkali water.
Embodiment 4.
(1) alkyl esterification method glyphosate mother solution 1000kg, 30% hydrochloric acid of adding 152kg, pH transfers to 2, enters the one-level film after filtering through cloth envelop collector and handles one-level dope 425kg, the light liquid 727kg of one-level; The one-level dope enters the processing of secondary film, secondary dope 245kg, the light liquid 460kg of secondary after adding water 280kg; The secondary dope enters three grades of films processing, three grades of dope 158kg, three grades of light liquid 332kg after adding water 245kg.Enter the level Four film after one, two, three light liquid mixes and handle, obtain 23kg level Four dope and the light liquid of 1496kg level Four.The level Four dope is applied mechanically to next batch one-level film processing import.
The glyphosate content of (2) three grades of dopes is 5.8%, salts contg is 0.76%.Glyphosate in the light liquid of level Four, increase in the mother liquors such as sweet phosphine, methyl glyphosate, aminomethyl phosphonic acid main organic content all≤0.1%; Salts contg is 12.5%; COD:2800ppm; Total phosphorus: 370ppm.
(3) three grades of dopes burn in new-type chain furnace after evaporation concentration is removed wherein 20～40% moisture, and incineration temperature is more than 1100 ℃, and the residence time is 2s.The pulverulent solids that obtains after the burning is used for the preparation of brick or cement.
Claims (10)
1. the membrane processing method of a glyphosate mother solution, comprise that the alkali liquor that glyphosate is reclaimed behind the triethylamine adds acid for adjusting pH to 1～5, remove by cloth envelop collector and activated charcoal filter and to enter the one-level film behind the visible particle impurity and handle, tell the light liquid of one-level dope and one-level, dope enters the secondary membrane sepn, tell the light liquid of secondary dope and secondary, the secondary dope is through three grades of films, be divided into three grades of dopes and three grades of light liquid, after mixing, handles one, two, three light liquid through the level Four film, isolate the light liquid of level Four dope and level Four, the level Four dope is applied mechanically to the import of one-level film.
2. according to the membrane processing method of claim 1, wherein glyphosate mother solution is the mother liquor of alkyl esterification method synthesizing glyphosate.
3. according to the membrane processing method of claim 2, wherein the one, two, three, four film is one or several in ultra-filtration membrane, nanofiltration membrane and the reverse osmosis membrane, and nanofiltration membrane at different levels and reverse osmosis membrane are low-pressure membrane or high-pressure membrane, and working pressure is 1～10MPa.
4. according to the membrane processing method of claim 3, wherein the I and II film is a nanofiltration membrane, three, the level Four film is reverse osmosis membrane.
5. according to the membrane processing method of claim 1, when wherein one-level dope and secondary dope enter secondary film and three grades of films processing respectively, can add the portion water dilution earlier.
6. according to the membrane processing method of claim 5, wherein every grade of dope amount of dilution of adding portion water is 0.5～2 times of every grade of dope amount.
7. according to each membrane processing method of claim 1-6, wherein add an amount of former powder of glyphosate, APG glyphosate auxiliary agent and ammonia or Isopropylamine or potassium hydroxide in three grades of dopes, be mixed with effective constituent and be 30～41% gyphosate solution.
8. according to each membrane processing method of claim 1-6, wherein three grades of dopes are removed after portion water divide through concentrating, and add an amount of ammonium glyphosate and APG glyphosate auxiliary agent is made 30～70% soluble powder or granule.
9. according to each membrane processing method of claim 1-6, wherein three grades of dopes through the wherein whole glyphosate of oxidation removal after, evaporation concentration is fallen wherein part moisture, carries out the powdery solid that spraying drying obtains being used to prepare composite fertilizer.
