CN110393188A

CN110393188A - The purification process technique of glyphosate mother solution

Info

Publication number: CN110393188A
Application number: CN201810378960.XA
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 purification process 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 purification process of glyphosate mother solution is realized, large-scale industrial production is suitble to.

Description

The purification process 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 purification process 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 technique 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 treatment process as disclosed in CN100537580, CN1676527 etc..It is female using this process glyphosate 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, purification process can be carried out to glyphosate mother solution by needing to develop one kind, remove inorganic salt and other material therein, The waste liquid or waste for being difficult to recycle are not generated, to obtain the novel work of the organic matters such as the glyphosate for being practically free of inorganic salts Skill.

Summary of the invention

It is an object of the invention to provide a kind of purification process techniques of glyphosate mother solution, to solve existing glyphosate mother solution Impurity is more in products therefrom in treatment process, generates the waste liquid or waste for being difficult to be recycled, 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 purification process 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:

(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 Degree is 100 ~ 130 DEG C, preferably 110 ~ 117 DEG C；Be performed under reduced pressure concentration temperature be 50 ~ 130 DEG C, preferably 60 ~ 100 ℃。

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 2 ~ 14 using pH adjusting agent, it is quiet It sets to solution and is layered, the solution after layering is separated, obtain the solution containing triethylamine hydrochloride and to contain organic phosphorus salt molten Liquid；The pH adjusting agent includes containing X⁺Alkali and triethylamine, wherein X Na⁺、K⁺Or NH₄ ⁺；

It is first added into the resulting glyphosate mother solution concentrate of step (a) and contains X⁺Alkali, then triethylamine is added thereto；It is added The dosage of the triethylamine entered does not have strict regulations, generally by the Cl in glyphosate mother solution concentrate^-How much decisions, work as Cl^-Content Gao Shi, the additional amount of triethylamine increase, on the contrary then reduce, and the additional amount of triethylamine can also be excessive, to adjust pH value, excessive three Ethamine is then located at top layer when solution is layered, and recycling can be carried out after separation.

Preferably, it is added into the resulting glyphosate mother solution concentrate of step (a) and contains X⁺Alkali, pH value is adjusted to 2 ~ 7.5, it is highly preferred that pH value is adjusted to 2 ~ 7.0；Triethylamine is added thereto again, the pH value of solution is adjusted to 5.0 ~ 14, it is excellent Select 7.0 ~ 14.

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, respectively obtain containing three second The solution of amine 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, respectively obtains the solution containing triethylamine hydrochloride and containing organic phosphorus salting liquid；It is collected Triethylamine obtain triethylamine finished product through dehydration.

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.

Contain X⁺Alkali be XOH, its solution or suspension, XHCO₃, its solution or suspension or X₂CO₃, its solution or outstanding Turbid.

Work as X⁺For Na⁺When, contain Na⁺Alkali be piece alkali, sodium hydroxide solution, sodium bicarbonate powder, sodium bicarbonate solution or Suspension, powdered sodium carbonate or sodium carbonate liquor or suspension；Preferably, the soda is sodium bicarbonate powder, sodium bicarbonate Solution or suspension.

Contain Na⁺Alkali be sodium hydroxide solution, it is preferable that contain Na⁺Alkali be sodium hydrate aqueous solution, concentration is 0.1 ~ 99.9wt%, preferably 30 ~ 60wt%, more preferable 30 ~ 32wt%.

Contain Na⁺Alkali be sodium bicarbonate solution or suspension, it is preferable that contain Na⁺Alkali be sodium bicarbonate aqueous solution or The concentration of sodium bicarbonate aqueous suspension, the sodium bicarbonate aqueous solution or sodium bicarbonate aqueous suspension is 0.1 ~ 99.9wt%；It is preferred that Ground, the concentration of sodium bicarbonate aqueous suspension are 60 ~ 98wt%.

Contain Na⁺Alkali be sodium carbonate liquor or suspension, it is preferable that contain Na⁺Alkali be aqueous sodium carbonate or carbonic acid The concentration of sodium aqueous suspension, the aqueous sodium carbonate or sodium carbonate suspension is 0.1 ~ 99.9wt%；Preferably, sodium carbonate The concentration of aqueous suspension is 60 ~ 98wt%.

Work as X⁺For K⁺When, contain K⁺Alkali be potassium hydroxide, potassium hydroxide solution, saleratus powder, potassium bicarbonate solution Or suspension, potassium carbonate powder, solution of potassium carbonate or suspension.

Contain K⁺Alkali be potassium hydroxide solution, it is preferable that contain K⁺Alkali be potassium hydroxide aqueous solution, concentration 0.1 ~ 99.9wt%, preferably 30 ~ 60wt%, more preferable 30 ~ 32wt%.

Contain K⁺Alkali be potassium bicarbonate solution or suspension, it is preferable that contain K⁺Alkali be potassium bicarbonate aqueous solution or carbon The concentration of potassium hydrogen phthalate aqueous suspension, the potassium bicarbonate aqueous solution or saleratus aqueous suspension is 0.1 ~ 99.9wt%；It is preferred that Ground, the concentration of saleratus aqueous suspension are 60 ~ 98wt%.

Contain K⁺Alkali be solution of potassium carbonate or suspension, it is preferable that contain K⁺Alkali be wet chemical or potassium carbonate The concentration of aqueous suspension, the wet chemical or potash water suspension is 0.1 ~ 99.9wt%；Preferably, potash water The concentration of suspension is 60 ~ 98wt%.

Work as X⁺For NH₄ ⁺When, contain NH₄ ⁺Alkali be ammonia, ammonium hydroxide, ammonium hydrogen carbonate powder, ammonium bicarbonate soln or suspension.

Contain NH₄ ⁺Alkali be ammonia or ammonium hydroxide, concentration be 0.1 ~ 99.9wt%, preferably 15 ~ 32wt%, more preferable 15 ~ 28wt%。

Contain NH₄ ⁺Alkali be ammonium bicarbonate soln or suspension, it is preferable that contain NH₄ ⁺Alkali be ammonium bicarbonate aqueous solution Or ammonium hydrogen carbonate aqueous suspension, the concentration of the ammonium bicarbonate aqueous solution or ammonium hydrogen carbonate aqueous suspension are 0.1 ~ 99.9wt%；It is excellent Selection of land, the concentration of ammonium hydrogen carbonate aqueous suspension are 60 ~ 98wt%.

(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.

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 solution, gained contains organic phosphorus ammonium salt solution 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 solution 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:

(b) pH value of the resulting glyphosate mother solution concentrate A of step (a) is adjusted to 2 ~ 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 containing X⁺Alkali and triethylamine, wherein X 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 converted, obtains triethylamine；

Step (a) and (b), (d), the process of (e) and preceding method are identical or essentially identical, can be used in step (c) following Two methods extract triethylamine and hydrochloride directly from the resulting solution containing triethylamine hydrochloride of step (b):

A kind of method is that calcium hydroxide and/or oxidation are added directly into the not concentrated solution containing triethylamine hydrochloride Calcium adjusts the pH value of solution to 9 ~ 14, is warming up to >=85 DEG C, obtains triethylamine steam and the alkali liquor containing calcium chloride, use Gained triethylamine steam prepares triethylamine finished product；Alkali liquor containing 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 It is concentrated, calcium chloride solid is precipitated, calcium chloride solid and remaining a small amount of liquid are obtained after being separated by solid-liquid separation, and will be remaining A small amount of liquid carries out burning disposal or carries out high temperature oxidation process.

