CN108084032B - A method of methyl triethylammonium hydroxide is prepared using glyphosate mother solution - Google Patents
A method of methyl triethylammonium hydroxide is prepared using glyphosate mother solution Download PDFInfo
- Publication number
- CN108084032B CN108084032B CN201711456440.8A CN201711456440A CN108084032B CN 108084032 B CN108084032 B CN 108084032B CN 201711456440 A CN201711456440 A CN 201711456440A CN 108084032 B CN108084032 B CN 108084032B
- Authority
- CN
- China
- Prior art keywords
- mother solution
- glyphosate
- methyl
- glyphosate mother
- basic fluxing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
-
- 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
-
- 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
-
- 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
- C07C211/05—Mono-, di- or tri-ethylamine
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The present invention provides a kind of method for preparing methyl triethylammonium hydroxide using glyphosate mother solution, comprising 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；The time of the Basic fluxing raction is 0.5~24 hour.The present invention is using glyphosate mother solution as direct material, it can not only recycle with triethylamine derivative-methyl triethyl ammonium chloride in glyphosate mother solution, produce the methyl triethylammonium hydroxide having 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 processing technique promotion for pushing glyphosate industry.Further, the present invention also continues the organic amine that production has more high added value using the methyl triethylammonium hydroxide of production, brings bigger economic value.
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 technique
Glyphosate is the maximum herbicide kind of current global dosage, and global year usage amount is more than 1,000,000 tons, accounts for all remove
The 48% of careless agent dosage, annual value of production are more than 6,000,000,000 dollars.With the expansion of resistance glyphosate genetically modified crops usable floor area, the following grass
The market prospects of sweet phosphine are still had an optimistic view of.
Currently, domestic glyphosate aggregated capacity is 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, inhibit the expansion of glyphosate technicals production capacity from source, on the other hand, by multinomial measure, to glyphosate industry
Environmentally friendly verification is carried out, self-discipline is guided, and to the by-product generated in glyphosate production process, 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 resource utilization benefit
With.The especially discovery and recycling of by-product chloromethanes facilitates the resources circulation of the big industry of glyphosate-organosilicon two, is formed
Circular economy advantage with conspicuous characteristics.
Glyphosate by using glycine production technology is using paraformaldehyde, glycine, dimethylphosphite as primary raw material, triethylamine
Glyphosate products are obtained by depolymerization, addition, hydrolysis for catalyst.Wherein, catalyst of triethylamine is in acid hydrolysis
Mainly exist in the form of triethylamine hydrochloride in journey, and ultimately resides 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 are as follows:
N(C2H5)3HCl+NaOH=N (C2H5)3+NaCl+H2O (1)
After the triethylamine hydrochloride being dissolved in glyphosate mother liquor system is reacted with alkali, it is layered because being insoluble in water, greatly
Part triethylamine is recycled by quantizer, and the triethylamine being entrained in glyphosate mother solution on a small quantity is recycled using rectification working process,
Distillation residual liquid is glyphosate mother solution.
In recent years, the glyphosate leading enterprise with Xin An group etc. for representative develops recycling mother solution of glyphosate and utilizes skill
Art solves by-product in glyphosate production process-high concentration organism P wastewater resource utilization problem, has obtained added value
Higher industrial phosphoric acid product salt sets up new model for the cleanly production of glyphosate industry.Nevertheless, glyphosate is raw
Still there are other by-products that effective use is not yet received during producing, has wasted valuable resource.
Summary of the invention
The purpose of the present invention is 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 lowering the difficulty of glyphosate mother solution subsequent processing, to promotion glyphosate row
The recycling mother solution processing technique promotion of industry is of great significance.
The present invention provides a kind of preparation method of methyl triethylammonium hydroxide, comprising 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 that Basic fluxing raction generates is recycled in rectifying；Distillation/distillation residual liquid obtains industrial product salt after being centrifuged.
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, In
Basic fluxing raction is carried out under reflux state, and 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；
The time of the Basic fluxing raction is 0.5~24 hour.
Preferably, the molar ratio of the alkali and methyl triethyl ammonium chloride are as follows: (1~10): 1.
It preferably, further include distillation or rectifying after the Basic fluxing raction；
The temperature of the distillation/rectifying is 50~200 DEG C；
The time of the distillation rectifying is 0.5~10 hour.
