CN105541909B - A kind of method for reducing total phosphorus in the glyphosate mother solution for having reclaimed triethylamine - Google Patents
A kind of method for reducing total phosphorus in the glyphosate mother solution for having reclaimed triethylamine Download PDFInfo
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- CN105541909B CN105541909B CN201510897007.2A CN201510897007A CN105541909B CN 105541909 B CN105541909 B CN 105541909B CN 201510897007 A CN201510897007 A CN 201510897007A CN 105541909 B CN105541909 B CN 105541909B
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- Prior art keywords
- triethylamine
- mother solution
- reclaimed
- glyphosate
- glyphosate mother
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
Abstract
A kind of method for reducing total phosphorus in the glyphosate mother solution for having reclaimed triethylamine, step are as follows：(1) pH adjusting agent is added in the glyphosate mother solution for reclaimed triethylamine, the pH value of the glyphosate mother solution is adjusted to 0~3, obtains acidified mother liquor；(2) calcium hydroxide powder or calcium hydroxide emulsion are added into acidified mother liquor obtained by step (1) and is well mixed, the addition of calcium hydroxide powder or calcium hydroxide emulsion should make the pH value of glyphosate mother solution be 10.5~12.3, then glyphosate mother solution is reacted 10 minutes~3 hours in normal pressure, 20~95 DEG C under agitation, the pH value of maintenance reaction system is 10.5~12.3 in course of reaction；(3) after the completion of reacting, the solid-liquid mixture for reacting formation is removed into volatile malodor material, then carries out separation of solid and liquid.Using the method for the invention, the efficient removal of total phosphorus is not only realized, while a large amount of phosphor resources can also be reclaimed.
Description
Technical field
The invention belongs to glyphosate mother solution process field, is related to a kind of reduce in the glyphosate mother solution for having reclaimed triethylamine always
The method of phosphorus.
Background technology
Glyphosate is a kind of efficient, low toxicity, wide spectrum steriland herbicide, is widely used in the agricultural plantings such as soybean, corn.
Glycine method (alkyl ester process) is a kind of main method for producing glyphosate, and the production of glycine method synthesizing glyphosate
In can produce substantial amounts of phosphorous acid mother liquid, the acid mother liquid is added to the alkaline mother liquor after alkali collection triethylamine, and (abbreviation alkali is female
Liquid) in phosphorus content it is still very high, total phosphorus content is in 2000~23000mg/L.Due to adding the alkaline mother liquor after alkali collection triethylamine
The phosphorous predominantly organophosphor of middle institute, it is difficult to remove, thus organophosphor is converted into the Wet Oxidation Process of Phos by aoxidizing
It has been introduced into the processing of glyphosate waste water.CN 201210350157.8 discloses a kind of glyphosate production wastewater catalytic wet oxygen
Change preprocess method, this method adjusts the ＜ pH ＜ 10 of waste water 8, adds multicomponent homogeneous catalyst first, using air as oxidation
Agent, using continuous catalysis wet oxidation reaction device to Pollutants in Wastewater carry out oxidative degradation, 210~230 DEG C of reaction temperature,
2~4Mpa of reaction pressure, 0.3~2h of reaction time.It is although using this method that the major part in glyphosate production wastewater is organic
Phosphorus is converted for Phos, but does not reduce total phosphorus content contained in glyphosate production wastewater, due to " using continuous catalysis wet type
Oxidation reaction apparatus to Pollutants in Wastewater carry out oxidative degradation, 210~230 DEG C, 2~4Mpa " of reaction pressure of reaction temperature, because
And equipment investment and operating cost are still higher.
The content of the invention
The glyphosate that triethylamine has been reclaimed it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of reduction is female
The method of total phosphorus in liquid, to improve the clearance of phosphor contaminant and simplify technique and reduction operating cost.
The glyphosate mother solution of the present invention for having reclaimed triethylamine, refer to plus alkali collection triethylamine after directly obtain it is careless sweet
Phosphine alkaline mother liquor will add the glyphosate alkaline mother liquor obtained after alkali collection triethylamine to carry out the grass after catalytic air oxidation processing
Sweet phosphine alkaline mother liquor.
