CN1824667A

CN1824667A - New method for treating glyphosate mother liquor

Info

Publication number: CN1824667A
Application number: CN 200510053290
Authority: CN
Inventors: 王伟; 刘侠; 周曙光; 邵振威; 秦龙; 李丽娟; 佘慧玲; 郑红朝
Original assignee: Zhejiang Xinan Chemical Industrial Group Co Ltd
Current assignee: Zhejiang Xinan Chemical Industrial Group Co Ltd
Priority date: 2005-02-25
Filing date: 2005-02-25
Publication date: 2006-08-30
Anticipated expiration: 2025-02-25
Also published as: CN100340565C

Abstract

The present invention relates to a treatment method of mother liquor obtained for synthesizing glyphosate by using alkyl ester process. Said method is mainly characterized by that the ammonia gas and carbon dioxide gas are successively introduced into the neutralized alkaline mother liquor, fully reacted and filtered, the filtrate is treated, and can be used for preparing glyphosate water preparation.

Description

The novel method that a kind of glyphosate mother solution is handled

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 the acid mother liquid (abbreviation acid mother liquor) of a large amount of chloride ion-containings when producing glyphosate technicals, the catalyst of triethylamine of using when wherein containing a large amount of synthesizing.Domestic glyphosate production producer common employing when handling acid 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 acid mother liquor, regulate pH value 10-12, standing demix, the upper strata is a triethylamine, it is synthetic that recovery is re-used in glyphosate, lower floor is called the alkaline mother liquor (abbreviation alkali liquor) that contains a large amount of sodium-chlor, tell a small amount of triethylamine that wherein contains through rectifying after, get concentrated mother liquor through concentrate removing part sodium-chlor again.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 repeatedly and containing 10% sodium glyphosate aqua of more sodium-chlor, will cause in the soil sodium chloride content too high, and easily cause soil bad dispersibility, soil property viscous, become soda soil, finally cause crop failure.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

For solving deficiency of the prior art, the invention provides and handle the method that mother liquor reclaims catalyzer in a kind of distinguished alkyl esterification method glyphosate production technology.This method can reduce production costs, improve the aqua drug effect of preparing with this technology in the energy efficient, protection environment.

For reaching the goal of the invention the technical solution adopted in the present invention be:

Solid sodium bicarbonate is added in the acid mother liquor, is 3-7 until the solution pH value, and adding sodium hydroxide solution adjusting pH value again is 10-12, standing demix, and it is synthetic that triethylamine recovery in upper strata is re-used in glyphosate; After a small amount of triethylamine is told in lower floor's mother liquor rectifying, in alkali liquor, feed ammonia, carbon dioxide successively again after, throw out (sodium bicarbonate) is removed in fully reaction, concentrating filter liquor is removed part ammonium chloride, is used to prepare 10% gyphosate solution.

Add sodium bicarbonate in the acid mother liquor, produce CO ₂Gas, reaction equation is:

Feed ammonia and carbonic acid gas in the alkali liquor of sodium chloride-containing, produce sodium bicarbonate precipitation (solubleness of sodium bicarbonate in this system is very little), reaction equation is:

The by-product sodium bicarbonate that said process produces can return be used for and glyphosate production process in the acid mother liquor that produces, compare the consumption that has reduced liquid caustic soda in former technology, the carbon dioxide that produces in the N-process also can reclaim and be used for subsequent reactions.

Adopting the inventive method to recycle glyphosate mother solution has the following advantages:

(1), 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.

(2), 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 to the problem of environmental pollutions such as soil salinization phenomenon that cause in the soil.

(3) but, adopt the present invention to handle to feed the sodium bicarbonate precipitation instead of part liquid caustic soda that generates behind ammonia, the carbon dioxide in the mother liquor process successively and be back in the treating processes of glyphosate mother solution, the carbon dioxide of generation can be back to the treating processes of mother liquor again.

(4), concentrated mother liquor obtains the ammonium chloride by-product of higher secondary valence value, economic benefit is comparatively remarkable.

Description of drawings

Schema of the present invention is seen accompanying drawing 1.

Being neutralized to PH with sodium bicarbonate and liquid caustic soda respectively from the acid mother liquor of glyphosate synthesis procedure is 10-12, layering, the upper strata is a triethylamine, lower floor is the mother liquor of sodium chloride-containing, still contains a small amount of triethylamine in this mother liquor, after rectifying steams triethylamine alkali liquor; In this alkali liquor, feed ammonia again, and upward go on foot with the carbon dioxide that produces in the sodium bicarbonate N-process, restock feeds an amount of carbonic acid gas in addition, ammonia, carbonic acid gas react in sodium chloride aqueous solution, generate the sodium bicarbonate crystallization and separate out, after filtration, sodium bicarbonate returns and is used for the neutralizing acid mother liquor, concentrating filter liquor can be prepared gyphosate solution, also produces by-product ammonium chloride in addition, concentrates the water of condensation that produces and discharges after biochemical treatment.

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

Feed the ammonia of 25g in the 1000g alkali liquor after in the preparation glyphosate production process, reclaiming triethylamine earlier, feed the carbon dioxide of 65g again, after fully stirring, filter and obtain the 113g sodium bicarbonate.Concentrated filtrate filters and obtains 32g ammonium chloride.The glyphosphonic acid that adds metering in the concentrated filtrate is 10% until glyphosate content, obtains 10% gyphosate solution.

Embodiment 2

Feed the ammonia of 75g in the 1000g alkali liquor after in the preparation glyphosate production process, reclaiming triethylamine earlier, feed the carbon dioxide of 200g again, after fully stirring, filter and obtain the 343g sodium bicarbonate.Concentrated filtrate filters and obtains 42g ammonium chloride.The glyphosphonic acid that adds metering in the concentrated filtrate is 10% until glyphosate content, obtains 10% gyphosate solution.

Embodiment 3

Get the 1000g acid mother liquid in the glyphosate production process, add the sodium bicarbonate 343g that produces among the embodiment 2, collect the carbon dioxide 151g that produces, reaction back pH value is 5.4, adds 30%NaOH516g again, and pH value is 11, layering, the upper strata gets triethylamine 206g, and lower floor's mother liquor gets triethylamine 13g through distillation; Feed the ammonia of 75g in the alkali liquor earlier, feed the carbon dioxide of collecting again, and supplementary carbon dioxide gas 49g, after fully stirring, filter and obtain the 352g sodium bicarbonate.Concentrated filtrate filters and obtains 41g ammonium chloride.The glyphosphonic acid that adds metering in the concentrated filtrate is 10% until glyphosate content, obtains 10% gyphosate solution.

Embodiment 4 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.A, b are handled in test, c is respectively embodiment 1,2,3 gained 10% gyphosate solution 9 grams, and d 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 2D value and weeds toxicity symptom

The D value	The 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	10.0	Whole strain is withered
8.0		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	6.0
4.0		1.0	Fragmentary blade tool calomel poisoning symptom

Table 1

Date	November 9				November 12				November 15				November 17				November 21
Date	November 9				November 12				November 15				November 17				November 21				Repeat	1	2	3	On average	1	2	3	On average	1	2	3	On average	1	2	3	On average	1	2	3	On average
a	1.6	1.8	1.6	1.7	3.2	3.2	3.3	3.2	4.6	4.6	4.7	4.6	6.7	6.8	6.7	6.7	8.3	8.5	8.4	8.4	Repeat	1	2	3	On average	1	2	3	On average	1	2	3	On average	1	2	3	On average	1	2	3	On average
a	1.6	1.8	1.6	1.7	3.2	3.2	3.3	3.2	4.6	4.6	4.7	4.6	6.7	6.8	6.7	6.7	8.3	8.5	8.4	8.4	b	1.9	1.8	1.9	1.9	3.5	3.4	3.5	3.5	4.9	4.8	4.9	4.9	6.9	7.1	7.1	7.1	8.7	8.6	8.7	8.7
c	1.7	1.8	1.9	1.8	3.4	3.3	3.4	3.4	5.0	4.8	4.8	4.9	6.8	6.9	7.0	6.9	8.6	8.6	8.7	8.6	b	1.9	1.8	1.9	1.9	3.5	3.4	3.5	3.5	4.9	4.8	4.9	4.9	6.9	7.1	7.1	7.1	8.7	8.6	8.7	8.7
c	1.7	1.8	1.9	1.8	3.4	3.3	3.4	3.4	5.0	4.8	4.8	4.9	6.8	6.9	7.0	6.9	8.6	8.6	8.7	8.6	d	1.5	1.4	1.5	1.5	3.0	3.1	3.0	3.0	4.3	4.4	4.3	4.4	6.2	6.3	6.3	6.3	8.0	7.9	8.1	8.0

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

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 liquors that produce in the glyphosate production process, reclaim catalyst of triethylamine, it is characterized in that: in the alkali liquor that reclaims behind the triethylamine, feed ammonia, carbon dioxide successively, fully reaction, filter sodium bicarbonate; Filtrate is treated to be used to prepare gyphosate solution.

2, the treatment process of glyphosate mother solution as claimed in claim 1 is characterized in that the by-product sodium bicarbonate is reused for the neutralizing acid mother liquor, reclaims the carbonic acid gas that produces, and is used for alkali liquor and handles.

3, by-product sodium bicarbonate as claimed in claim 2 is reused for the neutralizing acid mother liquor, it is characterized in that with sodium bicarbonate acid mother liquor being neutralized to PH earlier is 3-7, uses sodium hydroxide solution again, regulates PH to 10-12.

4, filtrate as claimed in claim 1, it is characterized in that preparing the ammonium glyphosate aqua before, through concentrating recovery part ammonium chloride.