Preferably, the recovery method further includes the steps that recycling by-product Nacl from glyphosate mother solution；
It is centrifuged after the Basic fluxing raction, by-product Nacl is recycled；
Or
It is evaporated concentration or UF membrane 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
One or more of oxide, the chloride of platinum, the oxide of rhodium and chloride of 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, the glyphosate mother solution is after preparing glyphosate by glycin method to be formed by original nut liquid recycling triethylamine
Obtained diluted alkaline mother liquor.
The present invention provides a kind of method for preparing methyl triethylammonium hydroxide, comprising the following steps: by glyphosate mother solution
It is concentrated by evaporation desalination, 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 distillation/rectifying recycling reaction production methyl triethylammonium hydroxide；It is described
The temperature of Basic fluxing raction is 50~200 DEG C；The time of the Basic fluxing raction is 0.5~24 hour.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, which is prepared into, saves valuable ammonium resource with the methyl triethylammonium hydroxide compared with high added value, and can reduce grass
The subsequent processing difficulty of sweet phosphine mother liquor, thus, the present invention promotes tool to the recycling mother solution processing technique for pushing glyphosate industry
It is significant.
Further, the present invention, which also continues production using the methyl triethylammonium hydroxide of production, has more high added value
Organic amine, bring bigger economic value.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical 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 for preparing quaternary ammonium base and organic amine using glyphosate mother solution, comprising the following steps:
Alkali is added from being concentrated by evaporation in the oil slick obtained after desalination in glyphosate diluted alkaline mother liquor, 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；
The time of the Basic fluxing raction is 0.5~24 hour.
Glyphosate by using glycine production technology is using paraformaldehyde, glycine, dimethylphosphite as primary raw material, triethylamine
Glyphosate products are obtained by depolymerization, addition, hydrolysis for catalyst.Wherein, catalyst of triethylamine is in acid hydrolysis
Mainly exist in the form of triethylamine hydrochloride in journey, and ultimately resides 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 are as follows:
N(C2H5)3HCl+NaOH=N (C2H5)3+NaCl+H2O (1)
After the triethylamine hydrochloride being dissolved in glyphosate mother liquor system is reacted with alkali, it is layered because being insoluble in water, greatly
Part triethylamine is recycled by quantizer, and the triethylamine being entrained in glyphosate mother solution on a small quantity 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 glyphosate, the three of loss
Ethamine remains essentially in glyphosate mother solution.However, applicant detects 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 layer is the oily liquids of brown or black, and lower layer is lurid glyphosate
Mother liquor.Upper layer oily liquids specific gravity 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 20% or more.Above- mentioned information absolutely prove that grass is sweet
In the presence of a kind of organic matter of the elements such as 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 has been 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 constituting 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., can also be modified to obtain more to it
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 in the glyphosate mother solution that then generates based on annual 350000 tons
Methyl triethyl ammonium chloride can reach nearly 30,000 tons, market value can reach 9000 Yu Wanyuan.
As it can be seen that can not only recycle using glyphosate mother solution as direct material with the methyl triethyl group chlorine compared with high added value
Change ammonium, saves valuable resource, and the subsequent difficulty of glyphosate mother solution can be reduced, thus the present invention is to promotion glyphosate industry
Recycling mother solution processing technique 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, is difficult to be recycled by conventional methods such as simple condensing crystallizings.
It being difficult to directly recycle in view of methyl triethyl ammonium chloride characteristic soluble easily in water, 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, mine
Object flotation agent and semiconductor circuit alkaline etchant etc., industrial use is wide.The product processes generally relate to be electrolysed
Deng reaction, high production cost, process conditions are harsher.If the thinking according to applicant directly recycles first from glyphosate mother solution
Triethylammonium chloride produces methyl triethylammonium hydroxide, and raw material sources are extensive, process flow 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 passes through following two method and carries out alkaline hydrolysis to the methyl triethyl ammonium chloride in glyphosate mother solution:
The first, as shown in Figure 1, alkali is added in glyphosate mother solution and carries out alkaline hydrolysis directly using glyphosate mother solution as raw material
Reaction, converts methyl triethylammonium hydroxide crude product for the methyl triethyl ammonium chloride in mother liquor, then obtain by rectifying
Then the methyl triethylammonium hydroxide of technical grade is centrifuged rectifying residual night, recycle by-product Nacl (sodium chloride).
