CN108948075B - Comprehensive utilization method of glyphosate byproduct ammonia water and alkali - Google Patents
Comprehensive utilization method of glyphosate byproduct ammonia water and alkali Download PDFInfo
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- CN108948075B CN108948075B CN201810961051.9A CN201810961051A CN108948075B CN 108948075 B CN108948075 B CN 108948075B CN 201810961051 A CN201810961051 A CN 201810961051A CN 108948075 B CN108948075 B CN 108948075B
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- glyphosate
- mother liquor
- sodium carbonate
- hydrolysate
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- 239000005562 Glyphosate Substances 0.000 title claims abstract description 219
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 219
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 219
- 238000000034 method Methods 0.000 title claims abstract description 45
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 235000011114 ammonium hydroxide Nutrition 0.000 title claims abstract description 28
- 239000003513 alkali Substances 0.000 title claims abstract description 22
- 239000006227 byproduct Substances 0.000 title claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 144
- 239000012452 mother liquor Substances 0.000 claims abstract description 116
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 78
- 239000000203 mixture Substances 0.000 claims abstract description 59
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 58
- 239000000413 hydrolysate Substances 0.000 claims abstract description 42
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 33
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 28
- KKTCWAXMXADOBB-UHFFFAOYSA-N azanium;hydrogen carbonate;hydrate Chemical compound [NH4+].O.OC([O-])=O KKTCWAXMXADOBB-UHFFFAOYSA-N 0.000 claims abstract description 28
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 238000004064 recycling Methods 0.000 claims abstract description 14
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 14
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 100
- 239000007788 liquid Substances 0.000 claims description 55
- 238000002156 mixing Methods 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 31
- 159000000011 group IA salts Chemical class 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 12
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 7
- 125000005907 alkyl ester group Chemical group 0.000 claims description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 239000012141 concentrate Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 30
- 239000001569 carbon dioxide Substances 0.000 abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 15
- 108010009736 Protein Hydrolysates Proteins 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- 230000002378 acidificating effect Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 229930040373 Paraformaldehyde Natural products 0.000 description 7
- 229920002866 paraformaldehyde Polymers 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009261 transgenic effect Effects 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
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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 Table
- 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 ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/026—Preparation of ammonia from inorganic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a comprehensive utilization method of glyphosate byproduct ammonia water and alkali, which adopts sodium carbonate and/or sodium bicarbonate to neutralize glyphosate hydrolysate, and the generated carbon dioxide escapes and is discharged, thereby avoiding the generation of water dissolved part glyphosate by the neutralization reaction of conventional sodium hydroxide, and simultaneously reducing the concentration treatment capacity of the subsequent glyphosate mother liquor; sodium carbonate and/or sodium bicarbonate are/is adopted to pre-neutralize the glyphosate acid mother liquor, and the generated carbon dioxide escapes and is discharged, so that the phenomenon that the subsequent concentration treatment capacity of the glyphosate mother liquor is increased because only sodium hydroxide is directly used for neutralization reaction to generate water in the conventional method is avoided; rectifying the glyphosate mother liquor oxidation solution to obtain an ammonium bicarbonate water mixture, adding proper 'excess' sodium hydroxide to recover ammonia water, and recycling the obtained sodium carbonate water mixture with high concentration to the neutralization reaction process of the glyphosate hydrolysate and/or the pre-neutralization reaction process of the glyphosate acid mother liquor so as to fully utilize alkali.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a comprehensive utilization method of glyphosate byproduct ammonia water and alkali.
Background
The glyphosate is a pesticide variety with the largest global sales and the fastest growth speed due to low toxicity, high efficiency, low residue and broad spectrum, and the paraquat exits the pesticide market along with the successful development and the popularization of the transgenic crops of the glyphosate and the sowing and the popularization of biofuel crops caused by energy shortage, thereby providing a new opportunity for the further development of the glyphosate.
At present, domestic enterprises generally adopt an alkyl ester method to produce glyphosate, main raw materials are paraformaldehyde (or formaldehyde), glycine, dimethyl phosphite, triethylamine, methanol and hydrochloric acid, wherein the paraformaldehyde is depolymerized under the catalysis of the triethylamine, then synthetic liquid is obtained through addition and condensation, the synthetic liquid is added with hydrochloric acid to carry out hydrolysis reaction, and after a solvent and excessive hydrochloric acid in a system are removed, glyphosate crystals are separated out to obtain glyphosate hydrolysate; and adding sodium hydroxide into the glyphosate hydrolysate to adjust the pH value, cooling and separating to obtain glyphosate technical product and glyphosate acid mother liquor, and neutralizing triethylamine salt contained in the glyphosate acid mother liquor with sodium hydroxide and then recycling. Therefore, the alkyl ester method is adopted to produce glyphosate, and different production steps require different acid-base conditions, so a large amount of acid-base needs to be consumed, wherein the market price of sodium hydroxide is relatively expensive, and the consumption of sodium hydroxide in the production process of glyphosate is high, so that the production cost of glyphosate is high; meanwhile, sodium chloride and water generated after the acid-base neutralization reaction are produced as glyphosate mother liquor, so that the amount of the glyphosate mother liquor is increased, and the cost for treating the glyphosate mother liquor is correspondingly increased.