10. according to each membrane processing method of claim 1-6, wherein the light liquid of level Four is through peroxidation, remove wherein organic matters after, as the chlor-alkali water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010109701 CN101786735A (en) | 2010-02-11 | 2010-02-11 | Film treatment method of glyphosate mother liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010109701 CN101786735A (en) | 2010-02-11 | 2010-02-11 | Film treatment method of glyphosate mother liquor |
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| CN101786735A true CN101786735A (en) | 2010-07-28 |
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|---|---|---|---|
| CN 201010109701 Pending CN101786735A (en) | 2010-02-11 | 2010-02-11 | Film treatment method of glyphosate mother liquor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321119A (en) * | 2011-07-07 | 2012-01-18 | 湘潭大学 | A kind of post-treating method with dichloride waste water acidifying ammonium glyphosate |
| CN102823935A (en) * | 2012-09-05 | 2012-12-19 | 浙江开创环保科技有限公司 | Concentrating treatment method of tobacco extracting solution |
| CN104130286A (en) * | 2014-08-14 | 2014-11-05 | 四川省乐山市福华通达农药科技有限公司 | Glyphosate mother liquor recycling process |
| CN105858928A (en) * | 2015-01-22 | 2016-08-17 | 浙江新安化工集团股份有限公司 | Treatment method and system for phosphorus-containing feed solution |
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| CN101058586A (en) * | 2007-04-06 | 2007-10-24 | 杭州天创净水设备有限公司 | Method of concentrating and separating glyphosate in high salt content glyphosate mother liquor by film technique |
| WO2009052303A2 (en) * | 2007-10-16 | 2009-04-23 | Monsanto Technology Llc | Processes for producing and recovering shikimic acid |
| CN101525351A (en) * | 2009-04-01 | 2009-09-09 | 杭州天创净水设备有限公司 | Treatment process of glyphosate mother liquor |
| CN101589724A (en) * | 2009-06-25 | 2009-12-02 | 浙江菱化实业股份有限公司 | Utilize the method for glyphosate mother solution preparation 30～70% active ingredient glyphosate formulations |
| CN101597306A (en) * | 2009-06-23 | 2009-12-09 | 武汉大学 | A kind of glyphosate mother solution nanofiltration separation and comprehensive utilization method |
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2010
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058586A (en) * | 2007-04-06 | 2007-10-24 | 杭州天创净水设备有限公司 | Method of concentrating and separating glyphosate in high salt content glyphosate mother liquor by film technique |
| WO2009052303A2 (en) * | 2007-10-16 | 2009-04-23 | Monsanto Technology Llc | Processes for producing and recovering shikimic acid |
| CN101525351A (en) * | 2009-04-01 | 2009-09-09 | 杭州天创净水设备有限公司 | Treatment process of glyphosate mother liquor |
| CN101597306A (en) * | 2009-06-23 | 2009-12-09 | 武汉大学 | A kind of glyphosate mother solution nanofiltration separation and comprehensive utilization method |
| CN101589724A (en) * | 2009-06-25 | 2009-12-02 | 浙江菱化实业股份有限公司 | Utilize the method for glyphosate mother solution preparation 30～70% active ingredient glyphosate formulations |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321119A (en) * | 2011-07-07 | 2012-01-18 | 湘潭大学 | A kind of post-treating method with dichloride waste water acidifying ammonium glyphosate |
| CN102321119B (en) * | 2011-07-07 | 2013-07-31 | 湘潭大学 | Post treatment method for acidifying ammonium glyphosate by dichloride wastewater |
| CN102823935A (en) * | 2012-09-05 | 2012-12-19 | 浙江开创环保科技有限公司 | Concentrating treatment method of tobacco extracting solution |
| CN104130286A (en) * | 2014-08-14 | 2014-11-05 | 四川省乐山市福华通达农药科技有限公司 | Glyphosate mother liquor recycling process |
| CN105858928A (en) * | 2015-01-22 | 2016-08-17 | 浙江新安化工集团股份有限公司 | Treatment method and system for phosphorus-containing feed solution |
| CN105858928B (en) * | 2015-01-22 | 2019-01-29 | 浙江新安化工集团股份有限公司 | A kind of processing method and system of phosphorous feed liquid |
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Application publication date: 20100728 |