CN110393189A

CN110393189A - The comprehensive processing technique of glyphosate mother solution

Info

Publication number: CN110393189A
Application number: CN201810378967.1A
Authority: CN
Inventors: 刘德亮
Original assignee: Individual
Current assignee: Individual
Priority date: 2018-04-25
Filing date: 2018-04-25
Publication date: 2019-11-01

Abstract

The present invention provides a kind of comprehensive processing techniques of glyphosate mother solution, including glyphosate mother solution to be concentrated to, is precipitated triethylamine hydrochloride, the triethylamine hydrochloride being precipitated is removed, glyphosate mother solution concentrate A is obtained, pH adjusting agent is added thereto, is layered solution；Triethylamine and hydrochloride are extracted from the solution containing triethylamine hydrochloride；Triethylamine hydrochloride is converted, triethylamine is obtained；It is handled to obtain corresponding phosphoric acid hydrogen disalt or gyphosate solution to containing organic phosphorus salting liquid again.Present invention process is scientific and reasonable, realize the high efficiente callback of triethylamine, a variety of byproducts also can be obtained, do not generate waste liquid and solid waste, the processing cost for significantly reducing glyphosate mother solution, has obvious economic and environmental benefits, and solves the problems, such as that the glyphosate mother solution for hindering glyphosate industry development can not be handled thoroughly, the integrated treatment of glyphosate mother solution is realized, large-scale industrial production is suitble to.

Description

The comprehensive processing technique of glyphosate mother solution

Technical field

The present invention relates to the processing of the disposing mother liquor of glyphosate, concretely relate to a kind of glyphosate of glycine method preparation The comprehensive processing technique of mother liquor.

Background technique

Glyphosate is a kind of steriland herbicide of high-efficiency broad spectrum, has the characteristics that broad weed-killing spectrum, low toxicity and noresidue.Mesh The preceding country generallys use preparing glyphosate by glycin method, i.e., using paraformaldehyde, glycine and dialkyl phosphite as raw material, with Triethylamine is catalyst, obtains glyphosate after addition, condensation, acidolysis.This method is fairly simple, yield is higher, at low cost, Good product quality, but since glyphosate has certain solubility in water, inevitably result from a certain amount of glyphosate Mother liquor, glyphosate mother solution are acidic liquid, containing a large amount of triethylamine hydrochlorides, hydrochloric acid, on a small quantity the glyphosate that dissolves and other have Machine object, complicated component, hardly degraded organic substance content are high, therefore, the processing of glyphosate mother solution and be glyphosate technology using technology Important content in research.

What the method handled at present glyphosate mother solution was mainly sodium liquid alkaline is added into glyphosate mother solution, recycles it In triethylamine, then ammonium hydrogen carbonate is added into remaining mother liquor, after sodium bicarbonate is precipitated, prepares 10% using remaining filtrate Gyphosate solution, the processing method as disclosed in CN100537580, CN1676527 etc..Processing glyphosate is female in this way When liquid, on the one hand, a large amount of sodium hydroxide powders or sodium liquid alkaline need to be consumed, be recycled the higher cost of glyphosate mother solution；It is another Aspect can not be recycled organic matter therein, and the effect for removing inorganic salts is poor, so that after recycling triethylamine Remaining mother liquor and be precipitated sodium bicarbonate after filtrate in still contain a large amount of inorganic salts (such as sodium chloride, sodium phosphite), If the gyphosate solution that long-term a large amount of applications are prepared using this solution, can cause the salinization of soil, and large amount of organic is direct Into in soil and water body, potential risks are brought to environment.It is below to have limited production glyphosate content 30% for country now Gyphosate solution, and be also difficult to for glyphosate to be concentrated to the concentration using existing method, then aforementioned processing glyphosate mother solution The obtained residual filtrate of method becomes the waste liquid for being difficult to recycle.

Therefore, need to develop it is a kind of can be by solid waste such as organic matters and inorganic salts such as glyphosates in glyphosate mother solution The novel process of integrated treatment is carried out with waste liquid.

Summary of the invention

It is an object of the invention to provide a kind of comprehensive processing techniques of glyphosate mother solution, to solve existing glyphosate mother solution Substance processing not exclusively, generates the waste liquid or waste for being difficult to be recycled in recovery and treatment method, and processing cost is high and dirty The problems such as contaminating environment.

The object of the present invention is achieved like this:

A kind of comprehensive processing technique of glyphosate mother solution, the glyphosate mother solution are resulting using producing glyphosate by using glycine Acid mother liquid includes the following steps:

(a) glyphosate mother solution is concentrated, triethylamine hydrochloride is precipitated, removed the triethylamine hydrochloride being precipitated, obtain grass Sweet phosphine mother liquor concentrations liquid A；

The pH value of glyphosate mother liquor is usually 0.1 ~ 2, and in extreme circumstances, glyphosate mother solution is highly acid.

Glyphosate mother solution is concentrated in atmospheric conditions or under reduced pressure, the temperature being concentrated in atmospheric conditions is 100 ~ 130 DEG C, preferably 110 ~ 117 DEG C；The temperature for being performed under reduced pressure concentration is 50 ~ 130 DEG C, preferably 60 ~ 100 DEG C.

Triethylamine hydrochloride and remaining mother liquor that the methods of existing separation of solid and liquid will be precipitated in concentration process can be used Separation, and collect triethylamine hydrochloride.

(b) pH value of the resulting glyphosate mother solution concentrate A of step (a) is adjusted to≤14 using pH adjusting agent, it is quiet Set to solution be layered, the isolated solution containing triethylamine hydrochloride with contain organic phosphorus salting liquid；The pH value is adjusted Agent includes triethylamine and XOH or triethylamine and XOH solution, wherein X Na⁺、K⁺Or NH₄ ⁺；

Triethylamine first is added into the resulting glyphosate mother solution concentrate of step (a), then XOH or XOH solution is added thereto；Institute The dosage of the triethylamine of addition does not have strict regulations, generally by the Cl in glyphosate mother solution concentrate^-How much decisions, work as Cl^-Contain On the contrary when measuring high, the additional amount of triethylamine is increased, then reduce, and the additional amount of triethylamine can also be excessive, adjusting pH value, and excessive three Ethamine is then located at top layer when solution is layered, and recycling can be carried out after separation.

Preferably, the additional amount of XOH or XOH solution determines as follows: taking weight first is the glyphosate mother solution of B1 The pH value of sample is adjusted to 2 as sample, using triethylamine, XOH or XOH solution by concentrate A；XOH or XOH solution is used again The pH value of sample is adjusted to 5.0 ~ 7.5 by 2, determines the additional amount m of XOH or XOH solution in the step；Then, it is determined that required The weight B2 of the glyphosate mother solution concentrate A of processing, the then XOH being added in the glyphosate mother solution concentrate A of required processing or The weight of XOH solution is (B2/B1) * m.

Preferably, first the pH value of solution is adjusted 0.5 ~ 14 by the triethylamine that is added into glyphosate mother solution concentrate, then to XOH or XOH solution is wherein added；It after XOH or XOH solution is added, can also continue to that triethylamine is added.

During standing is layered solution, it can be heated, to promote solution to be layered.Heating temperature is 25 DEG C ~ 100 DEG C, preferably 50 ~ 90 DEG C, more preferable 70 DEG C.

When the triethylamine being added is not excessive, solution is divided into 2 layers up and down, and upper layer is to contain the molten of triethylamine hydrochloride Liquid, lower layer are to separate upper and lower 2 layers of solution containing organic phosphorus salting liquid using existing method, obtain containing triethylamine salt The solution of hydrochlorate and contain organic phosphorus salting liquid.

When the triethylamine excess being added, solution is divided into 3 layers of upper, middle and lower, and upper layer is triethylamine, and middle layer is to contain three second The solution of amine hydrochlorate, lower layer are that the triethylamine on upper layer is separated and collected using existing method containing organic phosphorus salting liquid, Middle lower layer's solution is separated again, obtains the solution containing triethylamine hydrochloride and containing organic phosphorus salting liquid；Collected three Ethamine obtains triethylamine finished product through dehydration.

Preferably, piece alkali (NaOH) is directlyed adopt, is the aqueous solution of sodium hydroxide when using sodium hydroxide solution, Its concentration is 0.1 ~ 99.9wt%, preferably 30 ~ 60wt%, more preferable 30 ~ 32wt%.

It is the aqueous solution of potassium hydroxide when using KOH solution, concentration is 0.1 ~ 99.9wt%, preferably 30 ~ 60wt%, more preferable 30 ~ 32wt%.

When using ammonia or ammonium hydroxide, ammonia concn is 0.1 ~ 99.9wt%, preferably 15 ~ 32wt%, more preferable 15 ~ 28wt%.

(c) it by the resulting solution concentration containing triethylamine hydrochloride of step (b), precipitation triethylamine hydrochloride, removes The triethylamine hydrochloride of precipitation, then triethylamine and hydrochloride are extracted from remaining mother liquor；

Solution containing triethylamine hydrochloride is concentrated in atmospheric conditions or under reduced pressure, is carried out in atmospheric conditions The temperature of concentration is 100 ~ 130 DEG C, preferably 110 ~ 117 DEG C；The temperature for being performed under reduced pressure concentration is 50 ~ 130 DEG C, preferably 60~100℃。

Optionally, triethylamine and hydrochloride are extracted from remaining mother liquor using following two methods:

A kind of method is that piece alkali and/or sodium hydroxide solution is added in remaining mother liquor after recycling triethylamine hydrochloride, is adjusted PH value is warming up to >=85 DEG C, obtains triethylamine steam and the alkali liquor containing sodium chloride to 10 ~ 14；Using triethylamine steam system Standby triethylamine finished product；Solid sodium chloride is prepared using the alkali liquor containing sodium chloride.

Preferably, 85 ~ 110 DEG C are warming up to after adjusting pH value.

Gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains triethylamine finished product through dehydration.

Specific method using the alkali liquor preparation solid sodium chloride containing sodium chloride is: by the alkali liquor containing sodium chloride It is concentrated, precipitated sodium chloride, is separated by solid-liquid separation and obtains solid sodium chloride and remaining a small amount of liquid, remaining a small amount of liquid is carried out Burning or high temperature oxidation process.

The preferred sodium hydrate aqueous solution of sodium hydroxide solution, concentration be 0.1 ~ 99.9wt%, preferably 30 ~ 60wt%, it is more excellent Select 30 ~ 32wt%.

Alkali liquor containing sodium chloride is concentrated in 105 ~ 115 DEG C in atmospheric conditions, or at reduced pressure conditions, it is excellent It selects under vacuum condition, in 60 ~ 100 DEG C, preferably 85 ~ 100 DEG C are concentrated.

Gained solid sodium chloride is dissolved in water, ammonium hydrogen carbonate is added thereto, or is passed through ammonia and carbon dioxide or addition Ammonium hydroxide is passed through carbon dioxide, and solidliquid mixture obtained after reaction is separated by solid-liquid separation, sodium bicarbonate solid and chlorine are obtained Change aqueous ammonium, the reuse of gained sodium bicarbonate solid or sold as finished product, gained aqueous ammonium chloride solution is concentrated, is separated by solid-liquid separation After obtain chloride solid, can be used as finished product sale.

Another method be to recycling triethylamine hydrochloride after remaining mother liquor in be added calcium hydroxide, calcium hydroxide emulsion And/or calcium oxide, pH value is adjusted to 9 ~ 14, is warming up to >=85 DEG C, is obtained triethylamine steam and the alkali liquor containing calcium chloride；It adopts Triethylamine finished product is prepared with triethylamine steam；Calcium chloride solid is prepared using the alkali liquor containing calcium chloride.

The mass concentration of calcium hydroxide emulsion is 0.1 ~ 99.9wt%, preferably 10 ~ 25 wt %.

Preferably, 85 ~ 110 DEG C are warming up to.

It is using the specific method that the alkali liquor containing calcium chloride prepares calcium chloride solid: will be on a small quantity containing the alkali of calcium chloride Mother liquor is concentrated, calcium chloride is precipitated, and is separated by solid-liquid separation and obtains calcium chloride solid and remaining a small amount of liquid, by remaining a small amount of liquid Carry out burning or high temperature oxidation process.

