CN101838288A - Processing method of glyphosate mother liquor - Google Patents

Abstract

The invention provides a method for recovering triethylamine in glyphosate mother liquor. The method comprises the following steps of: firstly, deacidifying the glyphosate mother liquor to a pH value of 1.2 to 8.0 by the methods of diffusion dialysis, electric dialysis, electric dialysis for acid-base preparation, and the like; filtering and recovering glyphosate solid in a deacidifying process; and then, extracting triethylamine hydrochloride in the glyphosate mother liquor by concentration and electric dialysis and then preparing triethylamine by using the triethylamine hydrochloride as a raw material. The invention is suitable for processing the glyphosate mother liquor obtained after glyphosate is separated and extracted in a glyphosate production.

Description

Method for processing mother solution of glyphosate

Technical field

The present invention relates to a kind of treatment process of glyphosate mother solution, the treatment process of the acid mother liquid of gained when relating in particular to a kind of dimethylphosphite method synthesizing glyphosate.

Background technology

Glyphosate is the earliest by U.S. Monsanto Company exploitation, is a kind of efficient, low toxicity, low residue, broad spectrum organic phosphine post-emergence herbicide, farming, woods, herd, aspect application such as circle skill is very extensive, the present pesticide species that has become global marketing volume maximum.

The production technique of glyphosate mainly contains four kinds, i.e. chloroactic acid method, iminodiacetic acid (salt) acid system (being the IDA method), dialkyl phosphite method and trialkyl phosphite method.Wherein the dialkyl phosphite method is to be raw material with Paraformaldehyde 96, glycine, dialkyl phosphite, is catalyzer with the triethylamine, through addition, condensation, acidolysis and obtain glyphosate.This technology is simpler, and wastewater flow rate is less relatively, the yield height, and cost is low, good product quality, thereby domestic this processing method of main employing, output accounts for 85% of national glyphosate output.But a greatest problem that adopts this processing method is the mother liquor handling problem after acidolysis crystallization filtration obtains glyphosate technicals.Mother liquor after the glyphosate crystallization is a strong acidic liquid, includes a large amount of triethylamines, hydrochloric acid and glyphosate etc.Triethylamine is an important catalyst, and the price height, needs to recycle.The method for processing mother solution of glyphosate that generally adopts is to be neutralized to pH greater than 10 with liquid caustic soda at present, and triethylamine is separated from solution with oil phase; Aqueous phase after the separation also containsglyphosate 1～3%, triethylamine about 1%, and sodium-chlor is more than 10%, reconcentration with about glyphosate enrichment to 5%, is isolated the sodium-chlor crystallization, add glyphosate technicals and regulate glyphosate concentration to 7% or 10%, sell as 7% or 10% gyphosate solution.Owing to contain almost saturated sodium-chlor in this 7% or 10% gyphosate solution, life-time service can cause salting of soil and harden, and causes detrimentally affect to environment.Besides, the neutralizing treatment method of mother liquor has only reclaimed triethylamine wherein after the glyphosate crystallization, and the used raw material hydrochloric acid of acidic hydrolysis can not get recycling and has become sodium-chlor or other chloride contaminants, not only produced solid useless, also make and contain a large amount of sodium-chlor in 7% or 10% the gyphosate solution or other muriate works the mischief to environment, the more important thing is, this part hydrochloric acid that neutralizes is also wanted the additive decrementation liquid caustic soda, increased production cost, and make the waste water total amount increased (with in the liquid caustic soda and the time, contain a large amount of water in the liquid caustic soda), increased spissated energy consumption.Because in concentration process, produced a large amount of solid sodium chlorides or other muriate, made vaporizer be easy to stop up, operation is inconvenience extremely, and sodium-chlor or other muriate are very strong to the corrosive nature of vaporizer, and a general vaporizer has only the work-ing life of half a year.

In order to address the above problem, the disclosed treatment process of CN1277835C is in coming with ammonia and glyphosate mother solution, what contain in 10% gyphosate solution that obtains like this is ammonium chloride, and ammonium chloride is a kind of quick-acting nitrogen manure, and it is the weeding usefulness to glyphosate has synergism, so much smaller to the influence of environment.But neutralize with ammonia, security is relatively poor, the control condition harshness, and also a large amount of ammonium chloride makes body eutrophication after entering water body in the gyphosate solution, causes water pollution.This gyphosate solution that contains a large amount of ammonium chlorides of life-time service also can cause the soil fertility imbalance.The CN13083385C disclosed method is that glyphosate mother solution is neutralized with 30% liquid caustic soda earlier, handle with unsaturated carbonate hydrogen ammonium solution again, sodium-chlor in the mother liquor after the neutralization is converted into the sodium bicarbonate precipitation separates out, during sodium bicarbonate also can be used to and mother liquor, can reduce the consumption of 30% liquid caustic soda, removed the danger of using ammonia like this from, but operating procedure complexity, can produce ammonia in the treating processes, control requires high, still contain ammonium chloride in the gyphosate solution, make body eutrophication, also have the problem of soil fertility imbalance.The CN1824667A disclosed method then be with ammonia and carbonic acid gas replace bicarbonate of ammonia handle in liquid caustic soda and after glyphosate mother solution, but the problems referred to above still are not resolved.The CN1308336C patent of Hangzhou Jinfada Chemical Industry Co., Ltd is in directly coming with bicarbonate of ammonia and glyphosate mother solution, but can produce a large amount of carbonic acid gas in treating processes like this, carbonic acid gas is greenhouse gases, also can pollute environment, and also much higher with the bicarbonate of ammonia cost, and the problems referred to above still exist.

The treatment process of above-mentioned all glyphosate mother solution all is based on chemical neutralisation, just converts a kind of salt in the glyphosate mother solution to another kind of salt, does not tackle the problem at its root.In order to address the above problem, CN101195639 discloses a kind of dialysis treatment technology based on ion-exchange membrane, can directly reclaim triethylamine in glyphosate mother liquor, hydrochloric acid and glyphosate without the alkali neutralization, not produce salt in the entire treatment process, fundamentally solve the handling problem of salt.This technology is glyphosate mother solution to be handled through diffusion dialysis earlier reclaim free hydrochloric acid and part glyphosate, the triethylamine in glyphosate mother liquor hydrochloride is dissociated into triethylamine and hydrochloric acid and is reclaimed respectively through electrodialysis relieving haperacidity alkaline purification again.But it is low that this technology exists electrodialysis process efficient, facility investment is big, and the problem that processing cost is high, its major cause are constantly carrying out along with the electrodialysis process process, the concentration of triethylamine in glyphosate mother liquor hydrochloride constantly descends, and the current efficiency that continues to handle will constantly reduce.It is not thorough that the problem of another existence of this technology is that the triethylamine in glyphosate mother liquor hydrochloride removes.

Summary of the invention

The objective of the invention is to solve existing osmotic technique based on ion-exchange membrane exist current efficiency low, handle incomplete problem.A kind of method that reclaims triethylamine from glyphosate mother solution of the present invention is provided for this reason.This method not only can reclaim triethylamine in glyphosate mother liquor expeditiously, can also reclaim hydrochloric acid and glyphosate in the mother liquor; The triethylamine that reclaims can be back to production after dehydration, the hydrochloric acid of recovery is carried through absorption also can be back to production after dense; Glyphosate generally can be the form recovery with glyphosate technicals, can certainly be the form recovery with aqua.

For addressing the above problem, the technical solution used in the present invention is, described glyphosate mother solution is isolated the acid mother liquid of gained after the glyphosate products when adopting the dialkyl phosphite method to produce glyphosate, and its special character is: described glyphosate mother solution earlier through the dialysis depickling to the pH of glyphosate mother solution be 1.2～8.5; Glyphosate mother solution after the depickling extracts the triethylamine in glyphosate mother liquor hydrochloride through electrodialysis and/or concentration; Be that raw material adopts alkali neutral method or electrochemical method to prepare triethylamine again with the triethylamine hydrochloride.