In the prior art, a glyphosate mother liquor is usually subjected to wet oxidation, organic matters containing phosphorus and nitrogen are oxidized into inorganic matters such as phosphate, carbon dioxide, ammonia and the like to obtain a glyphosate mother liquor oxidation solution, the glyphosate mother liquor oxidation solution is cooled and crystallized, then, solid-liquid separation is carried out to obtain disodium hydrogen phosphate, obtained liquid materials are evaporated and concentrated to obtain a condensate, and alkali is added for rectification to recover ammonia water. The disodium hydrogen phosphate obtained by the method can carry partial ammonium to influence the product quality, and the ammonia recovery rate is low; and the condensate is low in alkali concentration after ammonia water is recovered by deamination, low in utilization value and generally used as part of process water for recycling after acid is added for neutralization or discharged after being treated by a sewage station, so that acid and alkali waste is caused.
Disclosure of Invention
The invention aims to provide a comprehensive utilization method of glyphosate byproduct ammonia water and alkali, which has the advantages of reasonable design, full utilization of reagents, avoidance of acid-base waste and low production cost.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a comprehensive utilization method of glyphosate byproduct ammonia water and alkali, which comprises the following steps:
(1) providing glyphosate hydrolysate which is prepared by taking triethylamine as a catalyst and adopting an alkyl ester method;
(2) mixing the glyphosate hydrolysate in the step (1) with alkaline salt for neutralization reaction, cooling the obtained system, and performing solid-liquid separation to obtain glyphosate acid mother liquor and glyphosate wet powder; the alkaline salt comprises sodium carbonate and/or sodium bicarbonate;
(3) mixing the glyphosate acid mother liquor obtained in the step (2) with alkaline salt for preneutralization reaction to obtain glyphosate preneutralized mother liquor; the alkaline salt comprises sodium carbonate and/or sodium bicarbonate;
(4) mixing the mother liquor obtained after the pre-neutralization of the glyphosate in the step (3) with sodium hydroxide for neutralization reaction, layering the obtained system, and separating to obtain an upper layer liquor and a lower layer liquor;
mixing the supernatant with sodium hydroxide solid for dehydration to obtain triethylamine, and reusing the triethylamine in the step (1) to prepare glyphosate hydrolysate;
carrying out stripping on the lower layer liquid to obtain glyphosate mother liquid;
(5) concentrating the glyphosate mother liquor obtained in the step (4) to obtain a glyphosate mother liquor concentrated liquor;
(6) oxidizing the glyphosate mother liquor concentrated solution obtained in the step (5) to obtain glyphosate mother liquor oxidized solution;
(7) rectifying the glyphosate mother liquor oxidation solution obtained in the step (6) to obtain an ammonium bicarbonate water mixture and a tower bottom effluent;
(8) cooling and crystallizing the tower bottom effluent obtained in the step (7) to obtain disodium hydrogen phosphate;
carrying out double decomposition reaction on the ammonium bicarbonate water mixture and sodium hydroxide, controlling the pH value of the obtained system to be 12.0-13.5, and rectifying the system to obtain an ammonia water and sodium carbonate water mixture;
recycling the sodium carbonate water mixture to the step (2) and/or step (3) in place of the alkaline salt, in whole or in part.
Preferably, the pH value of the glyphosate hydrolysate in the step (1) is-1.0-0.
Preferably, the pH value of the system obtained after the neutralization reaction in the step (2) is 0.3-1.2; and the cooling is to control the temperature of the system to be 10-50 ℃.
Preferably, the pH value of the system obtained after the preneutralization reaction in the step (3) is 0.3-5.0; the time of the pre-neutralization reaction is 1-120 min.
Preferably, the pH value of the system obtained after the neutralization reaction in the step (4) is 10.0-11.0; the water content of the triethylamine is less than or equal to 0.1 percent; the bottom temperature of the stripping tower in the stripping process is 105-115 ℃.
Preferably, the concentration treatment in the step (5) is to concentrate the glyphosate mother liquor to COD more than or equal to 50000mg/L and total phosphorus more than or equal to 30000 mg/L.
Preferably, the oxidation treatment in the step (6) is performed in an atmosphere of air or oxygen; the temperature of the oxidation treatment is 220-300 ℃, and the time is 30-90 min.
