CN105541909A - Method for reducing total phosphor of glyphosate mother liquor subjected to triethylamine recovery - Google Patents
Method for reducing total phosphor of glyphosate mother liquor subjected to triethylamine recovery Download PDFInfo
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- CN105541909A CN105541909A CN201510897007.2A CN201510897007A CN105541909A CN 105541909 A CN105541909 A CN 105541909A CN 201510897007 A CN201510897007 A CN 201510897007A CN 105541909 A CN105541909 A CN 105541909A
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- Prior art keywords
- glyphosate
- triethylamine
- mother solution
- mother liquor
- reclaimed
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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
The invention discloses a method for reducing total phosphor of a glyphosate mother liquor subjected to triethylamine recovery. The method comprises 1, adding a pH conditioning agent into a glyphosate mother liquor subjected to triethylamine recovery to adjust pH of the glyphosate mother liquor to 0-3 so that an acidified mother liquor is obtained, 2, adding a certain amount of calcium hydrate powder or a calcium hydrate emulsion into the acidified mother liquor obtained through the step 1, carrying out mixing to obtain a uniform mixed glyphosate mother liquor with pH of 10.5-12.3 and stirring the glyphosate mother liquor under normal pressure at a temperature of 20-95 DEG C for a reaction for 10min-3h, wherein the reaction system pH is kept in a range of 10.5-12.3 in the reaction, and 3, after the reaction, removing volatile odor substances in the produced solid-liquid mixture and carrying out solid-liquid separation. The method realizes high efficiency removal of total phosphor and recovery of a lot of phosphor resources.
Description
Technical field
The invention belongs to glyphosate mother solution process field, relate to a kind of method that total phosphorus in the glyphosate mother solution of triethylamine has been reclaimed in reduction.
Background technology
Glyphosate is a kind of efficient, low toxicity, wide spectrum steriland herbicide, is widely used in the agricultural planting such as soybean, corn.Glycine method (alkyl ester process) is a kind of main method of producing glyphosate, and a large amount of phosphoric acid aqueous mother liquor in the production of glycine method synthesizing glyphosate, can be produced, described acid mother liquid is added phosphorus content in the alkaline mother liquor after alkali collection triethylamine (abbreviation alkali liquor) still very high, total phosphorous is at 2000 ~ 23000mg/L.Owing to adding the phosphorous organophosphorus that is mainly in the alkaline mother liquor after alkali collection triethylamine, being difficult to remove, being thus introduced into the process of glyphosate waste water by being oxidized Wet Oxidation Process organophosphorus being converted into inorganic phosphorus.CN201210350157.8 discloses a kind of Catalytic wet oxidation pretreatment method of glyphosate production wastewater, first the method regulates waste water 8 < pH < 10, add polycomponent homogeneous catalyst again, take air as oxygenant, continuous catalysis wet oxidation reaction device is adopted to carry out oxidative degradation to Pollutants in Wastewater, temperature of reaction 210 ~ 230 DEG C, reaction pressure 2 ~ 4Mpa, reaction times 0.3 ~ 2h.Although adopt the method to transform the most of organophosphorus in glyphosate production wastewater in order to inorganic phosphorus, but do not reduce total phosphorus content contained in glyphosate production wastewater, due to " adopting continuous catalysis wet oxidation reaction device to carry out oxidative degradation to Pollutants in Wastewater; temperature of reaction 210 ~ 230 DEG C; reaction pressure 2 ~ 4Mpa ", thus facility investment and working cost are still higher.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of reduction to reclaim the method for total phosphorus in the glyphosate mother solution of triethylamine, to improve the clearance of phosphor contaminant and Simplified flowsheet and reduction working cost.
The glyphosate mother solution having reclaimed triethylamine of the present invention, refers to that the glyphosate alkaline mother liquor obtained after adding alkali collection triethylamine is maybe carried out the glyphosate alkaline mother liquor after catalytic air oxidation process by the glyphosate alkaline mother liquor that directly obtains after adding alkali collection triethylamine.
The method of total phosphorus in the glyphosate mother solution of triethylamine has been reclaimed in reduction of the present invention, and step is as follows:
(1) in the glyphosate mother solution reclaiming triethylamine, add pH adjusting agent, the pH value of described glyphosate mother solution is adjusted to 0 ~ 3, obtains acidified mother liquor;
(2) in step (1) gained acidified mother liquor, add calcium hydroxide powder or calcium hydroxide emulsion and mix, the add-on of calcium hydroxide powder or calcium hydroxide emulsion should make the pH value of glyphosate mother solution be 10.5 ~ 12.3, then by glyphosate mother solution under agitation in normal pressure, 20 ~ 95 DEG C reaction 10 minutes ~ 3 hours, maintain the pH value of reaction system in reaction process 10.5 ~ 12.3;
(3), after having reacted, solid-liquid mixture removing volatile malodor material reaction formed, then carry out solid-liquid separation, solid-liquid separation gained solid matter utilizes as reclamation of phosphorus resource, and gained liquid is collected treats further process.
