阅读说明：本技术 一种从甘氨酸法草甘膦反应液中回收三乙胺盐酸盐的方法 (Method for recovering triethylamine hydrochloride from glycine-method glyphosate reaction liquid ) 是由 王强 刘武平 马文琴 李小娟 于 2020-12-31 设计创作，主要内容包括：本发明公开了一种从甘氨酸法草甘膦反应液中回收三乙胺盐酸盐的方法,工艺的步骤中含有：S1：从草甘膦反应液中脱除出水和盐酸,得固态化混合物；S2：在固态化混合物中加入溶剂后升温进行相转移,得溶剂相；当然本步骤中还得固相,固相用于合成草甘膦；S3：溶剂相经过降温处理后得三乙胺盐酸盐粗品；S4：得到的三乙胺盐酸盐粗品经过离心、喷雾干燥后得三乙胺盐酸盐成品。它在保证三乙胺盐酸盐成品中三乙胺盐酸盐含量的前提下,提高三乙胺盐酸盐的收率。(The invention discloses a method for recovering triethylamine hydrochloride from glyphosate reaction liquid by a glycine method, which comprises the following steps: s1: removing water and hydrochloric acid from the glyphosate reaction solution to obtain a solid mixture; s2: adding a solvent into the solid mixture, and then heating for phase transfer to obtain a solvent phase; certainly, a solid phase is also obtained in the step and is used for synthesizing the glyphosate; s3: cooling the solvent phase to obtain a triethylamine hydrochloride crude product; s4: and centrifuging and spray drying the obtained triethylamine hydrochloride crude product to obtain a triethylamine hydrochloride finished product. The method improves the yield of the triethylamine hydrochloride on the premise of ensuring the content of the triethylamine hydrochloride in the finished product of the triethylamine hydrochloride.)

1. A method for recovering triethylamine hydrochloride from glyphosate reaction liquid by a glycine method is characterized by comprising the following process steps:

s1: removing water and hydrochloric acid from the glyphosate reaction solution to obtain a solid mixture;

s2: adding a solvent into the solid mixture, and then heating for phase transfer to obtain a solvent phase;

s3: cooling the solvent phase to obtain a triethylamine hydrochloride crude product;

s4: and centrifuging and spray drying the obtained triethylamine hydrochloride crude product to obtain a triethylamine hydrochloride finished product.

2. The method of claim 1,

in step S3, the solvent phase is cooled to obtain an oil phase, and the oil phase is washed to obtain a crude triethylamine hydrochloride.

3. The method of claim 2,

the oil phase is washed, the solvent is recovered for reusing in the step S2, and the phosphorous acid is obtained after the solvent is recovered.

4. The method of claim 1,

and adding the mother liquor obtained after centrifuging the triethylamine hydrochloride crude product into the triethylamine hydrochloride crude product in the centrifuging process at least once, and continuing centrifuging.

5. The method of claim 1,

the solvent is an alcohol solvent.

6. The method of claim 5,

the alcohol solvent is monohydric alcohol or polyhydric alcohol with monohydroxy group containing straight chain or branched chain isomer with 1 to 10 carbons in the carbon chain.

7. The method of claim 1,

in step S2, the temperature of phase transition is raised to 50 ℃ to 230 ℃.

8. The method of claim 1,

in step S1, the glyphosate reaction solution is subjected to removal of effluent and hydrochloric acid under vacuum conditions and temperature environment.

9. The method of claim 8,

the temperature environment is 100-180 ℃.

10. The method of claim 1,

in step S2, the solid mixture is cooled to 15-40 ℃ and then added with a solvent.

Technical Field

The invention relates to a method for recovering triethylamine hydrochloride from glyphosate reaction liquid by a glycine method.

