CN110396047A - The recoverying and utilizing method of glyphosate mother solution - Google Patents

The recoverying and utilizing method of glyphosate mother solution Download PDF

Info

Publication number
CN110396047A
CN110396047A CN201810379597.3A CN201810379597A CN110396047A CN 110396047 A CN110396047 A CN 110396047A CN 201810379597 A CN201810379597 A CN 201810379597A CN 110396047 A CN110396047 A CN 110396047A
Authority
CN
China
Prior art keywords
solution
triethylamine
obtains
chloride
calcium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810379597.3A
Other languages
Chinese (zh)
Inventor
刘德亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201810379597.3A priority Critical patent/CN110396047A/en
Publication of CN110396047A publication Critical patent/CN110396047A/en
Pending legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/86—Separation

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Toxicology (AREA)

Abstract

The present invention provides a kind of recoverying and utilizing methods 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.The method of the present invention 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 resource utilization for realizing glyphosate mother solution utilizes, and is suitble to scale industrial production.

Description

The recoverying and utilizing method 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 recoverying and utilizing method 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.
The method handled glyphosate mother solution is mainly disclosed in CN100537580, CN1676527 etc. to glyphosate Liquid alkaline is added in mother liquor, recycles triethylamine therein, then ammonium hydrogen carbonate is added into remaining mother liquor, after sodium bicarbonate is precipitated, 10% gyphosate solution is prepared using remaining filtrate.When handling glyphosate mother solution in this way, on the one hand, need to consume A large amount of sodium hydroxide powders or liquid alkaline, are recycled the higher cost of glyphosate mother solution；It on the other hand, can not be to therein organic Object is recycled, and the effect for removing inorganic salts is poor, so that remaining mother liquor and precipitation carbonic acid after recycling triethylamine Still contain a large amount of inorganic salts (such as sodium chloride, sodium phosphite) in filtrate after hydrogen sodium, if long-term a large amount of applications use this The gyphosate solution that solution is prepared, can cause the salinization of soil, and large amount of organic is directly entered in soil and water body, give ring Border brings potential risks.Country has limited the production gyphosate solution below of glyphosate content 30% now, and uses existing Method be also difficult to for glyphosate to be concentrated to the concentration, then the obtained residual filtrate of the method for aforementioned processing glyphosate mother solution at To be difficult to the waste liquid recycled.
Therefore, need to develop it is a kind of can be by solid waste such as organic matters and inorganic salts such as glyphosates in glyphosate mother solution The new processing method of comprehensive reutilization is carried out with waste liquid.
Summary of the invention
It is an object of the invention to provide a kind of recoverying and utilizing methods of glyphosate mother solution, to solve existing glyphosate mother solution Substance recycling not exclusively, generates the waste liquid or waste for being difficult to be recycled, processing cost height and pollution ring in processing method The problems such as border.
The object of the present invention is achieved like this:
A kind of recoverying and utilizing method 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 is 100 ~ 130 DEG C, preferably 110 ~ 117 DEG C；The temperature for being performed under reduced pressure concentration is 50 ~ 130 DEG C, preferably 60 ~ 100 DEG C.
Triethylamine hydrochloride and remaining mother liquor that the methods of existing separation of solid and liquid will be precipitated in concentration process can be used Separation, and collect triethylamine hydrochloride.
(b) pH value of the resulting glyphosate mother solution concentrate A of step (a) is adjusted to 5.0 ~ 7.5 using pH adjusting agent, It stands to solution and is divided into 2 layers, upper layer, lower layer's solution are separated, the solution containing triethylamine hydrochloride is respectively obtained and has The salting liquid of machine phosphorus；The pH adjusting agent is to contain X+Alkali, wherein X Na+、K+Or NH4 +；
Preferably, the pH value of glyphosate mother solution concentrate A is adjusted to 6.5 ~ 7 using pH adjusting agent.
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.Solution is divided into 2 layers up and down, and upper layer is the solution containing triethylamine hydrochloride, and lower layer is Contain organic phosphorus salting liquid.Upper and lower 2 layers of solution is separated using existing method, is respectively obtained containing triethylamine hydrochloride Solution and contain organic phosphorus salting liquid.
PH adjusting agent is to contain X+Alkali, the X+For Na+、K+Or NH4 +；Contain X+Alkali be XOH, its solution or outstanding Turbid, XHCO3, its solution or suspension or X2CO3, its solution or suspension.
Work as X+For Na+When, pH adjusting agent can be piece alkali, sodium hydroxide solution, and sodium bicarbonate powder, sodium bicarbonate are molten Liquid or suspension, powdered sodium carbonate or sodium carbonate liquor or suspension；Preferably, pH adjusting agent is sodium bicarbonate powder, carbon Sour hydrogen sodium solution or suspension.
PH adjusting agent is sodium hydroxide solution, it is preferable that pH adjusting agent is sodium hydrate aqueous solution, and concentration is 0.1 ~ 99.9wt%, preferably 30 ~ 60wt%, more preferable 30 ~ 32wt%.
PH adjusting agent be sodium bicarbonate solution or suspension, it is preferable that pH adjusting agent 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%.
PH adjusting agent is sodium carbonate liquor or suspension, it is preferable that pH adjusting agent is 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, pH adjusting agent can be potassium hydroxide, potassium hydroxide solution, saleratus powder, saleratus Solution or suspension, potassium carbonate powder, solution of potassium carbonate or suspension.
PH adjusting agent is potassium hydroxide solution, it is preferable that pH adjusting agent is potassium hydroxide aqueous solution, and concentration is 0.1 ~ 99.9wt%, preferably 30 ~ 60wt%, more preferable 30 ~ 32wt%.
PH adjusting agent be potassium bicarbonate solution or suspension, it is preferable that pH adjusting agent be potassium bicarbonate aqueous solution or The concentration of saleratus 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%.
PH adjusting agent is solution of potassium carbonate or suspension, it is preferable that pH adjusting agent is wet chemical or carbonic acid The concentration of potassium aqueous suspension, the wet chemical or potash water suspension is 0.1 ~ 99.9wt%；Preferably, potassium carbonate The concentration of aqueous suspension is 60 ~ 98wt%.
Work as X+For NH4 +When, pH adjusting agent is ammonia, ammonium hydroxide, ammonium hydrogen carbonate powder, ammonium bicarbonate soln or suspension.
PH adjusting agent be ammonia or ammonium hydroxide, concentration be 0.1 ~ 99.9wt%, preferably 15 ~ 32wt%, more preferable 15 ~ 28wt%。
PH adjusting agent be ammonium bicarbonate soln or suspension, it is preferable that pH adjusting agent be ammonium bicarbonate aqueous solution or The concentration of ammonium hydrogen carbonate aqueous suspension, the ammonium bicarbonate aqueous solution or ammonium hydrogen carbonate aqueous suspension is 0.1 ~ 99.9wt%；It is preferred that Ground, 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℃。
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.
Optionally, triethylamine and hydrochloride are extracted from remaining mother liquor using following two methods:
A kind of method is that piece alkali and/or sodium hydroxide solution is added in remaining mother liquor after recycling triethylamine hydrochloride, is adjusted PH value is warming up to >=85 DEG C, obtains triethylamine steam and the alkali liquor containing sodium chloride to 10 ~ 14；Using triethylamine steam system Standby triethylamine finished product；Solid sodium chloride is prepared using the alkali liquor containing sodium chloride.
Preferably, 85 ~ 110 DEG C are warming up to after adjusting pH value.
Gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains triethylamine finished product through dehydration.
Specific method using the alkali liquor preparation solid sodium chloride containing sodium chloride is: by the alkali liquor containing sodium chloride It is concentrated, precipitated sodium chloride, is separated by solid-liquid separation and obtains solid sodium chloride and remaining a small amount of liquid, remaining a small amount of liquid is carried out Burning or high temperature oxidation process.
The preferred sodium hydrate aqueous solution of sodium hydroxide solution, concentration be 0.1 ~ 99.9wt%, preferably 30 ~ 60wt%, it is more excellent Select 30 ~ 32wt%.
Alkali liquor containing sodium chloride is concentrated in 105 ~ 115 DEG C in atmospheric conditions, or at reduced pressure conditions, it is excellent It selects under vacuum condition, in 60 ~ 100 DEG C, preferably 85 ~ 100 DEG C are concentrated.
Gained solid sodium chloride is dissolved in water, ammonium hydrogen carbonate is added thereto, or is passed through ammonia and carbon dioxide or addition Ammonium hydroxide is passed through carbon dioxide, and solidliquid mixture obtained after reaction is separated by solid-liquid separation, sodium bicarbonate solid and chlorine are obtained Change aqueous ammonium, the reuse of gained sodium bicarbonate solid or sold as finished product, gained aqueous ammonium chloride solution is concentrated, is separated by solid-liquid separation After obtain chloride solid, can be used as finished product sale.
Another method be to recycling triethylamine hydrochloride after remaining mother liquor in be added calcium hydroxide, calcium hydroxide emulsion And/or calcium oxide, pH value is adjusted to 9 ~ 14, is warming up to >=85 DEG C, is obtained triethylamine steam and the alkali liquor containing calcium chloride；It adopts Triethylamine finished product is prepared with triethylamine steam；Calcium chloride solid is prepared using the alkali liquor containing calcium chloride.
The concentration of calcium hydroxide emulsion is 0.1 ~ 99.9wt%, preferably 10 ~ 25 wt %.
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.
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.
The mass concentration of calcium hydroxide emulsion is 0.1 ~ 99.9wt%, preferably 10 ~ 25 wt %.
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, calcium hydroxide, the calcium oxide in terms of calcium hydroxide or calcium hydroxide emulsion and triethylamine hydrochloride rub You are than being 1: 1.
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.
Gained triethylamine steam is obtained into aqueous triethylamine and water through condensation, obtains triethylamine finished product through dehydration.
Preferably, the molar ratio of ammonia or ammonium hydroxide and triethylamine hydrochloride handled in step (d) in terms of liquefied ammonia is 2 ∶1。
Obtained calcium hydroxide solid can reuse in the method, or as sale of finished goods.
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.
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.
Gained triethylamine steam is obtained into aqueous triethylamine and water through condensation, obtains triethylamine finished product through dehydration.
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.
Using being used to prepare gyphosate solution containing organic phosphorus salting liquid, when pH adjusting agent is to contain Na+Alkali when, It is resulting containing ammonium hydrogen carbonate is added in organic phosphorus salting liquid to step (b), or be passed through ammonia and carbon dioxide or ammonia is added Water is passed through carbon dioxide, obtains sodium bicarbonate solid and containing organic phosphorus ammonium salt mother liquor, it is female that gained contains organic phosphorus ammonium salt Liquid is for preparing gyphosate solution.
It is resulting containing being successively passed through ammonia and carbon dioxide in organic phosphorus salting liquid to step (b), or be added ammonium hydroxide, The amount for being passed through carbon dioxide, ammonia or ammonium hydroxide and carbon dioxide is subject to the ammonium hydrogen carbonate for generating corresponding amount.
Gained contains organic phosphorus ammonium salt mother liquor for preparing 30% or more gyphosate solution.
When pH adjusting agent is to contain K+Or NH4 +Alkali when, step (b) is resulting directly to be used containing organic phosphorus salting liquid In preparing gyphosate solution, 30% or more gyphosate solution is preferably prepared.
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: i.e. when used pH adjusting agent is to contain Na+Alkali when, obtain Na2HPO4；Work as pH value Regulator is to contain K+Alkali when, obtain K2HPO4；When pH adjusting agent is NH4 +Alkali when, obtain (NH4)2HPO4。
The purpose of the present invention can also be achieved:
A kind of recoverying and utilizing method 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；