The method of the present invention for reducing total phosphorus in the glyphosate mother solution for having reclaimed triethylamine, step are as follows：
(1) pH adjusting agent is added in the glyphosate mother solution for reclaimed triethylamine, the pH value of the glyphosate mother solution is adjusted
Whole is 0~3, obtains acidified mother liquor；
(2) calcium hydroxide powder or calcium hydroxide emulsion are added into acidified mother liquor obtained by step (1) and is well mixed, hydrogen
The addition of lime powder or calcium hydroxide emulsion should make the pH value of glyphosate mother solution be 10.5~12.3, then by glyphosate
Mother liquor reacts 10 minutes~3 hours in normal pressure, 20~95 DEG C under agitation, and the pH value of maintenance reaction system exists in course of reaction
10.5~12.3；
(3) after the completion of reacting, the solid-liquid mixture for reacting formation is removed into volatile malodor material, then carries out solid-liquid
Separation, solid matter is utilized as reclamation of phosphorus resource obtained by separation of solid and liquid, and gained liquid, which is collected, to be treated further to handle.
It is of the present invention to reduce the method for having reclaimed total phosphorus in the glyphosate mother solution of triethylamine, in step (1), reclaim three
Temperature of the glyphosate mother solution of ethamine before pH adjusting agent is added is 0~80 DEG C.
It is of the present invention to reduce the method for having reclaimed total phosphorus in the glyphosate mother solution of triethylamine, in step (1), acidified mother liquor
PH value preferably 0~2.
It is of the present invention to reduce the method for having reclaimed total phosphorus in the glyphosate mother solution of triethylamine, in step (3), pass through distillation
Or water vapour air lift desorption (being passed through the desorption of water vapour progress air lift) is except the volatility of the solid-liquid mixture of dereaction formation is smelly
Taste material.
It is of the present invention to reduce the method for having reclaimed total phosphorus in the glyphosate mother solution of triethylamine, pH used in step (1)
Conditioning agent is one kind in sulfuric acid, hydrochloric acid.
It is of the present invention to reduce the method for having reclaimed total phosphorus in the glyphosate mother solution of triethylamine, hydrogen-oxygen in calcium hydroxide emulsion
The mass concentration for changing calcium is 10%~25%.
The invention has the advantages that：
1st, the present invention provides a kind of new method to have reclaimed the dephosphorization of the glyphosate mother solution of triethylamine, uses institute of the present invention
Method is stated, not only realizes the efficient removal of total phosphorus, while a large amount of phosphor resources can also be reclaimed, experiment shows (see specific implementation
Mode part), for adding the glyphosate alkaline mother liquor directly obtained after alkali collection triethylamine, total tp removal rate is right up to 93%
Glyphosate alkaline mother liquor after catalytic air oxidation processing is carried out, total tp removal rate is up to 99.6%.
2nd, because the method for the invention is reacted at normal pressure, 20~95 DEG C, and special equipment is not required to, thus it is more energy efficient,
Operating cost is lower.
3rd, the method for the invention technique is simple, and easily operated control, equipment investment is few, thus is easy to promote, and has height
Application value.
Embodiment
The method of the present invention for reducing total phosphorus in the glyphosate mother solution for having reclaimed triethylamine is made below by embodiment
Further illustrate.
In following embodiments, add glyphosate alkaline mother liquor (the abbreviation glyphosate alkali mother directly obtained after alkali collection triethylamine
Liquid) total phosphorus content is 18200mg/L (predominantly organophosphor), the glyphosate alkaline mother liquor after progress catalytic air oxidation processing
(abbreviation oxidized glyphosate alkali liquor) total phosphorus content is 15928mg/L (predominantly Phos).
In following embodiments, the detection of total phosphorus is by GB 11893-1989 measure in liquid obtained by separation of solid and liquid.