Described dialysis depickling is at least a in diffusive dialysis method depickling, electroosmose process depickling, the depickling of electrodialysis relieving haperacidity alkaline process, reclaims in the depickling treating processes and obtains the pairing acid of contained inorganic anion and glyphosate and/or triethylamine in the glyphosate mother solution.

Described acid is the nitration mixture of hydrochloric acid or hydrochloric acid and phosphorous acid or the nitration mixture of hydrochloric acid, phosphorous acid and phosphoric acid.

Described concentrating is reverse osmosis concentration and/or evaporation concentration.

Described triethylamine hydrochloride is solution and/or the triethylamine hydrochloride solid that contains triethylamine hydrochloride.

Described alkali neutral method is that triethylamine hydrochloride is neutralized to pH with alkaline reagents is 9～13, reclaims the free triethylamine on upper strata through separatory.

Described electrochemical method is that triethylamine hydrochloride is prepared triethylamine and chlorine or prepares triethylamine and hydrochloric acid with electrodialysis relieving haperacidity alkaline process with ion-exchange membrane electrolysis.

Described alkaline reagents is at least a in sodium hydroxide, potassium hydroxide, ammonia, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, volatile salt, bicarbonate of ammonia, calcium hydroxide, the calcium oxide.

Its device of described diffusion dialysis is by at least one diffusion dialysis film M), at least one former liquid chamber I) and at least one reclaim liquid chamber II) form, the diffusion dialysis film is clipped between former liquid chamber and the recovery liquid chamber.Described diffusive dialysis method depickling feeds glyphosate mother solution in described former liquid chamber, feed pure water or diluted acid at described recovery liquid chamber.

Its device of described electroosmose process depickling is made up of the V of anolyte compartment of cathode compartment VI, former liquid chamber III, acid recovery chamber IV and the built-in anode an of built-in negative electrode ca, accompanying anion-exchange membrane A between cathode compartment and the former liquid chamber and between former liquid chamber and the acid recovery chamber, between acid recovery chamber and anolyte compartment, accompany cationic exchange membrane C.Described electroosmose process depickling is to feed glyphosate mother solution in described former liquid chamber, in described acid recovery chamber, feed dilute hydrochloric acid solution, feed sodium hydroxide solution at described cathode compartment, feed sulphuric acid soln, logical direct current between described anode and negative electrode in described anolyte compartment.

Described electrodialysis relieving haperacidity alkali is respectively equipped with the cathode compartment VI of built-in negative electrode ca and the V of anolyte compartment of built-in anode an with its both sides of device, it is right to be provided with between cathode compartment and the anolyte compartment by a cationic exchange membrane C and an anion-exchange membrane A component film of space, the cationic exchange membrane that described film is right and the relative position of anion-exchange membrane are that cationic exchange membrane is positioned at cathode direction, anion-exchange membrane is positioned at anode direction, cationic exchange membrane that described film is right and the zone between the anion-exchange membrane are set at former liquid chamber III, the right cationic exchange membrane of described film is set at triethylamine to a zone of cathode direction and reclaims chamber VII or cathode compartment VI, and a zone of the anion-exchange membrane anode direction that described film is right is set at acid recovery chamber IV.Described electrodialysis relieving haperacidity alkali is to import pending liquid at described former liquid chamber, reclaims chamber input dilute alkaline soln at described alkali, at described acid recovery chamber input dilute acid soln, and logical direct current between described anode and negative electrode.

Described electrodialysis relieving haperacidity alkali is provided with cationic exchange membrane C with a side of the described acid recovery chamber anode direction of device.

Described electrodialysis relieving haperacidity alkali is provided with Bipolar Membrane AC with a side of the described acid recovery chamber anode direction of device.

Described electrolysis is made up of cathode compartment VI, the acid recovery chamber IV of built-in negative electrode ca and the V of anolyte compartment of built-in anode an with device, accompanies anion-exchange membrane A between cathode compartment and acid recovery chamber, accompanies cationic exchange membrane C between acid recovery chamber and anolyte compartment.Described electrolytic process prepares triethylamine and chlorine is the solution that feeds triethylamine hydrochloride at cathode compartment, feeds the hydrochloric acid dilute solution in the acid recovery chamber, feeds the hydrochloric acid strong solution in the anolyte compartment, logical direct current between described anode and negative electrode.

Description of drawings

Fig. 1 contains the unitary diffusion dialysis device of a plurality of diffusion dialysis synoptic diagram;

Fig. 2 is the principle schematic of electrodialysis depickling simultaneously and salt;

Fig. 3 is an electrodialysis relieving haperacidity alkaline process principle schematic;

Fig. 4 is the principle schematic of another embodiment of electrodialysis relieving haperacidity alkaline process;

Fig. 5 is the principle schematic with electrodialysis relieving haperacidity alkaline process of Bipolar Membrane;

Fig. 6 is an electrodialysis depickling principle schematic;

Fig. 7 is the electrodialysis depickling principle schematic with Bipolar Membrane;

Fig. 8 is the principle schematic that electrolytic process with cationic membrane prepares triethylamine and chlorine;

Fig. 9 is the principle schematic that electrolytic process with anionic membrane prepares triethylamine and chlorine;

Figure 10 is the principle schematic that the electrolytic process that has cationic membrane and anionic membrane simultaneously prepares triethylamine and chlorine.

Be labeled as among the figure: 1 glyphosate mother solution, 2 water or dilute hydrochloric acid, 3 pending liquid, 4 rare saline solutions, 5 utmost point chamber liquid, 6 catholytes, 7 dilute hydrochloric acid, 8 anolytes, 9 triethylamines reclaim liquid, 10 triethylamine hydrochloride solution, 11 hydrochloric acid anolytes, I mother liquor chamber, II reclaims liquid chamber, the former liquid chamber of III, IV salt reclaims chamber, V anolyte compartment, VI cathode compartment, VII acid recovery chamber, the VIII triethylamine reclaims chamber, M diffusion dialysis film, A anion-exchange membrane, C cationic exchange membrane, the AC Bipolar Membrane, the ca negative electrode, an anode, n represents repetition.

The invention will be further described below in conjunction with accompanying drawing.

Glyphosate mother solution of the present invention refers in the standby production process of glyphosate of dialkyl phosphite legal system, remaining mother liquor behind the extraction glyphosate crystal, this mother liquor is highly acid, according to different production technologies, its pH value has bigger difference, generally between-0.6～0.8. The comparison of ingredients complexity of glyphosate aqueous mother liquor is except containing free acid, outside example hydrochloric acid, the phosphorous acid, also contain catalyst of triethylamine, in acid medium, triethylamine exists with the form of triethylamine hydrochloride, in addition also contains defecation not and left glyphosate and other accessory substances etc. Main ionic species is hydrogen ion (H in glyphosate mother solution⁺), triethyl ammonium cation (Et₃NH⁺), chlorion (Cl^-) and orthophosphite ions (PO₃^3-、HPO₃^2-Or H₂PO₃^-) etc.

We know that the disclosed electrodialysis relieving haperacidity of CN101195639 alkaline process reclaims the low basic reason of triethylamine current efficiency and is in the electrodialysis process process that the triethylamine hydrochloride concentration in the pending liquid constantly reduces to cause current efficiency constantly to reduce. If we can extract the triethylamine hydrochloride in the glyphosate mother solution, and then no matter adopt be chemical neutralization method or electrochemical process, and production efficiency is all much higher. Yet, because comparison of ingredients complexity in the glyphosate mother solution, directly glyphosate mother solution is concentrated and triethylamine hydrochloride can't be crystallized out at all, can only obtain the liquid of thickness. Research according to us is found, triethylamine hydrochloride be crystallized out, and must earlier the free acid in the glyphosate mother solution and glyphosate be separated earlier.

Adopt the dialysis depickling free acid in the glyphosate mother solution can be separated, the dialysis depickling comprises three kinds of diffusive dialysis method depickling, electroosmose process depickling and the depicklings of electrodialysis relieving haperacidity alkaline process.