Background

At present, the glyphosate is the herbicide with the largest output and sale quantity, and the Chinese productivity reaches more than 70 ten thousand tons per year. The main synthetic route of the glyphosate in China is a glycine method, a large amount of mother liquor is generated in the production process, and the main components in the mother liquor are glyphosate, phosphorous acid, sodium chloride, glyphosate, glycine and other organic matters. Each ton of glyphosate produced 5 tons of wastewater with high salt, phosphorus and organic content. At home and abroad, various treatment methods for the wastewater are available, such as membrane recovery, incineration, catalytic wet oxidation, precipitation, extraction and adsorption, or a combination of the above methods. However, due to the characteristics of high COD, high total phosphorus and high salt of the glyphosate mother liquor, the treatment difficulty is high, the treatment cost is high, and the treatment is not thorough. So far, no ideal solution exists in the industry.

Therefore, how to treat the waste water of glyphosate by a glycine method is a difficult problem which needs to be solved urgently in the industry.

The main sources of water in glyphosate by using a glycine method are as follows: 30-32% of dilute hydrochloric acid is added during acidolysis, 30-32% of sodium hydroxide is added to neutralize the water, synthesis reaction is carried out to generate water, and acid and alkali are neutralized to generate several parts of water. Moreover, the reaction water produced in the synthesis reaction process hydrolyzes the dimethyl phosphite to produce phosphorous acid, which also causes the yield of the dimethyl phosphite to be reduced.

Triethylamine is used as a catalyst to react with hydrochloric acid to generate triethylamine hydrochloride, due to the existence of triethylamine hydrochloride, the solute content in the glyphosate reaction liquid is increased, the specific gravity of the reaction liquid is increased, the viscosity is increased, the crystallization environment of glyphosate is deteriorated, and the yield of glyphosate is influenced. The triethylamine recovered in the later period of the original method is added with excessive sodium hydroxide, so that part of glyphosate is generated into glyphosate sodium salt, and the triethylamine hydrochloride is not easy to recover.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a method for recovering triethylamine hydrochloride from glyphosate reaction liquid by a glycine method, which improves the yield of triethylamine hydrochloride on the premise of ensuring the content of triethylamine hydrochloride in a triethylamine hydrochloride finished product.

The technical scheme for solving the technical problem of the invention is as follows: a method for recovering triethylamine hydrochloride from glyphosate reaction liquid by a glycine method comprises the following process steps:

s1: removing water and hydrochloric acid from the glyphosate reaction solution to obtain a solid mixture;

s2: adding a solvent into the solid mixture, and then heating for phase transfer to obtain a solvent phase; certainly, a solid phase is also obtained in the step and is used for synthesizing the glyphosate;

s3: cooling the solvent phase to obtain a triethylamine hydrochloride crude product;

s4: and centrifuging and spray drying the obtained triethylamine hydrochloride crude product to obtain a triethylamine hydrochloride finished product.

Further, in order to better improve the yield of triethylamine hydrochloride, in step S3, the solvent phase is cooled to obtain an oil phase, and the oil phase is washed to obtain a crude triethylamine hydrochloride.

The oil phase is washed, the solvent is recovered for reusing in the step S2, and the phosphorous acid is obtained after the solvent is recovered.

Further, mother liquor obtained after the triethylamine hydrochloride crude product is centrifuged is added into the triethylamine hydrochloride crude product in the centrifuging process at least once for continuous centrifugation.

Further, the solvent is an alcohol solvent.

Further, the alcohol solvent is monohydric alcohol or polyhydric alcohol containing monohydroxy group containing straight chain or branched chain isomer with carbon chain from 1 to 10.

Further, in step S2, the temperature of phase transition is raised to 50 ℃ to 230 ℃.

In step S1, the glyphosate reaction solution is subjected to removal of effluent and hydrochloric acid under vacuum conditions and temperature environment.

Further, the temperature environment is 100-180 ℃.

Further, in step S2, the solid-solidified mixture is cooled to 15 to 40 ℃ and then added with a solvent.

By adopting the technical scheme, the yield of triethylamine hydrochloride calculated by glycine can be improved by more than 98% through the steps of the method, phosphorous acid is effectively recovered, and meanwhile, sodium hydroxide is not needed to be used, and sodium chloride is not byproduct. The new process obtains triethylamine hydrochloride with high added value, recovers phosphorous acid, removes the addition of sodium hydroxide and a large amount of solid waste sodium chloride caused by the addition of sodium hydroxide, and greatly reduces the environmental protection cost of the glyphosate industry. The invention has not only economic benefit but also obvious environmental protection benefit.