Embodiment 1
The processing step of the present embodiment is as follows：
(1) 0 DEG C of glyphosate alkali mother liquor 500mL is added in reaction vessel, it is female then adds hydrochloric acid adjustment glyphosate alkali
The pH value of liquid is 1, obtains acidified mother liquor；
(2) calcium hydroxide powder is added into acidified mother liquor obtained by step (1) and is stirred by mixing, calcium hydroxide
Powder or addition should make glyphosate mother solution pH value be 10.5, then glyphosate mother solution is warming up in normal pressure under agitation
95 DEG C are reacted 3 hours, and the pH value of maintenance reaction system is 10.5 in course of reaction；
(3) after the completion of reacting, volatile malodor material is removed by distillation in the solid-liquid mixture for reacting formation, then
Separation of solid and liquid is carried out, solid matter is utilized as reclamation of phosphorus resource obtained by separation of solid and liquid, and gained liquid, which is collected, to be treated further to locate
Reason.After testing, total phosphorus content is 1229mg/L in gained liquid, and total tp removal rate is 93.3%.
Comparative example 1
The processing step of this comparative example is as follows：
(1) 0 DEG C of glyphosate alkali mother liquor 500mL is added in reaction vessel, then adds calcium hydroxide powder and pass through
It is stirred, the addition of calcium hydroxide powder should make the pH value of glyphosate mother solution be 10.5, and then glyphosate mother solution exists
95 DEG C are warming up under stirring in normal pressure to react 3 hours, the pH value of maintenance reaction system is 10.5 in course of reaction；
(2) after the completion of reacting, volatile malodor material is removed by distillation in the solid-liquid mixture for reacting formation, then
Carry out separation of solid and liquid.After testing, total phosphorus content is 5529mg/L in liquid obtained by separation of solid and liquid, and total tp removal rate is 69.6%.
Embodiment 1 and comparative example 1 show that the method for the invention can increase substantially phosphor contaminant in glyphosate alkali mother liquor
Clearance.
Embodiment 2
The processing step of the present embodiment is as follows：
(1) 25 DEG C of oxidized glyphosate alkali liquor 500mL is added in reaction vessel, then adds hydrochloric acid adjustment glyphosate
The pH value of alkali liquor is 1, obtains acidified mother liquor；
(2) calcium hydroxide powder is added into acidified mother liquor obtained by step (1) and is stirred by mixing, calcium hydroxide
The addition of powder should make the pH value of glyphosate mother solution be 12.0, and glyphosate mother solution then is warming up into 95 in normal pressure under agitation
DEG C reaction 2 hours, the pH value of maintenance reaction system is 12.0 in course of reaction；
(3) after the completion of reacting, it is smelly that the solid-liquid mixture progress water vapour air lift desorption for reacting formation is removed into volatility
Taste material, separation of solid and liquid is then carried out, solid matter is utilized as reclamation of phosphorus resource obtained by separation of solid and liquid, and gained liquid is collected
Treat further to handle.After testing, total phosphorus content is 69mg/L in gained liquid, total tp removal rate 99.6%.
Comparative example 2
The processing step of this comparative example is as follows：
(1) 25 DEG C of oxidized glyphosate alkali liquor 500mL is added in reaction vessel, then adds calcium hydroxide powder simultaneously
By being stirred, the addition of calcium hydroxide powder should make the pH value of glyphosate mother solution be 12.0, then that glyphosate is female
Liquid is warming up to 95 DEG C in normal pressure under agitation and reacted 2 hours, and the pH value of maintenance reaction system is 12.0 in course of reaction；
(2) after the completion of reacting, it is smelly that the solid-liquid mixture progress water vapour air lift desorption for reacting formation is removed into volatility
Taste material, then carry out separation of solid and liquid.After testing, total phosphorus content is 4148mg/L in liquid obtained by separation of solid and liquid, total phosphorus ligands
Rate 74.0%.
Embodiment 2 and comparative example 2 show that it is dirty that the method for the invention can increase substantially phosphorus in oxidized glyphosate alkali liquor
Contaminate the clearance of thing.