The diffusive dialysis method depickling must be adopted the diffusion dialysis device, reclaims the part hydrochloric acid in the glyphosate mother solution. The diffusion dialysis device is made up of at least one diffusion dialysis film, at least one former liquid chamber and at least one recovery chamber, and the diffusion dialysis film is clipped in former liquid chamber and reclaims between the chamber. What form like this is a diffusion dialysis unit, practical application can be made up of a plurality of such unit, be that a plurality of former liquid chambers and recovery chamber are stacked alternately, separate with the diffusion dialysis film between them, form a diffusion dialysis device that is formed by a plurality of diffusion dialysis unit serial connection.

As shown in Figure 1, a cell body is divided into two parts with a diffusion dialysis film M, one side wherein be called former liquid chamber I, another side is called and reclaims chamber II, has so just formed a diffusion dialysis unit. As being arranged in the following order by many diffusion dialysis films:

II M I M II M I M II ... I has so just formed a diffusion dialysis device with industrialization practical value that is made up of a plurality of diffusion dialysis unit.

The diffusion dialysis film is a special anion-exchange membrane, and it has and selective see through anion and stop cationic effect. Whenglyphosate mother solution 1, enter the former liquid chamber I of diffusion dialysis device, after chamber II are reclaimed in 2 inputs of pure water or watery hydrochloric acid, because the chlorion (Cl in the indoor liquid of stoste^-) the concentration solution indoor far above recovery, just exist an anion concentration poor in the both sides of diffusion dialysis film. Because anion can very successfully see through the diffusion dialysis film, so the Cl in the solution in the former liquid chamber I^-Will under the effect of concentration difference motive force, diffuse into and reclaim chamber II. In order to keep electroneutral, anion must carry the equivalent electric charge when diffusing into the recovery chamber cation together enters. Because anion-exchange membrane has the effect of stopping to cation, its resistance depends on charge number and the cationic ionic radius that cation is entrained. In glyphosate mother solution, the ionic radius minimum be H⁺So, H⁺Preferentially with Cl^-Enter and reclaim the chamber. And compare H⁺The Et that radius is much bigger₃NH⁺Or glyphosate cation etc. is difficult for having stayed former liquid chamber by the diffusion dialysis film. Like this, on macroscopic view, the hydrochloric acid HCl in the former liquid chamber just constantly diffuses under the motive force of concentration difference and reclaims the chamber, thereby has reached the purpose of glyphosate mother solution depickling, and reclaims the acid that removes.

But it is also noted that, when because of Cl^-The motive force that produces of concentration difference and the diffusion dialysis film to H⁺When the resistance that produces equated, diffusion dialysis had just stopped. So diffusion dialysis can only be reclaimed the part hydrochloric acid in the glyphosate mother solution. The maximum advantage of diffusion dialysis is that energy consumption is low, only needs consumable liquid to carry required power, almost can ignore. But its maximum shortcoming is that the rate of recovery is low, reclaims not thorough. Want further depickling must adopt the dialysis system with the motive force of adding, electrodialysis is the dialysis process with the motive force of adding.

The electrodialysis system as shown in Figure 2, reclaimed successively the V of anode chamber of chamber IV, cation exchange C, built-in anode an by cathode chamber VI, cation-exchange membrane C, former liquid chamber III, anion-exchange membrane A, the salt of a built-in negative electrode ca, form a traditional electrodialysis system that only contains an electrodialysis cell, cathode chamber and anode chamber are referred to as utmost point chamber. Be positioned at cation-exchange membrane on the cathode direction and be positioned at a anion-exchange membrane on the anode direction and consist of one group of film pair. If between cathode chamber and anode chamber, arranged pressing following particular order by many groups film:

VI C III A IV C III A IV ... IV C V so just consisted of one can industrial applications electrodialysis plant. The electrodialysis plant of an industrial applications can reach up to a hundred even thousands of groups of films pair. One group of film between the zone be made as former liquid chamber (claiming again light chamber), the right left and right sides of film all is made as salt and reclaims chamber (claiming again dense chamber).

Amberplex is that a kind of ion selectivity sees through film; Cation-exchange membrane only allows cation to see through and stops anion, anion-exchange membrane only to allow anion to see through and stop cation.

Pendingliquid 3 enters former liquid chamber III, andrare saline solution 4 enters salt and reclaims chamber IV, and utmostpoint chamber liquid 5 enters the V of anode chamber and cathode chamber VI. Described pending liquid (being commonly referred to as fresh water in the document) both can be through the glyphosate mother solution after the diffusion dialysis depickling, also can be the glyphosate mother solution of processing without diffusion dialysis. Described rare saline solution (being commonly referred to as dense water in the document) is the weak solution of triethylamine hydrochloride, so-called weak solution refers to for the concentration of institute's saliferous in the dense saline solution in salt recovery exit, chamber, it has marked difference according to different operating processes, for one-time continuous desalination flow process, the concentration of weak solution is much lower, such as 0.1mol/L. Described utmost point chamber liquid can be pendingliquid 3, also can be that salt reclaims the dense saline solution that comes out in the chamber, can also be the solution of the triethylamine hydrochloride of preparation, and preferred salt reclaims the dense saline solution in exit, chamber as utmost point chamber liquid.

When between negative electrode and anode, applying a suitable direct current, in whole electric dialyzator, set up an electric field from the anode directed negative electrode, all charged particles in this electric field all will be done the directional migration motion, according to two like magnetic poles repel each other, principle of opposite sex attraction, the particle of all positively chargeds moves to cathode direction, all electronegative particle anode direction migrations. Therefore be in film to the H of positively charged among the former liquid chamber III (except the former liquid chamber of next-door neighbour's cathode chamber) in middle zone⁺、Et₃NH₄⁺To cathode direction migration, that run in their motion way is cation-exchange membrane C under the effect of electric field force, can cross cation-exchange membrane very smoothly and enters film the salt in left side is reclaimed chamber IV. Similarly, the Cl in the former liquid chamber^-、^2-Deng anion anode direction migration under the effect of electric field force, that run in their motion way is anion-exchange membrane A, also can cross anion-exchange membrane very smoothly and enters film the salt on right side is reclaimed chamber IV.

Reclaim chamber IV, its H for salt⁺、Et₃NH₄⁺The former liquid chamber (except the salt recovery chamber of next-door neighbour anode chamber) that comes from the right side, Cl^-、HPO₃^2-The former liquid chamber that comes from the left side Deng anion. Under the effect of electric field force, salt reclaims indoor H⁺、Et₃NH₄⁺Also can move to cathode direction, but that run in their the motion way is anion-exchange membrane A, is subjected to stopping of anion-exchange membrane and can't enters the former liquid chamber in left side. Similarly, salt reclaims indoor Cl^-、HPO₃^2-Deng anion also can the anode direction migration, but that run in their the motion way is cation-exchange membrane C, is subjected to stopping of cation-exchange membrane and can't enters the former liquid chamber (except the salt of next-door neighbour anode chamber reclaims the chamber) on right side. So, along with constantly carrying out of electrodialytic process, the H that stoste is indoor⁺、Et₃NH₄⁺The salt that constantly enters the left side reclaims chamber, Cl^-、HPO₃^2-The salt that constantly enters the right side Deng anion reclaims the chamber, and the salt content in the former liquid chamber is just more and more lower, the salt in the stoste can be removed totally fully theoretically. Reclaim in the chamber H from the former liquid chamber in right side at salt⁺、Et₃NH₄⁺With the Cl from the former liquid chamber in left side^-、HPO₃^2-Constantly obtain accumulation Deng anion, concentration is more and more higher, can reach theoretically the saturated concentration of salt. Like this, the salt in the stoste has just constantly entered into salt recovery chamber and has obtained concentrating. But must be noted that the salinity difference that reclaims in chamber and the former liquid chamber along with salt is increasing, electrodialytic current efficiency can be more and more lower, and the required electric energy that adds is also increasing.

