CN108084032A - A kind of method that methyl triethylammonium hydroxide is prepared using glyphosate mother solution - Google Patents
A kind of method that methyl triethylammonium hydroxide is prepared using glyphosate mother solution Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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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
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/03—Monoamines
- C07C211/04—Mono-, di- or tri-methylamine
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/03—Monoamines
- C07C211/05—Mono-, di- or tri-ethylamine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
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Abstract
The present invention provides a kind of method that methyl triethylammonium hydroxide is prepared using glyphosate mother solution, comprises the following steps：Alkali is added in glyphosate mother solution, carries out Basic fluxing raction at reflux, recycles the methyl triethyl ammonium chloride in glyphosate mother solution；The temperature of the Basic fluxing raction is 50~200 DEG C；When the time of the Basic fluxing raction is 0.5~24 small.The present invention is using glyphosate mother solution as direct material, it can not only recycle with the triethylamine derivative methyl triethyl ammonium chloride in glyphosate mother solution, methyl triethylammonium hydroxide of the production with compared with high added value, save valuable resource, and the subsequent processing difficulty of glyphosate mother solution can be reduced, thus, the present invention is of great significance to the recycling mother solution treatment technology promotion for promoting glyphosate industry.Further, the present invention also continues organic amine of the production with more high added value using the methyl triethylammonium hydroxide of production, brings the economic value of bigger.
Description
Technical field
The invention belongs to multipurpose use of the three wastes technical fields more particularly to a kind of utilization glyphosate mother solution to prepare three second of methyl
The method of base ammonium hydroxide.
Background technology
Glyphosate is the herbicide kind of current global dosage maximum, and global year usage amount accounts for all remove more than 1,000,000 tons
The 48% of careless agent dosage, annual value of production is more than 6,000,000,000 dollars.With the expansion of resistance glyphosate genetically modified crops usable floor area, following grass
The market prospects of sweet phosphine are still had an optimistic view of.
At present, for domestic glyphosate aggregated capacity close to 900,000 tons/year, excess capacity is serious.Meanwhile in glyphosate production process
There is the generation of high-concentration phosphorus-containing wastewater, environmental hazard is big, for this purpose, national correlation department increases the supervision power to glyphosate industry
Degree.On the one hand, the expansion of glyphosate technicals production capacity is inhibited from source, on the other hand, by multinomial measure, to glyphosate industry
Environmentally friendly verification is carried out, self-discipline, and the by-product to being generated in glyphosate production process is guided, carries out the works such as standard formulation
Make, to realize the cleanly production of glyphosate industry.
By-product is more in glyphosate production process, such as chloromethanes, dimethoxym ethane, has been achieved with recycling recycling profit
With.The especially discovery and recycling of by-product chloromethanes facilitates the resources circulation of two big industry of glyphosate-organosilicon, is formed
Circular economy advantage with conspicuous characteristics.
Glyphosate by using glycine production technology is using paraformaldehyde, glycine, dimethylphosphite as primary raw material, triethylamine
For catalyst, by depolymerization, addition, hydrolysis, glyphosate products are obtained.Wherein, catalyst of triethylamine is in acid hydrolysis
Mainly exist in journey in the form of triethylamine hydrochloride, and ultimately reside in glyphosate mother liquor.Since triethylamine dosage is larger, and
And value is higher, therefore, in glyphosate production process needs to replace in triethylamine hydrochloride highly basic and recycle, technological principle is：
N(C2H5)3HCl+NaOH=N (C2H5)3+NaCl+H2O (1)
After being dissolved in the reaction of the triethylamine hydrochloride in glyphosate mother liquor system and alkali, it is layered when being insoluble in water, greatly
Part triethylamine is recycled by quantizer, and the triethylamine being entrained on a small quantity in glyphosate mother solution is recycled using rectification working process,
Distillation residual liquid is glyphosate mother solution.
In recent years, the glyphosate leading enterprise with Xin An groups etc. for representative develops recycling mother solution of glyphosate and utilizes skill
Art solves the recycling problem of by-product in glyphosate production process-high concentration organism P wastewater, has obtained added value
Higher industrial phosphoric acid product salt sets up new model for the cleanly production of glyphosate industry.Nevertheless, glyphosate is given birth to
Still there are other by-products to be not yet utilized effectively during production, wasted valuable resource.
The content of the invention
It is an object of the invention to provide a kind of resource utilization method of glyphosate mother solution, the method in the present invention can
Triethylamine derivative effectively in recycling glyphosate mother solution, and it is further prepared into the methyl triethyl group hydrogen-oxygen with high added value
Change ammonium and organic amine product, save precious resources, while lower the difficulty of glyphosate mother solution subsequent processing, to promoting glyphosate row
The recycling mother solution treatment technology promotion of industry is of great significance.
The present invention provides a kind of preparation method of methyl triethylammonium hydroxide, comprises the following steps：
Alkali is added in the glyphosate mother solution of recycling Triethylamine catalyst, then carries out Basic fluxing raction, then by distillation or
The methyl triethylammonium hydroxide of rectifying recycling Basic fluxing raction generation；Distillation/distillation residual liquid obtains industrial product salt after centrifugation.
Or
By the pretreatment desalination such as glyphosate mother solution evaporation and concentration or film process, glyphosate concentrated mother liquor is obtained；By glyphosate
The oil slick and mother liquor of the further isolated mainly triethylammonium hydroxide containing methyl of concentrated mother liquor；Alkali is added in oil slick,
Basic fluxing raction is carried out under reflux state, methyl triethylammonium hydroxide is further obtained by distillation or rectifying；Remaining raffinate warp
Nacl is obtained after centrifugation, raffinate goes glyphosate mother solution phosphorus recovery system.
The temperature of the Basic fluxing raction is 50~200 DEG C；
When the time of the Basic fluxing raction is 0.5~24 small.
Preferably, the molar ratio of the alkali and methyl triethyl ammonium chloride is：(1~10)：1.
Preferably, distillation or rectifying are further included after the Basic fluxing raction；
The temperature of the distillation/rectifying is 50~200 DEG C；
When the time of the distillation rectifying is 0.5~10 small.
Preferably, the recovery method further includes the step of by-product Nacl is recycled from glyphosate mother solution；
It is centrifuged after the Basic fluxing raction, by-product Nacl is recycled；
Or
Concentration or UF membrane are evaporated before the Basic fluxing raction, by-product Nacl is recycled.
Preferably, by the product of the Basic fluxing raction under catalysts conditions catalytic pyrolysis, obtain organic amine.
Preferably, the catalyst is nickel system metal complex, Ferrious material complex and cobalt system metal complex, platinum
Oxide, the chloride of platinum, one or more of the chloride of the oxide of rhodium and rhodium.
Preferably, the quality of the catalyst is the 0.01~1% of the quality of the product of the Basic fluxing raction.
Preferably, the temperature of the catalytic pyrolysis is 100~400 DEG C；
The pressure of the catalytic pyrolysis is 0.1~10MPa.
Preferably, which is characterized in that the organic amine is triethylamine and/or methylamine.
Preferably, after the glyphosate mother solution recycles triethylamine for the original nut liquid for being formed preparing glyphosate by glycin method
Obtained diluted alkaline mother liquor.
The present invention provides a kind of method for preparing methyl triethylammonium hydroxide, comprises the following steps：By glyphosate mother solution
Desalination is concentrated by evaporation, then the oil slick of the further isolated mainly triethylammonium hydroxide containing methyl；Alkali is added in oil slick,
Basic fluxing raction is carried out at reflux, and passes through the methyl triethylammonium hydroxide of distillation/rectifying recycling reaction production；It is described
The temperature of Basic fluxing raction is 50~200 DEG C；When the time of the Basic fluxing raction is 0.5~24 small.The present invention is with glyphosate mother solution
For direct material, it can not only recycle with triethylamine derivative-methyl triethyl ammonium chloride in glyphosate mother solution, go forward side by side
One step is prepared into the methyl triethylammonium hydroxide with compared with high added value, saves valuable ammonium resource, and can reduce grass
The subsequent processing difficulty of sweet phosphine mother liquor, thus, the present invention promotes tool to the recycling mother solution treatment technology for promoting glyphosate industry
It is significant.
Further, the present invention also continues production using the methyl triethylammonium hydroxide of production has more high added value
Organic amine, bring the economic value of bigger.
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 a kind of recycling process diagram of glyphosate mother liquor of the present invention；
Fig. 2 is another recycling process diagram of glyphosate mother liquor of the present invention；
Fig. 3 is the flow chart that organic amine is prepared in the present invention.
Specific embodiment
The present invention provides a kind of method that quaternary ammonium base and organic amine are prepared using glyphosate mother solution, comprises the following steps：
Alkali is added in the oil slick for being concentrated by evaporation from glyphosate diluted alkaline mother liquor and being obtained after desalination, is carried out at reflux
Basic fluxing raction, further distillation/rectifying obtain methyl triethylammonium hydroxide；
The temperature of the Basic fluxing raction is 50~200 DEG C；
When the time of the Basic fluxing raction is 0.5~24 small.
Glyphosate by using glycine production technology is using paraformaldehyde, glycine, dimethylphosphite as primary raw material, triethylamine
For catalyst, by depolymerization, addition, hydrolysis, glyphosate products are obtained.Wherein, catalyst of triethylamine is in acid hydrolysis
Mainly exist in journey in the form of triethylamine hydrochloride, and ultimately reside in glyphosate mother liquor.Since triethylamine dosage is larger, and
And value is higher, therefore, in glyphosate production process needs to replace in triethylamine hydrochloride highly basic and recycle, technological principle is：
N(C2H5)3HCl+NaOH=N (C2H5)3+NaCl+H2O (1)
After being dissolved in the reaction of the triethylamine hydrochloride in glyphosate mother liquor system and alkali, it is layered when being insoluble in water, greatly
Part triethylamine is recycled by quantizer, and the triethylamine being entrained on a small quantity in glyphosate mother solution is recycled using rectification working process,
Distillation residual liquid is glyphosate mother solution.
In domestic glyphosate enterprise production process the unit consumption of catalyst of triethylamine be 20~30kg/t glyphosates, the three of loss
Ethamine is remained essentially in glyphosate mother solution.However, applicant is detected triethylamine in glyphosate mother liquid, triethylamine content
It is very low, have a tremendous difference with theoretical estimated value.Applicant has found that glyphosate mother solution recycles chlorine in glyphosate mother solution treatment research
After changing sodium, there are laminations during storage：Upper strata is brown or the oily liquids of black, and lower floor is lurid glyphosate
Mother liquor.Upper strata oily liquids proportion is small, and about 1.0~1.1, it is significantly different with glyphosate mother solution, and chloride ion content and nitrogen
Content is higher.Particularly, oily liquids high organic content, COD are up to more than 20%.Above- mentioned information absolutely proves that grass is sweet
There are the organic matter of the elements such as a kind of nitrogenous and chlorine in phosphine mother liquor, and this organic matter can be dissolved in water and most of solvent.
Using analysis methods such as mass spectrum and liquid chromatograies, finally it is determined that there are triethylamine derivative-three second of methyl in glyphosate mother solution
Ammonium chloride is explored through applicant, formation basic theory of the methyl triethyl ammonium chloride in glyphosate mother solution may such as following formula (2) or
Shown in formula (3)：
N(C2H5)3+CH3Cl=CH3N(C2H5)3·Cl (2)
Or N (C2H5)3·HCl+CH3OH=CH3N(C2H5)3·Cl+H2O (3)
At present it has been determined that the derivative methyl triethyl ammonium chloride of catalyst of triethylamine is that grass is sweet after forming recycling sodium chloride
The main component of phosphine concentrated mother liquor oil slick at the middle and upper levels.Methyl triethyl ammonium chloride is a kind of quaternary amine, and English is entitled
Methyltriethylammonium chloride, molecular weight 151.68, fusing point are 282~284 DEG C, and appearance is white powder
End or crystallization, can be used as surfactant, phase transfer catalyst, metal extraction agent etc., it can also be modified to obtain more
The series of products of high added value.The content of methyl triethyl ammonium chloride is 0.5~1.0% in glyphosate mother solution, then domestic annual
In 600000 tons of glyphosate yield, glyphosate by using glycine yield contains based on annual 350000 tons in the glyphosate mother solution then generated
Methyl triethyl ammonium chloride can reach nearly 30,000 tons, market value can reach more than 9,000 ten thousand yuan.
As it can be seen that using glyphosate mother solution as direct material, the methyl triethyl group chlorine with compared with high added value can be not only recycled
Change ammonium, save valuable resource, and the follow-up difficulty of glyphosate mother solution can be reduced, thus the present invention is to promoting glyphosate industry
Recycling mother solution treatment technology promotion be of great significance.
However, applicants have found that, solubility of the methyl triethyl ammonium chloride in glyphosate mother solution is larger, and methyl
Triethyl ammonium chloride is soluble easily in water, and the two is combined in the form of hydrogen bond etc., very securely, it is difficult to be carried out by conventional dewatering
Dehydration, and impurity is more in glyphosate mother solution, it is difficult to be recycled by conventional methods such as simple condensing crystallizings.
In view of methyl triethyl ammonium chloride characteristic soluble easily in water and be difficult to directly recycle, applicant has found under study for action,
Methyl triethyl ammonium chloride can be decomposed by the method for alkaline hydrolysis, and then generate the higher methyl triethyl group hydroxide of added value
Ammonium, methyl triethylammonium hydroxide are a kind of organic alkalis, may be used as phase transfer catalyst, Zeolite synthesis template, ore deposit
Object flotation agent and semiconductor circuit alkaline etchant etc., industrial use is wide.The product processes generally relate to be electrolysed
Deng reaction, production cost is high, and process conditions are harsher.If first is directly recycled from glyphosate mother solution according to the thinking of applicant
Triethylammonium chloride produces methyl triethylammonium hydroxide, and raw material sources are extensive, technological process is simple, product quality is preferable,
It is thus a kind of production new technique for having the very strong market competitiveness.
The present invention preferably carries out alkaline hydrolysis by following two methods to the methyl triethyl ammonium chloride in glyphosate mother solution：
The first, as shown in Figure 1, directly using glyphosate mother solution as raw material, alkali is added in glyphosate mother solution and carries out alkaline hydrolysis
Reaction, is converted into methyl triethylammonium hydroxide crude product by the methyl triethyl ammonium chloride in mother liquor, then is obtained by rectifying
Then the methyl triethylammonium hydroxide of technical grade centrifuges rectifying residual night, recycling by-product Nacl (sodium chloride).
In first method, the alkali is preferably liquid caustic soda or piece alkali, the alkali be preferably potassium hydroxide, sodium hydroxide,
One or more of alkaline earth metal hydroxides such as lithium hydroxide；The molar ratio of the alkali and methyl triethyl ammonium chloride is preferred
For (1~10)：1, more preferably (1.2~5)：1, be most preferably (1.5~2)：1.
The temperature of the Basic fluxing raction is 50~200 DEG C, more preferably 100~150 DEG C；The time of the Basic fluxing raction is
0.5~24 it is small when, more preferably 2~10 it is small when, be most preferably 2~5 it is small when；Described in the present invention preferably carries out at reflux
Basic fluxing raction.
The temperature of the rectifying is preferably 50~200 DEG C；When the time of the rectifying is preferably 0.5~10 small.
The present invention preferably carries out Basic fluxing raction and rectifying in same device, such as reactive distillation column, so not only may be used
To keep the continuity of production, and the methyl triethylammonium hydroxide generated with quick separating, can be more advantageous to the life of product
Into raising production efficiency.
Second, as shown in Fig. 2, glyphosate mother solution is first concentrated by evaporation or the pretreatment of UF membrane, recycle by-product
Nacl sodium chloride, then by Liquid liquid Separation, obtain the oil slick of the mainly triethyl ammonium chloride containing methyl, alkali is being added to carry out oil slick
Basic fluxing raction obtains methyl triethylammonium hydroxide crude product, then carries out rectifying to it, obtains technical grade methyl triethyl group hydroxide
Ammonium.