Another method is that addition piece alkali and/or sodium hydroxide are water-soluble directly into the solution containing triethylamine hydrochloride Liquid adjusts the pH value of solution to 10 ~ 14, is warming up to >=85 DEG C, obtains triethylamine steam and the alkali liquor containing sodium chloride；Using Gained triethylamine steam prepares triethylamine finished product；Alkali liquor containing 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 solid, solid sodium chloride and remaining a small amount of solution is obtained after being separated by solid-liquid separation, it will be remaining a small amount of molten Liquid carries out burning disposal or carries out oxidation processes；Solid sodium chloride is dissolved in water, ammonium hydrogen carbonate is added thereto, by institute after reaction It obtains solidliquid mixture to be separated by solid-liquid separation, obtains sodium bicarbonate solid and aqueous ammonium chloride solution, the reuse of gained sodium bicarbonate or work For finished product sale, 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 purification process 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 more pure gyphosate solution and calcium hydroxide, ammonium chloride, sodium bicarbonate, calcium chloride or phosphoric acid hydrogen two A variety of valuable byproducts such as salt, gained byproduct can be applied or during glyphosate mother solution purification process as finished product It sells, does not generate the waste liquid and solid waste that is difficult to be utilized, pollute environment during processing crucially more, have There are apparent economic benefit and environmental benefit, solves and the glyphosate mother solution of glyphosate industry development is hindered not handle thoroughly Problem is truly realized the purification process of glyphosate mother solution so that glyphosate enterprise no longer because can not handle glyphosate mother solution, It generates environmental issue 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 pH adjusting agent is to contain Na⁺Alkali when, prepared using containing organic phosphorus sodium salt solution Before gyphosate solution, sodium bicarbonate is obtained after ammonium hydrogen carbonate or its analog is added thereto first, then using obtained Gyphosate solution is prepared containing organic phosphorus ammonium salt solution, the utilization rate of ammonium hydrogen carbonate on the one hand can be improved, reduces bicarbonate The carbon dioxide by-product of the dosage of ammonium, generation is also less；On the other hand, obtained sodium bicarbonate can also continue to be used as pH value Regulator reduces the dosage of sodium liquid alkaline during recycling glyphosate mother solution.

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 in atmospheric conditions 110 DEG C, triethylamine hydrochloride be precipitated is filtered when heating up concentration, and filtrate is back in mother liquor, steams 1500g water, 2263g triethylamine hydrochloride and 1737g glyphosate mother solution concentrate are obtained, glyphosate mother solution concentrate is highly acid.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 655g sodium liquid alkaline is added, adjusts pH=2 of solution, adds 595g Triethylamine adjusts the pH to 5.0 of solution, and fixed temperature is to 25 DEG C, and after standing 2h, solution is divided into 2 layers, and the upper layer 1691g is obtained after separation Solution containing triethylamine hydrochloride and 1292g lower layer are containing organic phosphorus sodium salt solution.

Solution containing triethylamine hydrochloride is concentrated in 100 DEG C in atmospheric conditions, steams 610g 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 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 940g 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 428g ammonium hydrogen carbonate are added in organic phosphorus sodium salt solution, in 60 DEG C of reaction 2h, 25 DEG C are cooled to, is filtered, It obtains 513g sodium bicarbonate solid and 1191g contains organic phosphorus ammonium salt solution.Gained contains organic phosphorus ammonium salt solution and is used for 30% gyphosate solution is prepared, indices meet national standard.

Embodiment 2

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.2 is warming up to 105 DEG C under normal pressure, Triethylamine hydrochloride be precipitated is filtered when heating up concentration, and filtrate is back in mother liquor, 1501g water is steamed, obtains 2264g triethylamine hydrochloride and 1735g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.2.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 755g sodium liquid alkaline is added, adjusts pH=7.5 of solution, adds 105g triethylamine adjusts the pH to 14 of solution, is warming up to 70 DEG C, and after standing 2h, solution is divided into 3 layers, and upper layer is obtained after separation Solution that 100g triethylamine, the middle layer 1091g contain triethylamine hydrochloride and 1292g lower layer are containing organic phosphorus sodium salt solution.

Contain to upper layer and 223g calcium hydroxide and 100g water be added in the solution of triethylamine hydrochloride, adjust the pH of solution to 9, be warming up to 85 DEG C under normal pressure, gained triethylamine steam obtains aqueous triethylamine and water through condensation, aqueous triethylamine through dehydration at Reason obtains 534.6g triethylamine finished product, the alkali liquor of 879g chloride containing calcium is also obtained, by the alkali liquor containing calcium chloride in normal pressure Under in 105 DEG C be concentrated, the CALCIUM CHLORIDE DIHYDRATE solid of 778g is obtained by filtration in gained solidliquid mixture, by bis- chloride hydrate of 778g Calcium obtains 587g 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, 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.

It is successively passed through 80g ammonia and 236g carbon dioxide into sodium salt solution of the lower layer containing organic phosphorus, in 60 DEG C of reaction 2h, 25 DEG C are cooled to, is filtered, is obtained 517g sodium bicarbonate solid and 1091g contains organic phosphorus ammonium salt solution.Gained contains organic The ammonium salt solution of phosphorus is used to prepare 30% gyphosate solution, and indices meet national standard.

Embodiment 3

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.4 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 2262g Triethylamine hydrochloride and 1738g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.4.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 651g sodium liquid alkaline is added, adjusts pH=5.6 of solution, adds 100g triethylamine adjusts the pH to 7.5 of solution, is warming up to 30 DEG C, and after standing 2h, solution is divided into 2 layers, obtains on 1195g after separation Solution of the layer containing triethylamine hydrochloride and 1293g lower layer are containing organic phosphorus sodium salt solution.

Solution containing triethylamine hydrochloride is concentrated in 105 DEG C under normal pressure, steams 414g water, remaining 781g mother liquor, 25 DEG C are cooled to, the side Bian Shengwen filters, and obtained filtrate returns, obtains 700g 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, 2100g water is added thereto and 5950g calcium hydroxide, pH=14 are warming up to 110 DEG C, 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 4

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.5 is warming up to 50 under vacuum conditions DEG C, triethylamine hydrochloride be precipitated is filtered when heating up concentration, and filtrate is back in mother liquor, steams 1501g water, obtain 2264g triethylamine hydrochloride and 1735g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.5.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 655g liquid alkaline is added, adjusts pH=5.6 of solution, adds 395g Triethylamine adjusts the pH to 14 of solution, is warming up to 40 DEG C, and after standing 2h, solution is divided into 3 layers, and the upper layer 100g three is obtained after separation Ethamine, solution that 1391g contains in middle layer triethylamine hydrochloride and 1292g lower layer are containing organic phosphorus sodium salt solution.

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 1106.4g chloride containing calcium, and 27g calcium hydroxide and 1079.4g filter is obtained by filtration Alkali liquor containing calcium chloride is concentrated in 110 DEG C liquid under normal pressure, and two water of 778g are obtained by filtration in gained solidliquid mixture Calcium chloride solid is closed, 778g CALCIUM CHLORIDE DIHYDRATE is obtained into 587g anhydrous calcium chloride in 300 DEG C of drying；Gained filtrate is burnt Burning or high temperature oxidation process.

1000g triethylamine hydrochloride is taken, 760g water is added thereto and 220g calcium oxide, pH=9 are warming up under normal pressure 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 2410g ammonia thereto, ammonia leakage recycling is at ammonium hydroxide, and after reacting 1h, centrifuge separation is obtained To the aqueous solution of 350g calcium hydroxide and 905g containing ammonium chloride, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride, 10g ammonium hydrogen carbonate is added into 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 containing ammonium chloride is concentrated at 115 DEG C under normal pressure, it obtains 377g purity and is 98.5% ammonium chloride, and recycle ammonia and obtain To 11400g ammonium hydroxide.

Lower layer is obtained into 913.3g disodium hydrogen phosphate through high-temperature oxydation containing organic phosphorus sodium salt solution.