In the first method, the alkali is preferably liquid alkaline 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, 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 hour, more preferably 2~10 hours, most preferably 2~5 hours；Described in the present invention preferably carries out at reflux
Basic fluxing raction.
The temperature of the rectifying is preferably 50~200 DEG C；The time of the rectifying is preferably 0.5~10 hour.
The present invention preferably carries out Basic fluxing raction and rectifying in same device, such as reactive distillation column, not only may be used in this way
To keep the continuity of production, and the methyl triethylammonium hydroxide generated can be more advantageous to the life of product with quick separating
At raising production efficiency.
Second, as shown in Fig. 2, glyphosate mother solution first to be carried out to the pretreatment of evaporation and concentration or 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, adding alkali 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.From being chromatographed in glyphosate mother solution in isolated oil slick, methyl
The content of triethyl ammonium chloride can reach 40% or more.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 to remove inorganic salts (such as sodium chloride) impurity and moisture, raising
Mother liquid concentration.In the present invention, being preferably concentrated by evaporation to the mass ratio of gained glyphosate concentrated mother liquor and glyphosate mother solution is 1:(5
~11).It can guarantee sufficiently to remove the impurity such as inorganic salts within the scope of the concentrating degree, and it is good to guarantee that mother liquor has
Rheological characteristic, be convenient for subsequent processing, concentration is evaporated to glyphosate mother solution and improves methyl triethyl ammonium chloride
Relative concentration in glyphosate mother solution reaches hypersaturated state, and more conducively subsequent methyl triethyl ammonium chloride and grass are 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
Concentration is preferably evaporated under reduced pressure in contracting；The temperature and pressure of the reduction vaporization is not particularly limited, and is steamed according to depressurizing in this field
The normal condition for sending out material executes, 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 the processing convenient for 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 evaporator is realized.After the evaporation and concentration, glyphosate concentrated mother liquor is obtained.
Alternatively, successively carrying out UF membrane and evaporative crystallization to glyphosate mother solution, the recycling to by-product Nacl can also be 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 contain in film separation system, and process object is first led to
It crosses ultrafiltration membrane and is handled and handled again by nanofiltration membrane, the rest may be inferred for other combined films.The present invention is to above-mentioned various films
Type 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, is stripped of a large amount of impurity, is convenient for subsequent processing.Glyphosate mother solution obtains film dope and the light liquid of film after UF membrane；Its
In, film dope mainly includes the organic matters such as glyphosate, can be used 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 crystallization removing sodium chloride to the light liquid of film, 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 the recycling for completing by-product Nacl by one of evaporation and concentration or UF membrane both methods, the present invention couple
Glyphosate concentrated mother liquor carries out Liquid liquid Separation, and separation process glyphosate concentrated mother liquor is layered, and upper layer is brown or black
Oil slick, lower layer 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 executed according to the condition well known to those skilled in the art for carrying out Liquid liquid Separation 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 condition that the present invention separates the dish-style is not particularly limited, and utilizes dish according to well known to those skilled in the art
The condition that formula separation carries out Liquid liquid Separation executes, preferably, the separation factor of dish-style separation 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 layer
Oil slick.The 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 layer oil slick, according to alkali is added in the oil slick of upper layer the step of Basic fluxing raction in first method, into
Row Basic fluxing raction obtains methyl triethylammonium hydroxide crude product, carries out rectifying according still further to the step in first method, can obtain
To technical grade methyl triethylammonium hydroxide.
It can be sold directly as product by methyl triethylammonium hydroxide obtained by the above method, it also can be by into one
Step processing, produces organic amine product.
The product of Basic fluxing raction (i.e. methyl triethylammonium hydroxide) 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 and produce
Product.
Compared with methyl triethyl ammonium chloride, it is clear that the market value of organic amine is higher, and market demand is also higher, because
The quaternary amine in glyphosate mother solution is converted organic amine product by this, and market value is more excellent.
The catalyst is preferably the oxygen of nickel system metal complex, Ferrious material complex and cobalt system metal complex, platinum
One or more of compound, the chloride of platinum, the oxide of rhodium and chloride of rhodium.Specifically, can be active constituent and be
The Fe-series catalyst of FeOOH, AlOOH etc.；It is also possible to the palladium series catalyst of carbon microcarrier, 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, and more preferably 200~250 DEG C, specifically
, it can be 220 DEG C or 260 DEG C；The time of the catalytic pyrolysis is preferably 0.5~24 hour, and more preferably 3~5 hours；Institute
The pressure for stating catalytic pyrolysis is preferably 0.5~10MPa, more preferably 1~5MPa, 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 be obtained different has
Machine amine product such as collects the fraction that boiling range is 88~92 DEG C, triethylamine can be obtained.