Preferably, the temperature at the bottom of the rectifying tower in the rectifying treatment process in the step (7) is 65-120 ℃, and the pressure is-0.050 MPa.
Preferably, the ammonium bicarbonate water mixture in the step (7) is a solution or a crystal slurry, and the mass content of ammonium bicarbonate in the ammonium bicarbonate water mixture is 10-50%.
Preferably, the mass content of the ammonia water in the step (8) is more than or equal to 15 percent; the sodium carbonate mixture is an aqueous solution or crystal slurry, and the mass content of sodium carbonate in the sodium carbonate mixture is 20-70%.
The invention provides a comprehensive utilization method of glyphosate byproduct ammonia water and alkali, which has the advantages of reasonable design, full utilization of reagents, avoidance of acid-alkali waste and low production cost. Specifically, sodium carbonate and/or sodium bicarbonate and the glyphosate hydrolysate are/is adopted to carry out neutralization reaction, and the generated carbon dioxide escapes and is discharged under an acidic condition, so that the water dissolved part of glyphosate generated by the neutralization reaction by adopting the conventional sodium hydroxide is avoided, and the subsequent concentration treatment capacity of the glyphosate mother liquor is reduced; sodium carbonate and/or sodium bicarbonate are/is adopted to pre-neutralize the glyphosate acid mother liquor, then sodium hydroxide is adopted to further neutralize, carbon dioxide generated in the pre-neutralization reaction escapes and is discharged under the acidic condition, and the phenomenon that the conventional method directly only uses sodium hydroxide to carry out the neutralization reaction to generate water, so that the subsequent concentration treatment capacity of the glyphosate mother liquor is increased; rectifying the glyphosate mother liquor oxidation solution to obtain an ammonium bicarbonate water mixture, adding appropriate 'excess' sodium hydroxide (controlling the pH value of the obtained system to be 12.0-13.5) to recycle ammonia water, wherein the concentration of the obtained sodium carbonate water mixture is high, and the sodium carbonate water mixture is recycled to the neutralization reaction process of the glyphosate hydrolysate and the pre-neutralization reaction process of the glyphosate acid mother liquor, and sodium ions in the sodium carbonate water mixture are conserved to fully utilize alkali, so that the addition of appropriate 'excess' sodium hydroxide can not waste alkali, but also improve the reaction alkalinity, and is more beneficial to ammonia recycling.
Drawings
FIG. 1 is a flow chart of a comprehensive utilization method of glyphosate byproduct ammonia water and alkali provided by the invention.
Detailed Description
The invention provides a comprehensive utilization method of glyphosate byproduct ammonia water and alkali, which comprises the following steps:
(1) providing glyphosate hydrolysate which is prepared by taking triethylamine as a catalyst and adopting an alkyl ester method;
(2) mixing the glyphosate hydrolysate in the step (1) with alkaline salt for neutralization reaction, cooling the obtained system, and performing solid-liquid separation to obtain glyphosate acid mother liquor and glyphosate wet powder; the alkaline salt comprises sodium carbonate and/or sodium bicarbonate;
(3) mixing the glyphosate acid mother liquor obtained in the step (2) with alkaline salt for preneutralization reaction to obtain glyphosate preneutralized mother liquor; the alkaline salt comprises sodium carbonate and/or sodium bicarbonate;
(4) mixing the mother liquor obtained after the pre-neutralization of the glyphosate in the step (3) with sodium hydroxide for neutralization reaction, layering the obtained system, and separating to obtain an upper layer liquor and a lower layer liquor;
mixing the supernatant with sodium hydroxide solid for dehydration to obtain triethylamine, and reusing the triethylamine in the step (1) to prepare glyphosate hydrolysate;
carrying out stripping on the lower layer liquid to obtain glyphosate mother liquid;
(5) concentrating the glyphosate mother liquor obtained in the step (4) to obtain a glyphosate mother liquor concentrated liquor;
(6) oxidizing the glyphosate mother liquor concentrated solution obtained in the step (5) to obtain glyphosate mother liquor oxidized solution;
(7) rectifying the glyphosate mother liquor oxidation solution obtained in the step (6) to obtain an ammonium bicarbonate water mixture and a tower bottom effluent;
(8) cooling and crystallizing the tower bottom effluent obtained in the step (7) to obtain disodium hydrogen phosphate;
carrying out double decomposition reaction on the ammonium bicarbonate water mixture and sodium hydroxide, controlling the pH value of the obtained system to be 12.0-13.5, and rectifying the system to obtain an ammonia water and sodium carbonate water mixture;
recycling the sodium carbonate water mixture to the step (2) and/or step (3) in place of the alkaline salt, in whole or in part.