Second method is to first have to carry out enrichment processing, i.e., will be in glyphosate mother solution by means such as dehydration, desalinations
Most of moisture and sodium chloride removing, realize recycling by-product Nacl while improve methyl triethyl ammonium chloride in glyphosate
Relative concentration in mother liquor reaches " hypersaturated state ", is layered and is precipitated with glyphosate mother solution, and as brown or black is floating
Oil realizes the initial gross separation of the quaternary amine and glyphosate mother solution.It is chromatographed from glyphosate mother solution in isolated oil slick, methyl
The content of triethyl ammonium chloride can reach more than 40%.But methyl triethyl ammonium chloride is soluble easily in water, thus also contain in oil slick
There is 40~50% moisture.
In the second approach, described be concentrated by evaporation is used for removing inorganic salts (such as sodium chloride) impurity and moisture, raising
Mother liquid concentration.In the present invention, it is 1 to be preferably concentrated by evaporation to the mass ratio of gained glyphosate concentrated mother liquor and glyphosate mother solution：(5
~11).It can ensure fully to remove the impurity such as inorganic salts in the range of the concentrating degree, and it is good to ensure that mother liquor has
Rheological characteristic, convenient for following process processing, concentration is evaporated to glyphosate mother solution and improves methyl triethyl ammonium chloride
Relative concentration in glyphosate mother solution, reaches hypersaturated state, is more conducive to follow-up methyl triethyl ammonium chloride and grass is sweet
The layering of phosphine mother liquor.
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 20~150 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.
Alternatively, carrying out UF membrane and evaporative crystallization successively to glyphosate mother solution, the recycling to by-product Nacl can be also realized,
The UF membrane can realize that the film that the UF membrane uses preferably includes microfiltration membranes, ultrafiltration membrane, nanofiltration by means of film separation system
One or more of film, reverse osmosis membrane and electrodialytic membranes.It is furthermore preferred that the present invention carries out UF membrane using combined films, it is described
Combined films are preferably ultrafiltration-nanofiltration combined films, micro-filtration-ultrafiltration-nanofiltration combined films, filtration-reverse osmosis combined films or ultrafiltration-electric osmose
Analyse combined films；In the present invention, the combined films define the sequencing of film process, i.e., needed in film separation system successively according to
The secondary various types of films by combined films, such as ultrafiltration-nanofiltration combined films are contained in film separation system, and process object is first led to
It crosses ultrafiltration membrane and is handled and handled again by NF membrane, the rest may be inferred for other combined films.The present invention is to above-mentioned various films
Species and material are not particularly limited, and are various types of films well known to those skilled in the art.
The present invention can remove suspended impurity, organic macromolecule and salt in glyphosate mother solution etc., separation effect by UF membrane
Fruit is preferable, a large amount of impurity is stripped of, convenient for subsequent processing.Glyphosate mother solution obtains film dope and the light liquid of film after UF membrane；Its
In, film dope is mainly comprising the organic matters such as glyphosate, available for recycling P elements, three second of the main sodium chloride-containing of the light liquid of film and methyl
Ammonium chloride.
The present invention is evaporated film light liquid in crystallization removing sodium chloride, obtains concentrate, can be by the sodium chloride industry of removing
Salt is recycled.The temperature of the evaporative crystallization is preferably 20~150 DEG C, and the time of the evaporative crystallization is preferably 0.5~10
Hour.
After recycling by a kind of completion by-product Nacl in evaporation and concentration or UF membrane both approaches, the present invention is right
Glyphosate concentrated mother liquor carries out Liquid liquid Separation, and separation process glyphosate concentrated mother liquor is layered, and upper strata is brown or black
Oil slick, lower floor are light yellow mother liquor.In the present invention, the Liquid liquid Separation preferably includes standing, rotary filter press or dish-style separation；For
Separative efficiency and separating effect are improved, is more preferably separated using rotary filter press or dish-style；The rotary filter press can be by means of spinning liquid
Separator realizes that the dish-style separation can be realized by means of disk centrifuge.The present invention does not have the condition of the rotary filter press
It is specifically limited, it is performed according to the condition well known to those skilled in the art that Liquid liquid Separation is carried out using rotary filter press, as
It is preferred that the inlet pressure of the rotary filter press is 0.1~1.0MPa, inlet temperature is 10~90 DEG C, pressure is reduced to 0.2~
0.5MPa.The present invention is not particularly limited the separated condition of the dish-style, and dish is utilized according to well known to those skilled in the art
The condition that formula separation carries out Liquid liquid Separation performs, preferably, the separated separation factor of the dish-style be preferably 5000~
9000。
The present invention carries out Liquid liquid Separation to glyphosate concentrated mother liquor, after glyphosate concentrated mother liquor is layered, collects upper strata
Oil slick.Collected mode is not particularly limited, and is by the way of collection stratified liquid well known to those skilled in the art
It can.