It is slightly different to reclaim the chamber situation for cathode chamber and adjacent former liquid chamber thereof and anode chamber and adjacent salt thereof. What pass in cathode chamber and anode chamber is identical utmostpoint chamber liquid 5, reclaims the dense saline solution in exit, chamber when this utmost point chamber liquid adopts salt, under the effect of electric field force, and the H in the anode chamber⁺、Et₃NH₄⁺See through the salt that the is adjacent recovery chamber that cationic membrane enters the left side, anode chamber. Therefore the salt adjacent with the anode chamber reclaims indoor H⁺、Et₃NH₄⁺The anode chamber that comes from the right side, and Cl^-、HPO₃^2-The former liquid chamber that comes from the left side Deng anion. Same under the effect of electric field force, the H in the former liquid chamber adjacent with cathode chamber⁺、Et₃NH₄⁺See through the cathode chamber that cationic membrane enters the left side, just in time remedied the H of moving to salt recovery chamber in the anode chamber⁺、Et₃NH₄⁺Loss, so just kept H in the liquid of utmost point chamber⁺、Et₃NH₄⁺Stable. Simultaneously at negative electrode evolving hydrogen reaction takes place:

2H⁺+2e^-→H₂↑ (1)

And at anode generation oxygen evolution reaction:

2H₂O→O₂↑+4H⁺+4e^- (2)

The H that the anode oxygen evolution reaction produces⁺Just in time remedied the H that cathode hydrogen evolution consumed⁺, the pH value in the liquid of utmost point chamber also keeps stable like this.

Along with constantly carrying out of electrodialysis process, the H that stoste is indoor⁺Constantly being removed, thereby playing the effect of depickling, is the mixing solutions of triethylamine hydrochloride and hydrochloric acid but it reclaims that the chamber obtains at salt, also contains phosphorous acid or phosphoric acid.Extracting triethylamine hydrochloride from this solution then is not a nothing the matter, if can directly prepare triethylamine in the electrodialysis deacidification, then will simplify operating process of the present invention greatly.

In order to realize this purpose, the invention provides a kind of embodiment of electrodialysis relieving haperacidity alkali, as shown in Figure 3, this electrodialysis system is made up of the V of anolyte compartment of the cathode compartment VI of a built-in negative electrode ca (cathode compartment also is used as triethylamine and is reclaimed the chamber), cationic exchange membrane C, former liquid chamber III, anion-exchange membrane A, acid recovery chamber VII, cationic exchange C, built-in anode an.The same with above-mentioned traditional electrical dialysis system, to constitute one group of film right by being positioned at the cationic exchange membrane on the cathode direction and being positioned at anion-exchange membrane on the anode direction.At film the intermediary zone is made as former liquid chamber, in the right left side of film is cathode compartment (also being that triethylamine reclaims the chamber), is the acid recovery chamber at film to the right side, is that a side of anode direction is provided with cationic exchange membrane C on right side, acid recovery chamber, and acid recovery chamber and anolyte compartment are separated.

Pendingliquid 3 enters former liquid chamber III, and dilutehydrochloric acid 7 enters acid recovery chamber VII, andcatholyte 6 enters cathode compartment VI, andanolyte 8 enters the V of anolyte compartment.Described catholyte is the sodium hydroxide solution of 0.5～2mol/L, and described anolyte is certain density sulphuric acid soln.When after energising between the cathode and anode, under the effect of electrical forces, the H in the former liquid chamber III in the pendingliquid 3⁺, Et₃NH⁺See through cationic exchange membrane C and migrate into cathode compartment VI.Because catholyte is a NaOH solution, the H that migration is come⁺, Et₃NH⁺Immediately with catholyte in OH^-Neutralization reaction takes place become H₂O and Et₃N (triethylamine).

On the negative electrode in cathode compartment evolving hydrogen reaction taking place and produces OH simultaneously^-:

2H₂O+2e→H₂↑+2OH^- (3)

The OH that produces^-Just in time remedy the OH that neutralizes^-, so just keep the OH in the catholyte^-Concentration is constant.The solubleness of triethylamine is low in basic solution, and when reaching supersaturation, triethylamine will be separated from catholyte, and two-layer about forming, it is triethylamine at the middle and upper levels, and lower floor is an alkali lye.Just triethylamine can be reclaimed by simple separatory operation.

Similarly, the Cl in the pendingliquid 3 in the former liquid chamber III^-, HPO₃^2-Under the electrical forces effect, migrate into acid recovery chamber VII Deng negatively charged ion, simultaneously the H in the anolyte compartment through anion-exchange membrane A⁺Also see through cationic exchange membrane C and enter into the acid recovery chamber under the electrical forces effect, the two is in conjunction with generating HCl, H₃PO₃Deng.On the anode in the anolyte compartment oxygen evolution reaction taking place and produces H⁺(reaction formula (2)), the H of generation⁺Just in time remedied the H that migrates into the acid recovery chamber in the anolyte compartment⁺, so just the acid concentration in the anolyte is remained unchanged.

We notice, reclaim the chamber with cathode compartment as triethylamine and have some problems, because negative electrode generation evolving hydrogen reaction meeting releasing hydrogen gas, and triethylamine is strong volatile matter, in the process that hydrogen is overflowed, will inevitably carry a certain amount of triethylamine, this volatilization loss that just causes triethylamine.Simultaneously, reactions such as electropolymerization also might take place in triethylamine on negative electrode, make cathode surface form the film of the thick brownish black of one deck, and cathodic reaction is suppressed, and have not only reduced current efficiency, also cause the loss of triethylamine.

In order to address the above problem, the present invention provides the scheme of another kind of electrodialysis relieving haperacidity alkali again, as shown in Figure 4, it is compared with above-mentioned electrodialysis relieving haperacidity alkali scheme, just between cathode compartment VI and former liquid chamber III, increase a triethylamine and reclaim chamber VIII, cathode compartment VI and triethylamine reclaim between the VIII of chamber and separate with anion-exchange membrane A, and triethylamine reclaims between chamber VIII and the former liquid chamber III and separates with cationic exchange membrane C, and triethylamine reclaims in the VIII of chamber and charges into certain density sodium hydroxide solution 9.Like this under the effect of electrical forces, the H in the former liquid chamber III in the pending liquid 3⁺, Et₃NH⁺See through cationic exchange membrane C and migrate into triethylamine and reclaim chamber VIII, reclaim OH in the sodium hydroxide solution in the VIII of chamber with triethylamine respectively^-Reaction generates H₂O and Et₃OH in the N, cathode compartment VI^-See through anion-exchange membrane A and migrate into the OH that triethylamine recovery chamber VIII supplement consumed is fallen^-, therefore the naoh concentration in triethylamine reclaims chamber VIII remains unchanged substantially.Under such alkaline condition, triethylamine is separated out from solution, is free in the top that triethylamine reclaims chamber VIII, can reclaim behind separatory and obtain triethylamine.Similarly, the Cl in the pending liquid 3 in the former liquid chamber III^-, HPO₃^2-Also under the effect of electrical forces, migrate into acid recovery chamber VII Deng negatively charged ion, with the H that comes from the V of anolyte compartment migration through anion-exchange membrane A⁺Be combined into hydrochloric acid and/or phosphorous acid and in the indoor accumulation of acid recovery, so hydrochloric acid and phosphorous acid just reclaim indoor the obtaining of acid recovery.Because triethylamine do not enter cathode compartment, just from solution, dissociate out and obtained recovery but reclaim the chamber at triethylamine, so just triethylamine is incurred loss, negative electrode has also obtained protection, has guaranteed cathodic activity.