The invention provides glyphosate hydrolysate which is prepared by taking triethylamine as a catalyst and adopting an alkyl ester method. In the invention, the pH value of the glyphosate hydrolysate is preferably-1.0-0, and more preferably-0.85-0.60. The source of the glyphosate hydrolysate is not particularly limited, and the glyphosate hydrolysate can be prepared by adopting triethylamine as a catalyst and adopting an alkyl ester method, which are well known to those skilled in the art. In the embodiment of the present invention, the preparation method of the glyphosate hydrolysate preferably includes the following steps:
carrying out depolymerization on paraformaldehyde under the catalysis of triethylamine, then carrying out addition and condensation to obtain a synthetic liquid, mixing the synthetic liquid with hydrochloric acid for hydrolysis reaction, removing a solvent and excessive hydrochloric acid in a system, and then separating out glyphosate crystals to obtain glyphosate hydrolysate.
After glyphosate hydrolysate is obtained, the glyphosate hydrolysate and alkaline salt are mixed for neutralization reaction, and the obtained system is cooled for solid-liquid separation to obtain glyphosate acid mother liquor and glyphosate wet powder; the alkaline salt comprises sodium carbonate and/or sodium bicarbonate. In the invention, the pH value of the system obtained after the neutralization reaction is preferably 0.3-1.2, and more preferably 0.5-0.8; the cooling is preferably performed by controlling the temperature of the system to be 10-50 ℃, and more preferably 20-40 ℃. In the invention, the glyphosate wet powder is preferably dried to obtain the finished glyphosate technical product. According to the invention, sodium carbonate and/or sodium bicarbonate are/is used as alkaline salt to perform neutralization reaction with the glyphosate hydrolysate, and the generated carbon dioxide escapes and is discharged under an acidic condition, so that the water-soluble part of glyphosate generated by the neutralization reaction with conventional sodium hydroxide is avoided, and the subsequent concentration treatment capacity of the glyphosate mother liquor is reduced.
After the glyphosate acid mother liquor is obtained, mixing the glyphosate acid mother liquor with alkaline salt for preneutralization reaction to obtain the glyphosate preneutralized mother liquor; the alkaline salt comprises sodium carbonate and/or sodium bicarbonate. In the invention, the pH value of the system obtained after the pre-neutralization reaction is preferably 0.3-5.0, and more preferably 3.0-4.0; the time of the pre-neutralization reaction is preferably 1-120 min, and more preferably 5-20 min.
After the mother liquor after glyphosate pre-neutralization is obtained, the mother liquor after glyphosate pre-neutralization is mixed with sodium hydroxide for neutralization reaction, the obtained system is layered, and the upper layer liquor and the lower layer liquor are obtained by separation; mixing the supernatant with sodium hydroxide solid for dehydration to obtain triethylamine, and reusing the triethylamine in the step of preparing glyphosate hydrolysate; and carrying out stripping on the lower layer liquid to obtain glyphosate mother liquid. In the invention, the pH value of the system obtained after the neutralization reaction is preferably 10.0-11.0; the water content in the triethylamine is preferably less than or equal to 0.1 percent; the bottom temperature of the stripping tower in the stripping process is preferably 105-115 ℃.
The method adopts sodium carbonate and/or sodium bicarbonate to pre-neutralize the glyphosate acid mother liquor, then adopts sodium hydroxide to further neutralize, and the carbon dioxide generated in the pre-neutralization reaction escapes and is discharged under the acidic condition, thereby avoiding the increase of the concentration treatment capacity of the subsequent glyphosate mother liquor caused by directly using only sodium hydroxide to neutralize the water generated in the reaction.
After the glyphosate mother liquor is obtained, the invention carries out concentration treatment on the glyphosate mother liquor to obtain the glyphosate mother liquor concentrated liquor. In the invention, the concentration treatment is preferably to concentrate the glyphosate mother liquor to COD more than or equal to 50000mg/L and total phosphorus more than or equal to 30000 mg/L; more preferably, the concentration is carried out until the COD is more than or equal to 60000mg/L and the total phosphorus is more than or equal to 40000 mg/L.
After the glyphosate mother liquor concentrated solution is obtained, the invention carries out oxidation treatment on the glyphosate mother liquor concentrated solution to obtain the glyphosate mother liquor oxidized solution. In the present invention, the oxidation treatment is preferably performed in an atmosphere of air or oxygen; the temperature of the oxidation treatment is preferably 220-300 ℃, and the time is preferably 30-90 min.
After the glyphosate mother liquor oxidation liquid is obtained, the glyphosate mother liquor oxidation liquid is rectified to obtain an ammonium bicarbonate water mixture and a tower bottom liquid. In the invention, the temperature of the bottom of the rectifying tower in the rectifying treatment process is 65-120 ℃, and preferably 105-115 ℃; the pressure is preferably-0.050 MPa, and more preferably 0-0.035 MPa; in the invention, the recovery rate of ammonia is more than or equal to 95.0 percent through the rectification treatment. In the invention, the ammonium bicarbonate water mixture is preferably a solution or a crystal slurry, and the mass content of ammonium bicarbonate in the ammonium bicarbonate water mixture is preferably 10-50%, and more preferably 20-35%.
After an ammonium bicarbonate water mixture and a tower bottom liquid are obtained, cooling and crystallizing the tower bottom liquid to obtain disodium hydrogen phosphate; carrying out double decomposition reaction on the ammonium bicarbonate water mixture and sodium hydroxide, controlling the pH value of the obtained system to be 12.0-13.5, and carrying out rectification treatment on the obtained system to obtain an ammonia water and sodium carbonate water mixture; and recycling the sodium carbonate water mixture to the neutralization reaction process of the glyphosate hydrolysate and/or the pre-neutralization reaction process of the glyphosate acid mother liquor to replace all or part of the alkaline salt. In the invention, the mass content of the ammonia water is preferably more than or equal to 15 percent; the sodium carbonate mixture is preferably an aqueous solution or a crystal slurry, and the mass content of sodium carbonate in the sodium carbonate mixture is preferably 20-70%, and more preferably 30-50%. In the invention, the ammonia nitrogen content in the sodium carbonate water mixture is less than or equal to 50ppm through the rectification treatment.
In the present invention, the sodium hydroxide is preferably used in the form of a sodium hydroxide solid or a sodium hydroxide solution; the mass concentration of the sodium hydroxide solution is preferably 30-50%, and more preferably 40-45%.
In the invention, after rectifying the glyphosate mother liquor oxidation solution to obtain an ammonium bicarbonate water mixture, adding appropriate 'excess' sodium hydroxide (controlling the pH value of the obtained system to be 12.0-13.5) to recycle ammonia water, wherein the obtained sodium carbonate water mixture has high concentration and is recycled to the neutralization reaction process of the glyphosate hydrolysate and the pre-neutralization reaction process of the glyphosate acid mother liquor, and sodium ions in the sodium carbonate water mixture are conserved so that alkali can be fully utilized. Therefore, the addition of proper 'excess' sodium hydroxide can not only waste alkali, but also improve the reaction alkalinity, and is more beneficial to the recovery of ammonia.
FIG. 1 is a flow chart of a comprehensive utilization method of glyphosate byproduct ammonia water and alkali, which is provided by the invention, and comprises the steps of synthesizing, hydrolyzing and desolventizing raw materials to obtain glyphosate hydrolysate, adding alkali, neutralizing, and carrying out solid-liquid separation to obtain glyphosate wet powder and glyphosate acid mother liquor; drying the glyphosate wet powder to obtain glyphosate technical, adding alkali into the glyphosate acid mother liquor to carry out pre-neutralization to obtain glyphosate pre-neutralized mother liquor; adding sodium hydroxide into the mother liquor after the glyphosate is preneutralized for neutralization, layering, and separating to obtain an upper layer liquor and a lower layer liquor; adding solid sodium hydroxide into the supernatant, dehydrating to obtain triethylamine, and recycling the triethylamine as a raw material; carrying out stripping on the lower layer liquid to obtain glyphosate mother liquid; concentrating the glyphosate mother liquor to obtain a glyphosate mother liquor concentrated liquor; oxidizing the glyphosate mother liquor to obtain glyphosate mother liquor oxidized liquor; rectifying the glyphosate mother liquor oxidation solution to obtain an ammonium bicarbonate water mixture and a tower bottom effluent; cooling and crystallizing the tower bottom liquid to obtain disodium hydrogen phosphate; adding a sodium hydroxide solution into the ammonium bicarbonate water mixture for double decomposition reaction, and rectifying the obtained system to obtain an ammonia water and sodium carbonate water mixture; and recycling the sodium carbonate water mixture to the neutralization reaction process of the glyphosate hydrolysate and/or the pre-neutralization reaction process of the glyphosate acid mother liquor to replace all or part of the alkaline salt.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Carrying out depolymerization on paraformaldehyde under the catalysis of triethylamine, then carrying out addition and condensation to obtain a synthetic liquid, mixing the synthetic liquid with hydrochloric acid for hydrolysis reaction, and separating out glyphosate crystals after removing a solvent and excessive hydrochloric acid in a system to obtain glyphosate hydrolysate with the pH value of-0.85;
(2) mixing the glyphosate hydrolysate with sodium carbonate for neutralization reaction until the pH value of the obtained system is 0.30, allowing generated carbon dioxide to escape and vent under acidic conditions, cooling the obtained system to 12 ℃, performing solid-liquid separation to obtain glyphosate acid mother liquor and glyphosate wet powder, and drying the glyphosate wet powder to obtain a finished product glyphosate technical product;