The method of total phosphorus in the glyphosate mother solution of triethylamine has been reclaimed in reduction of the present invention, and in step (1), the temperature of glyphosate mother solution before adding pH adjusting agent having reclaimed triethylamine is 0 ~ 80 DEG C.
The method of total phosphorus in the glyphosate mother solution of triethylamine has been reclaimed in reduction of the present invention, in step (1), and the pH value of acidified mother liquor preferably 0 ~ 2.
The method of total phosphorus in the glyphosate mother solution of triethylamine has been reclaimed in reduction of the present invention, in step (3), the volatile malodor material of the solid-liquid mixture formed except dereaction by distillation or water vapor air lift desorb (pass into water vapor and carry out air lift desorb).
The method of total phosphorus in the glyphosate mother solution of triethylamine has been reclaimed in reduction of the present invention, and pH adjusting agent used in step (1) is the one in sulfuric acid, hydrochloric acid.
The method of total phosphorus in the glyphosate mother solution of triethylamine has been reclaimed in reduction of the present invention, and in calcium hydroxide emulsion, the mass concentration of calcium hydroxide is 10% ~ 25%.
The present invention has following beneficial effect:
1, the present invention is that the dephosphorization of the glyphosate mother solution having reclaimed triethylamine provides a kind of novel method, use the method for the invention, not only achieve the efficient removal of total phosphorus, a large amount of phosphor resource can also be reclaimed simultaneously, test shows (see embodiment part), and for the glyphosate alkaline mother liquor directly obtained after adding alkali collection triethylamine, total tp removal rate can reach 93%, for the glyphosate alkaline mother liquor carried out after catalytic air oxidation process, total tp removal rate can reach 99.6%.
2, because the method for the invention is in normal pressure, reaction at 20 ~ 95 DEG C, and do not need specific equipment, thus more energy-conservation, working cost is lower.
3, the method for the invention technique is simple, and easy handling controls, and facility investment is few, is thus convenient to promote, has high using value.
Embodiment
The method below by embodiment reduction of the present invention having been reclaimed to total phosphorus in the glyphosate mother solution of triethylamine is described further.
In following embodiment, glyphosate alkaline mother liquor (abbreviation glyphosate alkali mother liquor) total phosphorous directly obtained after adding alkali collection triethylamine is 18200mg/L (being mainly organophosphorus), and carrying out the glyphosate alkaline mother liquor after catalytic air oxidation process (being called for short oxidized glyphosate alkali liquor) total phosphorous is 15928mg/L (being mainly inorganic phosphorus).
In following embodiment, in solid-liquid separation gained liquid, GB11893-1989 mensuration is pressed in the detection of total phosphorus.
Embodiment 1
The processing step of the present embodiment is as follows:
(1) add in reaction vessel by the glyphosate alkali mother liquor 500mL of 0 DEG C, the pH value then adding hydrochloric acid adjustment glyphosate alkali mother liquor is 1, obtains acidified mother liquor;
(2) in step (1) gained acidified mother liquor, calcium hydroxide powder is added and by being uniformly mixed, calcium hydroxide powder or add-on the pH value of glyphosate mother solution should be made to be 10.5, then glyphosate mother solution is under agitation warming up to 95 DEG C of reactions 3 hours in normal pressure, maintains the pH value of reaction system in reaction process 10.5;
(3), after having reacted, solid-liquid mixture reaction formed is by distillation removing volatile malodor material, and then carry out solid-liquid separation, solid-liquid separation gained solid matter utilizes as reclamation of phosphorus resource, and gained liquid is collected treats further process.After testing, in gained liquid, total phosphorous is 1229mg/L, and total tp removal rate is 93.3%.
Comparative example 1
The processing step of this comparative example is as follows:
(1) the glyphosate alkali mother liquor 500mL of 0 DEG C is added in reaction vessel, then calcium hydroxide powder is added and by being uniformly mixed all, the add-on of calcium hydroxide powder should make the pH value of glyphosate mother solution be 10.5, then glyphosate mother solution is under agitation warming up to 95 DEG C of reactions 3 hours in normal pressure, maintains the pH value of reaction system in reaction process 10.5;
(2), after having reacted, solid-liquid mixture reaction formed, by distillation removing volatile malodor material, then carries out solid-liquid separation.After testing, in solid-liquid separation gained liquid, total phosphorous is 5529mg/L, and total tp removal rate is 69.6%.