Yet we notice that each electrodialysis cell all comprises an anode and a negative electrode in the above-mentioned electrodialysis relieving haperacidity alkali scheme, so each electrodialysis cell all will produce H by brine electrolysis⁺And OH^-, so all want the ionization energy and the polarization of electrode energy of consume water.And what electrodialysis cell traditional electrodialysis comprises and all only is provided with an anode and a negative electrode at the two ends of electrodialysis unit, so, the energy consumption of above-mentioned electrodialysis relieving haperacidity alkali systems is more much higher than traditional electrodialysis, and it is complicated and huge much bigger that the structure of electrodialyzer is also wanted.

In order to cut down the consumption of energy and to guarantee same deacidification, the present invention provides another embodiment again, promptly adopts the electrodialysis relieving haperacidity alkali systems of Bipolar Membrane.As shown in Figure 5, " n " is the unit weighs plural number among the figure, this electrodialysis relieving haperacidity alkali systems is similar a bit to traditional electrodialysis in form, different is to be provided with a Bipolar Membrane AC on the direction of film to the right side anode of being made up of an anion-exchange membrane and a cationic exchange membrane, electrodialysis cell is separated into three compartments, is different from the electrodialytic two compartment systems of tradition.Described film pair is identical with traditional electrical dialysis system, film between zone (compartment) be made as former liquid chamber III, zone between the Bipolar Membrane on cationic exchange membrane C and the left side cathode direction thereof is made as triethylamine and reclaims chamber VIII (remove the alkali adjacent with cathode compartment and reclaim the chamber), and the zone between the Bipolar Membrane on anion-exchange membrane A and the right side anode direction thereof is made as acid recovery chamber VII.Cathode compartment itself also can be used as triethylamine and reclaims chamber (electrodialysis relieving haperacidity alkali systems as shown in Figure 3), but for prevent negative electrode in electrode process to reclaiming the influence of triethylamine, optimal scheme is to reclaim between the chamber at cathode compartment VI and the triethylamine adjacent with cathode compartment to separate (electrodialysis relieving haperacidity alkali systems as shown in Figure 4) with an anionic membrane.So its arrangement mode is:

VIA VIII C III A VII AC VIIIC III A VII AC ... VII AC V, constitute an electrodialysis relieving haperacidity alkali unit by one group of film to adding a Bipolar Membrane, an electrodialysis relieving haperacidity alkali device capable of being industrialized can be by hundreds and thousands of such electrodialysis relieving haperacidity alkali unit, but no matter what electrodialysis relieving haperacidity alkali unit are arranged, and whole electrodialysis relieving haperacidity alkali device all only needs pair of electrodes (i.e. an anode and a negative electrode).

Bipolar Membrane is the laminate of anion-exchange membrane and cationic exchange membrane, the difference of it and one pole anion-exchange membrane and one pole cationic exchange membrane be can be in electrodialytic electric field catalytic pyrolysis water effectively, be used to provide H⁺And OH^-, therefore can replace pair of electrodes and relevant supporting utmost point chamber and ion-exchange membrane, with the H of Bipolar Membrane splitting water generation with a Bipolar Membrane⁺And OH^-Replace H by the brine electrolysis generation⁺And OH^-

Adopt the electrodialysis relieving haperacidity alkali systems of Bipolar Membrane basic identical with the principle of work of above-mentioned electrodialysis system relieving haperacidity alkali systems (as shown in Figure 4), difference only is that it has adopted Bipolar Membrane splitting water generation H⁺And OH^-, replace relying in the above-mentioned electrodialysis relieving haperacidity alkali systems reaction of anode and cathodic electrolytic water to produce H⁺And OH^-In whole electrodialysis relieving haperacidity alkali systems, only pair of electrodes (i.e. an anode and a negative electrode) need be set like this, and needn't in each electrodialysis relieving haperacidity alkali unit, anode and negative electrode be set all.The more compact structure of electrodialysis relieving haperacidity alkali device like this, energy consumption is lower, operates simpler.

Adopt the situation of the anolyte compartment of the situation of the anolyte compartment at electrodialysis relieving haperacidity alkali systems two ends of Bipolar Membrane and cathode compartment and system both sides shown in Figure 4 and cathode compartment slightly different.In the electrodialysis relieving haperacidity alkali systems that adopts Bipolar Membrane, feed certain density alkaline solution in the cathode compartment as catholyte, under the electrical forces effect, the OH in the cathode compartment^-The anion-exchange membrane that sees through the cathode compartment right side migrates into the alkali that is adjacent and reclaims the chamber, and negative electrode generation water electrolysis evolving hydrogen reaction generates OH simultaneously^-[reaction formula (3)] have just in time remedied and have migrated into the OH that alkali reclaims the chamber^-Consumption, so the alkaline concentration in the cathode compartment is to keep stable.The anolyte that feeds in the anolyte compartment can be a metabisulfite solution, also can be sulphuric acid soln, can also be alkaline solution, this with system shown in Figure 4 in anolyte must be that acid solution is different.Oxygen evolution reaction takes place on anode, has consumed OH^-:

OH^-→O₂↑+H₂O+4e^- (4)

And the OH that the Bipolar Membrane dissociate water in left side, anolyte compartment produces^-Just in time remedied this part used up OH^-, strength of solution in the anolyte compartment and pH value also are to keep stable like this.

Along with constantly carrying out of electrodialysis process, the H in the pending liquid⁺, Et₃NH⁺Constantly move to triethylamine and reclaim chamber or salt recovery chamber, so reached the purpose of depickling.

Yet we have to be noted that and the objective of the invention is elder generation by depickling, and then the extraction triethylamine hydrochloride, are the feedstock production triethylamine at last with the triethylamine hydrochloride.So the purpose of above-mentioned electrodialysis process is for the H in the pending liquid⁺Take off, reclaiming triethylamine is not electrodialytic herein purpose, but because pending liquid is removing H⁺Process in inevitably also can be Et₃NH⁺Remove, and along with the H in the pending liquid⁺Concentration is more and more littler, removes H⁺Efficient can be more and more lower, that remove to the end nearly all is Et₃NH⁺.So adopt this electrodialysis or electrodialysis relieving haperacidity alkaline process depickling and differ an optimal scheme.

For this reason, the invention provides the scheme of another kind of electrodialysis depickling, as shown in Figure 6, it is identical with electrodialysis relieving haperacidity alkali systems shown in Figure 3 in form, the cationic exchange membrane C that just will be close to negative electrode replaces and becomes anion-exchange membrane A, the left side of former like this liquid chamber and right side all are anion-exchange membranes, so under the effect of electrical forces, change has just taken place the ion migration direction in the pending liquid.H in the pending liquid⁺, Et₃NH⁺When cathode direction moves, be subjected to stopping of anion-exchange membrane can't enter cathode compartment, and the OH in the cathode compartment^-Then can waltz through very much anion-exchange membrane and migrate into former liquid chamber, with the H in the former liquid chamber⁺Neutralization reaction takes place generate water, so just reached the purpose of pending liquid depickling.Because OH^-Earlier and free H always⁺Neutralization reaction takes place, so dissociate out as long as the suitable pH value in the pending liquid of control does not just have triethylamine.Adopt the advantage of this electrodialysis depickling to be when the pending liquid of neutralization, can not cause Et₃NH⁺Migration, and do not bring the xenogenesis ion into.

Simultaneously, the Cl in the pending liquid^-, HPO₃²Under the effect of electrical forces, migrate into acid recovery chamber VII Deng negatively charged ion, with the H that comes from anolyte compartment's migration⁺Be combined into hydrochloric acid or phosphorous acid etc., on macroscopic view, hydrochloric acid or phosphorous acid in the pending liquid are separated, and have obtained recovery.

The same with electrodialysis relieving haperacidity alkali systems, also can replace pair of electrodes (being anode and negative electrode) with a Bipolar Membrane, as shown in Figure 7, so just form one and the similar electrodialysis deacidification system runs of traditional electrical dialysis system, the mechanism of action of Bipolar Membrane is also identical with the electrodialysis relieving haperacidity alkali systems of band Bipolar Membrane.