(b) pH of the resulting glyphosate mother solution concentrate A of step (a) is adjusted to 5.0 ~ 7.5 using pH adjusting agent, stood extremely Solution is divided into 2 layers, and upper and lower level solution is separated, respectively obtain the solution containing triethylamine hydrochloride with it is molten containing organic phosphorus salt Liquid；The pH adjusting agent is to contain X+Alkali, wherein X+For Na+、K+Or NH4 +；
(c) triethylamine and hydrochloride are extracted directly from the resulting solution containing triethylamine hydrochloride of step (b)；
(d) the resulting triethylamine hydrochloride of step (a) is converted, obtains triethylamine；
(e) step (b) is resulting is used to prepare gyphosate solution or is used to prepare X containing organic phosphorus salting liquid2HPO4。
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.
Gained triethylamine steam is obtained into aqueous triethylamine and water through condensation, obtains triethylamine finished product through dehydration.
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.
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.
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.
Gained triethylamine steam is obtained into 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 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.
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.
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 methods of new comprehensive reutilization glyphosate mother solution, by carrying out glyphosate mother solution PH adjusting agent is added after concentration, solution is made to be divided into 2 layers, extracts triethylamine hydrochloride from glyphosate mother solution in batches, and right Triethylamine hydrochloride and upper layer, lower liquid are respectively processed, and not only realize the high efficiente callback of triethylamine, and the rate of recovery is up to 99.89%, but also available calcium hydroxide, ammonium chloride, gyphosate solution or phosphoric acid hydrogen disalt, sodium bicarbonate and calcium chloride Etc. a variety of valuable byproducts, gained byproduct can be applied in glyphosate mother solution removal process or be sold as finished product, It does not generate the waste liquid and solid waste that is difficult to be utilized, pollute environment during processing crucially more, has bright Aobvious economic benefit and environmental benefit solves the difficulty for hindering the glyphosate mother solution of glyphosate industry development not handle thoroughly Topic is truly realized the resource utilization processing of glyphosate mother solution, so that glyphosate enterprise is no longer because glyphosate can not be handled Mother liquor generates environmental issue and is forced the underproduction or halt production.
The gyphosate solution for using the method for the present invention 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 Containing organic phosphorus ammonium salt mother liquor gyphosate solution, the utilization rate of ammonium hydrogen carbonate on the one hand can be improved, reduce 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 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% 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 acid mother liquid 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 content for stating ammonium hydrogen carbonate, sodium bicarbonate, saleratus, sodium carbonate, potassium carbonate, calcium hydroxide and calcium oxide is 99%；It is described The concentration of 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 100 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, the pH value of 1378g liquid alkaline adjusting solution is added to 6.5, fixed temperature is extremely 25 DEG C, after standing 2h, solution is divided into 2 layers, separates 2 layers of solution up and down, obtains the solution that triethylamine hydrochloride is contained on the upper layer 1781g Contain organic phosphorus sodium salt solution with 1334g lower layer.
Solution containing triethylamine hydrochloride is concentrated in 100 DEG C in atmospheric conditions, steams 700g 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, the calcium hydroxide aqueous suspension of 1000g 33wt%, pH=9, heating are added thereto To 85 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716g triethylamine finished product through dehydration, female Liquid is cooled to 25 DEG C and obtains the aqueous solution of 1230g chloride containing calcium, and the alkali liquor containing calcium chloride is dense in 105 DEG C under normal pressure Contracting, the CALCIUM CHLORIDE DIHYDRATE solid of 1042g is obtained by filtration in gained solidliquid mixture, by 1042g CALCIUM CHLORIDE DIHYDRATE at 300 DEG C Drying obtains 787g anhydrous calcium chloride；Gained filtrate is subjected to burning or high temperature oxidation process.
To containing 415g ammonium hydrogen carbonate is added in organic phosphorus sodium salt solution, in 60 DEG C of reaction 2h, 25 DEG C are cooled to, is taken out Filter, obtains 521g sodium bicarbonate solid and 1210g contains organic phosphorus ammonium salt mother liquor.Gained, which contains organic phosphorus ammonium salt mother liquor, to be used In the gyphosate solution for preparing 30%, indices meet national standard.
Embodiment 2
Taking the obtained acid mother liquid of 5500g producing glyphosate by using glycine, pH=0.3 is warming up to 105 DEG C under condition of normal pressure, Triethylamine hydrochloride be precipitated is filtered when heating up concentration, and filtrate is back in mother liquor, 1500g water is steamed, obtains 2263g triethylamine hydrochloride and 1737g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.3.
Glyphosate mother solution concentrate is cooled to 25 DEG C, the pH value of 678g liquid alkaline adjusting solution is added to 5.0, is warming up to 35 DEG C, after standing 2h, solution is divided into 2 layers, separates 2 layers of solution up and down, obtain solution that triethylamine hydrochloride is contained on the upper layer 1081g and Organic phosphorus sodium salt solution is contained in 1334g lower layer.
Contain in the solution of triethylamine hydrochloride addition 223g calcium hydroxide to upper layer, adjust the pH to 9 of solution, under normal pressure 85 DEG C are warming up to, gained triethylamine steam obtains aqueous triethylamine and water through condensation, and aqueous triethylamine is obtained through dehydration 534.6g triethylamine finished product, also obtains the alkali liquor of 779g chloride containing calcium, by the alkali liquor containing calcium chloride under normal pressure in 105 DEG C concentration, the CALCIUM CHLORIDE DIHYDRATE solid of 778g is obtained by filtration in gained solidliquid mixture, by 778g CALCIUM CHLORIDE DIHYDRATE 300 DEG C drying obtains 587g anhydrous calcium chloride；Gained filtrate is subjected to burning or high temperature oxidation process.
1000g triethylamine hydrochloride is taken, 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 350g calcium hydroxide and 960g contain the aqueous solution of ammonium chloride, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride, 10g ammonium hydrogen carbonate is added into the aqueous solution containing ammonium chloride to be separated by solid-liquid separation after reaction, it is solid to obtain 12g calcium carbonate Body, and the 105 DEG C of aqueous solutions of concentration containing ammonium chloride under normal pressure obtain 377g purity and are 98.5% ammonium chloride, and recycle ammonia Obtain 15725g ammonium hydroxide.Gained filtrate is subjected to burning or high temperature oxidation process.
To containing 415g ammonium hydrogen carbonate is added in organic phosphorus sodium salt solution, in 60 DEG C of reaction 2h, 25 DEG C are cooled to, is taken out Filter, obtains 521g sodium bicarbonate solid and 1210g contains organic phosphorus ammonium salt mother liquor.Gained, which contains organic phosphorus ammonium salt mother liquor, to be used In the gyphosate solution for preparing 30%, indices meet national standard.
Embodiment 3
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.2 is warming up to 130 in atmospheric conditions DEG C, triethylamine hydrochloride be precipitated is filtered when heating up concentration, and filtrate is back in mother liquor, steams 1500g water, obtain 2263g triethylamine hydrochloride and 1737g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.2.
Glyphosate mother solution concentrate is cooled to 25 DEG C, the pH value of 700g liquid alkaline adjusting solution is added to 5.5, is warming up to 50 DEG C, after standing 2h, solution is divided into 2 layers, separates 2 layers of solution up and down, obtain solution that triethylamine hydrochloride is contained on the upper layer 1103g and Organic phosphorus sodium salt solution is contained in 1334g lower layer.
Solution containing triethylamine hydrochloride is concentrated in 105 DEG C under normal pressure, steams 322g 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, 730g water and 450g calcium hydroxide are added thereto, pH=14 heat 105 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 1380g chloride containing calcium and calcium hydroxide, and 180g calcium hydroxide and 1200g filtrate is obtained by filtration, and will contain There is the alkali liquor of calcium chloride to be concentrated under reduced pressure in 100 DEG C, two chloride hydrates of 1042g are obtained by filtration in gained solidliquid mixture 1042g CALCIUM CHLORIDE DIHYDRATE is obtained 787g anhydrous calcium chloride in 300 DEG C of drying by calcium solid；By gained filtrate carry out burn or High temperature oxidation process.
Organic phosphorus sodium salt solution is contained into lower layer and obtains 950g disodium hydrogen phosphate through high-temperature oxydation.
Embodiment 4
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.4 is warming up to 50 at reduced pressure conditions DEG C, triethylamine hydrochloride be precipitated is filtered when heating up concentration, and filtrate is back in mother liquor, steams 1500g water, obtain 2263g triethylamine hydrochloride and 1737g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.4.
Glyphosate mother solution concentrate is cooled to 25 DEG C, the pH value of 800g liquid alkaline adjusting solution is added to 7.5, is warming up to 70 DEG C, after standing 2h, solution is divided into 2 layers, separates 2 layers of solution up and down, obtain solution that triethylamine hydrochloride is contained on the upper layer 1203g and Organic phosphorus sodium salt solution is contained in 1334g lower layer.
Contain addition 250g calcium hydroxide in the solution of triethylamine hydrochloride to upper layer, adjusts the pH to 11 of solution, normal pressure Under be warming up to 105 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, and aqueous triethylamine is obtained through dehydration 534.6g triethylamine finished product, also obtains the alkali liquor of 918g chloride containing calcium, and 27g calcium hydroxide and 891g filtrate is obtained by filtration, will Alkali liquor containing calcium chloride is concentrated in 110 DEG C under normal pressure, and the two hydration chlorine of 778g are obtained by filtration in gained solidliquid mixture Change calcium solid, 778g CALCIUM CHLORIDE DIHYDRATE is obtained into 587g anhydrous calcium chloride in 300 DEG C of drying；By gained filtrate carry out burn or High temperature oxidation process.
1000g triethylamine hydrochloride is taken, 2100g water and 5950g calcium hydroxide are added thereto, pH=14 are anti-in 110 DEG C It answers, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716.3g triethylamine product, mother liquor through dehydration After being cooled to 25 DEG C, centrifuge separation obtains the aqueous solution of 5412g calcium hydroxide and 2921g chloride containing calcium, calcium hydroxide is in three second Reuse in the conversion processing of amine hydrochlorate, and at 105 DEG C be concentrated chloride containing calcium aqueous solution, gained solidliquid mixture is through filtering The CALCIUM CHLORIDE DIHYDRATE solid of 1042g is obtained, 1042g CALCIUM CHLORIDE DIHYDRATE is obtained into 787g anhydrous calcium chloride in 300 DEG C of drying； Gained filtrate is subjected to burning or high temperature oxidation process.
Organic phosphorus sodium salt solution is contained into lower layer and obtains 947g disodium hydrogen phosphate through high-temperature oxydation.
Embodiment 5
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.5 is warming up to 80 DEG C, side under reduced pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.5.
Glyphosate mother solution concentrate is cooled to 25 DEG C, the pH to 7.0 that 778g potassium liquid alkaline adjusts solution is added, is warming up to 90 DEG C, after standing 2h, solution is divided into 2 layers, separates 2 layers of solution up and down, obtain solution that triethylamine hydrochloride is contained on the upper layer 1081g and Organic phosphorus potassium salt soln is contained in 1434g lower layer.
Solution containing triethylamine hydrochloride is concentrated in 130 DEG C under normal pressure, steams 300g 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, 334g calcium oxide and 1476g water, 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.
Organic phosphorus potassium salt soln is contained into lower layer and obtains 1170g dipotassium hydrogen phosphate through high-temperature oxydation.
Embodiment 6
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.5 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=0.5.