Detailed Description

The invention provides a method for recovering triethylamine hydrochloride from glyphosate reaction liquid by a glycine method, and a person skilled in the art can use the contents for reference and appropriately improve process parameters to realize the method. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.

A method for recovering triethylamine hydrochloride from glyphosate reaction liquid by a glycine method comprises the following process steps:

s1: removing water and hydrochloric acid from the glyphosate reaction solution to obtain a solid mixture;

s2: adding a solvent into the solid mixture, and then heating for phase transfer to obtain a solvent phase; obtaining solid phase after phase transfer

The solid phase is used for extracting glyphosate;

s3: cooling the solvent phase to obtain a triethylamine hydrochloride crude product;

s4: and centrifuging and spray drying the obtained triethylamine hydrochloride crude product to obtain a triethylamine hydrochloride finished product.

Further, in order to better improve the yield of triethylamine hydrochloride, in step S3, the solvent phase is cooled to obtain an oil phase, and the oil phase is washed to obtain a crude triethylamine hydrochloride.

Further, the solvent is recovered after the oil phase is washed for reuse in step S2, and phosphorous acid is obtained after the solvent is recovered.

Further, mother liquor obtained after the triethylamine hydrochloride crude product is centrifuged is added into the triethylamine hydrochloride crude product in the centrifuging process at least once for continuous centrifugation.

Further, the solvent is an alcohol solvent.

Further, the alcohol solvent is at least one of methanol, ethanol, propanol, butanol and octanol.

Further, in step S2, the temperature of phase transition is raised to 50 ℃ to 230 ℃.

In step S1, the glyphosate reaction solution may be subjected to water removal and hydrochloric acid removal under vacuum conditions and temperature environment.

Further, the temperature environment may preferably be 100 ℃ to 180 ℃.

Further, in step S2, the solid-solidified mixture may be cooled to 15 to 40 ℃ and then added with a solvent.

In order that the present invention may be more clearly understood, the following detailed description of the present invention is given with reference to specific examples.

Example one

A method for recovering triethylamine hydrochloride from glyphosate reaction liquid by a glycine method comprises the following process steps:

s1: removing effluent and hydrochloric acid from glyphosate reaction liquid under vacuum condition and temperature environment (120 ℃) to obtain a solid-state mixture;

s2: cooling the solid mixture to 20 ℃, adding a solvent, and heating to 60 ℃ for phase transfer to obtain a solvent phase;

s3: cooling the solvent phase to obtain a triethylamine hydrochloride crude product and an oil phase, and washing the oil phase to obtain the triethylamine hydrochloride crude product; recycling the solvent for reusing in step S2 after the oil phase is washed, and obtaining phosphorous acid after the solvent is recycled;

s4: and centrifuging and spray drying the obtained triethylamine hydrochloride crude product to obtain a triethylamine hydrochloride finished product.

And adding the mother liquor obtained after the triethylamine hydrochloride crude product is centrifuged into the triethylamine hydrochloride crude product in the centrifuging process, continuing centrifuging, and repeating the adding step once.

The solvent in step S2 may be an alcohol solvent. The alcohol solvent is a mixture of methanol and ethanol.

In this example, the glyphosate reaction solution is about 750g, and the amount of glycine added in the glyphosate reaction solution is 150 g; theoretically, 275.2g of triethylamine hydrochloride is obtained, 269.7g of purity of the finally obtained triethylamine hydrochloride finished product is calculated, and the yield of the triethylamine hydrochloride is 98%; the yield of triethylamine hydrochloride is the amount of triethylamine hydrochloride that can be theoretically produced by adding glycine actually/the amount of triethylamine hydrochloride actually obtained by adding the same amount of glycine. The yield of triethylamine hydrochloride reaches the design requirement.

Meanwhile, the content of triethylamine hydrochloride in the triethylamine hydrochloride finished product obtained by the embodiment is detected to be 98.5%, and the quality requirement is met.

Example two

A method for recovering triethylamine hydrochloride from glyphosate reaction liquid by a glycine method comprises the following process steps:

s1: removing effluent and hydrochloric acid from glyphosate reaction liquid under vacuum condition and temperature environment (170 ℃) to obtain a solid-state mixture;

s2: cooling the solid mixture to 35 ℃, adding a solvent, and heating to 220 ℃ for phase transfer to obtain a solvent phase;

s3: cooling the solvent phase to obtain a triethylamine hydrochloride crude product and an oil phase, and washing the oil phase to obtain the triethylamine hydrochloride crude product; recycling the solvent for reusing in step S2 after the oil phase is washed, and obtaining phosphorous acid after the solvent is recycled;

s4: and centrifuging and spray drying the obtained triethylamine hydrochloride crude product to obtain a triethylamine hydrochloride finished product.

And adding the mother liquor obtained after the centrifugation of the triethylamine hydrochloride crude product into the triethylamine hydrochloride crude product in the centrifugation process, and continuing the centrifugation, wherein the adding step is repeated for 2 times.

The solvent in step S2 may be an alcohol solvent. The alcohol solvent is mixture of propanol, butanol and octanol.

In this example, the glyphosate reaction solution is about 750g, and the amount of glycine added in the glyphosate reaction solution is 150 g; theoretically, 275.2g of triethylamine hydrochloride is obtained, 269.7g of purity of the finally obtained triethylamine hydrochloride finished product is calculated, and the yield of the triethylamine hydrochloride is 98%; the yield of triethylamine hydrochloride is the amount of triethylamine hydrochloride that can be theoretically produced by adding glycine actually/the amount of triethylamine hydrochloride actually obtained by adding the same amount of glycine. The yield of triethylamine hydrochloride reaches the design requirement.

Meanwhile, the content of triethylamine hydrochloride in the triethylamine hydrochloride finished product obtained by the embodiment is detected to be 98.5%, and the quality requirement is met.

EXAMPLE III

A method for recovering triethylamine hydrochloride from glyphosate reaction liquid by a glycine method comprises the following process steps:

s1: removing effluent and hydrochloric acid from glyphosate reaction liquid under vacuum condition and temperature environment (150 ℃) to obtain a solid-state mixture;

s2: cooling the solid mixture to 20 ℃, adding a solvent, and heating to 80 ℃ for phase transfer to obtain a solvent phase;

s3: cooling the solvent phase to obtain a triethylamine hydrochloride crude product and an oil phase, and washing the oil phase to obtain the triethylamine hydrochloride crude product; recycling the solvent for reusing in step S2 after the oil phase is washed, and obtaining phosphorous acid after the solvent is recycled;

s4: and centrifuging and spray drying the obtained triethylamine hydrochloride crude product to obtain a triethylamine hydrochloride finished product.

And adding the mother liquor obtained after the centrifugation of the triethylamine hydrochloride crude product into the triethylamine hydrochloride crude product in the centrifugation process, and continuing the centrifugation, wherein the adding step is repeated for 1 time.

The solvent in step S2 may be an alcohol solvent. The alcohol solvent is methanol.

In this example, the glyphosate reaction solution is about 750g, and the amount of glycine added in the glyphosate reaction solution is 150 g; theoretically, 275.2g of triethylamine hydrochloride is obtained, 269.7g of purity of the finally obtained triethylamine hydrochloride finished product is calculated, and the yield of the triethylamine hydrochloride is 98%; the yield of triethylamine hydrochloride is the amount of triethylamine hydrochloride that can be theoretically produced by adding glycine actually/the amount of triethylamine hydrochloride actually obtained by adding the same amount of glycine. The yield of triethylamine hydrochloride reaches the design requirement.

Meanwhile, the content of triethylamine hydrochloride in the triethylamine hydrochloride finished product obtained by the embodiment is detected to be 98.5%, and the quality requirement is met.

The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.