Glyphosate mother solution is after diffusion dialysis, electrodialysis, electrodialysis relieving haperacidity alkali or electrodialysis depickling are handled, and the pH value of glyphosate mother solution can constantly rise.Because glyphosate is an amphiprotic substance, when locating, the solubleness of glyphosate is minimum in iso-electric point (this pH=1.5).In the uphill process of glyphosate mother solution pH value, the glyphosate in the mother liquor can be separated out gradually because of the decline of solubleness, in pH 1.2～1.8 scopes, the glyphosate crystallization is separated out at most, can leave standstill crystallization this moment, the filtered and recycled glyphosate, and filtrate can be proceeded depickling to required pH value.But the pH value that different treatment processs can be handled is different, and diffusive dialysis method can only be with the glyphosate mother solution depickling to pH about 0.8.Electrodialysis and electrodialysis relieving haperacidity alkaline process can take off to pH 2.0～3.0, and electrodialysis depickling rule can depickling to pH value arbitrarily, but should not be higher than pH 8.0 because have free triethylamine generation under the high again pH, can influence the yield of triethylamine hydrochloride.We know, when the pH value reaches 2.4 when above, have not almost contained free acid in the glyphosate mother solution.So the terminal point of depickling control is pH1.2～8.0, is preferably 1.8～6.0, more preferably 2.4～5.0.

The glyphosate mother solution of handling through depickling just can be used to concentrate, triethylamine in glyphosate mother liquor hydrochloride concentration is brought up to saturation concentration after, make its crystallization, and reclaim triethylamine salt acid by filtration.

Concentrate the conventional concentration method that can adopt in the chemical process, mainly contain evaporation concentration and reverse osmosis and concentrate thoroughly, they both may be used alone, can also be used in combination.Because evaporation concentration and reverse osmosis concentrate relative merits are arranged respectively, so preferred plan is that both are combined, concentrate with reverse osmosis earlier the triethylamine hydrochloride concentration in the mother liquor is brought up to a certain degree, the saturation concentration that improves with evaporation concentration again, through cooling, crystallization and filtration reclaims triethylamine hydrochloric acid, and filtrate is then returned above-mentioned deacidifying process again, realize closed cycle, so that triethylamine hydrochloride can access whole recovery.

Except reclaiming the triethylamine hydrochloride by concentration method, can also adopt electrodialytic method to reclaim triethylamine hydrochloric acid, electroosmose process i.e. as shown in Figure 2 electrodialysis system, and operating process and principle and aforesaid electrodialysis process are identical.But the difference of their maximums is, reclaims by electrodialysis this moment and no longer contains complicated free acid in the triethylamine hydrochloric acid that obtains, because pending liquid has been the glyphosate mother solution after the depickling processing, has not contained free H in the mother liquor⁺So what reclaim almost is pure triethylamine hydrochloride, just can prepare triethylamine easily with it.What the electrodialysis recovery obtained is the solution of triethylamine hydrochloride, and it both can be directly used in the preparation triethylamine, can certainly concentrate, and crystallization obtains the solid of triethylamine hydrochloride.

After triethylamine hydrochloride extracted from glyphosate mother solution, be that the feedstock production triethylamine is just more convenient with it again, both can have adopted the method for chemistry, also can adopt electrochemical method.

Chemical method is exactly a neutralisation, promptly use in the alkaline reagents and the solution of triethylamine hydrochloride, alkaline reagents comprises sodium hydroxide, potassium hydroxide, ammonia, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, volatile salt, bicarbonate of ammonia, calcium hydroxide, calcium oxide etc., preferred sodium hydroxide, calcium oxide and calcium hydroxide.

The triethylamine hydrochloride solution or the triethylamine hydrochloride solid that extract are mixed with certain density solution, with above-mentioned alkaline reagents the pH value is transferred to more than 10, triethylamine hydrochloride is converted into triethylamine and dissociates out on the upper strata of solution, can obtain triethylamine by simple separatory.

Directly compare with alkali neutral method with glyphosate mother solution, this method biggest advantage is that remaining salt processing is easy to after extracting triethylamine, and does not produce gyphosate solution.Because it is very pure to reclaim the triethylamine hydrochloride obtain, containing assorted also is very purified so reclaim the salt that obtains behind the triethylamine seldom, and this salt can be used as the industrial salt direct reuse.Another advantage of this method is that can to adopt more cheap calcium oxide and calcium hydroxide be lime because contain glyphosate in the glyphosate mother solution, with lime directly in and the time can produce the glyphosate calcium precipitation, make glyphosate obtain loss.Not containing glyphosate and reclaim the triethylamine hydrochloric acid that obtains with this method, just do not have the loss problem of glyphosate, and reclaim the calcium chloride of the salt that obtains behind the triethylamine, is not to be subjected to state control to its processing.

With the triethylamine hydrochloride is that the feedstock production triethylamine can be more convenient with electrochemical process, and can not produce the problem of extra salt.Electrochemical process can be electrolytic process and electrodialysis relieving haperacidity alkaline process.

Electrolytic process is similar with conventional ionic membrane method alkali-chloride technology, as shown in Figure 8, is divided into V of anolyte compartment and cathode compartment VI with a cationic exchange membrane C in an electrolyzer, and the anolyte compartment is built-in with anode an, and cathode compartment is built-in with negative electrode ca.Cathode compartment feeds certain density sodium hydroxide solution ascatholyte 6, and the anolyte compartment feeds thetriethylamine hydrochloride solution 10 of high density as anolyte.Behind logical direct current between the cathode and anode, the Cl in the anolyte^-Generate chlorine at anode generation electro-oxidation reaction:

2Cl^-→Cl₂↑+2e^- (5)

And the Et in the anolyte₃NH⁺Then under the effect of electrical forces, see through cationic exchange membrane and migrate into cathode compartment, with the OH in the catholyte^-Reaction generates triethylamine.This process and ionic membrane method alkali-chloride technology are identical, and triethylamine hydrochloride has prepared triethylamine and chlorine by such ion-exchange membrane electrolysis.

But, be inappropriate with triethylamine hydrochloride as anolyte, because Et₃NH⁺Complicated oxidizing reaction can not take place in resistance to oxidation under the effect of strong oxidizer chlorine, and triethylamine is incurred loss.

For this reason, the invention provides another kind of ion membrane electrolytic process, as shown in Figure 9, different with above-mentioned ion-exchange membrane electrolysis is that cationic exchange membrane is replaced to anion-exchange membrane, simultaneouslytriethylamine hydrochloride solution 10 is fed cathode compartment VI as catholyte, anolyte is then with sodium-chlor or hydrochloric acid soln 11.Under galvanic effect, negative electrode generation evolving hydrogen reaction [reaction formula (2)] and obtain OH^-, it and Et₃NH⁺Reaction obtains triethylamine.Simultaneously, Cl^-Under the effect of electrical forces, see through anion-exchange membrane and migrate into the anolyte compartment, on anode, anodic oxidation reactions takes place and be converted into chlorine [reaction formula (5)].Adopt this ion-exchange membrane electrolysis, triethylamine hydrochloride places cathode compartment, avoided by chlorine or anodised problem, but because the anion-exchange membrane scale resistance is poor, the erosion that is subjected to chlorine in the anolyte compartment will soon be lost efficacy.

Be exposed under the chlorine gas environment for fear of anion-exchange membrane, be subjected to the destruction of chlorine, the invention provides the scheme that another kind has actual operability, as shown in figure 10, the difference of it and scheme shown in Figure 9 is, every establishing a cationic exchange membrane C, two original like this compartment electrolytic systems have become three compartment electrolytic systems in the anolyte compartment, have increased an acid recovery chamber VII between anolyte compartment and cathode compartment.In the acid recovery chamber, feed dilutehydrochloric acid solution 7, under the electrical forces effect, the Cl of cathode compartment^-H with the anolyte compartment⁺All migrate into the acid recovery chamber and obtain accumulation, the concentrated hydrochloric acid solution of acid recovery chamber outlet is as anolyte, the Cl in the anolyte^-Become chlorine in anode generation electrooxidation, and H⁺Then migrated into the acid recovery chamber.Like this by the acid recovery chamber as middle transition, anion-exchange membrane and chlorine gas environment are isolated, thereby have protected anion-exchange membrane, also making triethylamine hydrochloride prepare triethylamine by electrolytic process becomes possibility.

Though adopt electrolytic process to prepare triethylamine from triethylamine hydrochloride, the front was mentioned, electric polymerization reaction also can take place at negative electrode in triethylamine, and cathode hydrogen evolution also can carry triethylamine and causes the triethylamine loss.So electrolytic process is not an optimal scheme yet.

We think that preparing another feasible scheme of triethylamine from triethylamine hydrochloride is to adopt the method for electrodialysis relieving haperacidity alkali, this same with previously described electrodialysis relieving haperacidity alkaline process (Fig. 3, Fig. 4 and scheme shown in Figure 5).But the pending liquid that foregoing electrodialysis relieving haperacidity alkaline process Central Plains liquid chamber feeds is glyphosate mother solution or the glyphosate mother solution after diffusion dialysis, and the pending liquid described here solution that to be the triethylamine hydrochloride that extracts be mixed with.Owing to have only a kind of material of triethylamine hydrochloride in this solution, so the ionic forms that can move in the pending liquid also has only Et₃NH⁺And Cl^-, the acid that obtains in the acid recovery chamber just has only hydrochloric acid like this.Compare with the electrodialysis relieving haperacidity alkaline process of front, the concentration of the triethylamine hydrochloride in the pending here liquid is to keep constant by adding the triethylamine hydrochloride solid, so just can current efficiency be diminished because of the minimizing of triethylamine hydrochloride content in the pending liquid.Adopt the great advantage of this method can expeditiously triethylamine hydrochloride be prepared triethylamine exactly, thereby the entire equipment investment is descended significantly with running cost, more possess the industrialization feasibility.

Usually, any ion-exchange membrane that is usually used in electrodialysis and electrolysis with ion-exchange film can be used for the present invention, preferably use commercially available ion-exchange membrane.These ion-exchange membranees are made up of the organic polymer with ionic side chain.Cationic exchange membrane contains sulfonate radical or carboxyl in polymeric matrix, and anion-exchange membrane is with uncle or the quaternary amine base substituting group as polymeric base material.Cationic exchange membrane and anion-exchange membrane can all be homogeneous, also can be out-phase, and body material can be the multipolymer of vinylbenzene and divinylbenzene, and perhaps other contains the matrix of inclined to one side fluorine or perfluor.

Can from glyphosate mother solution, reclaim triethylamine expeditiously by method of the present invention, and not produce salt and gyphosate solution, also significantly reduce the consumption of alkali, and reclaim hydrochloric acid and triethylamine.

Embodiment

Embodiment 1

The glyphosate mother solution that obtains when producing glyphosate with the dialkyl phosphite method, hydrochloric (comprising free acid and combined acid) is about 23.5%, and triethylamine is about 15%, glyphosate about 3%.Get the former liquid chamber I that such glyphosate mother solution 1000ml enters diffusion dialysis device as shown in Figure 1, the 3000ml pure water enters and reclaims chamber II, be about 0.96 through glyphosate mother solution pH value after 24 hours the diffusion dialysis, again the glyphosate mother solution after this diffusion dialysis is entered the former liquid chamber III in the electrodialysis relieving haperacidity alkali device shown in Figure 3, the hydrochloric acid soln that 1500ml concentration is about 0.3mol/L enters acid recovery chamber VII, anolyte is the sulphuric acid soln of 1mol/L, catholyte is the sodium hydroxide solution of 1mol/L, logical direct current is with 2A/dm²Current density electrodialysis 10 hours, the pH of glyphosate mother solution is increased to 1.5, leave standstill and make its sufficient crystallising, filter and obtain the 18.1g solid glyphosate.The filtrate evaporation concentration is to 150ml, and crystallisation by cooling filters and obtains triethylamine hydrochloride 105.2g, and filtrate is stand-by.With this triethylamine hydrochloride 100ml water dissolution, be neutralized to pH more than 11 with 30% liquid caustic soda, standing demix reclaims upper organic phase and obtains the 73ml triethylamine, and the rate of recovery of triethylamine is about 34.3%.

Embodiment 2

Repeat embodiment 1, be that with the difference ofembodiment 1 electrodialysis relieving haperacidity alkali device uses device shown in Figure 4 instead, aqua calcis is used in neutralization instead, obtains the 72.1ml triethylamine, and the rate of recovery of triethylamine is 33.8%.The middle filtrate that produces is stand-by.

Embodiment 3

Repeat embodiment 1, be that with the difference ofembodiment 1 electrodialysis relieving haperacidity alkali device uses device shown in Figure 5 instead, salt of wormwood is used in neutralization instead, obtains the 73.5ml triethylamine, and the rate of recovery of triethylamine is 34.5%.

Embodiment 4

Repeat embodiment 1, use ammoniacal liquor instead in being with the difference ofembodiment 1, obtain the 70.8ml triethylamine, the rate of recovery of triethylamine is 33.2%.

Embodiment 5

After merging, the filtrate that 1000ml glyphosate mother solution and embodiment 1 are produced enters among the former liquid chamber III in the electrodialysis relieving haperacidity alkali device as shown in Figure 4, except that triethylamine reclaims the sodium hydroxide solution of indoor feeding 1mol/L, consistent in the electrodialysis relieving haperacidity alkali device among the solution that all the other each chambers feed and the embodiment 1.Perfectly straight stream electrical treating to the pH value of solution in the former liquid chamber is about 1.7.Leave standstill crystallization, filter and obtain the 30.5g glyphosate.Filtrate enters electrodialytic desalting device shown in Figure 6 again, and corresponding each chamber is consistent in the solution that all the other each chambers feed and the above-mentioned electrodialysis relieving haperacidity alkali device.The pH to 5.0 of the solution of perfectly straight stream electrical treating to the former liquid chamber, with this solution reverse osmosis concentration to 500ml, revaporization is concentrated into 200ml, crystallization, filtration obtains triethylamine hydrochloride solid 211.6g, with this triethylamine hydrochloride 200ml water dissolution, feed the cathode compartment of electrolyzer shown in Figure 10, the anolyte compartment feeds the hydrochloric acid soln of 2mol/L, the acid recovery chamber feeds the 0.2mol/L dilute hydrochloric acid solution, and the indoor concentration of hydrochloric acid solution of acid recovery reaches and just is passed into more than the 1.5mol/L in the anolyte compartment, constantly adds the triethylamine hydrochloride solid in the catholyte and keeps its concentration constant substantially, through 8 hours electrolysis, obtain triethylamine 287.2ml.The current efficiency that triethylamine hydrochloride prepares triethylamine reaches 90.6%, and the triethylamine rate of recovery reaches 92.7%.

Embodiment 6

After merging, the filtrate that 1000ml glyphosate mother solution and embodiment 2 are produced enters among the former liquid chamber III in the electrodialysis relieving haperacidity alkali device as shown in Figure 4, except that triethylamine reclaims the sodium hydroxide solution of indoor feeding 1mol/L, consistent in the electrodialysis relieving haperacidity alkali device among the solution that all the other each chambers feed and the embodiment 1.Perfectly straight stream electrical treating to the pH value of solution in the former liquid chamber is about 1.4.Leave standstill crystallization, filter and obtain the 31.7g glyphosate.Filtrate is handled to pH 2.5 with identical device again, former liquid chamber in the electrodialysis unit that this solution feeding is shown in Figure 2, salt reclaims the triethylamine hydrochloride solution that the chamber feeds 0.2mol/L, cathode compartment feeds identical utmost point chamber liquid with the anolyte compartment, this utmost point chamber stream is that salt reclaims the salts solution that the exit, chamber obtains, and feeds 2A/dm²Direct current treatment 48 hours, reclaim the chamber at salt and obtain the triethylamine hydrochloride solution that concentration is 420g/L, this solution is directly fed former liquid chamber in the electrodialysis relieving haperacidity alkali device shown in Figure 5, the solution that all the other each chambers feed is with above-mentioned consistent, logical direct current constantly adds the triethylamine hydrochloride solid to keep the indoor triethylamine hydrochloride concentration unanimity of stoste in treating processes.Through 12 hours processing, triethylamine is reclaimed indoor liquid layering, reclaim upper organic phase, obtain the 168.9ml triethylamine, the current efficiency that is prepared triethylamine by triethylamine hydrochloride is 68.6%, the rate of recovery of triethylamine is 81.5%.

Embodiment 7

Repeat embodiment 6, difference is that the electrodialysis relieving haperacidity alkali device that triethylamine hydrochloride is prepared triethylamine changes device shown in Figure 4 into, then obtain the 153ml triethylamine, the rate of recovery 73.8% of triethylamine, the current efficiency that is prepared triethylamine by triethylamine hydrochloride is 70.9%.

Embodiment 8

Repeat embodiment 6, difference is that the electrodialysis relieving haperacidity alkali device that triethylamine hydrochloride is prepared triethylamine changes device shown in Figure 3 into, then obtain the 147ml triethylamine, the rate of recovery 70.9% of triethylamine, the current efficiency that is prepared triethylamine by triethylamine hydrochloride is 72.3%.

Claims (15)

1. method for processing mother solution of glyphosate, described glyphosate mother solution are isolated the acid mother liquid of gained after the glyphosate products when adopting the dialkyl phosphite method to produce glyphosate, it is characterized in that:

(1) described glyphosate mother solution earlier through the dialysis depickling to the pH of glyphosate mother solution be 1.2～8.0, become the depickling mother liquor, and the corresponding acid of contained inorganic anion in recovery and the glyphosate mother solution;

(2) triethylamine hydrochloride of described depickling mother liquor in electrodialytic desalting and/or concentration extraction depickling mother liquor;

(3) be that raw material adopts alkali neutral method or electrochemical method to prepare triethylamine with the triethylamine hydrochloride.

2. method for processing mother solution of glyphosate as claimed in claim 1 is characterized in that described dialysis depickling is at least a in diffusive dialysis method depickling, electroosmose process depickling, the depickling of electrodialysis relieving haperacidity alkaline process.

3. method for processing mother solution of glyphosate as claimed in claim 1 is characterized in that described glyphosate mother solution depickling is to pH at 1.2～1.8 o'clock, the glyphosate in crystallization, the filtered and recycled glyphosate mother solution.

4. method for processing mother solution of glyphosate as claimed in claim 1 is characterized in that described acid is the nitration mixture of hydrochloric acid or hydrochloric acid and phosphorous acid, or the nitration mixture of hydrochloric acid, phosphorous acid and phosphoric acid.

5. method for processing mother solution of glyphosate as claimed in claim 1 is characterized in that described concentrating is reverse osmosis concentration and/or evaporation concentration.

6. method for processing mother solution of glyphosate as claimed in claim 1 is characterized in that described triethylamine hydrochloride is solution and/or the triethylamine hydrochloride solid that contains triethylamine hydrochloride.

7. method for processing mother solution of glyphosate as claimed in claim 1 is characterized in that it is that triethylamine hydrochloride is neutralized to pH with alkaline reagents is 9～13 that described alkali neutral method prepares triethylamine, reclaims the free triethylamine on upper strata through separatory.

8. method for processing mother solution of glyphosate as claimed in claim 1 is characterized in that it is that triethylamine hydrochloride is prepared triethylamine and chlorine or prepares triethylamine and hydrochloric acid with electrodialysis relieving haperacidity alkaline process with ion-exchange membrane electrolysis that described electrochemical method prepares triethylamine.

9. method for processing mother solution of glyphosate as claimed in claim 7 is characterized in that described alkaline reagents is at least a in sodium hydroxide, potassium hydroxide, ammonia, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, volatile salt, bicarbonate of ammonia, calcium hydroxide, the calcium oxide.

10. method for processing mother solution of glyphosate as claimed in claim 2, it is characterized in that its device of described diffusion dialysis reclaims liquid chamber (II) by at least one diffusion dialysis film (M), at least one mother liquor chamber (I) and at least one and forms, the diffusion dialysis film is clipped between former liquid chamber and the recovery liquid chamber; Described diffusive dialysis method depickling is to feed glyphosate mother solution at described former liquid chamber, feeds pure water or diluted acid at described recovery liquid chamber.

11. method for processing mother solution of glyphosate as claimed in claim 2, it is characterized in that its device of described electroosmose process depickling is made up of the anolyte compartment (V) of cathode compartment (VI), at least one former liquid chamber (III), at least one acid recovery chamber (VII) and the built-in anode (an) of built-in negative electrode (ca), between cathode compartment and former liquid chamber, accompany anion-exchange membrane (A), between the acid recovery chamber that is adjacent on former liquid chamber and the anode direction, accompany anion-exchange membrane (A), between acid recovery chamber and anolyte compartment, accompany cationic exchange membrane (C) or Bipolar Membrane (AC); Described electroosmose process depickling is to feed glyphosate mother solution at described former liquid chamber, feeds dilute hydrochloric acid solution in described acid recovery chamber, feeds sodium hydroxide solution at described cathode compartment, feeds sulphuric acid soln in described anolyte compartment, logical direct current between described anode and negative electrode.

12. method for processing mother solution of glyphosate as claimed in claim 11 is characterized in that, towards anode direction, accompanies Bipolar Membrane (AC) between acid recovery chamber (VII) and the former liquid chamber (III) adjacent to this acid recovery chamber.

13. as claim 2 or 8 described method for processing mother solution of glyphosate, it is characterized in that described electrodialysis relieving haperacidity alkali is respectively equipped with the anolyte compartment (V) of cathode compartment (VI) and the built-in anode (an) of built-in negative electrode (ca) with its both sides of device, it is right to be provided with the film of being made up of a cationic exchange membrane (C) and an anion-exchange membrane (A) of space between cathode compartment and the anolyte compartment, the cationic exchange membrane that described film is right and the relative position of anion-exchange membrane are that cationic exchange membrane is positioned at cathode direction, anion-exchange membrane is positioned at anode direction, cationic exchange membrane that described film is right and the zone between the anion-exchange membrane are set at former liquid chamber (III), the right cationic exchange membrane of described film is set at triethylamine to a zone of cathode direction and reclaims chamber (VIII) or cathode compartment (VI), and a zone of the anion-exchange membrane anode direction that described film is right is set at acid recovery chamber (VII); Described electrodialysis relieving haperacidity alkali is to import pending liquid at described former liquid chamber, reclaims chamber input dilute alkaline soln at described alkali, at described acid recovery chamber input dilute acid soln, and logical direct current between described anode and negative electrode.

14. method for processing mother solution of glyphosate as claimed in claim 12 is characterized in that described electrodialysis relieving haperacidity alkali is provided with cationic exchange membrane (C) or Bipolar Membrane (AC) with a side of the described acid recovery chamber anode direction of device.

15. method for processing mother solution of glyphosate as claimed in claim 8, it is characterized in that described electrolysis forms with the anolyte compartment (V) of device by cathode compartment (VI), acid recovery chamber (VII) and the built-in anode (an) of built-in negative electrode (ca), between cathode compartment and acid recovery chamber, accompany anion-exchange membrane (A), between acid recovery chamber and anolyte compartment, accompany cationic exchange membrane (C); Described electrolytic process prepares triethylamine and chlorine is the solution that feeds triethylamine hydrochloride at cathode compartment, feeds the hydrochloric acid dilute solution in the acid recovery chamber, feeds the hydrochloric acid strong solution in the anolyte compartment, logical direct current between described anode and negative electrode.

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