Glyphosate mother solution concentrate is cooled to 25 DEG C, the pH value of 770g potassium liquid alkaline adjusting solution is added to 6.7, is warming up to 100 DEG C, after standing 2h, solution is divided into 2 layers, separates 2 layers of solution up and down, obtains the upper layer 1073g and contain the molten of triethylamine hydrochloride Organic phosphorus potassium salt soln is contained in liquid and 1434g lower layer.
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 938g chloride containing calcium and calcium hydroxide, filtrated stock obtain 200g calcium hydroxide and Alkali liquor containing calcium chloride is concentrated in 115 DEG C 738g mother liquor under normal pressure, and gained solidliquid mixture is through being obtained by filtration 778g CALCIUM CHLORIDE DIHYDRATE solid, 778g CALCIUM CHLORIDE DIHYDRATE is obtained into 587g anhydrous calcium chloride in 300 DEG C of drying；By gained filtrate Carry out burning or high temperature oxidation process.
1000g triethylamine hydrochloride is taken, 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 at 115 DEG C of normal pressure be concentrated chloride containing calcium aqueous solution, gained solidliquid mixture pass through Filter obtains the CALCIUM CHLORIDE DIHYDRATE solid of 1042g, and 1042g CALCIUM CHLORIDE DIHYDRATE is obtained the anhydrous chlorination of 787g in 300 DEG C of drying Calcium；Gained filtrate is subjected to burning or high temperature oxidation process.
Organic phosphorus potassium salt soln is contained into lower layer and obtains 1170g dipotassium hydrogen phosphate through high-temperature oxydation.
Embodiment 7
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, is highly acid, is warming up to 120 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, the pH value of 1580.5g potassium liquid alkaline adjusting solution is added to 6.8, rises To 100 DEG C, after standing 2h, solution is divided into 2 layers, separates 2 layers of solution up and down, obtains the upper layer 1881g and contain triethylamine hydrochloride Organic phosphorus potassium salt soln is contained in solution and 1434g lower layer.
Solution containing triethylamine hydrochloride is concentrated in 130 DEG C under reduced pressure, steams 945g 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, 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 sylvite mother liquor and meets national standard for preparing 30% gyphosate solution, indices.
Embodiment 8
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.6 is warming up to 100 DEG C, side under reduced pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.6.
Glyphosate mother solution concentrate is cooled to 25 DEG C, the pH value of 770g potassium liquid alkaline adjusting solution is added to 7, is warming up to 80 DEG C, after standing 2h, solution is divided into 2 layers, separates 2 layers of solution up and down, obtain solution that triethylamine hydrochloride is contained on the upper layer 1070g and Organic phosphorus potassium salt soln is contained in 1434g lower layer.
Contain to upper layer and 150g calcium oxide and 250g water be added in the solution of triethylamine hydrochloride, adjusts the pH to 9 of solution, 85 DEG C of heating, gained triethylamine steam obtain aqueous triethylamine and water through condensation, and aqueous triethylamine is obtained through dehydration 534.6g triethylamine finished product also obtains the alkali liquor that 932g contains calcium chloride, in 60 under the alkali liquor containing calcium chloride is depressurized DEG C concentration, 778g CALCIUM CHLORIDE DIHYDRATE solid is obtained by filtration in gained solidliquid mixture, by 778g CALCIUM CHLORIDE DIHYDRATE at 300 DEG C Drying obtains 587g anhydrous calcium chloride；Gained filtrate is subjected to burning or high temperature oxidation process.
1000g triethylamine hydrochloride is taken, 4083g water and 3967g calcium oxide 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 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 at 115 DEG C be concentrated chloride containing calcium aqueous solution, gained solidliquid mixture is through filtering To the CALCIUM CHLORIDE DIHYDRATE solid of 1042g, 1042g CALCIUM CHLORIDE DIHYDRATE is obtained into 787g anhydrous calcium chloride in 300 DEG C of drying；It will Gained filtrate carries out burning or high temperature oxidation process.
Gained contains organic phosphorus sylvite mother liquor and meets national standard for preparing 30% gyphosate solution, indices.
Embodiment 9
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.7 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=0.7.
Glyphosate mother solution concentrate is cooled to 25 DEG C, the pH value of 768g ammonium liquid alkaline adjusting solution is added to 7, is warming up to 80 DEG C, after standing 2h, solution is divided into 2 layers, separates 2 layers of solution up and down, the upper layer 1384g is obtained after separation and contains triethylamine hydrochloride Solution and 1118g lower layer are containing organic phosphorus ammonium salt solution.
Solution containing triethylamine hydrochloride is concentrated in 90 DEG C under reduced pressure, steams 448g water, remaining 936g mother liquor, drop To 25 DEG C, the side Bian Jiangwen filters temperature, and obtained filtrate returns, obtains 642g triethylamine hydrochloride and 294g contains triethylamine salt on a small quantity The mother liquor of hydrochlorate；27g calcium oxide solid is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjusts the pH to 12 of solution, rises For temperature to 109 DEG C, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 63g triethylamine finished product through dehydration, Also obtain the alkali liquor of 13g water and 245g chloride containing calcium；Filtering solution obtains 8g calcium hydroxide solid and 237g solution, by gained The alkali liquor of chloride containing calcium is concentrated in 80 DEG C under reduced pressure, and is separated by solid-liquid separation, and gained solidliquid mixture is through being obtained by filtration 67g CALCIUM CHLORIDE DIHYDRATE solid, 67g CALCIUM CHLORIDE DIHYDRATE is obtained into 50g anhydrous calcium chloride in 300 DEG C of drying；By gained filtrate into Row burns or high temperature oxidation process.
1000g triethylamine hydrochloride is taken, 710g water and 350g calcium hydroxide, pH=11 are added thereto, are heated to 85 DEG C, Gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 716g triethylamine finished product, mother liquor cooling through dehydration The aqueous solution of 1260g chloride containing calcium and calcium hydroxide is obtained to 25 DEG C, 60g calcium hydroxide and 1200g filtrate is obtained by filtration, will be contained There is the alkali liquor of calcium chloride to be concentrated under reduced pressure in 80 DEG C, two chloride hydrates of 1042g are obtained by filtration in gained solidliquid mixture 1042g CALCIUM CHLORIDE DIHYDRATE is obtained 787g anhydrous calcium chloride in 300 DEG C of drying by calcium solid；By gained filtrate carry out burn or High temperature oxidation process.
Gained contains organic phosphorus ammonium salt mother liquor and meets national standard for preparing 30% gyphosate solution, indices.
Embodiment 10
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.7 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=0.7.
Glyphosate mother solution concentrate is cooled to 25 DEG C, the pH value of 768g ammonium liquid alkaline adjusting solution is added to 6.9, is warming up to 90 DEG C, after standing 2h, solution is divided into 2 layers, separates 2 layers of solution up and down, the upper layer 1384g is obtained after separation and contains triethylamine hydrochloride Solution and 1118g lower layer containing organic phosphorus ammonium salt 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 1290g chloride containing calcium and calcium hydroxide, filtrated stock obtains 100g The alkali liquor containing calcium chloride is concentrated in 85 DEG C under reduced pressure for calcium hydroxide and 1190g mother liquor, and gained solidliquid mixture passes through 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.
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 contains organic phosphorus ammonium salt mother liquor and meets national standard for preparing 30% gyphosate solution, indices.
Embodiment 11
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.8 is warming up to 125 DEG C, side under normal pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.8.
Glyphosate mother solution concentrate is cooled to 25 DEG C, the pH value of 768g ammonium liquid alkaline adjusting solution is added to 7, is warming up to 100 DEG C, after standing 2h, solution is divided into 2 layers, separates 2 layers of solution up and down, the upper layer 1384g is obtained after separation and contains triethylamine hydrochloric acid The solution of salt and 1118g lower layer are containing organic phosphorus ammonium salt solution.
Solution containing triethylamine hydrochloride is concentrated in 50 DEG C under reduced pressure, steams 448g 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, 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 100 DEG C of aqueous solutions of concentration containing ammonium chloride, gained are solid under normal pressure 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 contains organic phosphorus ammonium salt mother liquor 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=0.9 is warming up to 125 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, the pH value of 764g ammonium liquid alkaline adjusting solution is added to 6.7, is warming up to 100 DEG C, after standing 2h, solution is divided into 2 layers, separates 2 layers of solution up and down, the upper layer 1380g is obtained after separation and contains triethylamine hydrochloric acid The solution of salt and 1118g lower layer are containing organic phosphorus ammonium salt solution.
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 1385g chloride containing calcium and calcium hydroxide, filtrated stock obtains 190g Calcium hydroxide and 1195g mother liquor the alkali liquor containing calcium chloride are concentrated in 100 DEG C under reduced pressure, gained solidliquid mixture warp The CALCIUM CHLORIDE DIHYDRATE solid of 778g is obtained by filtration, 778g CALCIUM CHLORIDE DIHYDRATE is obtained into the anhydrous chlorination of 587g in 300 DEG C of drying Calcium；Gained filtrate is subjected to burning or high temperature oxidation process.
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, in the aqueous solution of Xiang Hanyou ammonium chloride plus Enter 10g ammonium hydrogen carbonate, after reaction, be separated by solid-liquid separation, obtains 12g calcium carbonate solid, and be concentrated and contain the water-soluble of ammonium chloride Liquid, gained solidliquid mixture is through being obtained by filtration the ammonium chloride of 376g.Recycling ammonia obtains 11400g ammonium hydroxide.Gained filtrate is burnt Burning or high temperature oxidation process.
Gained contains organic phosphorus ammonium salt mother liquor high-temperature oxydation and obtains 873g diammonium hydrogen phosphate.
Embodiment 13
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.9 is warming up to 60 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, 300g water is added, gained 2034.8g mother liquor is added into 500g carbon Sour hydrogen ammonium, is neutralized to pH=6.8, obtains 2255g mother liquor, is heated to 80 DEG C, and after standing 2h, solution is divided into 2 layers up and down, after separation Solution that triethylamine hydrochloride is contained on the upper layer 1137g and 1118g lower layer are obtained containing organic phosphorus ammonium salt solution.
Solution containing triethylamine hydrochloride is concentrated in 100 DEG C under normal pressure, steams 182g 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 into filtrate for solid, and ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, residual filtrate repeats Sodium chloride is added in previous reaction into residual filtrate again, ammonium chloride is precipitated.
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 110 DEG C of aqueous solutions of concentration containing ammonium chloride, gained are solid under normal pressure 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.
Gained contains organic phosphorus ammonium salt mother liquor 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=1 is warming up to 130 DEG C, Bian Sheng under normal pressure Triethylamine hydrochloride be precipitated is filtered on temperature concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g Triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=1.
Glyphosate mother solution concentrate is cooled to 25 DEG C, 300g water is added, gained 2034.8g mother liquor is added into 500g carbon Sour hydrogen ammonium, is neutralized to pH=6.9, obtains 2255g mother liquor, is heated to 65 DEG C, and after standing 2h, solution is divided into 2 layers up and down, after separation Solution and 1118g lower layer of the upper layer 1137g containing triethylamine hydrochloride are obtained containing organic phosphorus ammonium salt solution.
230g piece alkali is added into the solution containing triethylamine hydrochloride, 300g water is added, adjusts the pH to 10 of solution, rises For temperature to 85 DEG C, gained triethylamine steam obtains triethylamine aqueous solution through condensation, obtains 535.3g triethylamine through dehydration, must Contain the alkali liquor of sodium chloride to 60g water and 1028g；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 obtains To 440g sodium bicarbonate solid, sodium chloride is added into filtrate, ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, remains Remaining filtrate repeats previous reaction.