(3) mixing the glyphosate acid mother liquor with sodium carbonate for preneutralization reaction until the pH value of the obtained system is 3.0, keeping the reaction for 5min, and discharging generated carbon dioxide escaping under an acidic condition to obtain glyphosate preneutralized mother liquor;
(4) mixing the mother liquor after the pre-neutralization of the glyphosate with sodium hydroxide for neutralization reaction until the pH value of the obtained system is 10.3, layering the obtained system, and separating to obtain an upper layer liquor and a lower layer liquor; mixing the supernatant with sodium hydroxide solid for dehydration to obtain triethylamine (the water content is 0.08%), and reusing the triethylamine in the step (1) to prepare glyphosate hydrolysate; under the condition that the bottom temperature of the stripping tower is 105 ℃, stripping the lower layer liquid to obtain glyphosate mother liquid;
(5) concentrating the glyphosate mother liquor until the CDO of the obtained system is 52000mg/L and the total phosphorus is 33000mg/L to obtain the glyphosate mother liquor concentrate;
(6) oxidizing the glyphosate mother liquor at 230 ℃ for 70min in air atmosphere to obtain glyphosate mother liquor oxidized liquor;
(7) rectifying the glyphosate mother liquor oxidation solution under the conditions that the temperature at the bottom of the rectifying tower is 68 ℃ and the pressure is-0.083 MPa, wherein the ammonia recovery rate is 95.0 percent, so as to obtain an ammonium bicarbonate water mixture (the mass content of ammonium bicarbonate is 18 percent) and tower bottom liquid, and cooling and crystallizing the tower bottom liquid to obtain disodium hydrogen phosphate;
(8) carrying out double decomposition reaction on the ammonium bicarbonate water mixture and a sodium hydroxide solution with the mass concentration of 40%, controlling the pH value of the obtained system to be 12.0, and carrying out rectification treatment on the obtained system to obtain an ammonia water (the mass content is 15%) and sodium carbonate water mixture (the mass content of sodium carbonate is 60%, and the ammonia nitrogen content is 30 ppm); and (3) recycling the sodium carbonate water mixture to the step (2) to completely replace sodium carbonate to neutralize the glyphosate hydrolysate.
Example 2
(1) Carrying out depolymerization on paraformaldehyde under the catalysis of triethylamine, then carrying out addition and condensation to obtain a synthetic liquid, mixing the synthetic liquid with hydrochloric acid for hydrolysis reaction, removing a solvent and excessive hydrochloric acid in a system, and then separating out glyphosate crystals to obtain a glyphosate hydrolysate with the pH value of-0.60;
(2) mixing the glyphosate hydrolysate with sodium carbonate for neutralization reaction until the pH value of the obtained system is 0.52, allowing generated carbon dioxide to escape and vent under acidic conditions, cooling the obtained system to 25 ℃, performing solid-liquid separation to obtain glyphosate acid mother liquor and glyphosate wet powder, and drying the glyphosate wet powder to obtain a finished product glyphosate technical product;
(3) mixing the glyphosate acid mother liquor with sodium carbonate for preneutralization reaction until the pH value of the obtained system is 3.5, keeping the reaction for 10min, and discharging generated carbon dioxide escaping under an acidic condition to obtain glyphosate preneutralized mother liquor;
(4) mixing the mother liquor after the pre-neutralization of the glyphosate with sodium hydroxide for neutralization reaction until the pH value of the obtained system is 10.5, layering the obtained system, and separating to obtain an upper layer liquor and a lower layer liquor; mixing the supernatant with sodium hydroxide solid for dehydration to obtain triethylamine (the water content is 0.06%), and reusing the triethylamine in the step (1) to prepare glyphosate hydrolysate; under the condition that the bottom temperature of the stripping tower is 110 ℃, stripping the lower layer liquid to obtain glyphosate mother liquid;
(5) concentrating the glyphosate mother liquor until the CDO of the obtained system is 63000mg/L and the total phosphorus is 41000mg/L to obtain the glyphosate mother liquor concentrate;
(6) oxidizing the glyphosate mother liquor at 245 ℃ for 60min in an air atmosphere to obtain glyphosate mother liquor oxidized liquor;
(7) under the conditions that the temperature at the bottom of a rectifying tower is 106 ℃ and the pressure is 0.0MPa, rectifying the glyphosate mother liquor oxidation solution, wherein the ammonia recovery rate is 96.5 percent, obtaining an ammonium bicarbonate water mixture (the mass content of ammonium bicarbonate is 22 percent) and tower bottom liquid, and cooling and crystallizing the tower bottom liquid to obtain disodium hydrogen phosphate;
(8) carrying out double decomposition reaction on the ammonium bicarbonate water mixture and a sodium hydroxide solution with the mass concentration of 45%, controlling the pH value of the obtained system to be 12.8, and carrying out rectification treatment on the obtained system to obtain an ammonia water (the mass content is 16.5%) and sodium carbonate water mixture (the mass content of sodium carbonate is 50%, and the ammonia nitrogen content is 15 ppm); and (4) recycling the sodium carbonate water mixture to the step (3) to completely replace sodium carbonate to pre-neutralize the glyphosate acid mother liquor.