Embodiment 1 and comparative example 1 show, the method for the invention can increase substantially the clearance of phosphor contaminant in glyphosate alkali mother liquor.
Embodiment 2
The processing step of the present embodiment is as follows:
(1) add in reaction vessel by the oxidized glyphosate alkali liquor 500mL of 25 DEG C, the pH value then adding hydrochloric acid adjustment glyphosate alkali mother liquor is 1, obtains acidified mother liquor;
(2) in step (1) gained acidified mother liquor, calcium hydroxide powder is added and by being uniformly mixed, the add-on of calcium hydroxide powder should make the pH value of glyphosate mother solution be 12.0, then glyphosate mother solution is under agitation warming up to 95 DEG C of reactions 2 hours in normal pressure, maintains the pH value of reaction system in reaction process 12.0;
(3) after having reacted, the solid-liquid mixture that reaction is formed is carried out water vapor air lift desorb removing volatile malodor material, then carry out solid-liquid separation, solid-liquid separation gained solid matter utilizes as reclamation of phosphorus resource, and gained liquid is collected treats further process.After testing, in gained liquid, total phosphorous is 69mg/L, total tp removal rate 99.6%.
Comparative example 2
The processing step of this comparative example is as follows:
(1) the oxidized glyphosate alkali liquor 500mL of 25 DEG C is added in reaction vessel, then calcium hydroxide powder is added and by being uniformly mixed all, the add-on of calcium hydroxide powder should make the pH value of glyphosate mother solution be 12.0, then glyphosate mother solution is under agitation warming up to 95 DEG C of reactions 2 hours in normal pressure, maintains the pH value of reaction system in reaction process 12.0;
(2), after having reacted, the solid-liquid mixture that reaction is formed is carried out water vapor air lift desorb removing volatile malodor material, then carry out solid-liquid separation.After testing, in solid-liquid separation gained liquid, total phosphorous is 4148mg/L, total tp removal rate 74.0%.
Embodiment 2 and comparative example 2 show, the method for the invention can increase substantially the clearance of phosphor contaminant in oxidized glyphosate alkali liquor.
Embodiment 3
The processing step of the present embodiment is as follows:
(1) add in reaction vessel by the oxidized glyphosate alkali liquor 500mL of 80 DEG C, the pH value then adding sulfuric acid adjustment glyphosate alkali mother liquor is 3, obtains acidified mother liquor;
(2) in step (1) gained acidified mother liquor, adding mass concentration being 10% calcium hydroxide emulsion and by being uniformly mixed, the add-on of calcium hydroxide emulsion should make the pH value of glyphosate mother solution be 10.5, then glyphosate mother solution is under agitation warming up to 95 DEG C of reactions 1 hour in normal pressure, maintains the pH value of reaction system in reaction process 10.5;
(3) after having reacted, the solid-liquid mixture that reaction is formed is carried out water vapor air lift desorb removing volatile malodor material, then carry out solid-liquid separation, solid-liquid separation gained solid matter utilizes as reclamation of phosphorus resource, and gained liquid is collected treats further process.After testing, total phosphorous 469mg/L in gained liquid, total tp removal rate 97.0%.
Embodiment 4
The processing step of the present embodiment is as follows:
(1) add in reaction vessel by the oxidized glyphosate alkali liquor 500mL of 10 DEG C, the pH value then adding hydrochloric acid adjustment glyphosate alkali mother liquor is 2, obtains acidified mother liquor;
(2) in step (1) gained acidified mother liquor, adding mass concentration being 25% calcium hydroxide emulsion and by being uniformly mixed, the add-on of calcium hydroxide emulsion should make the pH value of glyphosate mother solution be 12.3, then glyphosate mother solution is under agitation warming up to 60 DEG C of reactions 30 minutes in normal pressure, maintains the pH value of reaction system in reaction process 12.3;
(3) after having reacted, the solid-liquid mixture that reaction is formed is carried out water vapor air lift desorb removing volatile malodor material, then carry out solid-liquid separation, solid-liquid separation gained solid matter utilizes as reclamation of phosphorus resource, and gained liquid is collected treats further process.After testing, total phosphorous 173mg/L in gained liquid, total tp removal rate 98.9%.