Embodiment 5

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.6 is warming up to 110 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=0.6.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 651.2g potassium liquid alkaline is added, is neutralized to pH=6.0, obtains 2916.4g mother liquor adds triethylamine 150g, and pH=11 are heated to 50 DEG C, and after standing 2h, solution is divided into 3 layers, obtains after separation The triethylamine on the upper layer 50g, solution that 1108g contains in middle layer triethylamine hydrochloride and 1378g lower layer are containing organic phosphorus potassium salt soln.

Solution containing triethylamine hydrochloride is concentrated in 130 DEG C under normal pressure, steams 327g water, remaining 781g mother liquor, 25 DEG C are warming up to, the side Bian Shengwen filters, and obtained filtrate returns, obtains 700g triethylamine hydrochloride and 81g contains triethylamine on a small quantity The mother liquor of hydrochloride；12g calcium hydroxide is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjusts the pH to 14 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 115 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.

Lower layer is obtained into 1170g dipotassium hydrogen phosphate through high-temperature oxydation containing organic phosphorus sodium salt solution.

Embodiment 6

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.8 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=0.8.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 651.2g potassium liquid alkaline is added, is neutralized to pH=6.5, obtains 2916.4g mother liquor adds triethylamine 150g, and pH=11 are heated to 60 DEG C, and after standing 2h, solution is divided into 3 layers, obtains after separation The triethylamine on the upper layer 50g, solution that 1108g contains in middle layer triethylamine hydrochloride and 1378g lower layer are containing organic phosphorus potassium salt soln.

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 1045.4g chloride containing calcium and calcium hydroxide, filtrated stock obtain 200g calcium hydroxide and Alkali liquor containing calcium chloride is concentrated in 115 DEG C 1045.4g mother liquor under normal 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, 4083g water and 3967g 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 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.

Embodiment 7

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.9 is warming up to 115 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=0.9.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 651.2g potassium liquid alkaline is added, is neutralized to pH=6.6, obtains 2916.4g mother liquor adds triethylamine 170g, and pH=12 are heated to 70 DEG C, and after standing 2h, solution is divided into 3 layers, obtains after separation The triethylamine on the upper layer 58g, solution that 1180g contains in middle layer triethylamine hydrochloride and 1378g lower layer are containing organic phosphorus potassium salt soln.

Solution containing triethylamine hydrochloride is concentrated in 130 DEG C under reduced pressure, steams 240g 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, 105 DEG C are warming up to, 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 containing ammonium chloride is concentrated at 115 DEG C under normal pressure, gained is 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.

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

Embodiment 8

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=1.0 are 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=1.0.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 651.2g potassium liquid alkaline is added, is neutralized to pH=6.1, obtains 2916.4g mother liquor adds triethylamine 150g, and pH=11 are heated to 80 DEG C, and after standing 2h, solution is divided into 3 layers, obtains after separation The triethylamine on the upper layer 50g, solution that 1108g contains in middle layer triethylamine hydrochloride and 1378g lower layer are 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 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 973.4g contains calcium chloride, by containing calcium chloride alkali liquor decompression under in 60 DEG C of concentrations, gained solidliquid mixture are obtained by filtration the CALCIUM CHLORIDE DIHYDRATE solid of 778g, 778g CALCIUM CHLORIDE DIHYDRATE are existed 300 DEG C of drying obtain 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, 105 DEG C are warming up to, 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 containing ammonium chloride is concentrated at 110 DEG C under normal pressure, gained is 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 oxygen Change processing.

Embodiment 9

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=1.1 are warming up to 115 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=1.1.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 651.2g ammonium liquid alkaline is added, is neutralized to pH=7.0, obtains 2916.4g mother liquor adds triethylamine 350g, and pH=14 are heated to 90 DEG C, and after standing 2h, solution is divided into 3 layers, obtains after separation The triethylamine on the upper layer 300g, 1158g contain in middle layer the solution of triethylamine hydrochloride and 1278g lower layer to contain organic phosphorus ammonium salt molten Liquid.

Solution containing triethylamine hydrochloride is concentrated in 90 DEG C under reduced pressure, steams 222g 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 institute The alkali liquor for obtaining 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 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, 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 concentration contains chlorine at 115 DEG C under normal pressure Change 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.By gained Filtrate carries out burning or high temperature oxidation process.

Gained contains organic phosphorus ammonium salt solution 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=1.2 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=1.2.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 651.2g ammonium liquid alkaline is added, is neutralized to pH=6.6, obtains 2916.4g mother liquor adds triethylamine 150g, and pH=11 are heated to 100 DEG C, and after standing 2h, solution is divided into 3 layers, after separation To the triethylamine on the upper layer 50g, 1208g contains in middle layer the solution of triethylamine hydrochloride and organic phosphorus ammonium salt is contained in 1278g lower layer Solution.

Contain addition 200g calcium oxide in the solution of triethylamine hydrochloride to upper layer, and 250g water is added, adjusts solution PH to 13, is warming up to 113 DEG C, and gained triethylamine steam obtains aqueous triethylamine and water through condensation, aqueous triethylamine through dehydration at Reason obtains 534.6g triethylamine finished product, also obtains the alkali liquor of 1123.4g chloride containing calcium and calcium hydroxide, filtrated stock obtains 100g calcium hydroxide and 1223.4g mother liquor the alkali liquor containing calcium chloride are concentrated in 85 DEG C under reduced pressure, the mixing of gained solid-liquid The CALCIUM CHLORIDE DIHYDRATE solid of 778g is obtained by filtration in object, and by 778g CALCIUM CHLORIDE DIHYDRATE, in 300 DEG C of drying, to obtain 587g anhydrous Calcium chloride；Gained filtrate is subjected to burning or high temperature oxidation process.

1000g triethylamine hydrochloride is taken, 500g water and 400g calcium hydroxide, 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 Temperature is passed through 122g ammonia thereto, obtains 1305g solidliquid mixture, 420g calcium hydroxide and 885g is obtained by filtration to after 25 DEG C Solution containing ammonium chloride is added 10g ammonium hydrogen carbonate into the aqueous solution of containing ammonium chloride and is separated by solid-liquid separation, is obtained after reaction To 12g calcium carbonate solid, and in depressurizing the aqueous solution that lower temperature is 60 DEG C of concentration containing ammonium chlorides, 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, is highly acid, is warming up to 70 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 are highly acid.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 651.2g ammonium liquid alkaline is added, is neutralized to pH=2.5, obtains 2916.4g mother liquor adds triethylamine 350g, and pH=5.5 are heated to 70 DEG C, and after standing 2h, solution is divided into 2 layers, and separation is up and down Layer solution obtains the solution that triethylamine hydrochloride is contained on the upper layer 1658g and organic phosphorus ammonium salt solution is contained in 1278g lower layer.

Solution containing triethylamine hydrochloride is concentrated in 50 DEG C under reduced pressure, steams 572g 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, will The alkali liquor of gained 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 filtering To the CALCIUM CHLORIDE DIHYDRATE solid of 67g, 67g CALCIUM CHLORIDE DIHYDRATE is obtained into 50g anhydrous calcium chloride in 300 DEG C of drying；By gained Filtrate carries out burning or high temperature oxidation process.

1000g triethylamine hydrochloride is taken, 635g water and 267g calcium hydroxide, 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 Temperature is passed through 1122g ammonia thereto, obtains 1305g solidliquid mixture, 420g calcium hydroxide and 885g is obtained by filtration to after 25 DEG C Solution containing ammonium chloride is added 10g ammonium hydrogen carbonate into the aqueous solution of containing ammonium chloride and is separated by solid-liquid separation, is obtained after reaction To 12g calcium carbonate solid, and in depressurizing the aqueous solution that lower temperature is 85 DEG C of concentration containing ammonium chlorides, obtaining 376g purity is 98.5% Ammonium chloride.Recycling ammonia obtains ammonium hydroxide 5000g.Gained filtrate is subjected to burning or high temperature oxidation process.

Gained contains organic phosphorus ammonium salt solution high-temperature oxydation and obtains 873g diammonium hydrogen phosphate.

Embodiment 12

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=1.6 are 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=1.6.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 651.2g ammonium liquid alkaline is added, is neutralized to pH=7.0, obtains 2916.4g mother liquor adds triethylamine 50g, and pH=11 are heated to 70 DEG C, and after standing 2h, solution is divided into 3 layers, obtains after separation The triethylamine on the upper layer 50g, 1108g contain in middle layer the solution of triethylamine hydrochloride and 1278g lower layer to contain organic phosphorus ammonium salt molten Liquid.

Contain addition 250g calcium oxide in the solution of triethylamine hydrochloride to upper layer, and 350g water is added, adjusts solution PH to 14, is warming up to 115 DEG C, and gained triethylamine steam obtains aqueous triethylamine and water through condensation, aqueous triethylamine through dehydration at Reason obtains 534.6g triethylamine finished product, also obtains the alkali liquor of 1173.4g chloride containing calcium and calcium hydroxide, filtrated stock obtains The alkali liquor containing calcium chloride is concentrated in 100 DEG C under reduced pressure for 190g calcium hydroxide and 1283.4g mother liquor, and gained solid-liquid is mixed Close object and the CALCIUM CHLORIDE DIHYDRATE solid of 778g be obtained by filtration, by 778g CALCIUM CHLORIDE DIHYDRATE 300 DEG C of drying obtain 587g without Water calcium chloride；Gained filtrate is subjected to burning or high temperature oxidation process.

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 900g 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 in normal pressure The aqueous solution of containing ammonium chloride is concentrated at lower 110 DEG C, obtains 377g purity and is 98.5% ammonium chloride, and recycle ammonia and obtain 11400g Ammonium hydroxide.

Embodiment 13

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=2.0 are warming up to 90 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=2.0.

Glyphosate mother solution concentrate is cooled to 25 DEG C, the ammonium hydrogen carbonate aqueous suspension of 711g57.81% is added, is neutralized to 300g triethylamine is added in pH=7.0, and pH value=14 obtain 2555g mother liquor, is heated to 70 DEG C, and after standing 2h, solution is divided into 3 layers, Obtain upper layer 300g triethylamine after separation, 1119g contains in middle layer the solution of triethylamine hydrochloride and 1118g lower layer contain it is organic phosphorus Ammonium salt solution.

Solution containing triethylamine hydrochloride is concentrated in 100 DEG C under normal pressure, steams 183g 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, solid sodium chloride 52g 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 filtrate, ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, before residual filtrate repeats by solid State reaction.

1000g triethylamine hydrochloride is taken, 700g water and 330g calcium hydroxide are added thereto, pH=9 heat 85 DEG C, gained Triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716g triethylamine finished product through dehydration, mother liquor is cooled to 25 DEG C the aqueous solution of 1230g chloride containing calcium is obtained, the alkali liquor containing calcium chloride is concentrated in 60 DEG C under reduced pressure, gained solid-liquid is mixed The CALCIUM CHLORIDE DIHYDRATE solid that 1042g is obtained by filtration in object is closed, 1042g CALCIUM CHLORIDE DIHYDRATE is obtained into 787g in 300 DEG C of drying Anhydrous calcium chloride；Gained filtrate is subjected to burning or high temperature oxidation process.

Gained contains organic phosphorus ammonium salt solution high-temperature oxydation and obtains 836g diammonium hydrogen phosphate.

Embodiment 14

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.3 is warming up to 98 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, the ammonium hydrogen carbonate aqueous suspension of 711g57.81% is added, is neutralized to 200g triethylamine is added in pH=5.9, and pH=12 obtain 2555g mother liquor, is heated to 70 DEG C, and after standing 2h, solution is divided into 3 layers, point Obtain upper layer triethylamine 200g from after, 1119g contains in middle layer the solution of triethylamine hydrochloride and 1118g lower layer contain it is organic phosphorus Ammonium salt solution.

230g piece alkali is added into the solution containing triethylamine hydrochloride, 174.3g water is added, adjusts the pH to 10 of solution, 85 DEG C are warming up to, gained triethylamine steam obtains triethylamine aqueous solution through condensation, obtains 535.3g triethylamine through dehydration, also Obtain the alkali liquor that 60g water and 928g contain sodium chloride；Alkali liquor by gained containing sodium chloride is under vacuum conditions in 100 DEG C 286g solid sodium chloride and 50g filtrate is obtained by filtration in concentration, gained solidliquid mixture；Gained filtrate is subjected to burning or high temperature Oxidation processes.286g sodium chloride is dissolved in 957g water, 440g ammonium hydrogen carbonate is added, is warming up to 60 DEG C, reacts 2h, filtering has Sodium chloride is added filtrate, ammonium chloride is precipitated by 440g sodium bicarbonate solid, and ammonium chloride and residual filtrate, residue filter is obtained by filtration Liquid repeats previous reaction.

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.

Embodiment 15

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.4 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=0.4.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 57.8% ammonium hydrogen carbonate aqueous suspension of 712g is added, be neutralized to pH= 6.1,300g triethylamine is added, pH value=14 obtain 2555g mother liquor, are heated to 70 DEG C, and after standing 2h, solution is divided into 3 layers, separation After obtain upper layer triethylamine 230g, 1189g contains in middle layer the solution of triethylamine hydrochloride and organic phosphorus ammonium is contained in 1118g lower layer Salting liquid.

Solution containing triethylamine hydrochloride is concentrated in 123 DEG C under normal pressure, steams 253g 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, solid sodium chloride 52g 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, by sodium chloride Filtrate is added, ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, residual filtrate repeats previous 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 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.

Gained contain organic phosphorus ammonium salt solution for prepare 30% gyphosate solution, product qualification.

Embodiment 16

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.2 is 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=0.2.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 300g water is added, gained 2034.8g mother liquor is added into 411g carbon Sour hydrogen ammonium is neutralized to pH=5.7, and 300g triethylamine is added, and pH value=14 obtain 2555g mother liquor, is heated to 70 DEG C, after standing 2h, Solution is divided into 3 layers, and upper layer triethylamine 220g is obtained after separation, and 1339g contains in middle layer under the solution and 1118g of triethylamine hydrochloride Layer contains organic phosphorus ammonium salt solution.

265g piece alkali is added into the solution containing triethylamine hydrochloride, water 54.3g is added, adjusts the pH to 13 of solution, 110 DEG C are warming up to, gained triethylamine steam obtains triethylamine aqueous solution through condensation, 535.3g triethylamine is obtained through dehydration, Also obtain the alkali liquor that 60g water and 1063g contain sodium chloride；Alkali liquor by gained containing sodium chloride is under vacuum conditions in 60 DEG C concentration, 286g solid sodium chloride and 50g filtrate is obtained by filtration in gained solidliquid mixture；Gained filtrate is subjected to burning or height Warm oxidation processes.286g sodium chloride is dissolved in 957g water, 440g ammonium hydrogen carbonate is added, is warming up to 60 DEG C, reacts 2h, is filtered, There is 440g sodium bicarbonate solid, filtrate is added in sodium chloride, ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, it is remaining Filtrate repeats previous reaction.

1000g triethylamine hydrochloride is taken, the calcium hydroxide aqueous suspension of 950g47.37%, pH=13, heating are added thereto To 105 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716.3g triethylamine through dehydration and produces Product after mother liquor is cooled to 25 DEG C, are passed through 241g ammonia thereto, and ammonia leakage recycling is at ammonium hydroxide, after reacting 1h, centrifuge separation, The aqueous solution of 500g calcium hydroxide and 740g containing ammonium chloride is obtained, calcium hydroxide returns in the conversion processing of triethylamine hydrochloride With into the aqueous solution of containing ammonium chloride, addition 10g ammonium hydrogen carbonate is separated by solid-liquid separation after reaction, and it is solid to obtain 12g calcium carbonate Body, and the solution at 115 DEG C after concentration reaction under normal pressure, obtain 370g purity and are 98.5% ammonium chloride, and recycle ammonia and obtain 730g ammonium hydroxide.

Embodiment 17

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.14 is warming up to 85 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=0.14.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 59.3% sodium bicarbonate aqueous suspension of 737g is added, be neutralized to pH= 5.6,300g triethylamine is added, adjusts pH value=14, obtains 2586g mother liquor, is heated to 70 DEG C, after standing 2h, solution is divided into up and down 2 layers, upper layer triethylamine 150g is obtained after separation, obtains solution that triethylamine hydrochloride is contained in the middle layer 1218g and 1218g lower layer contains Organic phosphorus sodium salt solution.

Solution containing triethylamine hydrochloride is concentrated in 130 DEG C under normal pressure, steams 282g 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, solid sodium chloride 52g 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 filtrate, ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, before residual filtrate repeats by solid State reaction.

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 105 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.

Gained obtains 950g disodium hydrogen phosphate containing organic phosphorus sodium salt mother liquor high-temperature oxydation.

Embodiment 18

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.4 is warming up to 78 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=0.4.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 737g59.3% sodium bicarbonate aqueous suspension is added, be neutralized to pH= 6.0,100g triethylamine is added, adjusts pH value=7.8, obtains 2586g mother liquor, is heated to 70 DEG C, after standing 2h, solution is divided into Lower 2 layers, solution that triethylamine hydrochloride is contained on the upper layer 1168g and 1218g lower layer are obtained after separation containing organic phosphorus sodium salt 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 872.7g contains the alkali liquor of sodium chloride；Alkali liquor by gained containing sodium chloride is concentrated in 80 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 has 440g bicarbonate Sodium chloride is added filtrate, ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, residual filtrate repeats by sodium solid Previous reaction.

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 19

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.6 is warming up to 124 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=0.6.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 300g water is added, gained 2034.8g mother liquor is added into 437g carbon Sour hydrogen sodium is neutralized to pH=6.2, and 100g triethylamine is added, and adjusts pH value=7.5, obtains 2586g mother liquor, is heated to 70 DEG C, stands After 2h, solution is divided into 2 layers up and down, and solution that triethylamine hydrochloride is contained on the upper layer 1168g is obtained after separation and 1218g lower layer is contained The sodium salt solution of machine phosphorus.

Solution containing triethylamine hydrochloride is concentrated in 130 DEG C under reduced pressure, steams 232g 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；94g sodium liquid alkaline is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjusts the pH to 10 of solution, heats up 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 that 74g water and 255g contain sodium chloride；Alkali liquor by gained containing sodium chloride is concentrated in 60 DEG C under reduced pressure, And be separated by solid-liquid separation, solid sodium chloride 52g is obtained, by remaining liq burning disposal.52g sodium chloride is dissolved in 174g water, 18g ammonia is added, then is passed through 50g carbon dioxide, is warming up to 60 DEG C, reacts 2h, filtering obtains 80g sodium bicarbonate solid, by chlorine Change sodium and filtrate is added, ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, residual filtrate repeats previous reaction, i.e., Sodium chloride is continuously added into residual filtrate, and ammonium chloride is precipitated.

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.

To containing 415g ammonium hydrogen carbonate are added in organic phosphorus sodium salt solution, in 60 DEG C of reaction 2h, 25 DEG C are cooled to, is filtered, It obtains 521g sodium bicarbonate solid and 1100g contains organic phosphorus ammonium salt solution, gained contains organic phosphorus ammonium salt solution and is used for 30% gyphosate solution is prepared, product is qualified.

Embodiment 20

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.7 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=0.7.

Glyphosate mother solution concentrate is cooled to 25 DEG C, the sodium bicarbonate aqueous suspension of 737g59.29% is added, is neutralized to 100g triethylamine is added in pH=6.3, adjusts pH value=7.2, obtains 2586g mother liquor, and fixed temperature is to 25 DEG C, and after standing 2h, solution is divided into Upper and lower 2 layers, solution that triethylamine hydrochloride is contained on the upper layer 1168g is obtained after separation and 1218g lower layer is molten containing organic phosphorus sodium salt Liquid.

Contain addition 680g sodium liquid alkaline in the solution of triethylamine hydrochloride to upper layer, adjusts the pH to 10 of solution, be warming up to 85 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 that 1313g contains sodium chloride, and the alkali liquor containing sodium chloride is dense in 105 DEG C under normal pressure Contracting, gained solidliquid mixture carry out burning or high temperature oxidation process through the sodium chloride of 307g is obtained by filtration, by gained filtrate.It will 307g sodium chloride is dissolved in 1027g water, and 473g ammonium hydrogen carbonate is added, and is warming up to 60 DEG C, reacts 2h, and filtering obtains 473g carbonic acid Sodium chloride is added filtrate, ammonium chloride is precipitated by hydrogen sodium solid, is obtained by filtration ammonium chloride and residual filtrate, residual filtrate repeat into Row previous reaction.

1000g triethylamine hydrochloride is taken, 500g water and 500g calcium hydroxide are added thereto, pH=14 are reacted in 105 DEG C, Gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716.3g triethylamine product, mother liquor drop through dehydration Temperature is passed through 122g ammonia thereto, obtains 1405g solidliquid mixture, 520g calcium hydroxide and 885g is obtained by filtration to after 25 DEG C Solution containing ammonium chloride is added 10g ammonium hydrogen carbonate into the aqueous solution of containing ammonium chloride and is separated by solid-liquid separation, is obtained after reaction To 12g calcium carbonate solid, and the aqueous solution of 60 DEG C of concentration containing ammonium chlorides under reduced pressure, obtain the chlorination that 376g purity is 98.5% Ammonium.Gained filtrate is subjected to burning or high temperature oxidation process.

Embodiment 21

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.5 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=0.5.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 676g40.83% sodium carbonate suspension is added, be neutralized to pH= 5.8,150g triethylamine is added, adjusts pH value=7.5, obtains 2595g mother liquor, is heated to 100 DEG C, after standing 2h, solution is divided into Lower 2 layers, solution that triethylamine hydrochloride is contained on the upper layer 1227g and 1218g lower layer are obtained after separation containing organic phosphorus sodium salt solution.

Solution containing triethylamine hydrochloride is concentrated in 93 DEG C under reduced pressure, steams 291g 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；109g sodium liquid alkaline is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjusts the pH to 13 of solution, is warming up to 108 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 63g triethylamine finished product through dehydration, must Contain the alkali liquor of sodium chloride to 89g water and 255g；Alkali liquor by gained containing sodium chloride is concentrated in 80 DEG C under reduced pressure, and It is separated by solid-liquid separation, obtains solid sodium chloride 52g, by remaining liq burning disposal.52g sodium chloride is dissolved in 174g water, is added Enter 80g ammonium hydrogen carbonate, be warming up to 60 DEG C, react 2h, filtering obtains 80g sodium bicarbonate solid, filtrate is added in sodium chloride, analyses Ammonium chloride out, is obtained by filtration ammonium chloride and residual filtrate, and residual filtrate repeats previous reaction.

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.

Embodiment 22

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.9 is warming up to 117 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=0.9.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 400g water is added by gained 2134.8g mother liquor and adds 276g Sodium carbonate is neutralized to pH=6.2, and 100g triethylamine is added, and adjusts pH value=7.8, obtains 2595g mother liquor, is heated to 70 DEG C, stands After 2h, solution is divided into 2 layers up and down, and solution that triethylamine hydrochloride is contained on the upper layer 1177g is obtained after separation and 1218g lower layer is contained The sodium salt solution of machine phosphorus.

Contain addition 750g liquid alkaline in the solution of triethylamine hydrochloride to upper layer, adjusts the pH to 13 of solution, be warming up to 110 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, and aqueous triethylamine obtains tri- second of 534.6g through dehydration Amine finished product also obtains the alkali liquor that 1392g contains sodium chloride, and the alkali liquor containing sodium chloride is concentrated in 110 DEG C under normal pressure, Gained solidliquid mixture carries out burning or high temperature oxidation process through the sodium chloride of 307g is obtained by filtration, by gained filtrate.By 307g Sodium chloride is dissolved in 1027g water, and 473g ammonium hydrogen carbonate is added, and is warming up to 60 DEG C, reacts 2h, and filtering obtains 473g sodium bicarbonate Sodium chloride is added filtrate, ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, before residual filtrate repeats by solid State 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 913g 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 23

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.2 is warming up to 65 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, 400g water is added by gained 2134.8g mother liquor and adds 276g Sodium carbonate is neutralized to pH=5.7, and 200g triethylamine is added, and adjusts pH value=7.5, obtains 2595g mother liquor, is heated to 70 DEG C, stands After 2h, solution is divided into 2 layers up and down, and solution that triethylamine hydrochloride is contained on the upper layer 1277g is obtained after separation and 1218g lower layer is contained The sodium salt solution of machine phosphorus.

Solution containing triethylamine hydrochloride is concentrated in 50 DEG C under reduced pressure, steams 341g 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；Add 130g sodium liquid alkaline into the mother liquor on a small quantity containing triethylamine hydrochloride, adjusts the pH to 14 of solution, be warming up to 110 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 63g triethylamine finished product through dehydration, must Contain the alkali liquor of sodium chloride to 89g water and 276g；Alkali liquor by gained containing sodium chloride is concentrated in 100 DEG C under reduced pressure, And be separated by solid-liquid separation, solid sodium chloride 52g is obtained, gained filtrate is subjected to burning or high temperature oxidation process.By 52g sodium chloride It is dissolved in 174g water, 18g ammonia is added, then be passed through 50g carbon dioxide, be warming up to 60 DEG C, react 2h, filtering obtains 80g carbonic acid Sodium chloride is added filtrate, ammonium chloride is precipitated by hydrogen sodium solid, is obtained by filtration ammonium chloride and residual filtrate, residual filtrate repeat into Row previous reaction.

1000g triethylamine hydrochloride is taken, 500g water and 400g calcium hydroxide, 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 Temperature to 2407g ammonia after 25 DEG C, is passed through thereto, and ammonia leakage recycling is at ammonium hydroxide, and after reacting 1h, centrifuge separation obtains 450g The aqueous solution of calcium hydroxide and 740g containing ammonium chloride, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride, to containing chlorine Change addition 10g ammonium hydrogen carbonate in the aqueous solution of ammonium to be separated by solid-liquid separation after reaction, obtains 12g calcium carbonate solid, and be concentrated Solution after reaction obtains 370g purity and is 98.5% ammonium chloride, and recycles ammonia and obtain 11561g ammonium hydroxide.

Embodiment 24

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.3 is 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=0.3.

Glyphosate mother solution concentrate is cooled to 25 DEG C, the sodium carbonate suspension of 676g40.83% is added, be neutralized to pH= 5.6,100g triethylamine is added, adjusts pH value=6.5, obtains 2595g mother liquor, is heated to 70 DEG C, after standing 2h, solution is divided into Lower 2 layers, solution that triethylamine hydrochloride is contained on the upper layer 1177g and 1218g lower layer are obtained after separation containing organic phosphorus sodium salt solution.

Contain addition 850g sodium liquid alkaline 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 that 1490g contains sodium chloride, and the alkali liquor containing sodium chloride is dense in 115 DEG C under normal pressure Contracting, gained solidliquid mixture carry out burning or high temperature oxidation process through the sodium chloride of 307g is obtained by filtration, by gained filtrate.It will 307g sodium chloride is dissolved in 1027g water, and 473g ammonium hydrogen carbonate is added, and is warming up to 60 DEG C, reacts 2h, and filtering obtains 473g carbonic acid Sodium chloride is added filtrate, ammonium chloride is precipitated by hydrogen sodium solid, is obtained by filtration ammonium chloride and residual filtrate, residual filtrate repeat into Row previous 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 25

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.5 is warming up to 79 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=0.5.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 870g41.38% potash water suspension is added, be neutralized to pH= 5.8,150g triethylamine is added, adjusts pH value=7.7, obtains 2760g mother liquor, is heated to 70 DEG C, after standing 2h, solution is divided into Lower 2 layers, solution that triethylamine hydrochloride is contained on the upper layer 1192g and 1418g lower layer are obtained after separation containing organic phosphorus potassium salt soln.

Solution containing triethylamine hydrochloride is concentrated in 130 DEG C under normal pressure, steams 256g 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；110g sodium liquid alkaline is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjusts the pH to 13 of solution, heats up To 105 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 63g triethylamine finished product through dehydration, also Obtain the alkali liquor that 90g water and 240g contain sodium chloride；Alkali liquor by gained containing sodium chloride is dense in 110 DEG C under normal pressure Contracting, and be separated by solid-liquid separation, solid sodium chloride 52g is obtained, gained filtrate is subjected to burning or high temperature oxidation process.By 52g chlorine To change sodium to be dissolved in 174g water, 80g ammonium hydrogen carbonate is added, be warming up to 60 DEG C, reacts 2h, filtering obtains 80g sodium bicarbonate solid, Filtrate is added in sodium chloride, ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, residual filtrate repeats aforementioned anti- It answers.

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.

Gained obtains 1170g dipotassium hydrogen phosphate containing organic phosphorus sylvite mother liquor high-temperature oxydation.

Embodiment 26

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.6 is warming up to 85 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=0.6.

Glyphosate mother solution concentrate is cooled to 25 DEG C, the potash water suspension of 870g41.38% is added, be neutralized to pH= 5.9,100g triethylamine is added, adjusts pH value=6.8, obtains 2760g mother liquor, is heated to 100 DEG C, after standing 2h, solution is divided into Lower 2 layers, solution that triethylamine hydrochloride is contained on the upper layer 1142g and 1418g lower layer are obtained after separation containing organic phosphorus potassium salt soln.

Contain addition 400g calcium hydroxide in the solution of triethylamine hydrochloride to upper layer, adjust the pH to 14 of solution, heats up To 110 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 1000g chloride containing calcium and calcium hydroxide, filtrated stock obtain 200g calcium hydroxide and Alkali liquor containing calcium chloride is concentrated in 115 DEG C 800g mother liquor under normal pressure, and gained solidliquid mixture is through being obtained by filtration 433g CALCIUM CHLORIDE DIHYDRATE solid, 433g CALCIUM CHLORIDE DIHYDRATE is obtained into 327g 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, 500g water and 400g calcium hydroxide are added thereto, and is passed through 100g ammonia, pH= 14,105 DEG C are warming up 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 541g ammonia, ammonia leakage recycling is at ammonium hydroxide, after reacting 1h, centrifugation thereto Separation, obtains the aqueous solution of 450g calcium hydroxide and 740g containing ammonium chloride, conversion processing of the calcium hydroxide in triethylamine hydrochloride Middle reuse 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 carbonic acid Calcium solid, and the solution after reaction is concentrated, it obtains 370g purity and is 98.5% ammonium chloride, and recycle ammonia and obtain 2730g ammonium hydroxide.

Embodiment 27

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.9 is warming up to 55 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=0.9.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 510g water is added, by gained 2244.8g mother liquor, then plus 360g carbon Sour potassium is neutralized to pH=6.5, and 100g triethylamine is added, and adjusts pH value=7.5, obtains 2760g mother liquor, is heated to 70 DEG C, stands 2h Afterwards, solution is divided into 2 layers up and down, and solution that triethylamine hydrochloride is contained on the upper layer 1142g and 1418g lower layer are obtained after separation containing organic The potassium salt soln of phosphorus.

Solution containing triethylamine hydrochloride is concentrated in 50 DEG C under reduced pressure, steams 206g 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 hydroxide is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjusts the pH to 14 of solution, heats up To 105 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 95g water and 160g chloride containing calcium；Alkali liquor by gained containing sodium chloride is concentrated in 110 DEG C under normal pressure, And be separated by solid-liquid separation, calcium chloride solid 62g is obtained, gained filtrate is subjected to burning or high temperature oxidation process.

1000g triethylamine hydrochloride is taken, is added thereto, 500g water and 400g calcium hydroxide, and it is passed through 100g ammonia, pH =14,105 DEG C are warming up 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 341g ammonia, ammonia leakage recycling is at ammonium hydroxide, after reacting 1h, centrifugation thereto Separation, obtains the aqueous solution of 450g calcium hydroxide and 740g containing ammonium chloride, conversion processing of the calcium hydroxide in triethylamine hydrochloride Middle reuse 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 carbonic acid Calcium solid, and the aqueous solution of containing ammonium chloride is concentrated, it obtains 370g purity and is 98.5% ammonium chloride, and recycle ammonia and obtain 2230g ammonia Water.

Gained contain organic phosphorus sylvite mother liquor for prepare 30% gyphosate solution, product qualification.

Embodiment 28

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.2 is warming up to 114 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=0.2.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 510g water is added, by gained 2244.8g mother liquor, then plus 360g carbon Sour potassium, is neutralized to pH=5.5, adds triethylamine 700g, adjusts pH value=14, obtains 3160g mother liquor, is heated to 72 DEG C, after standing 2h, Solution is divided into 3 layers, and the upper layer 400g triethylamine is obtained after separation, and 1342g contains in middle layer under the solution and 1418g of triethylamine hydrochloride Layer is containing organic phosphorus potassium salt soln.

Contain addition 400g calcium hydroxide in the solution of triethylamine hydrochloride to upper layer, adjust the pH to 14 of solution, heats up To 110 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 1200g chloride containing calcium and calcium hydroxide, filtrated stock obtain 200g calcium hydroxide and Alkali liquor containing calcium chloride is concentrated in 115 DEG C 1000g mother liquor under normal pressure, and gained solidliquid mixture is through being obtained by filtration 433g CALCIUM CHLORIDE DIHYDRATE is obtained 327g anhydrous calcium chloride in 300 DEG C of drying by the CALCIUM CHLORIDE DIHYDRATE solid of 433g；By gained Filtrate carries out burning or high temperature oxidation process.

1000g triethylamine hydrochloride is taken, 500g water and 400g calcium hydroxide, 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 Temperature to 241g ammonia after 25 DEG C, is passed through thereto, and ammonia leakage recycling is at ammonium hydroxide, and after reacting 1h, centrifuge separation obtains 450g hydrogen The aqueous solution of calcium oxide and 740g 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, 12g calcium carbonate solid is obtained, and is concentrated anti- Solution after answering obtains 370g purity and is 98.5% ammonium chloride, and recycles ammonia and obtain 730g ammonium hydroxide.

Embodiment 29

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.3 is warming up to 117 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=0.3.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 952g54.83% saleratus aqueous suspension is added, be neutralized to pH= 5.5,150g triethylamine is added, adjusts pH value=7.5, obtains 2757g mother liquor, is heated to 70 DEG C, after standing 2h, solution is divided into Lower 2 layers, solution that triethylamine hydrochloride is contained on the upper layer 1189g and 1418g lower layer are obtained after separation containing organic phosphorus potassium salt soln.

Solution containing triethylamine hydrochloride is concentrated in 90 DEG C under reduced pressure, steams 253g 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 hydroxide is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjusts the pH to 14 of solution, heats up 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 90g water and 160g chloride containing calcium；Alkali liquor by gained containing sodium chloride is concentrated in 110 DEG C under normal pressure, And be separated by solid-liquid separation, the CALCIUM CHLORIDE DIHYDRATE solid of 82g is obtained by filtration in gained solidliquid mixture, by bis- chloride hydrate of 82g Calcium obtains 62g anhydrous calcium chloride in 300 DEG C of drying；Gained filtrate is subjected to burning or high temperature oxidation process.

Embodiment 30

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.2 is heated up 67 DEG C under reduced pressure, Bian Sheng 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=0.2.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 430g water is added, by gained 2164.8g mother liquor, then plus 522g carbon Potassium hydrogen phthalate is neutralized to pH=5.5, and 150g triethylamine is added, and adjusts pH value=7.5, obtains 2757g mother liquor, is heated to 70 DEG C, stands After 2h, solution is divided into 2 layers up and down, and solution that triethylamine hydrochloride is contained on the upper layer 1189g is obtained after separation and 1418g lower layer is contained The potassium salt soln of machine phosphorus.

Contain addition 400g calcium hydroxide in the solution of triethylamine hydrochloride to upper layer, adjust the pH to 14 of solution, heats up To 110 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 1050g chloride containing calcium and calcium hydroxide, filtrated stock obtain 200g calcium hydroxide and Alkali liquor containing calcium chloride is concentrated in 115 DEG C 850g mother liquor under normal pressure, and gained solidliquid mixture is through being obtained by filtration 433g CALCIUM CHLORIDE DIHYDRATE solid, 433g CALCIUM CHLORIDE DIHYDRATE is obtained into 327g 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, 500g water and 400g calcium hydroxide are added thereto, and is passed through 100g ammonia, pH= 14,95 DEG C of reactions are warming up to, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716.3g through dehydration Triethylamine product after mother liquor is cooled to 25 DEG C, is passed through 341g 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 the aqueous solution of containing ammonium chloride is concentrated, it obtains 370g purity and is 98.5% ammonium chloride, and recycle ammonia and obtain 2230g Ammonium hydroxide.

Embodiment 31

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.4 is warming up to 108 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=0.4.

Glyphosate mother solution concentrate is cooled to 25 DEG C, 430g water is added, by gained 2164.8g mother liquor, then plus 522g carbon Potassium hydrogen phthalate is neutralized to pH=5.7, and 150g triethylamine is added, and adjusts pH value=7.6, obtains 2757g mother liquor, is heated to 70 DEG C, stands After 2h, solution is divided into 2 layers up and down, and solution that triethylamine hydrochloride is contained on the upper layer 1189g is obtained after separation and 1418g lower layer is contained The potassium salt soln of machine phosphorus.

Solution containing triethylamine hydrochloride is concentrated in 130 DEG C under reduced pressure, steams 253g 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 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 aqueous triethylamine and water through condensation, obtains 63g triethylamine finished product through dehydration, Must 50g water and 210g chloride containing calcium alkali liquor；Alkali liquor by gained containing sodium chloride is concentrated in 110 DEG C under normal pressure, And be separated by solid-liquid separation, the CALCIUM CHLORIDE DIHYDRATE solid of 76g is obtained by filtration in gained solidliquid mixture, by bis- chloride hydrate of 76g Calcium obtains 58g 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, 500g water and 400g calcium hydroxide are added thereto, and is passed through 100g ammonia, pH= 14,105 DEG C are warming up 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 1037g ammonium hydroxide thereto, and ammonia leakage recycling is at ammonium hydroxide, after reacting 1h, from Heart separation, obtains the aqueous solution of 450g calcium hydroxide and 1777g 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 the solution after reaction is concentrated, it obtains 370g purity and is 98.5% ammonium chloride, and recycle ammonia and obtain 730g ammonium hydroxide.