1000g triethylamine hydrochloride is taken, 696g water and 334g calcium oxide are added thereto, is passed through 2410g ammonia, ammonia is let out Dew recycling is 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, in the aqueous solution of Xiang Hanyou ammonium chloride plus Enter 10g ammonium hydrogen carbonate, after reaction, be separated by solid-liquid separation, obtain 12g calcium carbonate solid, and 115 DEG C of concentrations contain under normal pressure The aqueous solution of ammonium chloride, gained solidliquid mixture is through being obtained by filtration the ammonium chloride of 376g.Recycling ammonia obtains 11400g ammonium hydroxide.By institute It obtains filtrate and carries out burning or high temperature oxidation process.
Gained contains organic phosphorus ammonium salt mother liquor high-temperature oxydation and obtains 836g diammonium hydrogen phosphate.
Embodiment 15
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.1 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=0.1.
Glyphosate mother solution concentrate is cooled to 25 DEG C, 300g water is added, gained 2034.8g mother liquor is added into 500g carbon Sour hydrogen ammonium, is neutralized to pH=6.5, obtains 2255g mother liquor, is heated to 45 DEG C, and after standing 2h, solution is divided into 2 layers up and down, after separation Solution that triethylamine hydrochloride is contained on the upper layer 1137g and 1118g lower layer are obtained containing organic phosphorus ammonium salt solution.
Solution containing triethylamine hydrochloride is concentrated in 123 DEG C under normal pressure, steams 182g 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, into filtrate Sodium chloride 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, 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 10g ammonium hydrogen carbonate is added in the aqueous solution of Xiang Hanyou ammonium chloride for solution containing ammonium chloride, after reaction, through being separated by solid-liquid separation, 12g calcium carbonate solid is obtained, and the 60 DEG C of aqueous solutions of concentration containing ammonium chloride under reduced pressure, obtaining 376g purity is 98.5% Ammonium chloride.Gained filtrate is subjected to burning or high temperature oxidation process.
Gained contain organic phosphorus ammonium salt mother liquor for prepare 30% gyphosate solution, product qualification.
Embodiment 16
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=1.1 are warming up to 112 DEG C, side under normal pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=1.1.
Glyphosate mother solution concentrate is cooled to 25 DEG C, 300g water is added, gained 2034.8g mother liquor is added into 500g carbon Sour hydrogen ammonium, is neutralized to pH=7, obtains 2255g mother liquor, is heated to 77 DEG C, and after standing 2h, solution is divided into 2 layers up and down, after separation The solution for containing triethylamine hydrochloride to the upper layer 1137g and 1118g lower layer are containing organic phosphorus ammonium salt solution.
265g piece alkali is added into the solution containing triethylamine hydrochloride, 300g water is added, adjusts the pH to 13 of solution, rises For temperature to 110 DEG C, gained triethylamine steam obtains triethylamine aqueous solution through condensation, obtains 535.3g triethylamine 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 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 obtains To 440g sodium bicarbonate solid, sodium chloride is added into filtrate, ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, remains Remaining filtrate repeats previous reaction.
1000g triethylamine hydrochloride is taken, 310g water and 600g calcium hydroxide are added thereto, pH=14 are reacted in 120 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 240g calcium hydroxide and 944g chloride containing calcium, calcium hydroxide is in triethylamine salt Reuse in the conversion processing of hydrochlorate, and the solution after reaction is concentrated, 707g CALCIUM CHLORIDE DIHYDRATE is obtained, dries, obtains at 300 DEG C To 534g anhydrous calcium chloride.
Gained contain organic phosphorus ammonium salt mother liquor for prepare 30% gyphosate solution, product qualification.
Embodiment 17
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=1.3 are warming up to 70 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=1.3.
Glyphosate mother solution concentrate is cooled to 25 DEG C, 300g water is added, gained 2034.8g mother liquor is added into 531g carbon Sour hydrogen sodium, is neutralized to pH=7, obtains 2286g mother liquor, is heated to 82 DEG C, and after standing 2h, solution is divided into 2 layers up and down, after separation The solution and 1218g lower layer for containing triethylamine hydrochloride to the upper layer 1068g contain organic phosphorus sodium salt solution.
Solution containing triethylamine hydrochloride is concentrated in 130 DEG C under normal pressure, steams 132g 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 into filtrate for solid, and ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, 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 in the aqueous solution of Xiang Hanyou ammonium chloride and is separated by solid-liquid separation, is obtained after reaction To 12g calcium carbonate solid, and the 90 DEG C of aqueous solutions of concentration containing ammonium chloride under reduced pressure, obtain the chlorine that 376g purity is 98.5% Change ammonium.Recycling ammonia obtains ammonium hydroxide 5000g.Gained filtrate is subjected to burning or high temperature oxidation process.
Gained contains organic phosphorus sodium salt mother liquor high-temperature oxydation and obtains 950g disodium hydrogen phosphate.
Embodiment 18
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=1.4 are warming up to 103 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=1.4.
Glyphosate mother solution concentrate is cooled to 25 DEG C, the sodium bicarbonate aqueous suspension of 831g63.9% is added, is neutralized to pH =7,2286g mother liquor is obtained, is heated to 88 DEG C, after standing 2h, solution is divided into 2 layers up and down, and the upper layer 1068g is obtained after separation and is contained Organic phosphorus sodium salt solution is contained in the solution of triethylamine hydrochloride and 1218g lower layer.
300g piece alkali is added into the solution containing triethylamine hydrochloride, 100g water is added, adjusts the pH to 14 of solution, rises For temperature to 105 DEG C, gained triethylamine steam obtains triethylamine aqueous solution through condensation, obtains 535.3g triethylamine through dehydration, also Obtain the alkali liquor that 60g water and 841g contain sodium chloride；Alkali liquor by gained containing sodium chloride is under vacuum conditions in 80 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 obtains To 440g sodium bicarbonate solid, sodium chloride is added into filtrate, ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, remains Remaining filtrate repeats previous reaction.
1000g triethylamine hydrochloride is taken, the calcium hydroxide aqueous suspension of 900g 44.44wt% is added thereto, and is passed through 100g ammonia, pH=14 are reacted in 105 DEG C, and gained triethylamine steam obtains aqueous triethylamine and water through condensation, through dehydration 716.3g triethylamine product is obtained, after mother liquor is cooled to 25 DEG C, is passed through 141g ammonia thereto, ammonia leakage is recycled into ammonium hydroxide, After reacting 1h, centrifuge separation obtains the aqueous solution that 450g calcium hydroxide and 740g contain ammonium chloride, calcium hydroxide is in triethylamine salt Reuse in the conversion processing of hydrochlorate 10g ammonium hydrogen carbonate is added in the aqueous solution of Xiang Hanyou ammonium chloride, after reaction, through solid-liquid Separation, obtains 12g calcium carbonate solid, and the solution after reaction is concentrated, and obtains 370g purity and is 98.5% ammonium chloride, and recycles Ammonia obtains 730g ammonium hydroxide.
Gained contains organic phosphorus sodium salt mother liquor high-temperature oxydation and obtains 950g disodium hydrogen phosphate.
Embodiment 19
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=1.5 are 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=1.5.
Glyphosate mother solution concentrate is cooled to 25 DEG C, 300g water is added, gained 2034.8g mother liquor is added into 530g carbon Sour hydrogen sodium, is neutralized to pH=7, obtains 2286g mother liquor, is heated to 91 DEG C, and after standing 2h, solution is divided into 2 layers up and down, after separation The solution and 1218g lower layer for containing triethylamine hydrochloride to the upper layer 1068g contain organic phosphorus sodium salt solution.
Solution containing triethylamine hydrochloride is concentrated in 130 DEG C under reduced pressure, steams 132g 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 liquid alkaline is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjusts the pH to 10 of solution, is warming up to 85 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 74g water and 255g；Alkali liquor by gained containing sodium chloride is concentrated in 60 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 18g ammonia, then be passed through 50g carbon dioxide, be warming up to 60 DEG C, react 2h, filtering obtains 80g sodium bicarbonate solid, to filtrate Middle addition sodium chloride is precipitated ammonium chloride, ammonium chloride and residual filtrate is obtained by filtration, residual filtrate repeats previous 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 Calcium oxide and 910g contain the aqueous solution of ammonium chloride, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride, Xiang Hanyou 10g ammonium hydrogen carbonate is added in the aqueous solution of ammonium chloride to be separated by solid-liquid separation after reaction, obtains 12g calcium carbonate solid, and Lower aqueous solution of 100 DEG C of concentrations containing ammonium chloride is depressurized, 377g purity is obtained and is 98.5% ammonium chloride, and recycle ammonia and obtain 11400g ammonium hydroxide.Gained filtrate is subjected to burning or high temperature oxidation process.
To containing 415g ammonium hydrogen carbonate is added in organic phosphorus sodium salt solution, in 60 DEG C of reaction 2h, 25 DEG C are cooled to, is taken out Filter, obtains 521g sodium bicarbonate solid and 1100g contains organic phosphorus ammonium salt mother liquor, and gained, which contains organic phosphorus ammonium salt mother liquor, to be used In preparing 30% gyphosate solution, product is qualified.
Embodiment 20
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.4 is warming up to 116 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, 300g water is added by gained 2034.8g mother liquor and adds 531g Sodium bicarbonate is neutralized to pH=6.8, obtains 2286g mother liquor, is heated to 92 DEG C, and after standing 2h, solution is divided into 2 layers up and down, separation Solution that triethylamine hydrochloride is contained on the upper layer 1068g is obtained afterwards and organic phosphorus sodium salt solution is contained in 1218g lower layer.
Contain addition 680g 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 tri- second of 534.6g through dehydration Amine finished product also obtains the alkali liquor that 1200g contains sodium chloride, and the alkali liquor containing sodium chloride is concentrated in 105 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 into filtrate for solid, and ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, residual filtrate repeats 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 Calcium and 2506g contain the aqueous solution of ammonium chloride, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride, Xiang Hanyou chlorination 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 Lower solution of 100 DEG C of concentrations containing ammonium chloride obtains 370g purity and is 98.5% ammonium chloride, and recycles ammonia and obtain 2100g ammonia Water.Gained filtrate is subjected to burning or high temperature oxidation process.
To containing 415g ammonium hydrogen carbonate is added in organic phosphorus sodium salt solution, in 60 DEG C of reaction 2h, 25 DEG C are cooled to, is taken out Filter, obtains 521g sodium bicarbonate solid and 1100g contains organic phosphorus ammonium salt mother liquor, and gained, which contains organic phosphorus ammonium salt mother liquor, to be used In preparing 30% gyphosate solution, product is qualified.
Embodiment 21
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=1.8 are warming up to 60 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=1.8.
Glyphosate mother solution concentrate is cooled to 25 DEG C, the sodium carbonate suspension of 735g 45.58% is added, is neutralized to pH =6.9,2330g mother liquor is obtained, is heated to 70 DEG C, after standing 2h, solution is divided into 2 layers up and down, and the upper layer 1112g is obtained after separation and is contained The solution and 1218g lower layer for having triethylamine hydrochloride contain organic phosphorus sodium salt solution.
Solution containing triethylamine hydrochloride is concentrated in 93 DEG C under reduced pressure, steams 176g 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 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 Entering 80g ammonium hydrogen carbonate, be warming up to 60 DEG C, reacts 2h, filtering obtains 80g sodium bicarbonate solid, sodium chloride is added into filtrate, Ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, residual filtrate repeats previous reaction.
1000g triethylamine hydrochloride is taken, 500g water and 400g calcium hydroxide are added thereto, and be passed through 1773g13.6%'s Ammonium hydroxide, pH=14 are reacted in 105 DEG C, and gained triethylamine steam obtains aqueous triethylamine and water through condensation, are obtained through dehydration 716.3g triethylamine product, after mother liquor is cooled to 25 DEG C, centrifuge separation obtains 450g calcium hydroxide and 2500g contains ammonium chloride Aqueous solution, 10g is added in the aqueous solution of Xiang Hanyou ammonium chloride in calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride Ammonium hydrogen carbonate is separated by solid-liquid separation after reaction, obtains 12g calcium carbonate solid, and 115 DEG C of concentrations contain chlorination under normal pressure The solution of ammonium obtains 370g purity and is 98.5% ammonium chloride, and recycles ammonia and obtain 2120g ammonium hydroxide.Gained filtrate is burned Or high temperature oxidation process.
Gained contains organic phosphorus sodium salt mother liquor high-temperature oxydation and obtains 950g disodium hydrogen phosphate.
Embodiment 22
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.8 is warming up to 50 DEG C, side under reduced pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.8.
Glyphosate mother solution concentrate is cooled to 25 DEG C, the sodium carbonate suspension of 735g45.58% is added, be neutralized to pH= 7,2330g mother liquor is obtained, is heated to 60 DEG C, after standing 2h, solution is divided into 2 layers up and down, and the upper layer 1112g is obtained after separation and contains three Organic phosphorus sodium salt solution is contained in the solution of ethylamine hydrochloride and 1218g lower layer.
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 1300g 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 into filtrate for solid, and ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, residual filtrate repeats Previous reaction.
1000g triethylamine hydrochloride is taken, 500g water and 400g calcium hydroxide are added thereto, and be passed through 1773g13.6%'s Ammonium hydroxide, pH=14 are reacted in 105 DEG C, and gained triethylamine steam obtains aqueous triethylamine and water through condensation, are obtained through dehydration 716.3g triethylamine product, after mother liquor is cooled to 25 DEG C, centrifuge separation obtains 450g calcium hydroxide and 2500g contains ammonium chloride Aqueous solution, 10g is added in the aqueous solution of Xiang Hanyou ammonium chloride in calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride Ammonium hydrogen carbonate is separated by solid-liquid separation after reaction, obtains 12g calcium carbonate solid, and 115 DEG C of concentrations contain chlorination under normal pressure The solution of ammonium obtains 370g purity and is 98.5% ammonium chloride, and recycles ammonia and obtain 2120g ammonium hydroxide.Gained filtrate is burned Or high temperature oxidation process.
Gained contains organic phosphorus sodium salt mother liquor high-temperature oxydation and obtains 950g disodium hydrogen phosphate.
Embodiment 23
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.9 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=0.9.
Glyphosate mother solution concentrate is cooled to 25 DEG C, the sodium carbonate suspension of 735g45.58% is added, be neutralized to pH= 6.8,2330g mother liquor is obtained, is heated to 88 DEG C, after standing 2h, solution is divided into 2 layers up and down, and the upper layer 1112g is obtained after separation and is contained Organic phosphorus sodium salt solution is contained in the solution of triethylamine hydrochloride and 1218g lower layer.
Solution containing triethylamine hydrochloride is concentrated in 50 DEG C under reduced pressure, steams 176g 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 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, also obtains 89g water and 276g contain the alkali liquor of sodium chloride；Alkali liquor by gained containing sodium chloride is concentrated in 100 DEG C under reduced pressure, and It is separated by solid-liquid separation, obtains solid sodium chloride 52g, gained filtrate is subjected to burning or high temperature oxidation process.52g sodium chloride is molten 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 bicarbonate Sodium solid, is added sodium chloride into filtrate, and ammonium chloride is precipitated, and is obtained by filtration ammonium chloride and residual filtrate, residual filtrate repeat into Row previous reaction.
1000g triethylamine hydrochloride is taken, 500g water and 600g 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 to 641g ammonia after 25 DEG C, is passed through thereto, and ammonia leakage recycling is at ammonium hydroxide, and after reacting 1h, centrifuge separation obtains 650g hydrogen Calcium oxide and 740g contain the aqueous solution of ammonium chloride, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride, Xiang Hanyou 10g ammonium hydrogen carbonate is added in the aqueous solution of ammonium chloride to be separated by solid-liquid separation after reaction, obtains 12g calcium carbonate solid, and dense Solution after contracting reaction obtains 370g purity and is 98.5% ammonium chloride, and recycles ammonia and obtain 2730g ammonium hydroxide.
To containing 415g ammonium hydrogen carbonate is added in organic phosphorus sodium salt solution, in 60 DEG C of reaction 2h, 25 DEG C are cooled to, is taken out Filter, obtains 521g sodium bicarbonate solid and 1100g contains organic phosphorus ammonium salt mother liquor, and gained, which contains organic phosphorus ammonium salt mother liquor, to be used In preparing 30% gyphosate solution, product is qualified.
Embodiment 24
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, 400g water is added by gained 2134.8g mother liquor and adds 335g Sodium carbonate is neutralized to pH=7, obtains 2330g mother liquor, is heated to 78 DEG C, and after standing 2h, solution is divided into 2 layers up and down, after separation The solution and 1218g lower layer for containing triethylamine hydrochloride to the upper layer 1112g contain organic phosphorus sodium salt solution.
Contain addition 850g 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 tri- second of 534.6g through dehydration Amine finished product also obtains the alkali liquor that 1400g contains sodium chloride, and the alkali liquor containing sodium chloride is concentrated in 115 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 into filtrate for solid, and ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, residual filtrate repeats Previous reaction.
1000g triethylamine hydrochloride is taken, 500g water and 400g calcium hydroxide are added thereto, and be passed through 1773g13.6%'s Ammonium hydroxide, pH=14 are reacted in 105 DEG C, and gained triethylamine steam obtains aqueous triethylamine and water through condensation, are obtained through dehydration 716.3g triethylamine product, after mother liquor is cooled to 25 DEG C, centrifuge separation obtains 450g calcium hydroxide and 2500g contains ammonium chloride Aqueous solution, 10g is added in the aqueous solution of Xiang Hanyou ammonium chloride in calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride Ammonium hydrogen carbonate is separated by solid-liquid separation after reaction, obtains 12g calcium carbonate solid, and 115 DEG C of concentrations contain chlorination under normal pressure The solution of ammonium obtains 370g purity and is 98.5% ammonium chloride, and recycles ammonia and obtain 2120g ammonium hydroxide.Gained filtrate is burned Or high temperature oxidation process.
To containing 415g ammonium hydrogen carbonate is added in organic phosphorus sodium salt solution, in 60 DEG C of reaction 2h, 25 DEG C are cooled to, is taken out Filter, obtains 521g sodium bicarbonate solid and 1100g contains organic phosphorus ammonium salt mother liquor, and gained, which contains organic phosphorus ammonium salt mother liquor, to be used In preparing 30% gyphosate solution, product is qualified.
Embodiment 25
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.2 is warming up to 106 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, the potash water suspension of 955g 46.6% is added, be neutralized to pH= 6.5,2547g mother liquor is obtained, is heated to 25 DEG C, after standing 2h, solution is divided into 2 layers up and down, and the upper layer 1129g is obtained after separation and is contained Organic phosphorus potassium salt soln is contained in the solution of triethylamine hydrochloride and 1418g lower layer.
Solution containing triethylamine hydrochloride is concentrated in 116 DEG C under normal pressure, steams 193g 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, Also obtain the alkali liquor of 90g water and 160g chloride containing calcium；Alkali liquor by gained containing sodium chloride is dense in 110 DEG C under normal pressure Contracting, and be separated by solid-liquid separation, the CALCIUM CHLORIDE DIHYDRATE solid of 77g is obtained by filtration in gained solidliquid mixture, and 77g bis- is hydrated chlorine Change calcium and 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, the calcium hydroxide aqueous suspension of 1000g 50%, pH=14, 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 the ammonium hydroxide of 1773g13.6% thereto, and after reacting 1h, centrifuge separation obtains 550g hydrogen-oxygen Change the aqueous solution that calcium and 2506g contain ammonium chloride, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride, Xiang Hanyou 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 subtracting The 100 DEG C of solution of concentration containing ammonium chloride are depressed, 370g purity is obtained and is 98.5% ammonium chloride, and recycle ammonia and obtain 2100g ammonia Water.Gained filtrate is subjected to burning or high temperature oxidation process.
Gained contains organic phosphorus sylvite mother liquor high-temperature oxydation and obtains 1170g dipotassium hydrogen phosphate.
Embodiment 26
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.5 is warming up to 67 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, 510g water is added, by gained 2244.8g mother liquor, then plus 445g carbon Sour potassium, is neutralized to pH=6.8, obtains 2547g mother liquor, is heated to 48 DEG C, and after standing 2h, solution is divided into 2 layers up and down, after separation The solution and 1418g lower layer for containing triethylamine hydrochloride to the upper layer 1129g contain organic phosphorus potassium salt soln.
Contain addition 850g liquid alkaline in the solution of triethylamine hydrochloride to upper layer, adjusts the pH to 14 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 1300g contains sodium chloride, and the alkali liquor containing sodium chloride is concentrated in 95 DEG C under reduced 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 into filtrate for solid, and ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, residual filtrate repeats Previous reaction.
1000g triethylamine hydrochloride is taken, 500g water and 400g 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 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 Calcium hydroxide and 740g contain the aqueous solution of ammonium chloride, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride, Xiang Han There is addition 10g ammonium hydrogen carbonate in the aqueous solution of ammonium chloride to be separated by solid-liquid separation after reaction, obtains 12g calcium carbonate solid, and Solution after concentration reaction obtains 370g purity and is 98.5% ammonium chloride, and recycles ammonia and obtain 11561g ammonium hydroxide.
Gained contains organic phosphorus sylvite mother liquor high-temperature oxydation and obtains 1170g dipotassium hydrogen phosphate.
Embodiment 27
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.3 is warming up to 80 DEG C, side under reduced pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.3.
Glyphosate mother solution concentrate is cooled to 25 DEG C, 510g water is added, by gained 2244.8g mother liquor, then plus 445g carbon Sour potassium, is neutralized to pH=7, obtains 2547g mother liquor, is heated to 62 DEG C, and after standing 2h, solution is divided into 2 layers up and down, obtains after separation 1129g contains on upper layer the solution of triethylamine hydrochloride and organic phosphorus potassium salt soln is contained in 1418g lower layer.
Solution containing triethylamine hydrochloride is concentrated in 123 DEG C under normal pressure, steams 190g 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；Add 130g liquid alkaline into the mother liquor on a small quantity containing triethylamine hydrochloride, adjusts the pH to 14 of solution, be 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 276g；Alkali liquor by gained containing sodium chloride is concentrated in 110 DEG C under normal 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, 80g ammonium hydrogen carbonate is added, is warming up to 60 DEG C, reacts 2h, filtering obtains 80g sodium bicarbonate solid, chlorination is added into filtrate Sodium is precipitated ammonium chloride, ammonium chloride and residual filtrate is obtained by filtration, residual filtrate repeats 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 Calcium and 2506g contain the aqueous solution of ammonium chloride, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride, Xiang Hanyou chlorination 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 Lower solution of 100 DEG C of concentrations containing ammonium chloride obtains 370g purity and is 98.5% ammonium chloride, and recycles ammonia and obtain 2100g ammonia Water.Gained filtrate is subjected to burning or high temperature oxidation process.