Embodiment 3
The processing step of the present embodiment is as follows：
(1) 80 DEG C of oxidized glyphosate alkali liquor 500mL is added in reaction vessel, then adds sulfuric acid adjustment glyphosate
The pH value of alkali liquor is 3, obtains acidified mother liquor；
(2) mass concentration is added into acidified mother liquor obtained by step (1) to be 10% calcium hydroxide emulsion and mix by stirring
Close uniformly, the addition of calcium hydroxide emulsion should make the pH value of glyphosate mother solution be 10.5, then stir glyphosate mother solution
Under in normal pressure be warming up to 95 DEG C react 1 hour, the pH value of maintenance reaction system is 10.5 in course of reaction；
(3) after the completion of reacting, it is smelly that the solid-liquid mixture progress water vapour air lift desorption for reacting formation is removed into volatility
Taste material, separation of solid and liquid is then carried out, solid matter is utilized as reclamation of phosphorus resource obtained by separation of solid and liquid, and gained liquid is collected
Treat further to handle.After testing, total phosphorus content 469mg/L in gained liquid, total tp removal rate 97.0%.
Embodiment 4
The processing step of the present embodiment is as follows：
(1) 10 DEG C of oxidized glyphosate alkali liquor 500mL is added in reaction vessel, then adds hydrochloric acid adjustment glyphosate
The pH value of alkali liquor is 2, obtains acidified mother liquor；
(2) mass concentration is added into acidified mother liquor obtained by step (1) to be 25% calcium hydroxide emulsion and mix by stirring
Close uniformly, the addition of calcium hydroxide emulsion should make the pH value of glyphosate mother solution be 12.3, then stir glyphosate mother solution
Under in normal pressure be warming up to 60 DEG C react 30 minutes, the pH value of maintenance reaction system is 12.3 in course of reaction；
(3) after the completion of reacting, it is smelly that the solid-liquid mixture progress water vapour air lift desorption for reacting formation is removed into volatility
Taste material, separation of solid and liquid is then carried out, solid matter is utilized as reclamation of phosphorus resource obtained by separation of solid and liquid, and gained liquid is collected
Treat further to handle.After testing, total phosphorus content 173mg/L in gained liquid, total tp removal rate 98.9%.
Embodiment 5
The processing step of the present embodiment is as follows：
(1) 0 DEG C of oxidized glyphosate alkali liquor 500mL is added in reaction vessel, then adds hydrochloric acid adjustment glyphosate
The pH value of alkali liquor is 0, obtains acidified mother liquor；
(2) mass concentration is added into acidified mother liquor obtained by step (1) to be 15% calcium hydroxide emulsion and mix by stirring
Close uniformly, the addition of calcium hydroxide emulsion should make the pH value of glyphosate mother solution be 11.6, then stir glyphosate mother solution
Under in normal pressure be warming up to 20 DEG C react 10 minutes, the pH value of maintenance reaction system is 11.6 in course of reaction；
(3) after the completion of reacting, it is smelly that the solid-liquid mixture progress water vapour air lift desorption for reacting formation is removed into volatility
Taste material, separation of solid and liquid is then carried out, solid matter is utilized as reclamation of phosphorus resource obtained by separation of solid and liquid, and gained liquid is collected
Treat further to handle.After testing, total phosphorus content 343mg/L in gained liquid, total tp removal rate 97.8%.
Device therefor of the present invention is conventional equipment, can be bought by market.
Claims (10)
- A kind of 1. method for reducing total phosphorus in the glyphosate mother solution for having reclaimed triethylamine, it is characterised in that step is as follows：(1) pH adjusting agent is added in the glyphosate mother solution for reclaimed triethylamine, the pH value of the glyphosate mother solution is adjusted to 0 ~3, obtain acidified mother liquor, the glyphosate mother solution for having reclaimed triethylamine for plus alkali collection triethylamine after directly obtain it is careless sweet Phosphine alkaline mother liquor will add the glyphosate alkaline mother liquor obtained after alkali collection triethylamine to carry out the grass after catalytic air oxidation processing Sweet phosphine alkaline mother liquor；(2) calcium hydroxide powder or calcium hydroxide emulsion are added into acidified mother liquor obtained by step (1) and is well mixed, hydroxide The addition of calcium powder or calcium hydroxide emulsion should make the pH value of glyphosate mother solution be 10.5~12.3, then by glyphosate mother solution Reacted 10 minutes~3 hours in normal pressure, 20~95 DEG C under agitation, in course of reaction the pH value of maintenance reaction system 10.5~ 12.3；(3) after the completion of reacting, the solid-liquid mixture for reacting formation is removed into volatile malodor material, then carries out solid-liquid point From solid matter is utilized as reclamation of phosphorus resource obtained by separation of solid and liquid, and gained liquid, which is collected, to be treated further to handle.