Example 3
(1) Carrying out depolymerization on paraformaldehyde under the catalysis of triethylamine, then carrying out addition and condensation to obtain a synthetic liquid, mixing the synthetic liquid with hydrochloric acid for hydrolysis reaction, removing a solvent and excessive hydrochloric acid in a system, and then separating out glyphosate crystals to obtain glyphosate hydrolysate with the pH value of-0.50;
(2) mixing the glyphosate hydrolysate with sodium carbonate for neutralization reaction until the pH value of the obtained system is 0.45, allowing generated carbon dioxide to escape and vent under acidic conditions, cooling the obtained system to 35 ℃, performing solid-liquid separation to obtain glyphosate acid mother liquor and glyphosate wet powder, and drying the glyphosate wet powder to obtain a finished product glyphosate technical product;
(3) mixing the glyphosate acid mother liquor with sodium carbonate for preneutralization reaction until the pH value of the obtained system is 4.0, keeping the reaction for 20min, and discharging generated carbon dioxide escaping under an acidic condition to obtain glyphosate preneutralized mother liquor;
(4) mixing the mother liquor after the pre-neutralization of the glyphosate with sodium hydroxide for neutralization reaction until the pH value of the obtained system is 10.8, layering the obtained system, and separating to obtain an upper layer liquor and a lower layer liquor; mixing the supernatant with sodium hydroxide solid for dehydration to obtain triethylamine (the water content is 0.05%), and reusing the triethylamine in the step (1) to prepare glyphosate hydrolysate; under the condition that the bottom temperature of the stripping tower is 112 ℃, stripping the lower layer liquid to obtain glyphosate mother liquid;
(5) concentrating the glyphosate mother liquor until the CDO of the obtained system is 70000mg/L and the total phosphorus is 45000mg/L to obtain glyphosate mother liquor concentrate;
(6) oxidizing the glyphosate mother liquor at 265 ℃ for 50min in an air atmosphere to obtain glyphosate mother liquor oxidized liquor;
(7) under the conditions that the temperature at the bottom of a rectifying tower is 110 ℃ and the pressure is 0.005MPa, rectifying the glyphosate mother liquor oxidation solution, wherein the ammonia recovery rate is 97.0 percent, obtaining an ammonium bicarbonate water mixture (the mass content of ammonium bicarbonate is 25 percent) and tower bottom liquid, and cooling and crystallizing the tower bottom liquid to obtain disodium hydrogen phosphate;
(8) carrying out double decomposition reaction on the ammonium bicarbonate water mixture and a sodium hydroxide solution with the mass concentration of 50%, controlling the pH value of the obtained system to be 13.1, and carrying out rectification treatment on the obtained system to obtain an ammonia water (the mass content is 19.0%) and sodium carbonate water mixture (the mass content of sodium carbonate is 40%, and the content of ammonia nitrogen is 10 ppm); and (3) recycling the sodium carbonate water mixture to the step (2) to partially replace sodium carbonate to neutralize the glyphosate hydrolysate.