Embodiment 32

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=2.0 are warming up to 111 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, the saleratus aqueous suspension of 952g54.83% is added, is neutralized to 300g triethylamine is added in pH=7.0, adjusts pH value=14, obtains 2757g mother liquor, is heated to 70 DEG C, and after standing 2h, solution is divided into 3 Layer, obtains the upper layer 300g triethylamine after separation, solution that 1339g contains in middle layer triethylamine hydrochloride and 1418g lower layer are containing organic The potassium salt soln of phosphorus.

1000g triethylamine hydrochloride is taken, 500g water and 400g calcium hydroxide are added thereto, and is passed through 735g ammonium hydroxide, pH= 14,105 DEG C are warming up 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 141g ammonia, ammonia leakage recycling is at ammonium hydroxide, after reacting 1h, centrifugation thereto Separation, obtains the aqueous solution of 450g calcium hydroxide and 1475g containing ammonium chloride, conversion processing of the calcium hydroxide in triethylamine hydrochloride Middle reuse 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 carbonic acid Calcium solid, and the solution after reaction is concentrated, it obtains 370g purity and is 98.5% ammonium chloride, and recycle ammonia and obtain 730g ammonium hydroxide.

Comparative example 1

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, 800g sodium liquid alkaline is added in pH=0.1 thereto, The pH value of solution is adjusted to 6.5 ~ 7, then addition 500g triethylamine (excess) thereto, is stirred, solution is not stratified, it is difficult to after progress Continuous processing.

Comparative example 2

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

3102g sodium liquid alkaline is added into the solution containing triethylamine hydrochloride, adjusts the pH value of solution to 12, is warming up to 105 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, and aqueous triethylamine obtains 2245g tri- through dehydration Ethamine finished product also obtains the alkali liquor that 7157g contains sodium chloride, and 300 ~ 600g chlorine is precipitated in the alkali liquor concentration containing sodium chloride Change sodium, residue 3000 ~ 6000g mother liquor, which is handled, under normal circumstances COD and total phosphorus exceeded 3 ~ 100 times.

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 value of solution is saved to 6.5 ~ 7.5, stirs, stands, 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 value of solution is saved to 5.5 ~ 6.5, stirs, stands, solution is divided into 2 layers, separates 2 layers of solution up and down, obtains the upper layer 5339g and contain The solution of triethylamine hydrochloride and 450g lower layer are containing organic phosphorus sodium salt solution.

3000g sodium liquid alkaline is added into the solution containing triethylamine hydrochloride, adjusts the pH value of solution to 12, is warming up to 105 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, and aqueous triethylamine obtains 2248g tri- through dehydration Ethamine finished product also obtains the alkali liquor that 6091g contains sodium chloride, and 300 ~ 600g chlorine is precipitated in the alkali liquor concentration containing sodium chloride Change sodium, residue 3000 ~ 5000g mother liquor, which is handled, under normal circumstances COD and total phosphorus exceeded 3 ~ 100 times.

Comparative example 5

The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, 3800g sodium liquid is added in pH=0.1 thereto Alkali adjusts the pH value of solution to 12, stirs, stand, and solution is divided into 2 layers, separates 2 layers of solution up and down, obtain 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 value of solution to 12, and stirring generates phosphorus cream, and heating extracts triethylamine, 2245g triethylamine finished product obtained, by institute Obtained solidliquid mixture is centrifuged, and the mother liquor that 4500g contains calcium chloride is obtained, and 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

The obtained alkaline mother liquor of 6500g producing glyphosate by using glycine is taken (gained after sodium liquid alkaline to be added in oxytropism mother liquor Solution), 1200g calcium hydroxide is added in pH=10.5 thereto, adjusts the pH value of solution to 12, and stirring generates phosphorus cream, Obtained solidliquid mixture is centrifuged, obtains 2200g solid phosphorus cream and 5500g mother liquor, obtained phosphorus cream can not be into Row subsequent processing, mother liquor carry out subsequent processing as waste water, under normal circumstances COD and exceeded 3 ~ 100 times of total phosphorus, it is virtually impossible to locate Reason.

Claims

1. a kind of purification process 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:

(b) pH value of the resulting glyphosate mother solution concentrate A of step (a) is adjusted to 2 ~ 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 containing X⁺Alkali and triethylamine, wherein X⁺For Na⁺、K⁺Or NH₄ ⁺；

(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 purification process 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:

3. the purification process 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 purification process technique of glyphosate mother solution according to claim 1 or 2, which is characterized in that in step (b), first It is added into the resulting glyphosate mother solution concentrate of step (a) and contains X⁺Alkali, pH value is adjusted to 2 ~ 7.5, then thereto plus Enter triethylamine.

5. the purification process technique of glyphosate mother solution according to claim 1 or 2, which is characterized in that described to contain X⁺Alkali For XOH, its solution or suspension, XHCO₃, its solution or suspension or X₂CO₃, its solution or suspension.

6. the purification process 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, 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；Solution or suspension after reaction obtain calcium hydroxide solid through being separated by solid-liquid separation.

7. 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.

8. the purification process technique of glyphosate mother solution according to claim 1 or 2, in step (d), by triethylamine hydrochloride It is dissolved in water, calcium hydroxide, calcium hydroxide emulsion and/or calcium oxide are added thereto, and is passed through ammonia or ammonium hydroxide is added, is warming up to >=85 DEG C, solution or suspension after obtaining triethylamine steam and reaction；Triethylamine finished product is prepared using gained triethylamine steam； Calcium hydroxide, ammonium chloride and calcium carbonate are extracted from the solution or suspension after reaction.

9. the purification process technique of glyphosate mother solution according to claim 1, which is characterized in that in step (c), to remaining mother Piece alkali and/or sodium hydroxide solution are added in liquid, adjusts pH value to 10 ~ 14, is warming up to >=85 DEG C, obtains triethylamine steam and contain There is the alkali liquor of sodium chloride；Triethylamine finished product is prepared using triethylamine steam；Chlorination is prepared using the alkali liquor containing sodium chloride Sodium solid.

10. the purification process technique of glyphosate mother solution according to claim 1, which is characterized in that in step (c), to remaining Calcium hydroxide, calcium hydroxide emulsion and/or calcium oxide are added in mother liquor, adjusts pH value to 9 ~ 14, is warming up to >=85 DEG C, obtains three Ethamine steam and alkali liquor containing calcium chloride；Triethylamine finished product is prepared using triethylamine steam；Using the alkali containing calcium chloride Mother liquor prepares calcium chloride solid.

11. the purification process 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 value to 9 ~ 14, be warming up to >=85 DEG C, obtain triethylamine steam and the alkali liquor containing calcium chloride, steamed using gained triethylamine Vapour prepares triethylamine finished product；Alkali liquor containing calcium chloride is used to prepare calcium chloride solid.

12. the purification process 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 hydroxide solution are added in the solution of triethylamine hydrochloride, adjusts the pH value of solution to 10 ~ 14, 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.

13. the purification process technique of the glyphosate mother solution according to claim 9 or 12, 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.

14. the purification process technique of glyphosate mother solution according to claim 1 or 2, which is characterized in that work as X⁺For Na⁺When, It is resulting containing ammonium hydrogen carbonate is added in organic phosphorus salting liquid to step (b) in step (e), or it is passed through ammonia and titanium dioxide Carbon is added ammonium hydroxide, is passed through carbon dioxide, obtains sodium bicarbonate solid and containing organic phosphorus ammonium salt solution, gained contains organic The ammonium salt solution of phosphorus is for preparing gyphosate solution.

15. the purification process technique of glyphosate mother solution according to claim 1 or 2, which is characterized in that work as X⁺For K⁺Or NH₄ ⁺ When, in step (e), step (b) is resulting to be directly used in preparation gyphosate solution containing organic phosphorus salting liquid.