- 2. the method for total phosphorus in the glyphosate mother solution for reclaimed triethylamine is reduced according to claim 1, it is characterised in that step Suddenly in (1), temperature of the glyphosate mother solution of triethylamine before pH adjusting agent is added has been reclaimed as 0~80 DEG C.
- 3. the method according to claim 1 or claim 2 for reducing total phosphorus in the glyphosate mother solution for having reclaimed triethylamine, it is characterised in that In step (1), the pH value of acidified mother liquor is 0~2.
- 4. the method according to claim 1 or claim 2 for reducing total phosphorus in the glyphosate mother solution for having reclaimed triethylamine, is characterised by walking Suddenly in (3), the volatile malodor material of the solid-liquid mixture formed by distillation or the desorption of water vapour air lift except dereaction.
- 5. reducing the method for total phosphorus in the glyphosate mother solution for reclaimed triethylamine according to claim 3, step is characterised by (3) in, the volatile malodor material of the solid-liquid mixture formed by distillation or the desorption of water vapour air lift except dereaction.
- 6. the method according to claim 1 or claim 2 for reducing total phosphorus in the glyphosate mother solution for having reclaimed triethylamine, it is characterised in that PH adjusting agent used is one kind in sulfuric acid, hydrochloric acid in step (1).
- 7. the method for total phosphorus in the glyphosate mother solution for reclaimed triethylamine is reduced according to claim 3, it is characterised in that step Suddenly pH adjusting agent used in (1) is one kind in sulfuric acid, hydrochloric acid.
- 8. the method for total phosphorus in the glyphosate mother solution for reclaimed triethylamine is reduced according to claim 4, it is characterised in that step Suddenly pH adjusting agent used in (1) is one kind in sulfuric acid, hydrochloric acid.
- 9. the method according to claim 1 or claim 2 for reducing total phosphorus in the glyphosate mother solution for having reclaimed triethylamine, is characterised by hydrogen The mass concentration of calcium hydroxide is 10%~25% in calcium oxide emulsion.
- 10. reducing the method for total phosphorus in the glyphosate mother solution for reclaimed triethylamine according to claim 3, hydrogen-oxygen is characterised by The mass concentration for changing calcium hydroxide in calcium emulsion is 10%~25%.
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| CN201510897007.2A CN105541909B (en) | 2015-12-07 | 2015-12-07 | A kind of method for reducing total phosphorus in the glyphosate mother solution for having reclaimed triethylamine |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101659673A (en) * | 2009-09-24 | 2010-03-03 | 南京工业大学 | Processing technology for recovering and utilizing mother solution of glyphosate as resource |
| CN101985426A (en) * | 2010-09-06 | 2011-03-16 | 山东潍坊润丰化工有限公司 | Method for treating glyphosate mother solution |
| CN102874786A (en) * | 2012-10-12 | 2013-01-16 | 山东潍坊润丰化工有限公司 | Processing method of glyphosate mother liquor |
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- 2015-12-07 CN CN201510897007.2A patent/CN105541909B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101659673A (en) * | 2009-09-24 | 2010-03-03 | 南京工业大学 | Processing technology for recovering and utilizing mother solution of glyphosate as resource |
| CN101985426A (en) * | 2010-09-06 | 2011-03-16 | 山东潍坊润丰化工有限公司 | Method for treating glyphosate mother solution |
| CN102874786A (en) * | 2012-10-12 | 2013-01-16 | 山东潍坊润丰化工有限公司 | Processing method of glyphosate mother liquor |
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