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=1.7 are warming up to 104 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=1.7.
Glyphosate mother solution concentrate is cooled to 25 DEG C, 46.60% potash water suspension of 955g is added, be neutralized to pH= 7,2547g mother liquor is obtained, is heated to 68 DEG C, after standing 2h, solution is divided into 2 layers up and down, and the upper layer 1129g is obtained after separation and contains three Organic phosphorus potassium salt soln is contained in the solution of ethylamine hydrochloride and 1418g lower layer.
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 1300g contains sodium chloride, and the alkali liquor containing sodium chloride is concentrated in 85 DEG C under reduced 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 into filtrate for solid, and ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, residual filtrate repeats Previous reaction.
1000g triethylamine hydrochloride is taken, 500g water and 400g 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 to 1241g 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 Calcium hydroxide and 740g contain the aqueous solution of ammonium chloride, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride, Xiang Han There is addition 10g ammonium hydrogen carbonate in the aqueous solution of ammonium chloride to be separated by solid-liquid separation after reaction, obtains 12g calcium carbonate solid, and Solution after concentration reaction obtains 370g purity and is 98.5% ammonium chloride, and recycles ammonia and obtain 2730g ammonium hydroxide.
Gained contain organic phosphorus sylvite mother liquor for prepare 30% gyphosate solution, product qualification.
Embodiment 29
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.6 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=0.6.
Glyphosate mother solution concentrate is cooled to 25 DEG C, the saleratus aqueous suspension of 1076g 60.04% is added, is neutralized To pH=6.9,2547g mother liquor is obtained, is heated to 80 DEG C, after standing 2h, solution is divided into 2 layers up and down, obtains on 1129g after separation Organic phosphorus potassium salt soln is contained in solution of the layer containing triethylamine hydrochloride and 1418g lower layer.
Solution containing triethylamine hydrochloride is concentrated in 116 DEG C under normal pressure, steams 193g 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 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 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 dense in 110 DEG C under normal pressure Contracting, and be separated by solid-liquid separation, the CALCIUM CHLORIDE DIHYDRATE solid of 82g is obtained by filtration in gained solidliquid mixture, and 82g bis- is hydrated chlorine Change calcium and obtains 62g anhydrous calcium chloride in 300 DEG C of drying；Gained filtrate is subjected to burning disposal.
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 Calcium and 2506g contain the aqueous solution of ammonium chloride, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride, Xiang Hanyou chlorination 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 Lower solution of 100 DEG C of concentrations containing ammonium chloride obtains 370g purity and is 98.5% ammonium chloride, and recycles ammonia and obtain 2100g ammonia Water.Gained filtrate is subjected to burning or high temperature oxidation process.
Gained contains organic phosphorus sylvite mother liquor high-temperature oxydation and obtains 1170g dipotassium hydrogen phosphate.
Embodiment 30
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.8 is warming up to 76 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, 430g water is added, by gained 2164.8g mother liquor, then plus 646g carbon Potassium hydrogen phthalate is neutralized to pH=6.9, obtains 2547g mother liquor, is heated to 71 DEG C, and after standing 2h, solution is divided into 2 layers up and down, after separation It obtains solution that triethylamine hydrochloride is contained on the upper layer 1129g and organic phosphorus potassium salt soln is contained in 1418g lower layer.
Contain addition 680g liquid alkaline in the solution of triethylamine hydrochloride to upper layer, adjusts the pH to 10 of solution, be warming up to 109 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 1200g 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 into filtrate for solid, and ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, residual filtrate repeats Previous reaction.
1000g triethylamine hydrochloride is taken, 2500g water and 5960g calcium hydroxide are added thereto, is reacted in 105 DEG C, pH= 14, 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, it is passed through 241g ammonia thereto, ammonia leakage recycling is at ammonium hydroxide, and after reacting 1h, centrifuge separation is obtained 6000g calcium hydroxide and 2900g contain the aqueous solution of ammonium chloride, and calcium hydroxide returns in the conversion processing of triethylamine hydrochloride With addition 10g ammonium hydrogen carbonate is separated by solid-liquid separation after reaction in the aqueous solution of Xiang Hanyou ammonium chloride, obtains 12g calcium carbonate 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.By institute It obtains filtrate and carries out burning or high temperature oxidation process.
Gained contains organic phosphorus sylvite mother liquor high-temperature oxydation and obtains 1170g dipotassium hydrogen phosphate.
Embodiment 31
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.4 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=0.4.
Glyphosate mother solution concentrate is cooled to 25 DEG C, 430g water is added, by gained 2164.8g mother liquor, then plus 646g carbon Potassium hydrogen phthalate is neutralized to pH=7.0, obtains 2547g mother liquor, is heated to 74 DEG C, and after standing 2h, solution is divided into 2 layers up and down, after separation It obtains solution that triethylamine hydrochloride is contained on the upper layer 1129g and organic phosphorus potassium salt soln is contained in 1418g lower layer.
Solution containing triethylamine hydrochloride is concentrated in 120 DEG C under normal pressure, steams 193g 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；36g solid sodium hydroxide is added into the mother liquor on a small quantity containing triethylamine hydrochloride, adjust the pH of solution to 13,108 DEG C are warming up to, gained triethylamine steam obtains aqueous triethylamine and water through condensation, obtains 63g triethylamine through dehydration Finished product also obtains the alkali liquor that 10g water and 251g 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, 80g ammonium hydrogen carbonate is added, is warming up to 60 DEG C, reacts 2h, filtering obtains 80g sodium bicarbonate solid, into filtrate Sodium chloride is added, ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, residual filtrate repeats previous reaction.
1000g triethylamine hydrochloride is taken, 500g water and 2980g calcium hydroxide are added thereto, is reacted in 105 DEG C, pH= 14, 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, it is passed through 241g ammonia thereto, ammonia leakage recycling is at ammonium hydroxide, and after reacting 1h, centrifuge separation is obtained 3200g calcium hydroxide and 800g contain the aqueous solution of ammonium chloride, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride, 10g ammonium hydrogen carbonate is added into the aqueous solution containing ammonium chloride to be separated by solid-liquid separation after reaction, it is solid to obtain 12g calcium carbonate Body, 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.
Gained contain organic phosphorus sylvite mother liquor for prepare 30% gyphosate solution, product qualification.
Embodiment 32
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, pH=0.1 is warming up to 87 DEG C, side under reduced pressure Triethylamine hydrochloride be precipitated is filtered on heating concentration side, and filtrate is back in mother liquor, steams 1500g water, obtains 2265.2g triethylamine hydrochloride and 1734.8g glyphosate mother solution concentrate, glyphosate mother solution concentrate pH=0.1.
Glyphosate mother solution concentrate is cooled to 25 DEG C, 430g water is added, by gained 2164.8g mother liquor, then plus 646g carbon Potassium hydrogen phthalate is neutralized to pH=6.5, obtains 2547g mother liquor, is heated to 73 DEG C, and after standing 2h, solution is divided into 2 layers up and down, after separation It obtains solution that triethylamine hydrochloride is contained on the upper layer 1129g and organic phosphorus potassium salt soln is contained in 1418g lower layer.
265g piece alkali is added into the solution containing triethylamine hydrochloride, water 264g is added, adjusts the pH to 13 of solution, rises For temperature to 110 DEG C, gained triethylamine steam obtains triethylamine aqueous solution through condensation, obtains 535.3g triethylamine through dehydration, also Obtain the alkali liquor that 60g water and 1050g contain sodium chloride；Alkali liquor by gained containing sodium chloride is under vacuum conditions in 60 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 obtains To 440g sodium bicarbonate solid, sodium chloride is added into filtrate, ammonium chloride is precipitated, ammonium chloride and residual filtrate is obtained by filtration, remains Remaining filtrate repeats previous 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 Calcium oxide and 905g contain the aqueous solution of ammonium chloride, calcium hydroxide reuse in the conversion processing of triethylamine hydrochloride, Xiang Hanyou 10g ammonium hydrogen carbonate is added in the aqueous solution of ammonium chloride to be separated by solid-liquid separation after reaction, obtains 12g calcium carbonate solid, and Lower aqueous solution of 100 DEG C of concentrations containing ammonium chloride is depressurized, 377g purity is obtained and is 98.5% ammonium chloride, and recycle ammonia and obtain 11400g ammonium hydroxide.Gained filtrate is subjected to burning or high temperature oxidation process.
Gained contain organic phosphorus sylvite mother liquor for prepare 30% gyphosate solution, product qualification.
Comparative example 1
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, 800g liquid alkaline is added in pH=0.1 thereto, adjusts The pH value of solution is saved to 6.5 ~ 7, then addition 500g triethylamine (excess) thereto, is stirred, solution is not stratified, it is difficult to carry out subsequent Processing.
Comparative example 2
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, 700g liquid alkaline is added in pH=0.1 thereto, adjusts The pH value of solution is saved to 5.5 ~ 6.5, then addition 600g triethylamine (excess) thereto, is stirred, solution is divided into three layers, and top layer is Triethylamine is directly separated, then separate again in lower 2 layers of solution, obtain solution that triethylamine hydrochloride is contained in the middle layer 6300g and Organic phosphorus sodium salt solution is contained in 300g lower layer.
3102g 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 triethylamine through dehydration Finished product also obtains the alkali liquor that 7157g contains sodium chloride, and 300 ~ 600g chlorination is precipitated in the alkali liquor concentration containing sodium chloride Sodium, residue 3000 ~ 6000g mother liquor, the partial mother liquid decontamination water treatment plant are 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 Organic phosphorus sodium salt solution is contained in the solution of triethylamine hydrochloride and 450g lower layer.
3000g 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 triethylamine through dehydration Finished product also obtains the alkali liquor that 6091g contains sodium chloride, and 300 ~ 600g chlorination is precipitated in the alkali liquor concentration containing sodium chloride Sodium, residue 3000 ~ 5000g mother liquor, the partial mother liquid decontamination water treatment plant are 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 5
The obtained acid mother liquid of 5500g producing glyphosate by using glycine is taken, 3800g liquid alkaline is added in pH=0.1 thereto, The pH value of solution is adjusted to 12, is stirred, is stood, 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
Take the obtained alkaline mother liquor of 6500g producing glyphosate by using glycine (resulting after addition liquid alkaline in oxytropism mother liquor Solution), 1200g calcium hydroxide is added in pH=10.5 thereto, adjusts the pH value of solution to 12, stirring generates phosphorus cream, will Obtained solidliquid mixture is centrifuged, and 2200g solid phosphorus cream and 5500g mother liquor are obtained, and obtained phosphorus cream can not carry out 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 (14)

