CN108084037A - A kind of preparation method of methyl triethyl ammonium chloride - Google Patents
A kind of preparation method of methyl triethyl ammonium chloride Download PDFInfo
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- CN108084037A CN108084037A CN201711456261.4A CN201711456261A CN108084037A CN 108084037 A CN108084037 A CN 108084037A CN 201711456261 A CN201711456261 A CN 201711456261A CN 108084037 A CN108084037 A CN 108084037A
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- glyphosate
- ammonium chloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
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Abstract
The present invention provides a kind of preparation methods of methyl triethyl ammonium chloride, comprise the following steps：A) glyphosate mother solution is evaporated concentration, obtains glyphosate concentrated mother liquor；B) the glyphosate concentrated mother liquor is extracted with extractant, obtains extract；C) by the extract evaporative crystallization, methyl triethyl ammonium chloride is obtained.The present invention carries out separation and Extraction as raw material using glyphosate mother solution and obtains methyl triethyl ammonium chloride, it is produced using the production waste material in glyphosate industry as raw material, greatly reduce production cost, also so that glyphosate production waste material is re-used, waste entrainment is not only reduced but also has realized the rational utilization of resource；And separation and Extraction is only needed in producing process, without harsh chemical reaction, operating process is simple and practicable, and with good purity and yield, is conducive to the production of market scale metaplasia.
Description
Technical field
The present invention relates to chemical technology field, more particularly to a kind of preparation method of methyl triethyl ammonium chloride.
Background technology
Methyl triethyl ammonium chloride is a kind of quaternary ammonium salt, and molecular weight 151.68, fusing point is 282~284 DEG C, and appearance is white
Color powder or crystallization can be used as surfactant, phase transfer catalyst, metal extraction agent etc., it can also be modified
To the series of products of more high added value.Therefore, methyl triethyl ammonium chloride is a kind of important fine chemicals in chemical field,
Its demand also increasingly increases.
In the prior art, the preparation method of methyl triethyl ammonium chloride be typically using quaternary ammonium base and ammonium chloride as raw material,
Certain reaction condition issues biochemical reaction and is made.However, this chemical reaction preparation method condition is harsh, operation difficulty
Greatly, using chemicals as raw material, manufacturing cost is higher, it is impossible to carry out marketability large-scale production well.Therefore, exploitation simply has
The preparation method of the methyl triethyl ammonium chloride of effect has a very important significance.
The content of the invention
In view of this, the present invention provides a kind of preparation method of methyl triethyl ammonium chloride, preparations provided by the invention
Method greatly reduces production cost, and separation and Extraction is only needed in producing process, without harsh chemical reaction, prepares letter
It is single easy, while there is good yield and purity, be conducive to the production of market scale metaplasia.
The present invention provides a kind of preparation methods of methyl triethyl ammonium chloride, comprise the following steps：
A) glyphosate mother solution is evaporated concentration, obtains glyphosate concentrated mother liquor；
B) the glyphosate concentrated mother liquor is extracted with extractant, obtains extract；
C) by the extract evaporative crystallization, methyl triethyl ammonium chloride is obtained.
Preferably, in the step a), the mass ratio of glyphosate concentrated mother liquor and glyphosate mother solution is 1：(5~11).
Preferably, in the step b), the mass ratio of the glyphosate concentrated mother liquor and extractant is 1: (0.1~50).
Preferably, in the step b), extractant includes main extractant and auxiliary extraction agent；
The main extractant includes one or more of methanol, ethyl alcohol, isoamyl alcohol, butanol and acetonitrile；
The auxiliary extraction agent includes one kind in acetone, ether, ethyl acetate, Ethyl formate, benzene, toluene and dimethylbenzene
It is or several.
Preferably, the main extractant and the mass ratio of auxiliary extraction agent are 1: (0.01~0.9).
Preferably, in the step c), evaporative crystallization crystallizes to be evaporated under reduced pressure.
Preferably, the temperature that crystallization is evaporated under reduced pressure is 20~200 DEG C, and pressure is 0.01~0.1MPa.
Preferably, in the step c), separation of solid and liquid and drying are further included after the evaporative crystallization.
Preferably, after the glyphosate mother solution recycles triethylamine for the original nut liquid for being formed preparing glyphosate by glycin method
Obtained mother liquor.
Preferably, the sweet ammonia process is prepared using paraformaldehyde, glycine and alkyl phosphite as raw material in glyphosate, and three
Ethamine is catalyst.
The present invention provides a kind of preparation methods of methyl triethyl ammonium chloride, comprise the following steps：A) it is glyphosate is female
Liquid is evaporated concentration, obtains glyphosate concentrated mother liquor；B) the glyphosate concentrated mother liquor is extracted with extractant, is extracted
Object；C) by the extract evaporative crystallization, methyl triethyl ammonium chloride is obtained.The present invention is divided by raw material of glyphosate mother solution
Methyl triethyl ammonium chloride is obtained from extraction, is produced, greatly reduced as raw material using the production waste material in glyphosate industry
Production cost also so that glyphosate production waste material is re-used, has not only reduced waste entrainment but also has realized the reasonable of resource
Change and utilize；And separation and Extraction is only needed in producing process, without harsh chemical reaction, operating process is simple and practicable, and has
There are good purity and yield, be conducive to the production of market scale metaplasia.
Description of the drawings
It in order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention, for those of ordinary skill in the art, without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the mass spectrogram of principal component analysis in oil slick；
Fig. 2 produces flow chart for inventive embodiments 1；
Fig. 3 is the liquid-phase chromatographic analysis test chart of 1 products obtained therefrom of the embodiment of the present invention.
Specific embodiment
The present invention provides a kind of preparation methods of methyl triethyl ammonium chloride, comprise the following steps：
A) glyphosate mother solution is evaporated concentration, obtains glyphosate concentrated mother liquor；
B) the glyphosate concentrated mother liquor is extracted with extractant, obtains extract；
C) by the extract evaporative crystallization, methyl triethyl ammonium chloride is obtained.
Present invention firstly provides using glyphosate mother solution as raw material carry out separation and Extraction obtain methyl triethyl ammonium chloride, with
Production waste material in glyphosate industry is waste, greatly reduces production cost, also so that glyphosate production waste material is able to
It re-uses, had not only reduced waste entrainment but also realized the rational utilization of resource；And it only needs to separate to carry in producing process
It takes, without harsh chemical reaction, operating process is simple and practicable, and with good purity and yield, is conducive to market scale
Metaplasia is produced.
Glyphosate is the herbicide products of current global yield maximum and the advantage pesticide species in China.It is domestic at present
Glyphosate production technique have two：First, IDA method techniques, using diethanol amine as primary raw material, prepare intermediate pmida,
Then aoxidized to obtain glyphosate again；Second is that glycine method technique, mainly with glycine, paraformaldehyde, dimethylphosphite
For raw material, methanol is solvent, triethylamine is catalyst.In two production process routes of glyphosate, amino acetic acid in China method technique
The production capacity of glyphosate accounts for 70%, is the glyphosate production technique of current mainstream.
Glyphosate mother solution is generated simultaneously in glyphosate by using glycine production process, one ton of glyphosate is often produced and about generates 5 tons
Glyphosate mother solution.And inorganic salts, high organic content in glyphosate mother solution, belong to high intractable organism P wastewater.State at present
It has inside succeeded in developing and has realized that the glyphosate mother solution treatment process of industrialization mainly has two lines, be catalytic wet oxidation work respectively
Skill and high temperature orientation conversion process, two glyphosate mother solution processing routes can be realized to the elements such as sodium, phosphorus in glyphosate mother solution
Recycling, not only saved valuable phosphate rock resource, but also solved the problem of outlet of glyphosate mother solution substantially.
However, due to glyphosate mother solution complicated component, the method for processing mother solution of glyphosate succeeded in developing at present is only right
The elements such as the phosphorus in mother liquor are recycled, the recycling without paying close attention to the other compositions in mother liquor.Glyphosate is female
Liquid obtains high phosphorous glyphosate concentrated mother liquor, substantially increases the calorific value of mother liquor, be very suitable for height after desalination is concentrated by evaporation
Temperature orientation conversion reaction.But there are laminations, i.e. mother liquor in placement process after being concentrated by evaporation desalination for glyphosate mother solution mother liquor
The lighter oil slick of the upper strata proportion glyphosate concentrated mother liquor larger with next proportion can be converted into during storage tank.Glyphosate is dense
Contracting mother liquor directly goes orientation conversion production phosphate product technology very ripe, but upper strata oil slick is fresh attracts attention less.By
It is difficult in oil slick with glyphosate concentrated mother liquor into follow-up phosphorus recovery system, thus oil slick is caused the more to accumulate the more more, seriously
Affect the normal production of glyphosate mother solution processing.
Applicant analyzes oil slick property, the results show：Appearance is brown, and proportion is 1.02~1.06, PH 7.5
~9, Cl content are that 10%~12%, COD is 20%~30%, and moisture is 40%~50%, can when temperature is 500 DEG C or more
Vigorous combustion simultaneously generates a large amount of smog.As it can be seen that oil slick is a kind of chloride organic matter.
Through applicants have found that, comprising methyl triethyl ammonium chloride and moisture in the upper strata oil slick, and three second of methyl
The content of ammonium chloride is up to more than 40%, and moisture is up to 40%~50%.Mass spectral analysis test is carried out to oil slick, as a result as schemed
Shown in 1, Fig. 1 is the mass spectrogram of principal component analysis in oil slick, it can be seen that ionized molecule amount is 116.1 under mass spectrum holotype, is changed
Structure is (CH3CH2)3N+CH3Cl-.To the methyl triethyl ammonium chloride test article of gained after separating-purifying oil slick into row element
Analysis is tested and compared with the theoretical value of each element in methyl triethyl ammonium chloride, and the results are shown in Table 1, it can be seen that is surveyed
Each element content distribution is sufficiently close to theoretical value in test product, wherein, C, H, Cl constituent content are slightly lower, and H content is slightly higher, be due to
Methyl triethyl ammonium chloride easy to absorb moisture, caused by absorbing the moisture in air during the test.
The elemental analysis test result of 1 methyl triethyl ammonium chloride test article of table
| Element | N | C | H | CL |
| Test value, wt% | 9.06 | 53.62 | 12.63 | 21.02 |
| Theoretical value, wt% | 9.24 | 55.45 | 11.88 | 23.43 |
It is analyzed by mass spectral analysis and element test, it was demonstrated that the main component of oil slick is methyl triethyl ammonium chloride.Through Shen
It asks someone to explore, formation basic theory of the methyl triethyl ammonium chloride in glyphosate mother solution may be as shown in following formula (1) or formula (2)：
N(C2H5)3+CH3Cl=CH3N(C2H5)3·Cl (1)；
N(C2H5)3·HCl+CH3OH=CH3N(C2H5)3·Cl+H2O (2)。
Since methyl triethyl ammonium chloride is soluble easily in water, in oil slick in addition to methyl triethyl ammonium chloride, also containing 40%~
50% moisture, the two are combined in the form of hydrogen bond etc., very securely, it is difficult to recycle methyl three by common methods such as evaporative crystallizations
Ethyl ammonium chloride product, and the present invention has carried out glyphosate mother solution a series of specially treateds to obtain methyl triethyl group chlorination
Ammonium.
As described above, at present before glyphosate mother solution is discharged, it can be first to side product chlorinated sodium, the chloromethane in glyphosate mother solution
Alkane and dimethoxym ethane are recycled, and realize the recycling of resource, are discharged again after recycling above-mentioned useful by-product or sewage
Processing.However, the present invention but produces methyl triethyl ammonium chloride this fine chemicals using glyphosate mother solution as raw material, this
It is to be difficult to it is contemplated that both at home and abroad also there is not yet related side in open source information in routine techniques processing in the prior art or in industry
The report in face, the present invention are to be put forward for the first time using glyphosate mother solution as raw material to extract methyl triethyl ammonium chloride.
It tests and finds through applicant, the content of methyl triethyl ammonium chloride is 0.5%~1.0% in glyphosate mother solution, state
In interior annual 600000 tons of glyphosate yield, glyphosate by using glycine yield is based on annual 350000 tons, then the glyphosate mother solution that generates
In the methyl triethyl ammonium chloride that contains reach as high as nearly 30,000 tons, market value may be up to more than 9,000 ten thousand yuan.It is as it can be seen that sweet with grass
Phosphine mother liquor is direct material, can not only produce the methyl triethyl ammonium chloride with high added value, saves valuable resource, and
And glyphosate mother solution subsequent processing difficulty can be reduced, thus the present invention handles skill to the recycling mother solution for promoting glyphosate industry
Art promotion is of great significance.
According to the present invention, glyphosate mother solution is first evaporated concentration, obtains glyphosate concentrated mother liquor.
In the present invention, the glyphosate mother solution is preferably the original nut liquid recycling three for being formed preparing glyphosate by glycin method
The mother liquor obtained after ethamine.In the technique of preparing glyphosate by glycin method, catalyst of triethylamine is main during acid hydrolysis
To exist in the form of triethylamine hydrochloride, after glyphosate products are prepared, glyphosate original nut liquid, triethylamine salt can be generated
Hydrochlorate is then stayed in the glyphosate original nut liquid.Since catalyst of triethylamine dosage is larger, and higher price, therefore, making
It is standby obtain glyphosate after, the usual processing mode of this field is triethylamine hydrochloride in the glyphosate original nut liquid by generation with strong
Alkali replaces to recycle triethylamine, is re-used as preparation of the catalyst for glyphosate.Wherein, triethylamine hydrochloride is put with highly basic
Shown in the principle such as reaction equation (3) for gaining receipts：
N(C2H5)3HCl+NaOH=N (C2H5)3+NaCl+H2O (3)；
It is dissolved in the triethylamine hydrochloride in glyphosate original nut liquid and after alkali reaction, the triethylamine of formation is due to being insoluble in water
Layering, most of triethylamine are recycled by quantizer, and the triethylamine being entrained on a small quantity in glyphosate mother solution uses rectifying column process
It is recycled, distillation residual liquid is glyphosate mother solution.
In the present invention, the glycine method is preferably alkyl ester process, i.e., with paraformaldehyde, glycine and phosphorous acid
Arrcostab is raw material, and triethylamine is the preparation method of catalyst.In the present invention, the species of the alkyl phosphite is not special
Limitation, to prepare conventional alkyl phosphite in glyphosate technique in this field, including dimethylphosphite, phosphorous acid three
Methyl esters or diethyl phosphite；Preferably phosphorous acid two more commonly used in alkyl ester process industrial production glyphosate route
Methyl esters.When alkyl phosphite method prepares glyphosate, depolymerization, addition and hydrolysis occur under catalyst action for raw material, raw
Into glyphosate products, to obtaining glyphosate mother solution after devil liquor recovery triethylamine.
The present invention is first evaporated glyphosate mother solution concentration, come remove inorganic salts (such as sodium chloride) impurity and moisture,
Improve mother liquid concentration.In the present invention, preferably it is concentrated by evaporation to the mass ratio of gained glyphosate concentrated mother liquor and glyphosate mother solution and is
1：(5~11).It can ensure fully to remove the impurity such as inorganic salts in the range of the concentrating degree, and can ensure that mother liquor has
Good rheological characteristic convenient for following process processing, is evaporated glyphosate mother solution concentration and improves methyl triethyl group chlorine
Change relative concentration of the ammonium in glyphosate mother solution, reach hypersaturated state, be more conducive to follow-up methyl triethyl ammonium chloride with
The separation of glyphosate mother solution.
In the present invention, for small batch glyphosate mother solution, to improve evaporation efficiency and reducing temperature of charge, the evaporation is dense
Contracting is preferably that concentration is evaporated under reduced pressure；The temperature and pressure of the reduction vaporization is not particularly limited, and is steamed according to being depressurized in this field
The normal condition of stimulating food material performs, and if pressure can be 0.01~0.1MPa, temperature can be 20~200 DEG C.Subtract described
After pressure is concentrated by evaporation, preferably also it is centrifuged.For ease of the processing of high-volume glyphosate mother solution, the side of the evaporation and concentration
Formula is preferably that single effect evaporation concentration, multiple-effect evaporation concentration or MVR are concentrated by evaporation, and can be steamed by means respectively of single effect evaporator, multiple-effect
It sends out device or MVR evaporators is realized.After the evaporation and concentration, glyphosate concentrated mother liquor is obtained.
According to the present invention, after glyphosate concentrated mother liquor is obtained, the glyphosate concentrated mother liquor is extracted with extractant, is obtained
Extract.
The mass ratio of the glyphosate concentrated mother liquor and extractant is preferably 1: (0.1~50), more preferably 1: (1~5).
In the present invention, due to the particularity of glyphosate concentrated mother liquor, it is difficult to it finds suitable single extractant and is extracted, institute of the present invention
It states extractant and preferably includes main extractant and auxiliary extraction agent；Wherein, the main extractant preferably includes methanol, ethyl alcohol, isoamyl
One or more of alcohol, butanol and acetonitrile；The auxiliary extraction agent preferably includes acetone, ether, ethyl acetate, formic acid second
One or more of ester, benzene, toluene and dimethylbenzene.Through applicants have found that, can be filled using said combination formula extractant
Divide extraction glyphosate concentrated mother liquor, methyl triethyl ammonium chloride ingredient is made to be sufficiently separated with ingredients such as other organic matter salt.At this
In one embodiment of invention, main extractant is methanol, and auxiliary extraction agent is acetone, ethyl acetate and toluene.The present invention's
In another embodiment, main extractant is ethyl alcohol and isoamyl alcohol, and auxiliary extraction agent is acetone, Ethyl formate and dimethylbenzene.At this
In the other embodiments of invention, the other combinations of main extractant and auxiliary extraction agent selected from above-mentioned listed species.
In the present invention, main extractant and the mass ratio of auxiliary extraction agent are preferably 1: (0.01~0.9).The one of the present invention
In a embodiment, main extractant is methanol, and auxiliary extraction agent is acetone, ethyl acetate and toluene, main extractant and auxiliary extraction
The mass ratio of agent is 1:0.82.In another embodiment of the present invention, main extractant be ethyl alcohol and isoamyl alcohol, auxiliary extraction agent
For acetone, Ethyl formate and dimethylbenzene, the mass ratio of main extractant and auxiliary extraction agent is 1:0.54.The present invention uses extractant
Extract glyphosate concentrated mother liquor, gained raffinate phase mainly comprising glyphosate, increase the organic matters salt such as sweet phosphorus, available for recycling phosphorus member
Element includes methyl triethyl ammonium chloride in gained extract.
According to the present invention, after extract is obtained, by the extract evaporative crystallization, methyl triethyl ammonium chloride is obtained.
The extractant in extract is evaporated off by evaporative crystallization by the present invention, to improve evaporative crystallization efficiency, the evaporation
Crystallization is preferably that crystallization is evaporated under reduced pressure.In the present invention, the temperature that crystallization is evaporated under reduced pressure is preferably 20~150 DEG C；Decompression is steamed
The pressure of hair crystallization is preferably 0.07~0.1MPa.It can be selected according to the selection of above-mentioned extractant in the range of the temperature and pressure
Select evaporative crystallization parameter.
In the present invention, after crystallization is evaporated, separation of solid and liquid and drying are preferably also carried out.The separation of solid and liquid is preferably
It centrifuges.The temperature of the drying is preferably 100~280 DEG C, more preferably 150~200 DEG C, in the temperature range both
It can ensure that drying effect can avoid methyl triethyl ammonium chloride from decomposing again, and then obtain the higher methyl triethyl group chlorine of content
Change ammonium product.
The present invention provides a kind of preparation methods of methyl triethyl ammonium chloride, and a system is carried out by raw material of glyphosate mother solution
The separation and Extraction of row is so as to obtaining methyl triethyl ammonium chloride, on the one hand, using the production waste material in glyphosate industry as raw material system
It takes, greatly reduces production cost, also so that glyphosate production waste material is re-used, both reduced waste entrainment, reduced
The intractability of glyphosate waste liquid, and realize the rational utilization of resource；Meanwhile it only needs to separate to carry in producing process
It takes, without harsh chemical reaction, operating process is simple and practicable, is conducive to the production of market scale metaplasia；Moreover, the preparation method energy
Good purity and yield are enough obtained, production and practical application request can be met.
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are simply for the feature and advantage that further illustrate the present invention rather than to the claims in the present invention
Limitation.In following embodiment, glyphosate mother solution used is that prepared by glycine method phosphorous acid dimethyl ester method glyphosate to be formed
The glyphosate mother solution obtained after glyphosate original nut liquid recycling triethylamine.It following embodiment glyphosate mother liquor raw material and produced
The extract and the component distributing of product formed in journey is tested by liquid-phase chromatographic analysis to be obtained.
Embodiment 1
With processing capacity it is 100kg/h's by 5000kg glyphosate mother solutions (methyl triethyl ammonium chloride content be 0.96%)
After triple-effect evaporation plant carries out continuous evaporation desalination, glyphosate concentrated mother liquor 476.2kg is obtained；Add in 571.44kg extractants into
Row extraction, extractant composition are：Methanol 55wt%, acetone 25wt%, ethyl acetate 18wt%, toluene 2wt%, extraction terminate
Afterwards, raffinate phase 478.5kg, extract 569.14kg are obtained (methyl triethyl ammonium chloride content is 8.15%).Extract is existed
Be evaporated under reduced pressure under 50~100 DEG C and 0.095MPa pressure crystallization 5 it is small when after be centrifuged, dried after at 180 DEG C, obtain
To methyl triethyl ammonium chloride product 45.70kg, methyl triethyl ammonium chloride content is 98.2%, overall recovery 93.49%.
Evaporative crystallization recycles extractant 520.12kg, can be applied to extraction process recycling.
Above-mentioned producing process produces flow chart referring to Fig. 2, Fig. 2 for the embodiment of the present invention 1.
Liquid-phase chromatographic analysis test is carried out to products obtained therefrom, test condition is as follows：
Reagent：Methyl triethyl ammonium chloride standard items 98%, acetonitrile (HPLC grades), ammonium acetate (analysis is pure), acetic acid (analysis
It is pure), water (ultra-pure water) treats test sample (i.e. above-mentioned preparation method products obtained therefrom)；
Instrument：Waters HPLC2695, evaporative light-scattering device (ELSP2424)；
Chromatographic column：Dikmaspuile C 18-EP, 5 μm, 250mm × 4.6mm；
Mobile phase：A phases：Acetic acid aqueous solution (mass concentration 0.1%), B phases：(mass concentration is ammonium acetate acetonitrile solution
0.08%)；A phases: B phase=40: 60 (volume ratios)；
Flow velocity：0.3mL/min.
Liquid-phase chromatographic analysis test result is as shown in figure 3, the liquid-phase chromatographic analysis that Fig. 3 is the present embodiment products obtained therefrom is tested
Figure, the results show that it is methyl triethyl ammonium chloride.
Embodiment 2
With processing capacity it is 100kg/h's by 5000kg glyphosate mother solutions (methyl triethyl ammonium chloride content be 0.96%)
After triple-effect evaporation plant carries out continuous evaporation desalination, glyphosate concentrated mother liquor 476.2kg is obtained；Add in 571.44kg extractants into
Row extraction, extractant composition are：Ethyl alcohol 50wt%, acetone 25wt%, isoamyl alcohol 15wt%, Ethyl formate 5wt%, dimethylbenzene
5wt% after extraction, obtains raffinate phase 477.2kg, and (methyl triethyl ammonium chloride content is extract 570.44kg
8.08%).Extract is evaporated under reduced pressure under 80 DEG C and 0.090 pressure crystallization 8 it is small when after be centrifuged, after 200
It is dried at DEG C, obtains methyl triethyl ammonium chloride product 46.15kg, methyl triethyl ammonium chloride content is 98.1%, total to recycle
Rate is 94.32%.Evaporative crystallization recycles extractant 523.50kg, can be applied to extraction process recycling.
Embodiment 3
With processing capacity it is 100kg/h's by 5000kg glyphosate mother solutions (methyl triethyl ammonium chloride content be 0.96%)
After triple-effect evaporation plant carries out continuous evaporation desalination, glyphosate concentrated mother liquor 476.2kg is obtained；Add in 1428.6kg extractants into
Row extraction, extractant composition are：Ethyl alcohol 50wt%, acetone 30wt%, isoamyl alcohol 5wt%, Ethyl formate 5wt%, dimethylbenzene
5wt% after extraction, obtains raffinate phase 478.9kg, and (methyl triethyl ammonium chloride content is extraction phase 1425.9kg
3.22%).Extract is evaporated under reduced pressure under 85 DEG C and 0.92MPa pressure crystallization 10 it is small when after be centrifuged, after
It is dried at 190 DEG C, obtains methyl triethyl ammonium chloride product 46.88kg, methyl triethyl ammonium chloride content is 98.5%, total to return
Yield is 96.21%.Evaporative crystallization recycles extractant 1405.7kg, can be applied to extraction process recycling.
Comparative example 1
With processing capacity it is 100kg/h's by 5000kg glyphosate mother solutions (methyl triethyl ammonium chloride content be 0.96%)
After triple-effect evaporation plant carries out continuous evaporation desalination, glyphosate concentrated mother liquor 476.2kg is obtained；Add in 23.81kg extractants into
Row extraction, extractant composition are：Ethyl alcohol 50wt%, acetone 30wt%, isoamyl alcohol 5wt%, Ethyl formate 5wt%, dimethylbenzene
5wt% after extraction, obtains raffinate phase 481.56kg, and (methyl triethyl ammonium chloride content is extract 18.45kg
20.5%).It is centrifuged after when by extract, reduction vaporization crystallization 2.5 is small under 60 DEG C and 0.096MPa pressure, afterwards
It is dried at 180 DEG C, obtains methyl triethyl ammonium chloride product 3.87kg, methyl triethyl ammonium chloride content is 97.8%, always
The rate of recovery is 7.89%.Evaporative crystallization recycles extractant 17.6kg, can be applied to extraction process recycling.
Comparative example 2
With processing capacity it is 100kg/h's by 5000kg glyphosate mother solutions (methyl triethyl ammonium chloride content be 0.96%)
After triple-effect evaporation plant carries out continuous evaporation desalination, glyphosate concentrated mother liquor 476.2kg is obtained；Add in the extraction of 571.44kg ethyl alcohol
Agent is extracted, and since ethyl alcohol with concentrated mother liquor mixes and can not be layered, thus extraction test fails, and can not obtain methyl triethyl group
Ammonium chloride.
Specific case used herein is set forth the principle of the present invention and embodiment, and above example is said
Bright to be only intended to help the method and its core concept for understanding the present invention, including best mode, and but also this field is appointed
What technical staff can put into practice the present invention, including manufacturing and using any device or system and the method for any combination of implementation.
It should be pointed out that for those skilled in the art, it without departing from the principle of the present invention, can also be right
Some improvement and modification can also be carried out by the present invention, these improvement and modification are also fallen into the protection domain of the claims in the present invention.This hair
The scope of bright patent protection is defined by the claims, and may include those skilled in the art it is conceivable that other implementation
Example.If these other embodiments have be similar to claim character express structural element or if they include with
Equivalent structural elements of the character express of claim without essence difference, then these other embodiments should also be included in right will
In the range of asking.
Claims (10)
1. a kind of preparation method of methyl triethyl ammonium chloride, which is characterized in that comprise the following steps：
A) glyphosate mother solution is evaporated concentration, obtains glyphosate concentrated mother liquor；
B) the glyphosate concentrated mother liquor is extracted with extractant, obtains extract；
C) by the extract evaporative crystallization, methyl triethyl ammonium chloride is obtained.
2. preparation method according to claim 1, which is characterized in that in the step a), glyphosate concentrated mother liquor and grass
The mass ratio of sweet phosphine mother liquor is 1：(5~11).
3. preparation method according to claim 1, which is characterized in that in the step b), the glyphosate concentrated mother liquor
Mass ratio with extractant is 1: (0.1~50).
4. the preparation method according to claim 1 or 3, which is characterized in that in the step b), extractant includes main extraction
Agent and auxiliary extraction agent；
The main extractant includes one or more of methanol, ethyl alcohol, isoamyl alcohol, butanol and acetonitrile；
The auxiliary extraction agent includes one kind or several in acetone, ether, ethyl acetate, Ethyl formate, benzene, toluene and dimethylbenzene
Kind.
5. preparation method according to claim 4, which is characterized in that the main extractant and the mass ratio of auxiliary extraction agent
For 1: (0.01~0.9).
6. preparation method according to claim 1, which is characterized in that in the step c), evaporative crystallization is reduction vaporization
Crystallization.
7. preparation method according to claim 6, which is characterized in that the temperature that crystallization is evaporated under reduced pressure is 20~200
DEG C, pressure is 0.01~0.1MPa.
8. preparation method according to claim 1, which is characterized in that in the step c), after the evaporative crystallization also
Including separation of solid and liquid and drying.
9. preparation method according to claim 1, which is characterized in that the glyphosate mother solution is that prepared by glycine method grass
The mother liquor obtained after the original nut liquid recycling triethylamine that sweet phosphine is formed.
10. preparation method according to claim 9, which is characterized in that the sweet ammonia process is prepared in glyphosate with poly first
Aldehyde, glycine and alkyl phosphite are raw material, and triethylamine is catalyst.
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