Embodiment 5
The processing step of the present embodiment is as follows:
(1) add in reaction vessel by the oxidized glyphosate alkali liquor 500mL of 0 DEG C, the pH value then adding hydrochloric acid adjustment glyphosate alkali mother liquor is 0, obtains acidified mother liquor;
(2) in step (1) gained acidified mother liquor, adding mass concentration being 15% calcium hydroxide emulsion and by being uniformly mixed, the add-on of calcium hydroxide emulsion should make the pH value of glyphosate mother solution be 11.6, then glyphosate mother solution is under agitation warming up to 20 DEG C of reactions 10 minutes in normal pressure, maintains the pH value of reaction system in reaction process 11.6;
(3) after having reacted, the solid-liquid mixture that reaction is formed is carried out water vapor air lift desorb removing volatile malodor material, then carry out solid-liquid separation, solid-liquid separation gained solid matter utilizes as reclamation of phosphorus resource, and gained liquid is collected treats further process.After testing, total phosphorous 343mg/L in gained liquid, total tp removal rate 97.8%.
Equipment used of the present invention is conventional equipment, buys by market.
Claims (10)
1. reduce the method having reclaimed total phosphorus in the glyphosate mother solution of triethylamine, it is characterized in that step is as follows:
(1) in the glyphosate mother solution reclaiming triethylamine, pH adjusting agent is added, the pH value of described glyphosate mother solution is adjusted to 0 ~ 3, obtain acidified mother liquor, the described glyphosate mother solution having reclaimed triethylamine is that the glyphosate alkaline mother liquor obtained after adding alkali collection triethylamine is maybe carried out the glyphosate alkaline mother liquor after catalytic air oxidation process by the glyphosate alkaline mother liquor that directly obtains after adding alkali collection triethylamine;
(2) in step (1) gained acidified mother liquor, add calcium hydroxide powder or calcium hydroxide emulsion and mix, the add-on of calcium hydroxide powder or calcium hydroxide emulsion should make the pH value of glyphosate mother solution be 10.5 ~ 12.3, then by glyphosate mother solution under agitation in normal pressure, 20 ~ 95 DEG C reaction 10 minutes ~ 3 hours, maintain the pH value of reaction system in reaction process 10.5 ~ 12.3;
(3), after having reacted, solid-liquid mixture removing volatile malodor material reaction formed, then carry out solid-liquid separation, solid-liquid separation gained solid matter utilizes as reclamation of phosphorus resource, and gained liquid is collected treats further process.
2. reduce the method for total phosphorus in the glyphosate mother solution having reclaimed triethylamine according to claim 1, it is characterized in that in step (1), the temperature of glyphosate mother solution before adding pH adjusting agent having reclaimed triethylamine is 0 ~ 80 DEG C.
3. according to claim 1 or 2, reduce the method for total phosphorus in the glyphosate mother solution having reclaimed triethylamine, it is characterized in that in step (1), the pH value of acidified mother liquor is 0 ~ 2.
4. according to claim 1 or 2, reduce the method for total phosphorus in the glyphosate mother solution having reclaimed triethylamine, be characterised in that in step (3), the volatile malodor material of the solid-liquid mixture formed except dereaction by distillation or the desorb of water vapor air lift.
5. reduce the method for total phosphorus in the glyphosate mother solution having reclaimed triethylamine according to claim 3, be characterised in that in step (3), the volatile malodor material of the solid-liquid mixture formed except dereaction by distillation or the desorb of water vapor air lift.
6. according to claim 1 or 2, reduce the method for total phosphorus in the glyphosate mother solution having reclaimed triethylamine, it is characterized in that pH adjusting agent used in step (1) is the one in sulfuric acid, hydrochloric acid.
7. reduce the method for total phosphorus in the glyphosate mother solution having reclaimed triethylamine according to claim 3, it is characterized in that pH adjusting agent used in step (1) is the one in sulfuric acid, hydrochloric acid.
8. reduce the method for total phosphorus in the glyphosate mother solution having reclaimed triethylamine according to claim 4, it is characterized in that pH adjusting agent used in step (1) is the one in sulfuric acid, hydrochloric acid.
9. according to claim 1 or 2, reduce the method for total phosphorus in the glyphosate mother solution having reclaimed triethylamine, be characterised in that the mass concentration of calcium hydroxide in calcium hydroxide emulsion is 10% ~ 25%.
10. reduce the method for total phosphorus in the glyphosate mother solution having reclaimed triethylamine according to claim 3, be characterised in that the mass concentration of calcium hydroxide in calcium hydroxide 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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| 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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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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