The conventional process mode of glyphosate mother solution is direct emission, but due to the demand and output of glyphosate herbicidal
It is huge, cause the discharge amount of this kind of waste liquid of glyphosate mother solution also very big, larger harm is caused to environment.Currently, 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, carried out discharge or sewage treatment again after recycling above-mentioned useful by-product.However, the present invention is but with glyphosate mother solution
This fine chemicals of methyl triethylammonium hydroxide is produced for raw material, this routine techniques in the prior art or in industry
To be difficult in processing it is contemplated that both at home and abroad also there is not yet the report of related fields in open source information, the present invention be put forward for the first time with
Glyphosate mother solution is raw material to produce methyl triethylammonium hydroxide.
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% that mass concentration, which is added,
Sodium hydroxide 0.70kg has been warming up to reflux and has generated, maintained the reflux for state response 2h, then carry out rectifying after mixing evenly, from
Survey line discharge port obtains colourless transparent liquid 0.82kg, and through detecting, 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, through detecting, 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, obtaining content is 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, crystallization, spinning liquid point are evaporated
From operation, the brown oil liquid 88.14kg that triethyl ammonium chloride containing methyl is 48.5% is obtained.By brown oil liquid with
It after the sodium hydroxide that 56.20kg mass concentration is 30% is sufficiently mixed, has been warming up to reflux and has generated, insulation reaction 8h is then smart
It evaporates, obtains colourless transparent liquid 38.10kg from survey line discharge port, methyl triethylammonium hydroxide content is 95.48%, and moisture contains
Amount is 4.20%.After molecular sieve drying and dehydrating, 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, crystallization, spinning liquid point are evaporated
From operation, the brown oil liquid 88.14kg that triethyl ammonium chloride containing methyl is 48.5% is obtained.By brown oil liquid with
It after the sodium hydroxide that 15.26kg mass concentration is 96% is sufficiently mixed, has been warming up to reflux and has generated, insulation reaction 3h is then smart
It evaporates, obtains colourless transparent liquid 37.88kg from survey line discharge port, methyl triethylammonium hydroxide content is 96.10%, and moisture contains
Amount is 3.62%.After molecular sieve drying and dehydrating, 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, micro-filtration-ultrafiltration-nanofiltration group is carried out
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%.The hydroxide for being 30% by light brown oil slick 79.40kg mass concentration
After sodium is sufficiently mixed, reflux has been warming up to it and has generated, insulation reaction 5h, then rectifying obtains colorless and transparent liquid from survey line discharge port
Body 39.5kg, methyl triethylammonium hydroxide content are 96.30%, moisture content 3.70%.After molecular sieve drying and dehydrating,
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
50g Fe-series catalyst (active constituent FeOOH, AlOOH etc.) stirring, heating, after 220 DEG C, 3MPa reaction 5h, cooling, mistake
Filtrate is added rectifying column and carries out rectifying by filter, the fraction 2.24kg that boiling range is 88~92 DEG C is collected into, through analyzing, three in fraction
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
40g palladium series catalyst (palladium content 2%, charcoal microcarrier) stirring, heating, after 260 DEG C, 5MPa reaction 3h, cooling, filtering,
Rectifying column is added in filtrate 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 be 99.5%, meet glyphosate production requirement.
The above is only a 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 are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of method for preparing methyl triethylammonium hydroxide using glyphosate mother solution, comprising the following steps:
Alkali is added in glyphosate mother solution, Basic fluxing raction is carried out at reflux, obtains methyl triethylammonium hydroxide；
The glyphosate mother solution is that preparing glyphosate by glycin method is formed by original nut liquid to recycle the diluted alkaline obtained after triethylamine
Mother liquor；Contain methyl triethyl ammonium chloride in the glyphosate mother solution；
The temperature of the Basic fluxing raction is 50~200 DEG C；
The time of the Basic fluxing raction is 0.5~24 hour.
2. the method according to claim 1, wherein the molar ratio of the alkali and methyl triethyl ammonium chloride is (1
~10): 1.