After obtaining upper strata oil slick, according to adding in alkali in the oil slick of upper strata the step of Basic fluxing raction in first method, into
Row Basic fluxing raction obtains methyl triethylammonium hydroxide crude product, and rectifying is carried out according still further to the step in first method, you can
To technical grade methyl triethylammonium hydroxide.
The methyl triethylammonium hydroxide obtained by the above method can be sold directly as product, also can be by into one
Step processing, produces organic amine product.
The product (i.e. methyl triethylammonium hydroxide) of Basic fluxing raction is preferably catalyzed by the present invention under catalysts conditions to be split
Solution obtains organic amine, and shown in reaction principle formula (4), production procedure is as shown in figure 3, (C2H5)3N(OH)CH3→N(C2H5)3+CH3N
(C2H5)2+CH3NH2+NH2CH2CH3 (4)
At high temperature under high pressure, methyl triethyl ammonium chloride can be broken down into a variety of organic amines, but be related to different organic
Therefore later separation problem between amine, is cracked by the directional catalyzing of catalyst as much as possible, obtain desired organic amine production
Product.
Compared with methyl triethyl ammonium chloride, it is clear that the market value higher of organic amine, market demand also higher, because
Quaternary amine in glyphosate mother solution is converted into organic amine product by this, and market value is more excellent.
The catalyst is preferably nickel system metal complex, Ferrious material complex and cobalt system metal complex, the oxygen of platinum
Compound, the chloride of platinum, one or more of the chloride of the oxide of rhodium and rhodium.Specifically, can be that active ingredient is
The Fe-series catalyst of FeOOH, AlOOH etc.；Can also be carbon microcarrier, the palladium series catalyst of palladium content 2%.The catalyst
Quality is preferably the 0.01~1% of methyl triethylammonium hydroxide quality, more preferably 0.1~1%, most preferably 0.5~
1%, specifically, can be 0.8% or 1%.
In the present invention, the temperature of the catalytic pyrolysis is preferably 100~400 DEG C, more preferably 200~250 DEG C, specifically
, can be 220 DEG C or 260 DEG C；When the time of the catalytic pyrolysis is preferably 0.5~24 small, more preferably 3~5 it is small when；Institute
The pressure for stating catalytic pyrolysis is preferably 0.5~10MPa, more preferably 1~5MPa, is most preferably 3~5MPa.
After completing the catalytic pyrolysis, the product of catalytic pyrolysis is preferably carried out rectifying by the present invention, and can obtain different has
Machine amine product such as collects the fraction that boiling range is 88~92 DEG C, you can obtain triethylamine.
The conventional process mode of glyphosate mother solution is directly to discharge, but due to the demand and output of glyphosate herbicidal
Huge, the discharge capacity for causing this kind of waste liquid of glyphosate mother solution is also very big, and larger harm is caused to environment.At present, in discharge grass
Before sweet phosphine mother liquor, first side product chlorinated sodium, chloromethanes and the dimethoxym ethane in glyphosate mother solution can be recycled, realize resource
It recycles, was discharged again after recycling above-mentioned useful by-product or sewage disposal.However, the present invention is but with glyphosate mother solution
Methyl triethylammonium hydroxide this fine chemicals is produced for raw material, this routine techniques in the prior art or in industry
To be difficult to it is contemplated that both at home and abroad also there is not yet the report of related fields in open source information in processing, the present invention be put forward for the first time with
Glyphosate mother solution produces methyl triethylammonium hydroxide for raw material.
In order to further illustrate the present invention, with reference to embodiments to a kind of utilization glyphosate mother solution system provided by the invention
The method of standby methyl triethylammonium hydroxide is described in detail, but cannot be understood as the limit to the scope of the present invention
It is fixed.
Embodiment 1
The glyphosate mother solution 100kg that triethyl ammonium chloride containing methyl is 0.95% is weighed, it is 40% to add in mass concentration
Sodium hydroxide 0.70kg after stirring evenly, has been warming up to reflux and has generated, maintained the reflux for state response 2h, then carry out rectifying, from
Survey line discharge port obtains colourless transparent liquid 0.82kg, and after testing, the content of methyl triethylammonium hydroxide is in liquid
96.3%, moisture 3.5%, ammonia taste is strong；After material molecular sieve dehydration, the methyl triethyl group that content is 98.1% is obtained
Ammonium hydroxide product 0.76kg.Total yield of products is 89.40%.
Embodiment 2
The glyphosate mother solution 1000kg that triethyl ammonium chloride containing methyl is 0.95% is weighed, being slowly added to mass concentration is
96% sodium hydroxide 3.2kg is stirred to being completely dissolved, and has been then heated to reflux and has been generated, has maintained the reflux for state response 5h, so
After carry out rectification under vacuum, obtain colourless transparent liquid 8.29kg from survey line discharge port, after testing, methyl triethyl group hydrogen-oxygen in liquid
The content for changing ammonium is 96.5%, and moisture 3.2%, ammonia taste is strong；After material molecular sieve dehydration, content is obtained as 98.5%
Methyl triethylammonium hydroxide product 7.71kg.Total yield of products is 91.06%.
Embodiment 3
The glyphosate mother solution 5000kg that triethyl ammonium chloride containing methyl is 0.95% is weighed, is evaporated crystallization, spinning liquid point
From operation, the brown oil liquid 88.14kg that triethyl ammonium chloride containing methyl is 48.5% is obtained.By brown oil liquid with
After the sodium hydroxide that 56.20kg mass concentrations are 30% is sufficiently mixed, it has been warming up to reflux and has generated, insulation reaction 8h, Ran Houjing
It evaporates, obtains colourless transparent liquid 38.10kg from survey line discharge port, methyl triethylammonium hydroxide content is 95.48%, and moisture contains
It measures as 4.20%.After being dehydrated with molecular sieve drying, 98.2% methyl triethylammonium hydroxide 35.19kg is obtained.Product is always received
Rate is 82.87%.
Embodiment 4
The glyphosate mother solution 5000kg that triethyl ammonium chloride containing methyl is 0.95% is weighed, is evaporated crystallization, spinning liquid point
From operation, the brown oil liquid 88.14kg that triethyl ammonium chloride containing methyl is 48.5% is obtained.By brown oil liquid with
After the sodium hydroxide that 15.26kg mass concentrations are 96% is sufficiently mixed, it has been warming up to reflux and has generated, insulation reaction 3h, Ran Houjing
It evaporates, obtains colourless transparent liquid 37.88kg from survey line discharge port, methyl triethylammonium hydroxide content is 96.10%, and moisture contains
It measures as 3.62%.After being dehydrated with molecular sieve drying, 98.4% methyl triethylammonium hydroxide 35.52kg is obtained.Product is always received
Rate is 83.82%.
Embodiment 5
The glyphosate mother solution 5000kg that triethyl ammonium chloride containing methyl is 0.95% is weighed, carries out micro-filtration-ultrafiltration-nanofiltration group
UF membrane is closed, after the light liquid of obtained film to be further concentrated by evaporation to recycling Nacl, rotary filter press is carried out and obtains three second containing methyl
The light brown oil slick 90.20kg of ammonium chloride 50.10%.By the hydroxide that light brown oil slick 79.40kg mass concentrations are 30%
After sodium is sufficiently mixed, reflux has been warming up to it and has generated, insulation reaction 5h, then rectifying obtains water white transparency liquid from survey line discharge port
Body 39.5kg, methyl triethylammonium hydroxide content are 96.30%, moisture 3.70%.After being dehydrated with molecular sieve drying,
Obtain 98.5% methyl triethylammonium hydroxide 37.85kg.Total yield of products is 89.17%.
Embodiment 6
The methyl triethylammonium hydroxide 5kg that content is 98.4% is weighed, is added in stainless steel autoclave, is added in
50g Fe-series catalysts (active ingredient FeOOH, AlOOH etc.) stirring, heating, after 220 DEG C, 3MPa reactions 5h, cooling, mistake
Filtrate is added in rectifying column and carries out rectifying, be collected into the fraction 2.24kg that boiling range is 88~92 DEG C, through analyzing, three in fraction by filter
The content of ethamine is 99.2%, meets glyphosate production requirement.
Embodiment 7
The methyl triethylammonium hydroxide 5kg that content is 98.4% is weighed, is added in stainless steel autoclave, is added in
40g palladium series catalysts (palladium content 2%, charcoal microcarrier) stirring, heating, after 260 DEG C, 5MPa reactions 3h, cooling, filtering,
Filtrate is added in into rectifying column and carries out rectifying, is collected into the fraction 2.35kg that boiling range is 88~92 DEG C, through analyzing, triethylamine in fraction
Content for 99.5%, meet glyphosate production requirement.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of method that methyl triethylammonium hydroxide is prepared using glyphosate mother solution, is comprised the following steps：
Alkali is added in glyphosate mother solution, Basic fluxing raction is carried out at reflux, obtains methyl triethylammonium hydroxide；
The temperature of the Basic fluxing raction is 50~200 DEG C；
When the time of the Basic fluxing raction is 0.5~24 small.
2. according to the method described in claim 1, it is characterized in that, the molar ratio of the alkali and methyl triethyl ammonium chloride is (1
~10)：1.
3. according to the method described in claim 1, it is characterized in that, further include distillation or rectifying after the Basic fluxing raction；
The temperature of the distillation or rectifying is 20~200 DEG C；
When the time of the distillation or rectifying is 0.5~10 small.
4. according to the method described in claim 1, it is characterized in that, the recovery method is further included and recycled from glyphosate mother solution
The step of by-product Nacl；
It is centrifuged after the Basic fluxing raction, by-product Nacl is recycled；
Or
Concentration or UF membrane are evaporated before the Basic fluxing raction, by-product Nacl is recycled.
5. according to the method described in claim 1, it is characterized in that, the product of the Basic fluxing raction is urged under catalysts conditions
Change cracking, obtain organic amine.
6. according to the method described in claim 5, it is characterized in that, the catalyst is nickel system metal complex, Ferrious material
Complex and cobalt system metal complex, the oxide of platinum, the chloride of platinum, the oxide of rhodium and rhodium chloride in one kind or
It is several.
7. according to the method described in claim 5, it is characterized in that, the quality of the catalyst is the product of the Basic fluxing raction
Quality 0.01~1%.
8. according to the method described in claim 5, it is characterized in that, the temperature of the catalytic pyrolysis is 100~400 DEG C；
The pressure of the catalytic pyrolysis is 0.1~10MPa.
9. according to the method described in claim 5, it is characterized in that, the organic amine is triethylamine and/or methylamine.
10. according to method as described in any one of claim 1 to 9, which is characterized in that the glyphosate mother solution is by glycine
Method prepares the diluted alkaline mother liquor obtained after the original nut liquid recycling triethylamine that glyphosate is formed.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838288A (en) * | 2009-03-18 | 2010-09-22 | 湖州四方格林自动化技术有限公司 | Processing method of glyphosate mother liquor |
| CN101843255A (en) * | 2010-05-28 | 2010-09-29 | 吴伦飞 | Deepen processing method of glyphosate mother liquid |
-
2017
- 2017-12-28 CN CN201711456440.8A patent/CN108084032B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838288A (en) * | 2009-03-18 | 2010-09-22 | 湖州四方格林自动化技术有限公司 | Processing method of glyphosate mother liquor |
| CN101843255A (en) * | 2010-05-28 | 2010-09-29 | 吴伦飞 | Deepen processing method of glyphosate mother liquid |
Non-Patent Citations (2)
| Title |
|---|
| 刘志英等: "草甘膦母液的沉淀处理研究", 《安徽农业科学》 * |
| 高静雅: "离子膜法处理草甘膦母液工艺技术的研究", 《中国优秀硕士学位论文全文数据库（电子期刊）工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333519A (en) * | 2020-03-11 | 2020-06-26 | 陈兴华 | Comprehensive treatment and resource recycling method for glyphosate mother liquor |
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