Alkali liquor on a small quantity containing calcium chloride is concentrated in 105 ~ 115 DEG C in atmospheric conditions, or in reduced pressure Under, preferably under vacuum condition, in 60 ~ 100 DEG C, preferably 85 ~ 100 DEG C are concentrated.

(d) by triethylamine hydrochloride obtained in step (a), step (c) respectively or merge convert, obtain three second Amine；

Optionally, conversion processing is carried out to triethylamine hydrochloride using following three kinds of methods:

The first method for carrying out conversion processing to triethylamine hydrochloride is that triethylamine hydrochloride is dissolved in water, and hydrogen is added thereto Calcium oxide, calcium hydroxide emulsion and/or calcium oxide, calcium hydroxide, the calcium oxide in terms of calcium hydroxide or calcium hydroxide emulsion with The molar ratio of triethylamine hydrochloride is 0.5 ~ 10: 1, adjusts pH value to 9 ~ 14, is warming up to >=85 DEG C, obtains triethylamine steam and anti- Solution or suspension after answering；Triethylamine finished product is prepared using gained triethylamine steam；By after reaction solution or suspension into Row is separated by solid-liquid separation, and obtains calcium hydroxide solid and the solution containing calcium chloride；Solution containing calcium chloride is used to prepare calcium chloride.

Preferably, calcium hydroxide, the calcium oxide in terms of calcium hydroxide or calcium hydroxide emulsion and triethylamine hydrochloride rub You are than being 1: 1.

Preferably, pH value is adjusted to 13 ~ 14.

Preferably, 85 ~ 110 DEG C are warming up to.

Gained triethylamine steam is obtained into aqueous triethylamine and water through condensation, obtains triethylamine finished product through dehydration.

Obtained calcium hydroxide solid can reuse in the method, or as sale of finished goods.

The specific method that solution containing calcium chloride is used to prepare calcium chloride is: the solution containing calcium chloride being carried out dense CALCIUM CHLORIDE DIHYDRATE is precipitated in contracting, obtains CALCIUM CHLORIDE DIHYDRATE and remaining a small amount of liquid through being separated by solid-liquid separation；By CALCIUM CHLORIDE DIHYDRATE Drying, obtains anhydrous calcium chloride；Remaining a small amount of liquid is subjected to burning disposal or the reuse in dissolution triethylamine hydrochloride.

The method that second pair of triethylamine hydrochloride carries out conversion processing is that triethylamine hydrochloride is dissolved in water, thereto plus Enter calcium hydroxide, calcium hydroxide emulsion and/or calcium oxide, calcium hydroxide, the calcium oxide in terms of calcium hydroxide or calcium hydroxide cream The molar ratio of liquid and triethylamine hydrochloride is 0.5 ~ 10: 1, is warming up to >=85 DEG C, the solution after obtaining triethylamine steam and reaction Or suspension；Triethylamine finished product is prepared using gained triethylamine steam；Hydroxide is extracted from the solution or suspension after reaction Calcium and ammonium chloride.

Preferably, 85 ~ 110 DEG C are warming up to.

Preferably, the molar ratio of ammonia or ammonium hydroxide and triethylamine hydrochloride handled in step (d) in terms of liquefied ammonia is 2 ∶1。

Calcium hydroxide is extracted from the solution or suspension after reaction and the specific method of ammonium chloride is: will be molten after reaction Liquid or suspension cooling, and be passed through ammonia thereto or be added locating in ammonium hydroxide, ammonia or ammonium hydroxide in terms of liquefied ammonia and step (d) The molar ratio of the triethylamine hydrochloride of reason is 1 ~ 20: 1, and the solidliquid mixture that reaction is formed is separated by solid-liquid separation, hydrogen-oxygen is obtained Change calcium solid and the solution containing ammonium chloride；Ammonium chloride is extracted from the solution containing ammonium chloride.

Ammonium chloride can be extracted from the solution containing ammonium chloride using following two methods:

A kind of method is to obtain chloride solid after the solution containing ammonium chloride is concentrated, and detailed process is: will contain chlorine The solution for changing ammonium is concentrated, chloride solid is precipitated, and obtains chloride solid and remaining liq through being separated by solid-liquid separation；Gained chlorination Ammonium solid can be used as by-product sale；Remaining liq is burned or is carried out high temperature oxidation process.

Another method is that ammonium hydrogen carbonate or its analog are added into the solution containing ammonium chloride, is precipitated contained therein It after a small amount of calcium ion, then is concentrated, obtains chloride solid.Detailed process is: carbon is added in the solution of Xiang Hanyou ammonium chloride Sour hydrogen ammonium, or be passed through ammonia and carbon dioxide or ammonium hydroxide is added, be passed through carbon dioxide, calcium carbonate is obtained through being separated by solid-liquid separation after reaction Solid and remaining a small amount of mother liquor；Remaining a small amount of mother liquor is concentrated, chloride solid is precipitated, is separated by solid-liquid separation, is obtained Chloride solid and remaining a small amount of liquid；Gained chloride solid can be used as by-product sale；By remaining a small amount of liquid Burned or carried out high temperature oxidation process.

The third to triethylamine hydrochloride carry out conversion processing method be that triethylamine hydrochloride is dissolved in water, thereto plus Enter calcium hydroxide, calcium hydroxide emulsion and/or calcium oxide, and be passed through ammonia or ammonium hydroxide is added, adjusts pH to 14, wherein hydrogen-oxygen The molar ratio for changing calcium, the calcium oxide in terms of calcium hydroxide or calcium hydroxide emulsion and triethylamine hydrochloride is 0.5 ~ 10: 1, ammonia Or the molar ratio of the ammonium hydroxide and triethylamine hydrochloride in terms of liquefied ammonia be 1 ~ 20: 1, be warming up to >=85 DEG C, obtain triethylamine steam and Solution or suspension after reaction prepare triethylamine finished product using gained triethylamine steam, from the solution or suspension after reaction Middle extraction calcium hydroxide, ammonium chloride and calcium carbonate.

Preferably, calcium hydroxide, the calcium oxide in terms of calcium hydroxide or calcium hydroxide emulsion and triethylamine hydrochloride rub , than being 1: 1, the molar ratio of ammonia or ammonium hydroxide and triethylamine hydrochloride handled in step (d) in terms of liquefied ammonia is 2: 1 for you.

Preferably, 85 ~ 110 DEG C are warming up to.

The specific method that calcium hydroxide, ammonium chloride and calcium carbonate are extracted from the solution or suspension after reaction is: will be anti- Solution or suspension cooling after answering, obtain calcium hydroxide and containing the solution of ammonium chloride through being separated by solid-liquid separation；To containing ammonium chloride Solution in ammonium hydrogen carbonate is added, or be passed through ammonia and carbon dioxide or ammonium hydroxide be added, be passed through carbon dioxide, through solid-liquid after reaction Isolated calcium carbonate solid and remaining a small amount of mother liquor；Remaining a small amount of mother liquor is concentrated, chloride solid is precipitated, is passed through It is separated by solid-liquid separation, obtains chloride solid and remaining a small amount of liquid；Gained chloride solid can be used as by-product sale；It will remain Remaining a small amount of liquid is burned or is carried out high temperature oxidation process.

(e) step (b) is resulting is used to prepare gyphosate solution or is used to prepare X containing organic phosphorus salting liquid₂HPO₄。

Step (b) is resulting, and containing organic phosphorus salting liquid, there are two types of different purposes, and one is for preparing glyphosate Aqua, another kind are to be used to prepare to obtain corresponding phosphoric acid hydrogen disalt.

, for preparing gyphosate solution, work as X using containing organic phosphorus salting liquid⁺For Na⁺When, contain to step (b) is resulting Have and ammonium hydrogen carbonate is added in organic phosphorus salting liquid, or be passed through ammonia and carbon dioxide or ammonium hydroxide is added, is passed through carbon dioxide, obtains To sodium bicarbonate solid and containing organic phosphorus ammonium salt mother liquor, gained contains organic phosphorus ammonium salt mother liquor for preparing glyphosate water Agent.

It is resulting containing being successively passed through ammonia and carbon dioxide in organic phosphorus salting liquid to step (b), or be added ammonium hydroxide, The amount for being passed through carbon dioxide, ammonia or ammonium hydroxide and carbon dioxide is subject to the ammonium hydrogen carbonate for generating corresponding amount.

Gained contains organic phosphorus ammonium salt mother liquor for preparing 30% or more gyphosate solution.

Work as X⁺To contain K⁺Or NH₄ ⁺When, step (b) is resulting to be directly used in preparation glyphosate containing organic phosphorus salting liquid Aqua preferably prepares 30% or more gyphosate solution.

Corresponding phosphoric acid hydrogen disalt is prepared containing organic phosphorus salting liquid using step (b) is resulting, is to pass through routine High-temperature oxydation and obtain X₂HPO₄: work as X⁺For Na⁺When, obtain Na₂HPO₄；Work as X⁺For K⁺When, obtain K₂HPO₄；Work as X⁺For NH₄ ⁺ When, obtain (NH₄)₂HPO₄。

The purpose of the present invention can also be achieved:

A kind of comprehensive processing technique of glyphosate mother solution, the glyphosate mother solution are using in process of producing glyphosate by using glycine Obtained acid mother liquid, includes the following steps:

(b) pH value of the resulting glyphosate mother solution concentrate A of step (a) is adjusted to≤14 using pH adjusting agent, stood extremely Solution layering, the solution after layering is separated, and is obtained the solution containing triethylamine hydrochloride and is contained organic phosphorus salting liquid；Institute Stating pH adjusting agent includes triethylamine and XOH or triethylamine and XOH solution, wherein X⁺For Na⁺、K⁺Or NH₄ ⁺；

(c) triethylamine and hydrochloride are extracted from the resulting solution containing triethylamine hydrochloride of step (b)；

(d) the resulting triethylamine hydrochloride of step (a) is parsed, obtains triethylamine；

Step (a) and (b), (d), (e) are identical as the process of preceding method, and it is straight that following two methods can be used in step (c) It connects and extracts triethylamine and hydrochloride from the resulting solution containing triethylamine hydrochloride of step (b):

A kind of method that extracting triethylamine and hydrochloride from the solution containing triethylamine hydrochloride is: directly to not concentrated Calcium hydroxide and/or calcium oxide are added in solution containing triethylamine hydrochloride, adjusts the pH to 10 ~ 14 of solution, be warming up to >= 85 DEG C, triethylamine steam and the alkali liquor containing calcium chloride are obtained, triethylamine finished product is prepared using gained triethylamine steam；Contain The alkali liquor of calcium chloride is used to prepare calcium chloride solid.

Preferably, 85 ~ 110 DEG C are warming up to.

It is using the specific method that the alkali liquor containing calcium chloride prepares calcium chloride solid: by the alkali liquor containing calcium chloride Be concentrated, calcium chloride be precipitated, be separated by solid-liquid separation and obtain calcium chloride solid and remaining a small amount of filtrate, remaining a small amount of filtrate into Row burning disposal or high temperature oxidation process.

Another kind extracts triethylamine from the solution containing triethylamine hydrochloride and the method for hydrochloride is: directly to containing Piece alkali and/or sodium hydrate aqueous solution are added in the solution of triethylamine hydrochloride, adjusts the pH to 10 ~ 14 of solution, be warming up to >= 85 DEG C, obtain triethylamine steam and the alkali liquor containing sodium chloride；Triethylamine finished product is prepared using gained triethylamine steam；Contain The alkali liquor of sodium chloride is used to prepare solid sodium chloride.

Preferably, 85 ~ 110 DEG C are warming up to.

Specific method using the alkali liquor preparation solid sodium chloride containing sodium chloride is: by the alkali liquor containing sodium chloride It is concentrated, precipitated sodium chloride, is separated by solid-liquid separation and obtains solid sodium chloride and remaining a small amount of solution, by remaining a small amount of solution Carry out burning or high temperature oxidation process；Solid sodium chloride is dissolved in water, ammonium hydrogen carbonate is added thereto, by gained solid-liquid after reaction Mixture is separated by solid-liquid separation, and obtains sodium bicarbonate solid and aqueous ammonium chloride solution, gained sodium bicarbonate reuse or as finished product It sells, gained aqueous ammonium chloride solution is concentrated, separation of solid and liquid obtains chloride solid, can be used as finished product sale.

The ammonium hydrogen carbonate being added into sodium-chloride water solution can also be to be successively passed through ammonia and carbon dioxide, or ammonia is added Water is passed through carbon dioxide to substitute, and the amount of ammonia or ammonium hydroxide and carbon dioxide, which is subject to, generates ammonium hydrogen carbonate.

The present invention provides a kind of techniques of new integrated treatment glyphosate mother solution, by the way that glyphosate mother solution to be concentrated After pH adjusting agent is added, be layered solution, extract triethylamine hydrochloride from glyphosate mother solution in batches, and to triethylamine salt Hydrochlorate and upper layer, lower liquid are respectively processed, and not only realize the high efficiente callback of triethylamine, and the rate of recovery is up to 99.89%, But also available calcium hydroxide, ammonium chloride, gyphosate solution or phosphoric acid hydrogen disalt, sodium bicarbonate and calcium chloride etc. are a variety of has The byproduct of value, gained byproduct can be applied in glyphosate mother solution removal process or be sold as finished product, more crucial Be not generate be difficult to be utilized, pollute the waste liquid and solid waste of environment during processing, have apparent economical Benefit and environmental benefit solve the problems, such as that the glyphosate mother solution for hindering glyphosate industry development can not be handled thoroughly, really real The integrated treatment of glyphosate mother solution is showed, so that glyphosate enterprise is no longer because glyphosate mother solution can not be handled, generation environmental protection is asked It inscribes and is forced the underproduction or halt production.

The gyphosate solution for using present invention process to prepare, still for liquid condition, has excellent at -30 DEG C Low-temperature stabilization performance, and the content for being wherein substantially free of the inorganic salts such as sodium chloride or inorganic salts is very low, drug effect is more preferable, solves and applies When with the gyphosate solution for containing a large amount of sodium chloride the problem of caused saline Land.

In the present invention, when containing NaOH in pH adjusting agent, grass is being prepared using containing organic phosphorus sodium salt solution Before sweet phosphine aqua, sodium bicarbonate is obtained after ammonium hydrogen carbonate or its analog is added thereto first, then contain using obtained There is organic phosphorus ammonium salt mother liquor gyphosate solution, the utilization rate of ammonium hydrogen carbonate on the one hand can be improved, reduces ammonium hydrogen carbonate Dosage, the carbon dioxide by-product of generation is also less；On the other hand, obtained sodium bicarbonate can also continue to be used as pH value tune Agent is saved, the dosage of sodium liquid alkaline during recycling glyphosate mother solution is reduced.

The present invention is by using ammonium hydrogen carbonate, calcium hydroxide, calcium oxide, sodium bicarbonate or sodium carbonate, saleratus or carbon Sour potassium, ammonia or ammonium hydroxide replace sodium hydroxide, compare the existing technique using liquid alkaline processing glyphosate mother solution, save 60 ~ 100% sodium liquid alkaline, significantly reduces the processing cost of glyphosate mother solution.

Technological design of the invention is scientific and reasonable, easy to operate, easily controllable, and equipment investment is few, is suitble to large-scale industry Production has extensive prospects for commercial application.

Specific embodiment

Below with reference to embodiment, the present invention is further elaborated, and following embodiments are only as explanation, not with any Mode limits the scope of the invention.

Glyphosate mother solution of the invention is with preparing glyphosate by glycin method i.e. with paraformaldehyde, glycine and phosphorous acid two Arrcostab is raw material, using triethylamine as catalyst, is produced in the technical process of glyphosate through addition, condensation, acidolysis, in glyphosate Acidic hydrolysis terminates, and glyphosate technicals crystal is precipitated in system, remaining mother liquor after glyphosate crystals are separated.

Agents useful for same is commercially available in embodiment or is prepared by method well known within the skill of those ordinarily skilled, used to set Standby is conventional equipment, can pass through commercially available acquisition.Sodium liquid alkaline described in embodiment is the NaOH aqueous solution that concentration is 32wt%, institute The concentration for stating ammonium hydroxide is 13.6wt%, and potassium liquid alkaline is the KOH aqueous solution that concentration is 45.6wt%.

Following embodiments realize the purpose of the present invention.

Embodiment 1

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, is highly acid, is warming up to 100 DEG C under normal pressure, Triethylamine hydrochloride be precipitated is filtered when heating up concentration, and filtrate is back in mother liquor, 1500g water is steamed, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate are highly acid.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 1000g triethylamine is added, adjusts pH=14 of solution, adds 651.2g sodium liquid alkaline, is neutralized to pH=14, obtains 3386.2g mother liquor, is heated to 50 DEG C, and after standing 2h, solution is divided into 3 layers, separation After obtain the upper layer 300g triethylamine, 1795g contains in middle layer the solution of triethylamine hydrochloride and organic phosphorus sodium is contained in 1290g lower layer Salting liquid.

Solution containing triethylamine hydrochloride is concentrated in 100 DEG C in atmospheric conditions, steams 714g water, remaining 1081g Mother liquor is cooled to 25 DEG C, and the side Bian Jiangwen filters, and obtained filtrate returns, obtains 1000g triethylamine hydrochloride and 81g contains on a small quantity The mother liquor of triethylamine hydrochloride；8g calcium hydroxide is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjust the pH of solution to 9,85 DEG C are warming up to, gained triethylamine steam obtains triethylamine aqueous solution through condensation, 17.3g triethylamine is obtained through dehydration, Also obtain the alkali liquor of 20g water and 50g chloride containing calcium；The alkali liquor of gained chloride containing calcium is concentrated in 105 DEG C under normal pressure, institute It obtains solidliquid mixture and 13.5g CALCIUM CHLORIDE DIHYDRATE solid and 15g filtrate is obtained by filtration；By 13.5g CALCIUM CHLORIDE DIHYDRATE 300 DEG C drying obtains 10.1g anhydrous calcium chloride；Gained filtrate is subjected to burning or high temperature oxidation process.

1000g triethylamine hydrochloride is taken, 960g water and 220g calcium oxide, pH=9 are added thereto.Temperature is under normal pressure 85 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716.3g triethylamine product through dehydration, female After liquid is cooled to 25 DEG C, it is passed through 3265g ammonia thereto, ammonia leakage recycling is at ammonium hydroxide, and after reacting 1h, centrifuge separation is obtained The aqueous solution of 350g calcium hydroxide and 960g containing ammonium chloride, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride, to 10g ammonium hydrogen carbonate is added in the aqueous solution of containing ammonium chloride to be separated by solid-liquid separation after reaction, 12g calcium carbonate solid is obtained, and The aqueous solution of 105 DEG C of concentration containing ammonium chlorides under normal pressure obtains 377g purity and is 98.5% ammonium chloride, and recycles ammonia and obtain 15725g ammonium hydroxide.Gained filtrate is subjected to burning or high temperature oxidation process.

To containing 412g ammonium hydrogen carbonate is added in organic phosphorus sodium salt solution, in 60 DEG C of reaction 2h, 25 DEG C are cooled to, is taken out Filter, obtains 512g sodium bicarbonate solid and 1180g contains organic phosphorus ammonium salt mother liquor.Gained, which contains organic phosphorus ammonium salt mother liquor, to be used In the gyphosate solution for preparing 30%, indices meet national standard.

Embodiment 2

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.8 is warming up to 120 DEG C, side under normal pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.8.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 200g triethylamine is added, adjusts pH=2 of solution, adds 651.2g sodium liquid alkaline, is neutralized to pH=7, obtains 2586.2g mother liquor, is heated to 100 DEG C, and after standing 2h, solution is divided into 2 layers, separation Solution that triethylamine hydrochloride is contained on the upper layer 1296g is obtained afterwards and organic phosphorus sodium salt solution is contained in 1290g lower layer.

Contain in the solution of triethylamine hydrochloride addition 223g calcium hydroxide to upper layer, adjust the pH to 9 of solution, under normal pressure 85 DEG C are warming up to, gained triethylamine steam obtains aqueous triethylamine and water through condensation, and aqueous triethylamine is obtained through dehydration 534.6g triethylamine finished product, also obtains the alkali liquor of 984g chloride containing calcium, by the alkali liquor containing calcium chloride under normal pressure in 105 DEG C concentration, the CALCIUM CHLORIDE DIHYDRATE solid of 778g is obtained by filtration in gained solidliquid mixture, by 778g CALCIUM CHLORIDE DIHYDRATE 300 DEG C drying obtains 587g anhydrous calcium chloride；Gained filtrate is subjected to burning or high temperature oxidation process.

1000g triethylamine hydrochloride is taken, 1476g water and 334g calcium oxide, pH=14 are added thereto, are warming up to 105 DEG C, Gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716.3g triethylamine product, mother liquor drop through dehydration For temperature to after 25 DEG C, centrifuge separation obtains the aqueous solution of 120g calcium hydroxide and 1973g chloride containing calcium, calcium hydroxide is in triethylamine Reuse in the conversion processing of hydrochloride, and the aqueous solution of 115 DEG C of concentration chloride containing calcium, gained solidliquid mixture pass through under normal pressure Filter obtains the CALCIUM CHLORIDE DIHYDRATE solid of 778g, and 778g CALCIUM CHLORIDE DIHYDRATE is obtained 587g anhydrous calcium chloride in 300 DEG C of drying； Gained filtrate is subjected to burning or high temperature oxidation process.

Embodiment 3

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, is highly acid, is warming up to 130 DEG C under normal pressure, Triethylamine hydrochloride be precipitated is filtered when heating up concentration, and filtrate is back in mother liquor, 1500g water is steamed, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate highly acid.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 1500g triethylamine is added, adjusts pH=14 of solution, adds 651.2g sodium liquid alkaline, is neutralized to pH=14, obtains 2386.2g mother liquor, is heated to 25 DEG C, and after standing 2h, solution is divided into 3 layers, separation Upper layer 800g triethylamine is obtained, 1796g contains in middle layer the solution of triethylamine hydrochloride and organic phosphorus sodium salt is contained in 1290g lower layer Solution.

Solution containing triethylamine hydrochloride is concentrated in 105 DEG C under normal pressure, steams 615g water, remaining 1181g mother liquor, 25 DEG C are cooled to, the side Bian Shengwen filters, and obtained filtrate returns, obtains 1100g triethylamine hydrochloride and 81g contains triethylamine on a small quantity The mother liquor of hydrochloride；10g calcium hydroxide is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjusts the pH to 13 of solution, rises For temperature to 105 DEG C, gained triethylamine steam obtains triethylamine aqueous solution through condensation, obtains 17.3g triethylamine through dehydration, must To the alkali liquor of 20g water and 50g chloride containing calcium；The alkali liquor of gained chloride containing calcium is concentrated in 110 DEG C under normal pressure, gained is solid 13.5g CALCIUM CHLORIDE DIHYDRATE solid and 15g filtrate is obtained by filtration in liquid mixture；13.5g CALCIUM CHLORIDE DIHYDRATE is dried at 300 DEG C It is dry to obtain 10.1g anhydrous calcium chloride；Gained filtrate is subjected to burning or high temperature oxidation process.

1000g triethylamine hydrochloride is taken, 4083g water and 3967g calcium oxide, pH=14 are added thereto, are warming up to 110 DEG C, Gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716.3g triethylamine product, mother liquor drop through dehydration For temperature to after 25 DEG C, centrifuge separation obtains the aqueous solution of 5412g calcium hydroxide and 2921g chloride containing calcium, calcium hydroxide is in triethylamine Reuse in the conversion processing of hydrochloride, and the aqueous solution of chloride containing calcium is concentrated at 115 DEG C under normal pressure, gained solidliquid mixture warp The CALCIUM CHLORIDE DIHYDRATE solid of 1042g is obtained by filtration, 1042g CALCIUM CHLORIDE DIHYDRATE is obtained into the anhydrous chlorine of 787g in 300 DEG C of drying Change calcium；Gained filtrate is subjected to burning or high temperature oxidation process.

Disodium hydrogen phosphate 950g will be obtained through high-temperature oxydation containing organic phosphorus sodium salt solution.

Embodiment 4

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.2 is warming up to 50 DEG C, side under reduced pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.2.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 295g triethylamine is added, adjusts pH=2 of solution, adds 641.2g sodium liquid alkaline, is neutralized to pH=6.7, obtains 2671.2g mother liquor, adds 300g triethylamine, and pH=14 are heated to 70 DEG C, After standing 2h, solution is divided into 3 layers up and down, and the upper layer 290g triethylamine is obtained after separation, the middle layer 1391g is obtained and contains triethylamine hydrochloric acid Organic phosphorus sodium salt solution is contained in the solution of salt and 1290g lower layer.

Contain addition 250g calcium hydroxide in the solution of triethylamine hydrochloride to upper layer, adjusts the pH to 11 of solution, normal pressure Under be warming up to 105 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, and aqueous triethylamine is obtained through dehydration 534.6g triethylamine finished product, also obtains the alkali liquor of 1106g chloride containing calcium, and 27g calcium hydroxide and 1079g filtrate is obtained by filtration, Alkali liquor containing calcium chloride is concentrated in 110 DEG C under normal pressure, two hydrations of 778g are obtained by filtration in gained solidliquid mixture 778g CALCIUM CHLORIDE DIHYDRATE is obtained 587g anhydrous calcium chloride in 300 DEG C of drying by calcium chloride solid；Gained filtrate is burned Or high temperature oxidation process.

1000g triethylamine hydrochloride is taken, the calcium hydroxide aqueous suspension of 1000g33%, pH=9, heating 85 are added thereto DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716g triethylamine finished product, mother liquor drop through dehydration Temperature obtains the aqueous solution of 1230g chloride containing calcium to 25 DEG C, the alkali liquor containing calcium chloride is concentrated in 60 DEG C under reduced pressure, gained The CALCIUM CHLORIDE DIHYDRATE solid of 1042g is obtained by filtration in solidliquid mixture, and 1042g CALCIUM CHLORIDE DIHYDRATE is dried at 300 DEG C To 787g anhydrous calcium chloride；Gained filtrate is subjected to burning or high temperature oxidation process.

Embodiment 5

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.3 is warming up to 80 DEG C, side under reduced pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.3.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 280g triethylamine is added, adjusts pH=2 of solution, adds 551.2g potassium liquid alkaline, is neutralized to pH=5.0, obtains 2566.2g mother liquor, is heated to 70 DEG C, and after standing 2h, solution is divided into upper and lower 2 Layer obtains solution that triethylamine hydrochloride is contained on the upper layer 1188g and 1378g lower layer containing organic phosphorus potassium salt soln after separation.

Solution containing triethylamine hydrochloride is concentrated in 105 DEG C under normal pressure, steams 252g water, remaining 936g mother liquor, 25 DEG C are cooled to, the side Bian Shengwen filters, and obtained filtrate returns, obtains 855g triethylamine hydrochloride and 81g contains triethylamine on a small quantity The mother liquor of hydrochloride；10g calcium hydroxide is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjusts the pH to 13 of solution, rises For temperature to 105 DEG C, gained triethylamine steam obtains triethylamine aqueous solution through condensation, obtains 17.3g triethylamine through dehydration, must To the alkali liquor of 20g water and 50g chloride containing calcium；The alkali liquor of gained chloride containing calcium is concentrated in 110 DEG C under normal pressure, gained is solid 13.5g CALCIUM CHLORIDE DIHYDRATE solid and 15g filtrate is obtained by filtration in liquid mixture；13.5g CALCIUM CHLORIDE DIHYDRATE is dried at 300 DEG C It is dry to obtain 10.1g anhydrous calcium chloride；Gained filtrate is subjected to burning or high temperature oxidation process.

1000g triethylamine hydrochloride is taken, 710g water and 350g calcium hydroxide are added thereto, pH=11 heat 85 DEG C, institute It obtains triethylamine steam and obtains aqueous triethylamine and water through condensation, obtain 716g triethylamine finished product through dehydration, mother liquor is cooled to 25 DEG C obtain the aqueous solution of 1260g chloride containing calcium and calcium hydroxide, and 60g calcium hydroxide and 1200g filtrate is obtained by filtration, and will contain The alkali liquor of calcium chloride is concentrated in 80 DEG C under reduced pressure, and gained solidliquid mixture is through being obtained by filtration the CALCIUM CHLORIDE DIHYDRATE of 1042g 1042g CALCIUM CHLORIDE DIHYDRATE is obtained 787g anhydrous calcium chloride in 300 DEG C of drying by solid；Gained filtrate is subjected to burning or height Warm oxidation processes.

Gained is used to prepare 30% gyphosate solution containing organic phosphorus sylvite mother liquor, and indices meet national standard.

Embodiment 6

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.1 is warming up to 100 DEG C, side under reduced pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.1.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 50g triethylamine is added, adjusts pH=0.5 of solution, adds 651.2g potassium liquid alkaline, is neutralized to pH=5.5, obtains 2486.2g mother liquor, is heated to 80 DEG C, and after standing 2h, solution is divided into upper and lower 2 Layer obtains solution that triethylamine hydrochloride is contained on the upper layer 1158g and 1378g lower layer containing organic phosphorus potassium salt soln after separation.

Contain addition 400g calcium hydroxide in the solution of triethylamine hydrochloride to upper layer, adjust the pH to 14 of solution, heats up To 113 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, and aqueous triethylamine obtains 534.6g through dehydration Triethylamine finished product, also obtains the alkali liquor of 1020g chloride containing calcium and calcium hydroxide, filtrated stock obtain 200g calcium hydroxide and Alkali liquor containing calcium chloride is concentrated in 115 DEG C 820g mother liquor under normal pressure, and gained solidliquid mixture is through being obtained by filtration 778g CALCIUM CHLORIDE DIHYDRATE solid, 778g CALCIUM CHLORIDE DIHYDRATE is obtained into 587g anhydrous calcium chloride in 300 DEG C of drying；By gained filtrate Carry out burning or high temperature oxidation process.

1000g triethylamine hydrochloride is taken, 2100g water and 5950g calcium hydroxide are added thereto, pH=14 are anti-in 110 DEG C It answers, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716.3g triethylamine product, mother liquor through dehydration After being cooled to 25 DEG C, centrifuge separation obtains the aqueous solution of 5412g calcium hydroxide and 2921g chloride containing calcium, calcium hydroxide is in three second Reuse in the conversion processing of amine hydrochlorate, and the aqueous solution of 100 DEG C of concentration chloride containing calcium under reduced pressure, gained solidliquid mixture warp The CALCIUM CHLORIDE DIHYDRATE solid of 1042g is obtained by filtration, 1042g CALCIUM CHLORIDE DIHYDRATE is obtained into the anhydrous chlorine of 787g in 300 DEG C of drying Change calcium；Gained filtrate is subjected to burning or high temperature oxidation process.

Embodiment 7

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=2.0 are warming up to 130 DEG C, side under normal pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=2.0.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 300g triethylamine is added, adjusts the pH=3.5 of solution, adds 651.2g potassium liquid alkaline, is neutralized to pH=9.5, obtains 2686.2g mother liquor, is heated to 70 DEG C, and after standing 2h, solution is divided into 3 layers, point The upper layer 20g triethylamine is obtained from after, solution that 1288g contains in middle layer triethylamine hydrochloride and 1378g lower layer are containing organic phosphorus potassium Salting liquid.

Solution containing triethylamine hydrochloride is concentrated in 130 DEG C under reduced pressure, steams 352g water, remaining 936g mother liquor, 25 DEG C are cooled to, the side Bian Jiangwen filters, and obtained filtrate returns, obtains 642g triethylamine hydrochloride and 294g contains triethylamine on a small quantity The mother liquor of hydrochloride；22g calcium oxide solid is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjusts the pH to 9 of solution, rises For temperature to 85 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 63g triethylamine finished product through dehydration, Also obtain the alkali liquor of 13g water and 240g chloride containing calcium；The alkali liquor of gained chloride containing calcium is concentrated in 100 DEG C under reduced pressure, And be separated by solid-liquid separation, the CALCIUM CHLORIDE DIHYDRATE solid of 67g is obtained by filtration in gained solidliquid mixture, by bis- chloride hydrate of 67g Calcium obtains 50g anhydrous calcium chloride in 300 DEG C of drying；Gained filtrate is subjected to burning or high temperature oxidation process.

1000g triethylamine hydrochloride is taken, 696g water and 334g calcium oxide are added thereto, is passed through 120g ammonia, pH=14, It is reacted in 105 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716.3g triethylamine through dehydration Product, after mother liquor is cooled to 25 DEG C, centrifuge separation obtains the aqueous solution of 450g calcium hydroxide and 983g chloride containing ammonia, hydroxide Calcium reuse in the conversion processing of triethylamine hydrochloride, and the aqueous solution of 100 DEG C of concentration containing ammonium chlorides under normal pressure, gained solid-liquid Mixture is through being obtained by filtration the ammonium chloride of 376g.Gained filtrate is subjected to burning or high temperature oxidation process.

Dipotassium hydrogen phosphate 1170g will be obtained through high-temperature oxydation containing organic phosphorus potassium salt soln.

Embodiment 8

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.1 is warming up to 130 DEG C, side under reduced pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.1.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 100g triethylamine is added, adjusts pH=1.0 of solution, adds 701.2g potassium liquid alkaline, is neutralized to pH=6.0, obtains 2536g mother liquor, is heated to 70 DEG C, and after standing 2h, solution is divided into 2 layers up and down, Solution that triethylamine hydrochloride is contained on the upper layer 1158g and 1378g lower layer are obtained after separation containing organic phosphorus potassium salt soln.

Contain to upper layer and 150g calcium oxide and 250g water be added in the solution of triethylamine hydrochloride, adjusts the pH to 9 of solution, 85 DEG C of heating, gained triethylamine steam obtain aqueous triethylamine and water through condensation, and aqueous triethylamine is obtained through dehydration 534.6g triethylamine finished product, also obtains the alkali liquor of 1000g chloride containing calcium, in 60 DEG C under the alkali liquor containing calcium chloride is depressurized Concentration, the CALCIUM CHLORIDE DIHYDRATE solid of 778g is obtained by filtration in gained solidliquid mixture, by 778g CALCIUM CHLORIDE DIHYDRATE at 300 DEG C Drying obtains 587g anhydrous calcium chloride；Gained filtrate is subjected to burning or high temperature oxidation process.

1000g triethylamine hydrochloride is taken, 696g water and 334g calcium oxide are added thereto, is passed through 240g ammonia, pH=14, It is reacted in 105 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716.3g triethylamine through dehydration Product, after mother liquor is cooled to 25 DEG C, centrifuge separation obtains the aqueous solution of 450g calcium hydroxide and 983g chloride containing ammonia, hydroxide Calcium reuse in the conversion processing of triethylamine hydrochloride, and the aqueous solution of 110 DEG C of concentration containing ammonium chlorides under normal pressure, gained solid-liquid Mixture is through being obtained by filtration the ammonium chloride of 376g.Recycling ammonia obtains 600g ammonium hydroxide.Gained filtrate is subjected to burning or high-temperature oxydation Processing.

Embodiment 9

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=1.5 are warming up to 122 DEG C, side under normal pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=1.5.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 150g triethylamine is added, adjusts pH=2 of solution, adds 681.2g ammonium liquid alkaline, is neutralized to pH=7.5, obtains 2566.2g mother liquor, is heated to 70 DEG C, and after standing 2h, solution is divided into upper and lower 2 Layer obtains solution that triethylamine hydrochloride is contained on the upper layer 1448g and 1118g lower layer containing organic phosphorus ammonium salt solution after separation.

Solution containing triethylamine hydrochloride is concentrated in 90 DEG C under reduced pressure, steams 512g water, remaining 936g mother liquor, drop To 25 DEG C, the side Bian Jiangwen filters temperature, and obtained filtrate returns, obtains 642g triethylamine hydrochloride and 294g contains triethylamine salt on a small quantity The mother liquor of hydrochlorate；27g calcium oxide solid is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjusts the pH to 12 of solution, rises For temperature to 109 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 63g triethylamine finished product through dehydration, Also obtain the alkali liquor of 13g water and 245g chloride containing calcium；Filtering solution obtains 8g calcium hydroxide solid and 237g solution, by gained The alkali liquor of chloride containing calcium is concentrated in 80 DEG C under reduced pressure, and is separated by solid-liquid separation, and gained solidliquid mixture is through being obtained by filtration 67g CALCIUM CHLORIDE DIHYDRATE solid, 67g CALCIUM CHLORIDE DIHYDRATE is obtained into 50g anhydrous calcium chloride in 300 DEG C of drying；By gained filtrate into Row burns or high temperature oxidation process.

1000g triethylamine hydrochloride is taken, 696g water and 334g calcium oxide are added thereto, is passed through 2410g ammonia, ammonia is let out Dew recycling is reacted at ammonium hydroxide, pH=14 in 105 DEG C, and gained triethylamine steam obtains aqueous triethylamine and water through condensation, through being dehydrated Processing obtains 716.3g triethylamine product, and after mother liquor is cooled to 25 DEG C, centrifuge separation obtains 450g calcium hydroxide and 983g containing chlorine Change the aqueous solution of ammonia, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride is added into the aqueous solution of containing ammonium chloride 10g ammonium hydrogen carbonate is separated by solid-liquid separation after reaction, obtains 12g calcium carbonate solid, and 115 DEG C of concentration chloride containings under normal pressure The aqueous solution of ammonium, gained solidliquid mixture is through being obtained by filtration the ammonium chloride of 376g.Recycling ammonia obtains 11400g ammonium hydroxide.Gained is filtered Liquid carries out burning or high temperature oxidation process.

Gained contains organic phosphorus ammonium salt mother liquor and meets national standard for preparing 30% gyphosate solution, indices.

Embodiment 10

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.1 is warming up to 130 DEG C, side under normal pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.1.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 250g triethylamine is added, adjusts pH=1.5 of solution, adds 710.2g ammonium liquid alkaline, is neutralized to pH=7, obtains 2695g mother liquor, is heated to 70 DEG C, and after standing 2h, solution is divided into 2 layers up and down, point Solution that triethylamine hydrochloride is contained on the upper layer 1577g and 1118g lower layer are obtained from after containing organic phosphorus ammonium salt solution.

Contain addition 200g calcium oxide in the solution of triethylamine hydrochloride to upper layer, adjusts the pH to 13 of solution, be warming up to 113 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, and aqueous triethylamine obtains 534.6g tri- through dehydration Ethamine finished product, also obtains the alkali liquor of 1233g chloride containing calcium and calcium hydroxide, filtrated stock obtain 100g calcium hydroxide and Alkali liquor containing calcium chloride is concentrated in 85 DEG C 1133g mother liquor under reduced pressure, and gained solidliquid mixture is through being obtained by filtration 778g CALCIUM CHLORIDE DIHYDRATE solid, 778g CALCIUM CHLORIDE DIHYDRATE is obtained into 587g anhydrous calcium chloride in 300 DEG C of drying；By gained filtrate Carry out burning or high temperature oxidation process.

1000g triethylamine hydrochloride is taken, the calcium hydroxide aqueous suspension of 1000g 50%, pH=14, in 105 are added thereto DEG C reaction, gained triethylamine steam through condensation obtain aqueous triethylamine and water, obtain 716.3g triethylamine product through dehydration, After mother liquor is cooled to 25 DEG C, it is passed through 122g ammonia thereto, obtains 1405g solidliquid mixture, 520g calcium hydroxide is obtained by filtration The solution for containing ammonium chloride with 885g 10g ammonium hydrogen carbonate is added into the aqueous solution of containing ammonium chloride, after reaction, through solid-liquid Separation, obtains 12g calcium carbonate solid, and the aqueous solution of 60 DEG C of concentration containing ammonium chlorides under reduced pressure, and obtaining 376g purity is 98.5% Ammonium chloride.Gained filtrate is subjected to burning or high temperature oxidation process.

Embodiment 11

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.1 is warming up to 109 DEG C, side under normal pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.1.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 300g triethylamine is added, adjusts pH=2 of solution, adds 651.2g ammonium liquid alkaline, is neutralized to pH=7, obtains 2686.2g mother liquor, is heated to 70 DEG C, and after standing 2h, solution is divided into 2 layers up and down, Solution that triethylamine hydrochloride is contained on the upper layer 1568g and 1118g lower layer are obtained after separation containing organic phosphorus ammonium salt solution.

Solution containing triethylamine hydrochloride is concentrated in 50 DEG C under reduced pressure, steams 632g water, remaining 936g mother liquor, drop To 25 DEG C, the side Bian Jiangwen filters temperature, and obtained filtrate returns, obtains 642g triethylamine hydrochloride and 294g contains triethylamine salt on a small quantity The mother liquor of hydrochlorate；35g calcium oxide solid is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjusts the pH to 14 of solution, rises For temperature to 115 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 63g triethylamine finished product through dehydration, Also obtain the alkali liquor of 13g water and 250g chloride containing calcium；Filtering solution obtains 20g calcium hydroxide solid and 230g solution, by institute The alkali liquor for obtaining chloride containing calcium is concentrated in 60 DEG C under reduced pressure, and is separated by solid-liquid separation, and gained solidliquid mixture is through being obtained by filtration 67g CALCIUM CHLORIDE DIHYDRATE is obtained 50g anhydrous calcium chloride in 300 DEG C of drying by the CALCIUM CHLORIDE DIHYDRATE solid of 67g；Gained is filtered Liquid carries out burning or high temperature oxidation process.

1000g triethylamine hydrochloride is taken, 635g water and 267g calcium oxide are added thereto, pH=13 are reacted, institute in 110 DEG C It obtains triethylamine steam and obtains aqueous triethylamine and water through condensation, obtain 716.3g triethylamine product, mother liquor cooling through dehydration To after 25 DEG C, it is passed through 1122g ammonia thereto, obtains 1305g solidliquid mixture, 420g calcium hydroxide is obtained by filtration and 885g contains There is the solution of ammonium chloride, 10g ammonium hydrogen carbonate is added into the aqueous solution of containing ammonium chloride and is separated by solid-liquid separation, is obtained after reaction 12g calcium carbonate solid, and the aqueous solution of 90 DEG C of concentration containing ammonium chlorides under reduced pressure, obtain the ammonium chloride that 376g purity is 98.5%. Recycling ammonia obtains ammonium hydroxide 5000g.Gained filtrate is subjected to burning or high temperature oxidation process.

Diammonium hydrogen phosphate 873g will be obtained through high-temperature oxydation containing organic phosphorus ammonium salt solution.

Embodiment 12

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=2 are warming up to 105 DEG C, Bian Sheng under normal pressure Triethylamine hydrochloride be precipitated is filtered on temperature concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g Triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=2.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 100g triethylamine is added, adjusts pH=2.8 of solution, adds 651.2g ammonium liquid alkaline is added 300g water, is neutralized to pH=7.5, obtains 2786.2g mother liquor, is heated to 100 DEG C, molten after standing 2h Liquid is divided into 2 layers up and down, and solution that triethylamine hydrochloride is contained on the upper layer 1668g and 1118g lower layer are obtained after separation containing organic phosphorus Ammonium salt solution.

Contain addition 250g calcium oxide in the solution of triethylamine hydrochloride to upper layer, adjusts the pH to 14 of solution, be warming up to 115 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, and aqueous triethylamine obtains 534.6g tri- through dehydration Ethamine finished product, also obtains the alkali liquor of 1383g chloride containing calcium and calcium hydroxide, filtrated stock obtain 190g calcium hydroxide and Alkali liquor containing calcium chloride is concentrated in 100 DEG C 1193g mother liquor under reduced pressure, and gained solidliquid mixture is through being obtained by filtration 778g CALCIUM CHLORIDE DIHYDRATE is obtained 587g anhydrous calcium chloride in 300 DEG C of drying by the CALCIUM CHLORIDE DIHYDRATE solid of 778g；By gained Filtrate carries out burning or high temperature oxidation process.

1000g triethylamine hydrochloride is taken, 500g water and 400g calcium hydroxide are added thereto, and is passed through 100g ammonia, pH= 14,105 DEG C are heated to, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716.3g tri- through dehydration Ethamine product after mother liquor is cooled to 25 DEG C, is passed through 1141g ammonia thereto, and ammonia leakage recycling is at ammonium hydroxide, after reacting 1h, from Heart separation, obtains the aqueous solution of 450g calcium hydroxide and 740g containing ammonium chloride, calcium hydroxide is at the conversion of triethylamine hydrochloride Reuse in reason is added 10g ammonium hydrogen carbonate into the aqueous solution of containing ammonium chloride and is separated by solid-liquid separation after reaction, obtains 12g carbon Sour calcium solid, and depressurizing lower temperature is the solution after 95 DEG C of concentration reactions, obtains the ammonium chloride that 370g purity is 98.5%, and return It receives ammonia and obtains 5730g ammonium hydroxide.

Embodiment 13

Glyphosate mother solution concentrate is cooled to 25 DEG C, 200g triethylamine is added, adjusts pH=4.1 of solution, adds 651.2g ammonium liquid alkaline, is neutralized to pH=14, obtains 2586g mother liquor, is heated to 75 DEG C, and after standing 2h, solution is divided into 3 layers up and down, point The triethylamine on the upper layer 50g, the solution that triethylamine hydrochloride is contained in the middle layer 1418g and 1118g lower layer are obtained from after containing organic phosphorus Ammonium salt solution.

230g piece alkali is added into the solution containing triethylamine hydrochloride, adjusts the pH to 10 of solution, is warming up to 85 DEG C, institute Triethylamine steam through condensation obtain triethylamine aqueous solution, obtain 535.3g triethylamine through dehydration, also obtain 60g water and 1050g contains the alkali liquor of sodium chloride；Alkali liquor by gained containing sodium chloride is concentrated in 100 DEG C under vacuum conditions, gained 286g solid sodium chloride and 50g filtrate is obtained by filtration in solidliquid mixture；Gained filtrate is subjected to burning or high temperature oxidation process. 286g sodium chloride is dissolved in 957g water, 440g ammonium hydrogen carbonate is added, is warming up to 60 DEG C, reacts 2h, filtering obtains 440g carbonic acid Sodium chloride is added into gained filtrate for hydrogen sodium solid and filtrate, and ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, and remains Remaining filtrate repeats above-mentioned reaction.

1000g triethylamine hydrochloride is taken, 760g water and 220g calcium oxide, pH=9 are added thereto, are warming up to 105 DEG C, institute It obtains triethylamine steam and obtains aqueous triethylamine and water through condensation, obtain 716.3g triethylamine product, mother liquor cooling through dehydration To after 25 DEG C, it is passed through 2410g ammonia thereto, ammonia leakage recycling is at ammonium hydroxide, and after reacting 1h, centrifuge separation obtains 350g hydrogen The aqueous solution of calcium oxide and 908g containing ammonium chloride, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride, to chloride containing 10g ammonium hydrogen carbonate is added in the aqueous solution of ammonium to be separated by solid-liquid separation after reaction, obtains 12g calcium carbonate solid, and be warming up to The aqueous solution of 105 DEG C of concentration containing ammonium chlorides obtains 377g purity and is 98.5% ammonium chloride, and recycles ammonia and obtain 11400g ammonium hydroxide.

Embodiment 14

Glyphosate mother solution concentrate is cooled to 25 DEG C, 300g triethylamine is added, pH=2 of solution are adjusted, by gained 2034.8g mother liquor adds 651.2g ammonium liquid alkaline, is neutralized to pH=7, obtains 2686.2g mother liquor, is heated to 70 DEG C, after standing 2h, Solution is divided into 2 layers up and down, and solution that triethylamine hydrochloride is contained on the upper layer 1568g and 1118g lower layer are obtained after separation containing organic phosphorus Ammonium salt solution.