3. the method according to claim 1, wherein further including distillation or rectifying after the Basic fluxing raction；
The temperature of the distillation or rectifying is 20~200 DEG C；
The time of the distillation or rectifying is 0.5~10 hour.
4. the method according to claim 1, wherein the recovery method further includes recycling from glyphosate mother solution
The step of by-product Nacl；
It is centrifuged after the Basic fluxing raction, by-product Nacl is recycled；
Or
It is evaporated concentration or UF membrane before the Basic fluxing raction, by-product Nacl is recycled.
5. the method according to claim 1, wherein the product of the Basic fluxing raction is urged under catalysts conditions
Change cracking, obtains 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 one of chloride 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711456440.8A CN108084032B (en) | 2017-12-28 | 2017-12-28 | A method of methyl triethylammonium hydroxide is prepared using glyphosate mother solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711456440.8A CN108084032B (en) | 2017-12-28 | 2017-12-28 | A method of methyl triethylammonium hydroxide is prepared using glyphosate mother solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108084032A CN108084032A (en) | 2018-05-29 |
| CN108084032B true CN108084032B (en) | 2019-11-05 |
Family
ID=62180232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711456440.8A Active CN108084032B (en) | 2017-12-28 | 2017-12-28 | A method of methyl triethylammonium hydroxide is prepared using glyphosate mother solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108084032B (en) |
Families Citing this family (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 |
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 |
|---|
| 离子膜法处理草甘膦母液工艺技术的研究;高静雅;《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》;20160531;第B027-461页 * |
| 草甘膦母液的沉淀处理研究;刘志英等;《安徽农业科学》;20121231;第40卷(第29期);第14271-14273页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108084032A (en) | 2018-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108840310B (en) | Device and process for producing hydrogen chloride by deep analysis from dilute hydrochloric acid | |
| CN106699808B (en) | A kind of acidolysis of producing glyphosate by using glycine and solvent recovery process and device | |
| CN103382170A (en) | Preparation method for taurine | |
| CN104086362A (en) | Method for recycling organic solvents of wastewater generated in synthesis of hydrazine hydrate by ketazine method | |
| CN104130138A (en) | 2,4-dinitraniline continuous ammonification production technology | |
| CN106185810A (en) | A kind of joint disposal technique of acidic copper chloride waste etching solution | |
| CN108084032B (en) | A method of methyl triethylammonium hydroxide is prepared using glyphosate mother solution | |
| CN115196654A (en) | Liquid lithium hexafluorophosphate synthesis device and application thereof | |
| CN104926690A (en) | Method and device for recycling and refining acetonitrile in ceftriaxone sodium synthesis | |
| CN103253711B (en) | Comprehensive resource utilization method of tungsten-containing crystallization mother liquor and ammonia-containing steam | |
| CN204400883U (en) | Pentamethylene diamine purification system | |
| CN107311878A (en) | A kind of device for reclaiming glycine waste liquid and the method for reclaiming glycine waste liquid | |
| CN113827992A (en) | Method for recycling water separated from alkali mother liquor rectification tower top fraction in glyphosate production process | |
| CN108129328B (en) | Preparation method of methyl triethyl ammonium chloride | |
| CN102633314A (en) | Low-concentration formaldehyde wastewater resource recycling process | |
| CN218778875U (en) | Device for separating and recovering alcohol and aldehyde from glyphosate mother liquor | |
| CN101993381B (en) | Synthetic method of 3-amino-1, 2-propanediol | |
| CN217511220U (en) | Device for separating and recovering extracted material of MIBK light component tower | |
| CN204727810U (en) | A kind of purification and recover device for acetonitrile in ceftriaxone sodium synthesis | |
| CN103665035A (en) | Method for treating glyphosate mother liquor | |
| CN108047063B (en) | A kind of preparation method of methyl triethyl ammonium chloride | |
| CN202705267U (en) | Glycol dimethyl ether component recovery device in synthetic product waste salt | |
| CN205461091U (en) | Modified underpressure distillation tower and acetonitrile system of refining | |
| CN105820056B (en) | A kind of synthetic method and production system of 4,4 '-dimethyl diphenylamines | |
| CN103130636B (en) | A kind of method of polyphosphoric acid and sodium formiate reaction dense, the high-purity formic acid of coproduction height and SODIUM PHOSPHATE, MONOBASIC |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |