CN100537580C - Glyphosate mother liquid treating method - Google Patents
Glyphosate mother liquid treating method Download PDFInfo
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- CN100537580C CN100537580C CNB2005100546261A CN200510054626A CN100537580C CN 100537580 C CN100537580 C CN 100537580C CN B2005100546261 A CNB2005100546261 A CN B2005100546261A CN 200510054626 A CN200510054626 A CN 200510054626A CN 100537580 C CN100537580 C CN 100537580C
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Abstract
This invention relates to a treatment method of mother liquid from alkyl esterification composing glyphosate. This method mainly reclaims TEA, condenses alkali mother liquid to get off large amount of byproduct soldium chloride, after which adds ammonium bicarbonate in the alkali mother liquid, fully reacts, filters to collocate glyphosate solution. This invention can not only get rid of the alkalization problem cause by too much sodium chloride in glyphosate, and also improves the medical effect of this solution collocated by this method, and lower the cost and save the energy consumption.
Description
Technical field
The present invention relates to the novel method that alkyl esterification method prepares a kind of glyphosate mother solution processing of glyphosate.
Background technology
Glyphosate is a kind of steriland herbicide, and present domestic preparation glyphosate adopts alkyl esterification method more.This technology produces a large amount of Na that contains when producing glyphosate technicals
+Acid mother liquid (abbreviation acid mother liquor), the catalyst of triethylamine of using when containing a large amount of synthesizing in the mother liquor.Domestic glyphosate production producer common employing when handling this kind mother liquor recovery catalyst of triethylamine adds in the liquid caustic soda and technology: be about to 30% sodium hydroxide solution and add in the mother liquor, regulate pH value 10-12, standing demix, upper strata triethylamine recovery is re-used in glyphosate synthesizes, and a small amount of triethylamine is told in lower floor's mother liquor rectifying, and remainder is through concentrating, remove part sodium-chlor, sodium chloride concentration is saturated in the concentrated mother liquor, and glyphosate content is about 2%-2.5%, is used to prepare 10% sodium glyphosate aqua.After having used this kind and containing 10% sodium glyphosate aqua of more sodium-chlor, make that sodium chloride content is too high in the soil, easily cause soil bad dispersibility, soil property viscous, become soda soil, crop is caused damage, finally cause crop failure and downgrade.In addition, the weeding usefulness of 10% sodium glyphosate aqua (quick-acting and thoroughness) is slightly inferior than other glyphosate formulation.
Summary of the invention
Purpose of the present invention just provides and handles the method that mother liquor is recycled in a kind of alkyl esterification method glyphosate production technology.This method not only can be eliminated because of using the problem of the salting of soil that the gyphosate solution that contains more sodium-chlor causes, and also can improve the aqua drug effect with this technology preparation simultaneously, reduces cost energy efficient.
According to the present invention, can be achieved through the following technical solutions the object of the invention:
Solid sodium bicarbonate is added in the acid mother liquid that produces in the preparation glyphosate production process, pH value is 3～7, add sodium hydroxide, regulating pH value is 10-12, standing demix, it is synthetic that upper strata triethylamine recovery is re-used in glyphosate, after a small amount of triethylamine is told in lower floor's mother liquor rectifying, the alkaline mother liquor heating is concentrated a large amount of sodium-chlor of removal, 10%～35% of the concentrated alkali liquor amount of adding bicarbonate of ammonia in the concentrated alkali liquor of removal sodium-chlor after past the concentrating (being called for short concentrated alkali liquor), temperature is 10 ℃～50 ℃, fully reacts, remove throw out (sodium bicarbonate), filtrate being used to prepared gyphosate solution.
Also having another scheme, is exactly without concentrating, and directly adds the amount of ammonium bicarbonate reaction in the neutralization bases mother liquor.This method also can change sodium-chlor in the mother liquor into ammonium chloride, improve the drug effect of the gyphosate solution of mother liquor preparation, but this method is not owing to have to remove wherein a large amount of sodium-chlor through concentrating, the utilization ratio of the bicarbonate of ammonia of adding is little, the bicarbonate of ammonia amount that consumes is big, and by product is also many.
And the present invention be at the neutralization bases mother liquor after concentrate removing a large amount of sodium-chlor, toward wherein adding an amount of bicarbonate of ammonia, fully react, we can improve the utilization ratio of bicarbonate of ammonia thus again, reduce the consumption of bicarbonate of ammonia, the by product carbonic acid gas of generation is also less.
During the by product sodium bicarbonate that produces can be reused for and the acid mother liquid that produces in the glyphosate production process, can reduce the consumption of liquid caustic soda thus.
Characteristics of the present invention are that also the bicarbonate of ammonia that adds can be with logical ammonia, carbonic acid gas replace successively.Toward concentrating in the alkali liquor behind logical successively ammonia, the carbon dioxide, throw out (sodium bicarbonate) is removed in fully reaction, and concentrating filter liquor is removed part ammonium chloride, is used to prepare 10% gyphosate solution.
Adopting the inventive method to recycle glyphosate mother solution has the following advantages:
(1), adopt in the mother liquor after the present invention handles and contain the ammonium chloride that in a large number the gyphosate solution drug effect is had synergism, and sodium chloride-containing or content is not seldom substantially.
(2), adopt 10% gyphosate solution of the mother liquor preparation after the present invention handles owing to contain the ammonium chloride that has synergism in a large number.Therefore, the herbicidal effect of 10% gyphosate solution improves.
(3), adopt the mother liquor preparation after the present invention handles 10% gyphosate solution since substantially not sodium chloride-containing or content seldom, therefore having eliminated a large amount of sodium-chlor is released in the soil problem of environmental pollutions such as the soil salinization phenomenon that causes.
(4), adopt the present invention to handle in the mother liquor process and add bicarbonate of ammonia, the sodium bicarbonate precipitation that generates can replace other alkaline matter to be back in the glyphosate mother solution treating processes, thereby can't consume the exhaust emission that is caused too much with mother liquor in fundamentally having avoided.
(5), adopting the present invention to handle mother liquor, to also have an advantage be that existing apparatus does not need big change.
Description of drawings
Schema of the present invention is seen accompanying drawing 1
Accompanying drawing 2 is traditional glyphosate mother solution treatment process, and acid mother liquor is in liquid caustic soda and after reclaiming triethylamine, and direct concentrating is used to prepare gyphosate solution, byproduct sodium chloride.
Embodiment
Embodiment 1
Get the 1000g concentrated mother liquor in the glyphosate production process, add bicarbonate of ammonia 250g, under 10 ℃～50 ℃ conditions, fully stir after-filtration, obtain throw out (sodium bicarbonate precipitation) 435g, filtrate 800g.The glyphosphonic acid that adds metering in filtrate is 10% until glyphosate content, obtains 10% gyphosate solution.
Embodiment 2
Get the 1000g concentrated mother liquor in the glyphosate production process, add bicarbonate of ammonia 350g, under 10 ℃～50 ℃ conditions, fully stir after-filtration, obtain throw out (sodium bicarbonate precipitation) 500g, filtrate 845g.The glyphosphonic acid that adds metering in filtrate is 10% until glyphosate content, obtains 10% gyphosate solution.
Embodiment 3
Get the 1000g concentrated mother liquor in the glyphosate production process, add bicarbonate of ammonia 150g, under 10 ℃～50 ℃ conditions, fully stir after-filtration, obtain throw out (sodium bicarbonate precipitation) 295g, filtrate 844g.The glyphosphonic acid that adds metering in filtrate is 10% until glyphosate content, obtains 10% gyphosate solution.
Embodiment 4
Get the 1450g acid mother liquid in the glyphosate production process, add the sodium bicarbonate 435g that produces among the embodiment 1, reaction back pH value is 5.4, add 30%NaOH 450g again, pH value is 11, layering, the upper strata gets triethylamine 245g, and lower floor's mother liquor gets triethylamine 6.5g through distillation; Concentrate remaining alkali liquor, remove sodium-chlor 295g, get concentrated mother liquor 1015g, in concentrated mother liquor, add 275g bicarbonate of ammonia, under 10 ℃～50 ℃ conditions, fully stir after-filtration, get the 442g sodium bicarbonate, filtrate 834g, the glyphosphonic acid that adds metering in filtrate is 10% until glyphosate content, obtains 10% gyphosate solution.
Embodiment 5
In the preparation glyphosate production process, concentrate and remove sodium-chlor after mother liquor 1000g in feed the ammonia of 25g earlier, feed the carbon dioxide of 65g again, after fully stirring, centrifugation obtains 105g sodium bicarbonate and filtrate.The glyphosphonic acid that adds metering to filtrate is 10% until glyphosate content, obtains finished product 10% gyphosate solution.
Embodiment 6
In the preparation glyphosate production process, concentrate and remove sodium-chlor after mother liquor 1000g in feed the ammonia of 75g earlier, feed the carbon dioxide of 200g again, after fully stirring, centrifugation obtains 319g sodium bicarbonate and filtrate.The glyphosphonic acid that adds metering to filtrate is 10% until glyphosate content, obtains finished product 10% gyphosate solution.
Embodiment 7
Get the 1000g acid mother liquid in the glyphosate production process, add the sodium bicarbonate 105g that produces among the embodiment 1, collect the carbon dioxide 53g that produces, reaction back pH value is 5.4, adds 30%NaOH880g again, and pH value is 11, layering, the upper strata gets triethylamine 206g, and lower floor's mother liquor gets triethylamine 13g through distillation; Concentrate remaining alkali liquor, remove sodium-chlor 41g, concentrated mother liquor 500g, feed the ammonia of 28g in the concentrated mother liquor earlier, feed the carbon dioxide of collecting again, and supplementary carbon dioxide gas 20g, after fully stirring, filtration obtains the 103g sodium bicarbonate.The glyphosphonic acid that adds metering in the filtrate is 10% until glyphosate content, obtains 10% gyphosate solution.
Embodiment 8
Get the 2000g acid mother liquid in the glyphosate production process, add the sodium bicarbonate 319g that produces among the embodiment 6, collect the carbon dioxide 151g that produces, reaction back pH value is 5.4, adds 30%NaOH1620g again, and pH value is 11, layering, the upper strata gets triethylamine 411g, and lower floor's mother liquor gets triethylamine 26g through distillation; Concentrate remaining alkali liquor, remove sodium-chlor 79g, concentrated mother liquor 1000g, feed the ammonia of 75g in the concentrated mother liquor earlier, feed the carbon dioxide of collecting again, and supplementary carbon dioxide gas 45g, after fully stirring, filtration obtains the 315g sodium bicarbonate.The glyphosphonic acid that adds metering in the concentrated filtrate is 10% until glyphosate content, obtains 10% gyphosate solution.
Embodiment 9 tests of pesticide effectiveness
The old field that test is selected in night watch tower carries out, and the weeds kind is mainly nutgrass flatsedge, Bermuda grass etc.Adopt Red Star participants in a bridge game pressure pressure atomizer, 5 processing are established in test, triplicate, and district's group is arranged at random, 5 square metres of each sub-district areas.Test processing a, b, c, d, e, f, g, h are respectively embodiment 1,2,3,4,5,6,7,8 gained 10% gyphosate solution 9 grams, and i is former technology gained 10% gyphosate solution 9 grams.
Test in medication on November 2 in 2004, each is handled and converts water 30-40Kg/ mu by institute's dosage, directed even spraying, and blank only sprays clear water.Fine during medication, about temperature 15-20 ℃, rained heavily in the 6th day after the medication, temperature all is about 8-18 ℃.Utilize CD method log, see Table 1.
Annotate: the CD method is meant the product with effect of herbicides relative coverage and drug effect degree, passes judgment on steriland herbicide to mixing the method for living weed community preventive effect.Formulate is: Wc is the preventive effect of steriland herbicide to the living weed community of mud in Wc=C * D formula.C is a drug effect relative coverage value in the medication district, i.e. have in the weeds that are subjected to the medicine symptom and the medication district the relative level of coverage that whole weeds are compared in the medication district, gives the C assignment with the method for range estimation with the number between 1.0 to 10.0.If all weeds all show and are subjected to the medicine symptom in the medication district, no matter the weight of its symptom then, the C value is 10.0; If only have fragmentary weeds tool to be subjected to the medicine symptom in the medication district, its area is no more than 10%, and then the C value is 1.0.D is the drug effect degree of weeds in the medication district, looks weight that weeds poison and same the tax with the numerical value between 1.0 to 10.0, and the relation of its main numerical value and toxicity symptom sees Table 2.
The relation of table 2 D value and weeds toxicity symptom
| The D value | The weeds toxicity symptom |
| 10.0 | Whole strain is withered |
| 8.0 | Blade, young stem or rachis are withered, big slight yellow of stem or chlorosis.Can not continued growth, the plant part is withered |
| 6.0 | Leaf chlorosis or jaundice or partial blade are withered, and stem is near normally, still can slowly grow |
| 4.0 | Minority leaf chlorosis or jaundice, plant strain growth are normal substantially |
| 1.0 | Fragmentary blade tool calomel poisoning symptom |
Table 1
As can be seen from Table 1, the gyphosate solution drug effect that is prepared by the inventive method obviously is better than the gyphosate solution of former explained hereafter.
Claims (4)
1, a kind of treatment process of glyphosate mother solution, comprise and add liquid caustic soda, in and alkyl esterification method prepare a large amount of acid mother liquids that produce in the glyphosate production process, regulate pH value to 10-12, reclaim catalyst of triethylamine, concentrated mother liquor, be left alkali liquor after filtering a large amount of sodium chloride crystals of removal, it is characterized in that: add bicarbonate of ammonia in remaining alkali liquor, fully reaction is filtered; Sodium bicarbonate precipitation, filtrate is treated to be used to prepare the ammonium glyphosate aqua.
2, the treatment process of glyphosate mother solution as claimed in claim 1, it is characterized in that the by product sodium bicarbonate reclaim be reused in and the acid mother liquid that produces in the glyphosate production process.
3, the treatment process of glyphosate mother solution as claimed in claim 2 is characterized in that with the by product sodium bicarbonate acid mother liquor being neutralized to the pH value is 3-7, adds a certain amount of liquid caustic soda solution again, regulates the pH value to 10-12.
4, the treatment process of glyphosate mother solution as claimed in claim 1 is characterized in that described bicarbonate of ammonia replaces to feed ammonia and carbonic acid gas.
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| CNB2005100546261A CN100537580C (en) | 2005-03-07 | 2005-03-07 | Glyphosate mother liquid treating method |
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| CNB2005100546261A CN100537580C (en) | 2005-03-07 | 2005-03-07 | Glyphosate mother liquid treating method |
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| CN1676527A CN1676527A (en) | 2005-10-05 |
| CN100537580C true CN100537580C (en) | 2009-09-09 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100340566C (en) * | 2005-02-25 | 2007-10-03 | 浙江新安化工集团股份有限公司 | Treatment method of glyphosate mother liquor |
| CN1775786B (en) * | 2005-11-28 | 2011-01-19 | 杭州天创净水设备有限公司 | Method for separating and concentrating glyphosate stock solution |
| CN101704841B (en) * | 2009-04-27 | 2012-11-21 | 南通泰禾化工有限公司 | Method for recovering glyphosate mother liquor |
| CN108483462B (en) * | 2018-03-12 | 2020-02-18 | 江西金龙化工有限公司 | Process for recovering ammonium sulfate from glyphosate mother liquor |
| CN108503393B (en) * | 2018-03-12 | 2021-08-20 | 浙江金帆达生化股份有限公司 | Comprehensive utilization method of nitrogen resources in glyphosate mother liquor |
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2005
- 2005-03-07 CN CNB2005100546261A patent/CN100537580C/en active Active
Non-Patent Citations (8)
| Title |
|---|
| 烷基酯法草甘膦生产工艺中的三乙胺连续化回收. 任不凡等.农药，第43卷第6期. 2004 |
| 烷基酯法草甘膦生产工艺中的三乙胺连续化回收. 任不凡等.农药，第43卷第6期. 2004 * |
| 烷基酯生产草甘膦的技术进展. 陈晓祥等.现代化工，第2期. 1998 |
| 烷基酯生产草甘膦的技术进展. 陈晓祥等.现代化工，第2期. 1998 * |
| 草甘膦生产中三乙胺的连续回收工艺. 陈锡华.现代化工，第24卷第3期. 2004 |
| 草甘膦生产中三乙胺的连续回收工艺. 陈锡华.现代化工，第24卷第3期. 2004 * |
| 草甘膦结晶母液处理新工艺. 薛光才等.湖北化工，第增刊期. 1998 |
| 草甘膦结晶母液处理新工艺. 薛光才等.湖北化工，第增刊期. 1998 * |
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