1. a kind of recoverying and utilizing method 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:
(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；
(b) pH value of the resulting glyphosate mother solution concentrate A of step (a) is adjusted to 5.0 ~ 7.5 using pH adjusting agent, stood Be divided into 2 layers to solution, by upper layer, lower layer's solution separate, respectively obtain the solution containing triethylamine hydrochloride with contain it is organic phosphorus Salting liquid；The pH adjusting agent is to contain X+Alkali, 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；
(e) step (b) is resulting is used to prepare gyphosate solution or is used to prepare X containing organic phosphorus salting liquid2HPO4。
2. a kind of recoverying and utilizing method 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:
(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；
(b) pH of the resulting glyphosate mother solution concentrate A of step (a) is adjusted to 5.0 ~ 7.5 using pH adjusting agent, stood extremely Solution is divided into 2 layers, and upper layer, lower layer's solution are separated, and respectively obtains the solution containing triethylamine hydrochloride and containing organic phosphorus Salting liquid；The pH adjusting agent is to contain X+Alkali, wherein X+For Na+、K+Or NH4 +；
(c) triethylamine and hydrochloride are extracted directly from the resulting solution containing triethylamine hydrochloride of step (b)；
(d) the resulting triethylamine hydrochloride of step (a) is converted, obtains triethylamine；
(e) step (b) is resulting is used to prepare gyphosate solution or is used to prepare X containing organic phosphorus salting liquid2HPO4。
3. the recoverying and utilizing method 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 recoverying and utilizing method 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.
5. the recoverying and utilizing 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；By after reaction solution or suspension be separated by solid-liquid separation, obtain calcium hydroxide solid and the solution containing calcium chloride； Solution containing calcium chloride is used to prepare calcium chloride.
6. the recoverying and utilizing method of glyphosate mother solution according to claim 1 or 2, which is characterized in that, will in step (d) Triethylamine hydrochloride is dissolved in water, thereto addition calcium hydroxide, calcium hydroxide emulsion and/or calcium oxide, adjusting pH value to 9 ~ 14, >=85 DEG C are warming up to, the solution or suspension after obtaining triethylamine steam and reaction；Three second are prepared using gained triethylamine steam Amine finished product；Calcium hydroxide and ammonium chloride are extracted from the solution or suspension after reaction.
7. the recoverying and utilizing 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, and calcium hydroxide, calcium hydroxide emulsion and/or calcium oxide are added thereto, and is passed through ammonia or adds Enter ammonium hydroxide, is warming up to >=85 DEG C, the solution or suspension after obtaining triethylamine steam and reaction；Using gained triethylamine steam system Standby triethylamine finished product；Calcium hydroxide, ammonium chloride and calcium carbonate are extracted from the solution or suspension after reaction.
8. the recoverying and utilizing method 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.
9. the recoverying and utilizing method of glyphosate mother solution according to claim 1, which is characterized in that in step (c), to remaining mother Calcium hydroxide, calcium hydroxide emulsion and/or calcium oxide are added in liquid, adjusts pH value to 9 ~ 14, is warming up to >=85 DEG C, obtains three second Amine steam and alkali liquor containing calcium chloride；Triethylamine finished product is prepared using triethylamine steam；It is female using the alkali containing calcium chloride Liquid prepares calcium chloride solid.
10. the recoverying and utilizing method 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.
11. the recoverying and utilizing method 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.
12. the recoverying and utilizing method of the glyphosate mother solution according to claim 8 or 11, which is characterized in that by gained chlorination Sodium solid is dissolved in water, and ammonium hydrogen carbonate is added thereto, or is passed through ammonia and carbon dioxide or ammonium hydroxide is added, is passed through carbon dioxide, Sodium bicarbonate solid and aqueous ammonium chloride solution are obtained through being separated by solid-liquid separation, gained aqueous ammonium chloride solution is used to prepare chloride solid.
13. the recoverying and utilizing method of glyphosate mother solution according to claim 1 or 2, which is characterized in that the pH value is adjusted Agent is to contain Na+Alkali when, it is resulting containing ammonium hydrogen carbonate is added in organic phosphorus salting liquid to step (b) in step (e), Or be passed through ammonia and carbon dioxide or ammonium hydroxide is added, is passed through carbon dioxide, obtain sodium bicarbonate solid and containing organic phosphorus ammonium Salt mother liquor, gained contain organic phosphorus ammonium salt mother liquor for preparing gyphosate solution.
14. the recoverying and utilizing method of glyphosate mother solution according to claim 1 or 2, which is characterized in that the pH value is adjusted Agent is to contain K+Or NH4 +Alkali when, step (b) is resulting to be directly used in preparation gyphosate solution containing organic phosphorus salting liquid.
CN201810379597.3A 2018-04-25 2018-04-25 The recoverying and utilizing method of glyphosate mother solution Pending CN110396047A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810379597.3A CN110396047A (en) 2018-04-25 2018-04-25 The recoverying and utilizing method of glyphosate mother solution