Solution containing triethylamine hydrochloride is concentrated in 100 DEG C under normal pressure, steams 630g water, remaining 936g mother liquor, 25 DEG C are cooled to, the side Bian Jiangwen filters, and obtained filtrate returns, obtains 642g triethylamine hydrochloride and 294g contains triethylamine on a small quantity The mother liquor of hydrochloride；30g solid sodium hydroxide is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjust the pH of solution to 10,85 DEG C are warming up to, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 63g triethylamine through dehydration Finished product also obtains the alkali liquor that 10g water and 245g contain sodium chloride；Alkali liquor by gained containing sodium chloride under normal pressure in 110 DEG C of concentrations, and be separated by solid-liquid separation, 52g solid sodium chloride is obtained, by remaining liq burning disposal.52g sodium chloride is dissolved in In 174g water, 18g ammonia is added, then be passed through 50g carbon dioxide, is warming up to 60 DEG C, react 2h, filtering obtains 80g sodium bicarbonate Sodium chloride is added into filtrate for solid, and ammonium chloride is precipitated, and ammonium chloride and residual filtrate is obtained by filtration, and residual filtrate repeats above-mentioned Reaction adds sodium chloride into residual filtrate, ammonium chloride is precipitated.

1000g triethylamine hydrochloride is taken, 760g water and 220g calcium oxide, pH=9 are added thereto, are warming up to 105 DEG C, institute It obtains triethylamine steam and obtains aqueous triethylamine and water through condensation, obtain 716.3g triethylamine product, mother liquor cooling through dehydration To after 25 DEG C, it is passed through 2410g ammonia thereto, ammonia leakage recycling is at ammonium hydroxide, and after reacting 1h, centrifuge separation obtains 350g hydrogen The aqueous solution of calcium oxide and 910g containing ammonium chloride, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride, to chloride containing 10g ammonium hydrogen carbonate is added in the aqueous solution of ammonium to be separated by solid-liquid separation after reaction, obtains 12g calcium carbonate solid, and depressurizing The aqueous solution of lower 100 DEG C of concentrations containing ammonium chloride, obtains 377g purity and is 98.5% ammonium chloride, and recycle ammonia and obtain 11400g ammonia Water.Gained filtrate is subjected to burning or high temperature oxidation process.

Embodiment 15

Glyphosate mother solution concentrate is cooled to 25 DEG C, 1295g triethylamine is added, adjusts pH=14 of solution, adds 651.2g sodium liquid alkaline, is neutralized to pH=14, obtains 3681.2g mother liquor, is heated to 70 DEG C, and after standing 2h, solution is divided into 3 layers up and down, Obtained after separation the upper layer 1000g triethylamine, the solution that triethylamine hydrochloride is contained in the middle layer 1391g and 1290g lower layer contain it is organic The sodium salt solution of phosphorus.

265g piece alkali is added into the solution containing triethylamine hydrochloride, adjusts the pH to 13 of solution, is warming up to 110 DEG C, Gained triethylamine steam through condensation obtain triethylamine aqueous solution, obtain 535.3g triethylamine through dehydration, also obtain 60g water and 1060g contains the alkali liquor of sodium chloride；Alkali liquor by gained containing sodium chloride is concentrated in 60 DEG C under vacuum conditions, and gained is solid 286g solid sodium chloride and 50g filtrate is obtained by filtration in liquid mixture；Gained filtrate is subjected to burning or high temperature oxidation process.It will 286g sodium chloride is dissolved in 957g water, and 440g ammonium hydrogen carbonate is added, and is warming up to 60 DEG C, reacts 2h, and filtering obtains 440g bicarbonate Sodium solid, is added sodium chloride into filtrate, and ammonium chloride is precipitated, and ammonium chloride and residual filtrate is obtained by filtration, on residual filtrate repeats State reaction.

1000g triethylamine hydrochloride is taken, the calcium hydroxide aqueous suspension of 1000g50% is added thereto, pH=14 are warming up to 105 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716.3g triethylamine product through dehydration, After mother liquor is cooled to 25 DEG C, it is passed through the ammonium hydroxide of 1773g13.6% thereto, after reacting 1h, centrifuge separation obtains 550g hydroxide The aqueous solution of calcium and 2506g containing ammonium chloride, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride, to containing ammonium chloride 10g ammonium hydrogen carbonate is added in aqueous solution to be separated by solid-liquid separation after reaction, obtains 12g calcium carbonate solid, and under reduced pressure 100 DEG C solution of the concentration containing ammonium chloride, obtains the ammonium chloride that 370g purity is 98.5%, and recycles ammonia and obtain 2100g ammonium hydroxide.By institute It obtains filtrate and carries out burning or high temperature oxidation process.

Embodiment 16

Glyphosate mother solution concentrate is cooled to 25 DEG C, 300g triethylamine is added, adjusts the pH=3.5 of solution, adds 651.2g potassium liquid alkaline, is neutralized to pH=9.7, obtains 2686.2g mother liquor, is heated to 70 DEG C, and after standing 2h, solution is divided into 3 layers, point The upper layer 20g triethylamine is obtained from after, solution that 1288g contains in middle layer triethylamine hydrochloride and 1378g lower layer are containing organic phosphorus potassium Salting liquid.

Solution containing triethylamine hydrochloride is concentrated in 123 DEG C under normal pressure, steams 352g water, remaining 936g mother liquor, 25 DEG C are cooled to, the side Bian Jiangwen filters, and obtained filtrate returns, obtains 642g triethylamine hydrochloride and 294g contains triethylamine on a small quantity The mother liquor of hydrochloride；35g solid sodium hydroxide is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjust the pH of solution to 11,108 DEG C are warming up to, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 63g triethylamine through dehydration Finished product also obtains the alkali liquor that 15g water and 245g contain sodium chloride；Alkali liquor by gained containing sodium chloride under normal pressure in 105 DEG C of concentrations, and be separated by solid-liquid separation, 52g solid sodium chloride is obtained, by remaining liq burning disposal.52g sodium chloride is dissolved in In 174g water, 80g ammonium hydrogen carbonate is added, is warming up to 60 DEG C, reacts 2h, filtering obtains 80g sodium bicarbonate solid, into filtrate Sodium chloride is added, ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, residual filtrate repeats above-mentioned reaction.

1000g triethylamine hydrochloride is taken, 696g water and 334g calcium oxide are added thereto, is passed through 2410g ammonia, ammonia is let out Dew recycling is warming up to 105 DEG C at ammonium hydroxide, pH=14, and gained triethylamine steam obtains aqueous triethylamine and water through condensation, through being dehydrated Processing obtains 716.3g triethylamine product, and after mother liquor is cooled to 25 DEG C, centrifuge separation obtains 450g calcium hydroxide and 983g containing chlorine Change the aqueous solution of ammonia, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride is added into the aqueous solution of containing ammonium chloride 10g ammonium hydrogen carbonate is separated by solid-liquid separation after reaction, obtains 12g calcium carbonate solid, and 90 DEG C of concentrations contain at reduced pressure conditions The aqueous solution of ammonium chloride, gained solidliquid mixture is through being obtained by filtration the ammonium chloride of 376g.Recycling ammonia obtains 11400g ammonium hydroxide.By institute It obtains filtrate and carries out burning or high temperature oxidation process.

Embodiment 17

Glyphosate mother solution concentrate is cooled to 25 DEG C, 300g triethylamine is added, adjusts the pH=4.5 of solution, adds 651.2g potassium liquid alkaline, is neutralized to pH=13, obtains 2686.2g mother liquor, is heated to 70 DEG C, and after standing 2h, solution is divided into 3 layers, separation After obtain the upper layer 100g triethylamine, solution that 1208g contains in middle layer triethylamine hydrochloride and 1378g lower layer are containing organic phosphorus sylvite Solution.

300g piece alkali is added into the solution containing triethylamine hydrochloride, adjusts the pH to 14 of solution, is warming up to 105 DEG C, Gained triethylamine steam through condensation obtain triethylamine aqueous solution, obtain 535.3g triethylamine through dehydration, also obtain 60g water and 912g contains the alkali liquor of sodium chloride；Alkali liquor by gained containing sodium chloride is concentrated in 80 DEG C under vacuum conditions, and gained is solid 286g solid sodium chloride and 50g filtrate is obtained by filtration in liquid mixture；Gained filtrate is subjected to burning or high temperature oxidation process.It will 286g sodium chloride is dissolved in 957g water, and 440g ammonium hydrogen carbonate is added, and is warming up to 60 DEG C, reacts 2h, and filtering obtains 440g bicarbonate Sodium solid, is added sodium chloride into filtrate, and ammonium chloride is precipitated, and ammonium chloride and residual filtrate is obtained by filtration, on residual filtrate repeats State reaction.

1000g triethylamine hydrochloride is taken, 500g water and 400g calcium hydroxide are added thereto, and be passed through 1773g13.6%'s Ammonium hydroxide, pH=14 are reacted in 105 DEG C, and gained triethylamine steam obtains aqueous triethylamine and water through condensation, are obtained through dehydration 716.3g triethylamine product, after mother liquor is cooled to 25 DEG C, centrifuge separation obtains 450g calcium hydroxide and 2500g containing ammonium chloride 10g carbonic acid is added into the aqueous solution of containing ammonium chloride for aqueous solution, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride Hydrogen ammonium is separated by solid-liquid separation after reaction, obtains 12g calcium carbonate solid, and 115 DEG C of concentrations contain ammonium chloride under normal pressure Solution obtains 370g purity and is 98.5% ammonium chloride, and recycles ammonia and obtain 2120g ammonium hydroxide.Gained filtrate is subjected to burning or height Warm oxidation processes.

Embodiment 18

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=2.0 are warming up to 110 DEG C, side under normal pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=2.0.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 300g triethylamine is added, adjusts pH=4.7 of solution, adds 651.2g potassium liquid alkaline, is neutralized to pH=14, obtains 2686.2g mother liquor, is heated to 76 DEG C, and after standing 2h, solution is divided into 3 layers, separation After obtain the upper layer 120g triethylamine, solution that 1188g contains in middle layer triethylamine hydrochloride and 1378g lower layer are containing organic phosphorus sylvite Solution.

Solution containing triethylamine hydrochloride is concentrated in 130 DEG C under normal pressure, steams 252g water, remaining 936g mother liquor, 25 DEG C are cooled to, the side Bian Jiangwen filters, and obtained filtrate returns, obtains 642g triethylamine hydrochloride and 294g contains triethylamine on a small quantity The mother liquor of hydrochloride；40g solid sodium hydroxide is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjust the pH of solution to 14,108 DEG C are warming up to, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 63g triethylamine through dehydration Finished product also obtains the alkali liquor that 10g water and 255g contain sodium chloride；Alkali liquor by gained containing sodium chloride under normal pressure in 115 DEG C of concentrations, and be separated by solid-liquid separation, 52g solid sodium chloride is obtained, by remaining liq burning disposal.52g sodium chloride is dissolved in In 174g water, 18g ammonia is added, then be passed through 50g carbon dioxide, is warming up to 60 DEG C, react 2h, filtering obtains 80g sodium bicarbonate Sodium chloride is added into filtrate for solid, and ammonium chloride is precipitated, and ammonium chloride and residual filtrate is obtained by filtration, and residual filtrate repeats above-mentioned Reaction.

1000g triethylamine hydrochloride is taken, 334g calcium oxide is added, is passed through the ammonium hydroxide of 882g13.6%, pH=14 are warming up to 115 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716.3g triethylamine product through dehydration, After mother liquor is cooled to 25 DEG C, centrifuge separation obtains the aqueous solution of 450g calcium hydroxide and 1049g chloride containing ammonia, calcium hydroxide exists Reuse in the conversion processing of triethylamine hydrochloride, and the aqueous solution of 115 DEG C of concentration containing ammonium chlorides under normal pressure, the mixing of gained solid-liquid Object is through being obtained by filtration the ammonium chloride of 376g.Gained filtrate is subjected to burning or high temperature oxidation process.

Embodiment 19

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.1 is warming up to 105 DEG C, side under normal pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.1.

Contain addition 680g liquid sodium hydroxide in the solution of triethylamine hydrochloride to upper layer, adjust the pH to 10 of solution, 85 DEG C are warming up to, gained triethylamine steam obtains aqueous triethylamine and water through condensation, and aqueous triethylamine is obtained through dehydration 534.6g triethylamine finished product also obtains the alkali liquor that 1710g contains sodium chloride, by the alkali liquor containing sodium chloride under normal pressure in 105 DEG C of concentrations, gained solidliquid mixture carry out gained filtrate at burning or high-temperature oxydation through the sodium chloride of 307g is obtained by filtration Reason.307g sodium chloride is dissolved in 1027g water, 473g ammonium hydrogen carbonate is added, is warming up to 60 DEG C, reacts 2h, filtering has 473g carbon Sodium chloride is added into filtrate for sour hydrogen sodium solid, and ammonium chloride is precipitated, ammonium chloride and residual filtrate, residual filtrate weight is obtained by filtration Multiple above-mentioned reaction.

1000g triethylamine hydrochloride is taken, 2100g water and 5950g calcium hydroxide are added thereto, pH=14 are anti-in 110 DEG C It answers, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716.3g triethylamine product, mother liquor through dehydration After being cooled to 25 DEG C, centrifuge separation obtains the aqueous solution of 5412g calcium hydroxide and 2921g chloride containing calcium, calcium hydroxide is in three second Reuse in the conversion processing of amine hydrochlorate, and the aqueous solution of chloride containing calcium, gained solidliquid mixture is concentrated at 115 DEG C under normal pressure The CALCIUM CHLORIDE DIHYDRATE solid of 1042g is obtained by filtration, to obtain 787g anhydrous in 300 DEG C of drying by 1042g CALCIUM CHLORIDE DIHYDRATE Calcium chloride；Gained filtrate is subjected to burning or high temperature oxidation process.

Embodiment 20

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.1 is warming up to 50 DEG C, side under reduced pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.1.

Contain addition 750g liquid sodium hydroxide in the solution of triethylamine hydrochloride to upper layer, adjust the pH to 13 of solution, 110 DEG C are warming up to, gained triethylamine steam obtains aqueous triethylamine and water through condensation, and aqueous triethylamine is obtained through dehydration 534.6g triethylamine finished product also obtains the alkali liquor that 1780g contains sodium chloride, by the alkali liquor containing sodium chloride under normal pressure in 110 DEG C of concentrations, gained solidliquid mixture carry out gained filtrate at burning or high-temperature oxydation through the sodium chloride of 307g is obtained by filtration Reason.307g sodium chloride is dissolved in 1027g water, 473g ammonium hydrogen carbonate is added, is warming up to 60 DEG C, reacts 2h, filtering has 473g carbon Sodium chloride is added into filtrate for sour hydrogen sodium solid, and ammonium chloride is precipitated, ammonium chloride and residual filtrate, residual filtrate weight is obtained by filtration Multiple above-mentioned reaction.

1000g triethylamine hydrochloride is taken, the calcium hydroxide aqueous suspension of 1060g33.02% is added thereto, pH=11 add 100 DEG C of heat, gained triethylamine steam obtain aqueous triethylamine and water through condensation, obtain 716g triethylamine finished product through dehydration, Mother liquor is cooled to 25 DEG C and obtains the aqueous solution of 1260g chloride containing calcium and calcium hydroxide, and 60g calcium hydroxide and 1200g is obtained by filtration Alkali liquor containing calcium chloride is concentrated in 110 DEG C filtrate under normal pressure, and gained solidliquid mixture is through being obtained by filtration 1042g's 1042g CALCIUM CHLORIDE DIHYDRATE is obtained 787g anhydrous calcium chloride in 300 DEG C of drying by CALCIUM CHLORIDE DIHYDRATE solid；By gained filtrate Carry out burning or high temperature oxidation process.

Embodiment 21

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.1 is warming up to 112 DEG C, side under normal pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.1.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 500g triethylamine is added, adjusts pH=4.0 of solution, adds 651.2g ammonium liquid alkaline, is neutralized to pH=11, obtains 2686.2g mother liquor, is heated to 70 DEG C, and after standing 2h, solution is divided into 3 layers, separation Upper layer 80g triethylamine, the solution that triethylamine hydrochloride is contained in the middle layer 1688g and 1118g lower layer are obtained afterwards containing organic phosphorus ammonium salt Solution.

Contain addition 850g liquid sodium hydroxide in the solution of triethylamine hydrochloride to upper layer, adjust the pH to 14 of solution, 115 DEG C are warming up to, gained triethylamine steam obtains aqueous triethylamine and water through condensation, and aqueous triethylamine is obtained through dehydration 534.6g triethylamine finished product also obtains the alkali liquor that 2000g contains sodium chloride, by the alkali liquor containing sodium chloride under normal pressure in 115 DEG C of concentrations, gained solidliquid mixture carry out gained filtrate at burning or high-temperature oxydation through the sodium chloride of 307g is obtained by filtration Reason.307g sodium chloride is dissolved in 1027g water, 473g ammonium hydrogen carbonate is added, is warming up to 60 DEG C, reacts 2h, filtering has 473g carbon Sodium chloride is added into filtrate for sour hydrogen sodium solid, and ammonium chloride is precipitated, ammonium chloride and residual filtrate, residual filtrate weight is obtained by filtration Multiple above-mentioned reaction.

1000g triethylamine hydrochloride is taken, the calcium hydroxide aqueous suspension of 1000g33%, pH=9, heating 105 are added thereto DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716g triethylamine finished product, mother liquor drop through dehydration Temperature obtains the aqueous solution of 1230g chloride containing calcium to 25 DEG C, the alkali liquor containing calcium chloride is concentrated in 60 DEG C under reduced pressure, gained The CALCIUM CHLORIDE DIHYDRATE solid of 1042g is obtained by filtration in solidliquid mixture, and 1042g CALCIUM CHLORIDE DIHYDRATE is dried at 300 DEG C To 787g anhydrous calcium chloride；Gained filtrate is subjected to burning or high temperature oxidation process.

Embodiment 22

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, is highly acid, is warming up to 100 DEG C under reduced pressure, Triethylamine hydrochloride be precipitated is filtered when heating up concentration, and filtrate is back in mother liquor, 1500g water is steamed, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate highly acid.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 1500g triethylamine is added, adjusts pH=14 of solution, adds 651.2g sodium liquid alkaline, is neutralized to pH=14, obtains 2386.2g mother liquor, is heated to 28 DEG C, and after standing 2h, solution is divided into 3 layers, separation It obtains upper layer 800g triethylamine, the solution that triethylamine hydrochloride is contained in the middle layer 1796g and 1290g lower layer and contains organic phosphorus sodium salt Solution.

Solution containing triethylamine hydrochloride is concentrated in 130 DEG C under reduced pressure, steams 615g water, remaining 1181 mother liquors, 25 DEG C are cooled to, the side Bian Jiangwen filters, and obtained filtrate returns, obtains 887g triethylamine hydrochloride and 294g contains triethylamine on a small quantity The mother liquor of hydrochloride；94g liquid sodium hydroxide is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjust the pH of solution to 10,85 DEG C are warming up to, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 63g triethylamine through dehydration Finished product also obtains the alkali liquor that 74g water and 255g contain sodium chloride；Alkali liquor by gained containing sodium chloride is under reduced pressure in 60 DEG C concentration, and is separated by solid-liquid separation, 52g solid sodium chloride is obtained, by remaining liq burning disposal.52g sodium chloride is dissolved in In 174g water, 18g ammonia is added, then be passed through 50g carbon dioxide, is warming up to 60 DEG C, react 2h, filtering obtains 80g sodium bicarbonate Sodium chloride is added into filtrate for solid, and ammonium chloride is precipitated, and ammonium chloride and residual filtrate is obtained by filtration, and residual filtrate repeats above-mentioned Reaction.

1000g triethylamine hydrochloride is taken, 4083g water and 3967g calcium oxide, pH=14 are added thereto, are warming up to 112 DEG C, Gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716.3g triethylamine product, mother liquor drop through dehydration For temperature to after 25 DEG C, centrifuge separation obtains the aqueous solution of 5412g calcium hydroxide and 2921g chloride containing calcium, calcium hydroxide is in triethylamine Reuse in the conversion processing of hydrochloride the alkali liquor containing calcium chloride is concentrated in 80 DEG C under reduced pressure, gained solidliquid mixture The CALCIUM CHLORIDE DIHYDRATE solid of 1042g is obtained by filtration, to obtain 787g anhydrous in 300 DEG C of drying by 1042g CALCIUM CHLORIDE DIHYDRATE Calcium chloride；Gained filtrate is subjected to burning or high temperature oxidation process.

Disodium hydrogen phosphate 950g is obtained through high-temperature oxydation to organic phosphorus sodium salt solution will be contained.

Embodiment 23

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, is highly acid, is warming up to 106 DEG C under normal pressure, Triethylamine hydrochloride be precipitated is filtered when heating up concentration, and filtrate is back in mother liquor, 1500g water is steamed, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate highly acid.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 1500g triethylamine is added, adjusts pH=14 of solution, adds 651.2g sodium liquid alkaline, is neutralized to pH=14, obtains 2386.2g mother liquor, is heated to 78 DEG C, and after standing 2h, solution is divided into 3 layers, separation It obtains upper layer 800g triethylamine, the solution that triethylamine hydrochloride is contained in the middle layer 1796g and 1290g lower layer and contains organic phosphorus sodium salt Solution.

Solution containing triethylamine hydrochloride is concentrated in 93 DEG C under reduced pressure, steams 610g water, remaining 1181g mother liquor, 25 DEG C are cooled to, the side Bian Jiangwen filters, and obtained filtrate returns, obtains 887g triethylamine hydrochloride and 294g contains triethylamine on a small quantity The mother liquor of hydrochloride；109g liquid sodium hydroxide is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjust the pH of solution to 13,108 DEG C are warming up to, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 63g triethylamine through dehydration Finished product also obtains the alkali liquor that 89g water and 255g contain sodium chloride；Alkali liquor by gained containing sodium chloride is under reduced pressure in 80 DEG C concentration, and is separated by solid-liquid separation, 52g solid sodium chloride is obtained, by remaining liq burning disposal.52g sodium chloride is dissolved in In 174g water, 80g ammonium hydrogen carbonate is added, is warming up to 60 DEG C, reacts 2h, filtering obtains 80g sodium bicarbonate solid, into filtrate Sodium chloride is added, ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, residual filtrate repeats above-mentioned reaction.

1000g triethylamine hydrochloride is taken, 476g water and 334g calcium oxide, pH=14 are added thereto, are warming up to 105 DEG C, institute It obtains triethylamine steam and obtains aqueous triethylamine and water through condensation, obtain 716.3g triethylamine product, mother liquor cooling through dehydration To after 25 DEG C, centrifuge separation obtains the aqueous solution of 120g calcium hydroxide and 973g chloride containing calcium, calcium hydroxide is in triethylamine hydrochloric acid Reuse in the conversion processing of salt, and the alkali liquor containing calcium chloride is concentrated in 100 DEG C under reduced pressure, gained solidliquid mixture warp The CALCIUM CHLORIDE DIHYDRATE solid of 778g is obtained by filtration, 778g CALCIUM CHLORIDE DIHYDRATE is obtained into the anhydrous chlorination of 587g in 300 DEG C of drying Calcium；Gained filtrate is subjected to burning or high temperature oxidation process.

Embodiment 24

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, is highly acid, is warming up to 110 DEG C under normal pressure, Triethylamine hydrochloride be precipitated is filtered when heating up concentration, and filtrate is back in mother liquor, 1500g water is steamed, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate highly acid.

Solution containing triethylamine hydrochloride is concentrated in 50 DEG C under reduced pressure, steams 610g water, remaining 1181g mother liquor, 25 DEG C are cooled to, the side Bian Jiangwen filters, and obtained filtrate returns, obtains 887g triethylamine hydrochloride and 294g contains triethylamine on a small quantity The mother liquor of hydrochloride；Add 130g liquid sodium hydroxide into the mother liquor on a small quantity containing triethylamine hydrochloride, adjust the pH to 14 of solution, Be warming up to 110 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, through dehydration obtain 63g triethylamine at Product also obtain the alkali liquor that 89g water and 276g contain sodium chloride；Alkali liquor by gained containing sodium chloride is under reduced pressure in 100 DEG C concentration, and is separated by solid-liquid separation, obtains 52g solid sodium chloride, and gained filtrate burn or high temperature oxidation process.It will 52g sodium chloride is dissolved in 174g water, 18g ammonia is added, then be passed through 50g carbon dioxide, is warming up to 60 DEG C, reacts 2h, and filtering obtains To 80g sodium bicarbonate solid, sodium chloride is added into filtrate, ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, it is remaining Filtrate repeats above-mentioned reaction.