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810379597.3A CN110396047A (en) 2018-04-25 2018-04-25 The recoverying and utilizing method of glyphosate mother solution

Publications (1)

Publication Number Publication Date
CN110396047A true CN110396047A (en) 2019-11-01

Family

ID=68319503

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810379597.3A Pending CN110396047A (en) 2018-04-25 2018-04-25 The recoverying and utilizing method of glyphosate mother solution

Country Status (1)

Country Link
CN (1) CN110396047A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113072580A (en) * 2021-04-19 2021-07-06 浙江新安化工集团股份有限公司 Method for recovering glyphosate from glyphosate acid mother liquor by glycine method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101508700A (en) * 2008-09-08 2009-08-19 陈桢铭 Treatment process for glyphosate mother liquid
CN101570547A (en) * 2009-06-16 2009-11-04 吴伦飞 Method for processing glyphosate mother liquor
CN101838288A (en) * 2009-03-18 2010-09-22 湖州四方格林自动化技术有限公司 Processing method of glyphosate mother liquor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101508700A (en) * 2008-09-08 2009-08-19 陈桢铭 Treatment process for glyphosate mother liquid
CN101838288A (en) * 2009-03-18 2010-09-22 湖州四方格林自动化技术有限公司 Processing method of glyphosate mother liquor
CN101570547A (en) * 2009-06-16 2009-11-04 吴伦飞 Method for processing glyphosate mother liquor

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113072580A (en) * 2021-04-19 2021-07-06 浙江新安化工集团股份有限公司 Method for recovering glyphosate from glyphosate acid mother liquor by glycine method

Similar Documents

Publication Publication Date Title
CN109734061A (en) A kind of preparation method of double fluorine sulfimide lithiums
CN101605721A (en) The manufacture method of phosphorus pentafluoride and hexafluorophosphate
CN107720717A (en) A kind of preparation method of difluorophosphate
US6514474B1 (en) Method of purifying lithium hexafluorosphate
CN110393189A (en) The comprehensive processing technique of glyphosate mother solution
CN110396047A (en) The recoverying and utilizing method of glyphosate mother solution
JPS5851884B2 (en) Method for producing highly concentrated phosphoric acid containing gypsum hemihydrate with good filterability
CN106830021A (en) A kind of preparation technology of magnesium nitrate hexahydrate
CN109264683A (en) A kind of extraction and purification method of bis- (fluorine sulphonyl) imines
CN110182830A (en) A method of preparing high-purity fluorination reason
JP2021519738A (en) Manufacture of lithium hexafluorophosphate
CN103193271B (en) Method for producing high-quality sodium bichromate
CN110467167A (en) Precipitate the wet defluorination of phosphoric acid method that pre- defluorinate is coupled with stripping defluorinate
CN110396048A (en) The comprehensive recovering process of glyphosate mother solution
CN108383097B (en) A method of utilizing extraction Wet-process Phosphoric Acid Production water solubility ammonium polyphosphate
CA2259985A1 (en) Lipf6 production process
CN110393188A (en) The purification process technique of glyphosate mother solution
CN100567141C (en) A kind of preparation method of lithium hexafluoro phosphate
CN112457270A (en) Preparation method of dichloro pentachloromethyl thiazole
CN107500260A (en) A kind of method that iron oxide waste material using metal-working industry prepares battery-grade iron phosphate
CN110316747A (en) A method of synthetical recovery lithium and phosphorus from lithium phosphate
CN101070167A (en) Potassium nitrate preparing technology
CN109574893A (en) A kind of method of sodium thiocarbonate synthesis mercaptoethylamine hydrochloride
US4154800A (en) Process of producing phosphates and phosphoric acid
KR20160002573A (en) Method for manufacturing high purity lithium hydroxide and efficient method for recovery of lithium hydroxide from brine using the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20191101