1000g triethylamine hydrochloride is taken, 760g water is added thereto and 220g calcium oxide, pH=9 are warming up under normal pressure 85 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716.3g triethylamine product through dehydration, female After liquid is cooled to 25 DEG C, it is passed through 3265g ammonia thereto, ammonia leakage recycling is at ammonium hydroxide, and after reacting 1h, centrifuge separation is obtained The aqueous solution of 350g calcium hydroxide and 905g containing ammonium chloride, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride, to 10g ammonium hydrogen carbonate is added in the aqueous solution of containing ammonium chloride to be separated by solid-liquid separation after reaction, 12g calcium carbonate solid is obtained, and The aqueous solution of 105 DEG C of concentration containing ammonium chlorides under normal pressure obtains 377g purity and is 98.5% ammonium chloride, and recycles ammonia and obtain 15725g ammonium hydroxide.

Comparative example 1

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, 800g liquid alkaline is added in pH=0.1 thereto, adjusts The pH to 6.5 ~ 7 of solution is saved, then 500g triethylamine (excess) is added thereto, is stirred, solution is not stratified, it is difficult to carry out subsequent place Reason.

Comparative example 2

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, 700g liquid alkaline is added in pH=0.1 thereto, adjusts The pH to 5.5 ~ 6.5 of solution is saved, then 600g triethylamine (excess) is added thereto, stirring, solution is divided into 3 layers, top layer three Ethamine is directly separated, then separate again in lower 2 layers of solution, obtain the solution and 300g that triethylamine hydrochloride is contained in the middle layer 6300g Organic phosphorus sodium salt solution is contained in lower layer.

3102g liquid alkaline is added into the solution containing triethylamine hydrochloride, adjusts the pH to 12 of solution, is warming up to 105 DEG C, Gained triethylamine steam obtains aqueous triethylamine and water through condensation, aqueous triethylamine through dehydration obtain 2245g triethylamine at Product also obtain the alkali liquor that 7157g contains sodium chloride, and 300 ~ 600g sodium chloride is precipitated in the alkali liquor concentration containing sodium chloride, Residue 3000 ~ 6000g mother liquor, partial mother liquid decontamination water treatment plant processing, under normal circumstances COD and exceeded 3 ~ 100 times of total phosphorus.

It is difficult to carry out subsequent processing containing organic phosphorus sodium salt solution, which is waste liquid, without purposes.

Comparative example 3

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, 260g piece alkali is added in pH=0.1 thereto, adjusts The pH to 6.5 ~ 7.5 of solution is saved, is stirred, is stood, solution is not stratified, it is difficult to carry out subsequent processing.

Comparative example 4

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, 289g piece alkali is added in pH=0.1 thereto, adjusts The pH to 5.5 ~ 6.5 of solution is saved, is stirred, is stood, solution is divided into 2 layers, separates 2 layers of solution up and down, obtains the upper layer 5339g and contain three Organic phosphorus sodium salt solution is contained in the solution of ethylamine hydrochloride and 450g lower layer.

3000g liquid alkaline is added into the solution containing triethylamine hydrochloride, adjusts the pH to 12 of solution, is warming up to 105 DEG C, Gained triethylamine steam obtains aqueous triethylamine and water through condensation, aqueous triethylamine through dehydration obtain 2248g triethylamine at Product also obtain the alkali liquor that 6091g contains sodium chloride, and 300 ~ 600g sodium chloride is precipitated in the alkali liquor concentration containing sodium chloride, Residue 3000 ~ 5000g mother liquor, partial mother liquid decontamination water treatment plant processing, under normal circumstances COD and exceeded 3 ~ 100 times of total phosphorus.

Comparative example 5

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, 3800g liquid alkaline is added in pH=0.1 thereto, The pH to 12 of solution is adjusted, is stirred, is stood, solution is divided into 2 layers, separates 2 layers of solution up and down, obtains 2104g triethylamine and 7196g Alkali liquor.

Alkali liquor is concentrated, 300 ~ 600g sodium chloride is precipitated, obtains 145g triethylamine finished product, residue 3000 ~ 6200g mother liquor should Partial mother liquid decontamination water treatment plant carries out subsequent processing, under normal circumstances COD and exceeded 3 ~ 100 times of total phosphorus, or carries out high temperature Oxidation, obtains 450g disodium hydrogen phosphate and 3000 ~ 5000g residue mother liquor, then quick lime is added into remaining mother liquor, generates phosphorus Cream obtains 3000 ~ 4500g after separation of solid and liquid and removes the mother liquor after dephosphorization cream, which carries out subsequent processing, several It can not handle, obtained phosphorus cream can not carry out subsequent processing.

Comparative example 6

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, 1200g hydroxide is added in pH=0.1 thereto Calcium adjusts the pH to 12 of solution, stirring, generates phosphorus cream, and heating extracts triethylamine, 2245g triethylamine finished product obtained, by gained To solidliquid mixture be centrifuged, obtain the mother liquor that 4500g contains calcium chloride, obtained phosphorus cream can not carry out subsequent place Reason, contains the mother liquor of calcium chloride as waste water progress subsequent processing, under normal circumstances COD and exceeded 3 ~ 100 times of total phosphorus, almost without Method processing.

Comparative example 7

Take the obtained alkaline mother liquor of 6500g producing glyphosate by using glycine (resulting after addition liquid alkaline in oxytropism mother liquor Solution), 1200g calcium hydroxide is added thereto, adjusts the pH to 12 of solution for pH=10.5, stirs, and phosphorus cream is generated, by institute Obtained solidliquid mixture is centrifuged, and 2200g solid phosphorus cream and 5500g mother liquor is obtained, after obtained phosphorus cream can not carry out Continuous processing, mother liquor is as waste water progress subsequent processing, COD and exceeded 3 ~ 100 times of total phosphorus under normal circumstances, it is virtually impossible to handle.

Claims

1. a kind of comprehensive processing technique of glyphosate mother solution, the glyphosate mother solution is using process of producing glyphosate by using glycine In obtained acid mother liquid, which comprises the steps of:

(c) by the resulting solution concentration containing triethylamine hydrochloride of step (b), precipitation triethylamine hydrochloride, removing has been precipitated Triethylamine hydrochloride, then triethylamine and hydrochloride are extracted from remaining mother liquor；

(d) by triethylamine hydrochloride obtained in step (a), step (c) respectively or merge convert, obtain triethylamine；

2. a kind of comprehensive processing technique of glyphosate mother solution, the glyphosate mother solution is using process of producing glyphosate by using glycine In obtained acid mother liquid, which comprises the steps of:

(d) the resulting triethylamine hydrochloride of step (a) is converted, obtains triethylamine；

3. the comprehensive processing technique of glyphosate mother solution according to claim 1 or 2, which is characterized in that, will in step (a) Glyphosate mother solution is concentrated in 100 ~ 130 DEG C in atmospheric conditions, or is concentrated at reduced pressure conditions in 50 ~ 130 DEG C.

4. the comprehensive processing technique of glyphosate mother solution according to claim 1 or 2, which is characterized in that in step (b), first Triethylamine is added into the resulting glyphosate mother solution concentrate A of step (a), pH value is adjusted to≤14, then XOH is added thereto Or XOH solution.

5. the comprehensive processing technique of glyphosate mother solution according to claim 1 or 2, which is characterized in that in step (d), step Suddenly in (d), triethylamine hydrochloride is dissolved in water, calcium hydroxide, calcium hydroxide emulsion and/or calcium oxide are added thereto, is adjusted PH value is warming up to >=85 DEG C, the solution or suspension after obtaining triethylamine steam and reaction to 9 ~ 14；It is steamed using gained triethylamine Vapour prepares triethylamine finished product；By after reaction solution or suspension be separated by solid-liquid separation, obtain calcium hydroxide solid and contain chlorine Change the solution of calcium；Solution containing calcium chloride is used to prepare calcium chloride.

6. the recovery and treatment method of glyphosate mother solution according to claim 1 or 2, which is characterized in that, will in step (d) Triethylamine hydrochloride is dissolved in water, thereto addition calcium hydroxide, calcium hydroxide emulsion and/or calcium oxide, adjusting pH value to 9 ~ 14, >=85 DEG C are warming up to, the solution or suspension after obtaining triethylamine steam and reaction；Three second are prepared using gained triethylamine steam Amine finished product；Calcium hydroxide and ammonium chloride are extracted from the solution or suspension after reaction.

7. the comprehensive processing technique of glyphosate mother solution according to claim 1 or 2, which is characterized in that, will in step (d) Triethylamine hydrochloride is dissolved in water, and calcium hydroxide, calcium hydroxide emulsion and/or calcium oxide are added thereto, and is passed through ammonia or adds Enter ammonium hydroxide, is warming up to >=85 DEG C, the solution or suspension after obtaining triethylamine steam and reaction；Using gained triethylamine steam system Standby triethylamine finished product；Calcium hydroxide, ammonium chloride and calcium carbonate are extracted from the solution or suspension after reaction.

8. the comprehensive processing technique of glyphosate mother solution according to claim 1, which is characterized in that in step (c), to residue Mother liquor in piece alkali and/or sodium hydroxide solution is added, adjust pH value to 10 ~ 14, be warming up to >=85 DEG C, obtain triethylamine steam With the alkali liquor containing sodium chloride；Triethylamine finished product is prepared using triethylamine steam；Using the alkali liquor preparation containing sodium chloride Solid sodium chloride.

9. the comprehensive processing technique of glyphosate mother solution according to claim 1, which is characterized in that in step (c), to residue Mother liquor in calcium hydroxide, calcium hydroxide emulsion and/or calcium oxide is added, adjust pH value to 9 ~ 14, be warming up to >=85 DEG C, obtain Triethylamine steam and alkali liquor containing calcium chloride；Triethylamine finished product is prepared using triethylamine steam；Using containing calcium chloride Alkali liquor prepares calcium chloride solid.

10. the comprehensive processing technique of glyphosate mother solution according to claim 2, which is characterized in that in step (c), directly to step Suddenly calcium hydroxide and/or calcium oxide are added in (b) resulting not concentrated solution containing triethylamine hydrochloride, adjusts solution PH to 9 ~ 14, be warming up to >=85 DEG C, obtain triethylamine steam and the alkali liquor containing calcium chloride, using gained triethylamine steam Prepare triethylamine finished product；Alkali liquor containing calcium chloride is used to prepare calcium chloride solid.

11. the comprehensive processing technique of glyphosate mother solution according to claim 2, which is characterized in that in step (c), directly to containing Have and piece alkali and/or sodium hydrate aqueous solution are added in the solution of triethylamine hydrochloride, adjusts the pH to 10 ~ 14 of solution, be warming up to >=85 DEG C, obtain triethylamine steam and the alkali liquor containing sodium chloride；Triethylamine finished product is prepared using gained triethylamine steam；Contain There is the alkali liquor of sodium chloride to be used to prepare solid sodium chloride.

12. the comprehensive processing technique of the glyphosate mother solution according to claim 8 or 11, which is characterized in that by gained chlorination Sodium solid is dissolved in water, and ammonium hydrogen carbonate is added thereto, or is passed through ammonia and carbon dioxide or ammonium hydroxide is added, is passed through carbon dioxide, Sodium bicarbonate solid and aqueous ammonium chloride solution are obtained through being separated by solid-liquid separation, gained aqueous ammonium chloride solution is used to prepare chloride solid.

13. the comprehensive processing technique of glyphosate mother solution according to claim 1 or 2, which is characterized in that when X is Na⁺When, to Step (b) is resulting containing ammonium hydrogen carbonate is added in organic phosphorus salting liquid, or be passed through ammonia and carbon dioxide or be added ammonium hydroxide, It is passed through carbon dioxide, sodium bicarbonate solid is obtained and containing organic phosphorus ammonium salt mother liquor, gained contains organic phosphorus ammonium salt mother liquor For preparing gyphosate solution.

14. the comprehensive processing technique of glyphosate mother solution according to claim 1 or 2, which is characterized in that when X is K⁺Or NH₄ ⁺ When, step (b) is resulting to be directly used in preparation gyphosate solution containing organic phosphorus salting liquid.