Example 4
(1) Carrying out depolymerization on paraformaldehyde under the catalysis of triethylamine, then carrying out addition and condensation to obtain a synthetic liquid, mixing the synthetic liquid with hydrochloric acid for hydrolysis reaction, and separating out glyphosate crystals after removing a solvent and excessive hydrochloric acid in a system to obtain glyphosate hydrolysate with the pH value of-0.65;
(2) mixing the glyphosate hydrolysate with sodium carbonate for neutralization reaction until the pH value of the obtained system is 0.70, allowing generated carbon dioxide to escape and vent under acidic conditions, cooling the obtained system to 45 ℃, performing solid-liquid separation to obtain glyphosate acid mother liquor and glyphosate wet powder, and drying the glyphosate wet powder to obtain a finished product glyphosate technical product;
(3) mixing the glyphosate acid mother liquor with sodium carbonate for preneutralization reaction until the pH value of the obtained system is 5.0, keeping the reaction for 100min, and discharging generated carbon dioxide escaping under an acidic condition to obtain glyphosate preneutralized mother liquor;
(4) mixing the mother liquor after the pre-neutralization of the glyphosate with sodium hydroxide for neutralization reaction until the pH value of the obtained system is 11.0, layering the obtained system, and separating to obtain an upper layer liquor and a lower layer liquor; mixing the supernatant with sodium hydroxide solid for dehydration to obtain triethylamine (the water content is 0.06%), and reusing the triethylamine in the step (1) to prepare glyphosate hydrolysate; under the condition that the bottom temperature of the stripping tower is 115 ℃, carrying out stripping on the lower layer liquid to obtain glyphosate mother liquid;
(5) concentrating the glyphosate mother liquor until the CDO of the obtained system is 75000mg/L and the total phosphorus is 47000mg/L to obtain a glyphosate mother liquor concentrated liquor;
(6) oxidizing the glyphosate mother liquor at 275 ℃ for 40min in air atmosphere to obtain glyphosate mother liquor oxidized liquor;
(7) under the conditions that the temperature at the bottom of a rectifying tower is 115 ℃ and the pressure is 0.035MPa, rectifying the glyphosate mother liquor oxidation liquid, wherein the ammonia recovery rate is 98.2 percent, obtaining an ammonium bicarbonate water mixture (the mass content of ammonium bicarbonate is 28 percent) and tower bottom liquid, and cooling and crystallizing the tower bottom liquid to obtain disodium hydrogen phosphate;
(8) carrying out double decomposition reaction on the ammonium bicarbonate water mixture and sodium hydroxide solid, controlling the pH value of the obtained system to be 13.5, and carrying out rectification treatment on the obtained system to obtain ammonia water (the mass content is 20.5%) and a sodium carbonate water mixture (the mass content of sodium carbonate is 23%, and the content of ammonia nitrogen is 8 ppm); and (4) recycling the sodium carbonate water mixture to the step (3) to partially replace sodium carbonate to pre-neutralize the glyphosate acid mother liquor.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A comprehensive utilization method of glyphosate byproduct ammonia water and alkali comprises the following steps:
(1) providing glyphosate hydrolysate which is prepared by taking triethylamine as a catalyst and adopting an alkyl ester method;
(2) mixing the glyphosate hydrolysate in the step (1) with alkaline salt for neutralization reaction, cooling the obtained system, and performing solid-liquid separation to obtain glyphosate acid mother liquor and glyphosate wet powder; the alkaline salt is selected from sodium carbonate and/or sodium bicarbonate;
(3) mixing the glyphosate acid mother liquor obtained in the step (2) with alkaline salt for preneutralization reaction to obtain glyphosate preneutralized mother liquor; the alkaline salt is selected from sodium carbonate and/or sodium bicarbonate;
(4) mixing the mother liquor obtained after the pre-neutralization of the glyphosate in the step (3) with sodium hydroxide for neutralization reaction, layering the obtained system, and separating to obtain an upper layer liquor and a lower layer liquor;
mixing the supernatant with sodium hydroxide solid for dehydration to obtain triethylamine, and reusing the triethylamine in the step (1) to prepare glyphosate hydrolysate;
carrying out stripping on the lower layer liquid to obtain glyphosate mother liquid;
(5) concentrating the glyphosate mother liquor obtained in the step (4) to obtain a glyphosate mother liquor concentrated liquor;
(6) oxidizing the glyphosate mother liquor concentrated solution obtained in the step (5) to obtain glyphosate mother liquor oxidized solution;
(7) rectifying the glyphosate mother liquor oxidation solution obtained in the step (6) to obtain an ammonium bicarbonate water mixture and a tower bottom effluent;
(8) cooling and crystallizing the tower bottom effluent obtained in the step (7) to obtain disodium hydrogen phosphate;
carrying out double decomposition reaction on the ammonium bicarbonate water mixture and sodium hydroxide, controlling the pH value of the obtained system to be 12.0-13.5, and rectifying the system to obtain an ammonia water and sodium carbonate water mixture;
recycling the sodium carbonate water mixture to the step (2) and/or step (3) in place of the alkaline salt, in whole or in part.
2. The method as claimed in claim 1, wherein the pH value of the glyphosate hydrolysate in the step (1) is-1.0-0.
3. The method according to claim 1, wherein the pH value of the system obtained after the neutralization reaction in the step (2) is 0.3-1.2; and the cooling is to control the temperature of the system to be 10-50 ℃.
4. The method according to claim 1, wherein the pH value of the system obtained after the preneutralization reaction in the step (3) is 0.3-5.0; the time of the pre-neutralization reaction is 1-120 min.
5. The method according to claim 1, wherein the pH value of the system obtained after the neutralization reaction in the step (4) is 10.0-11.0; the water content of the triethylamine is less than or equal to 0.1 percent; the bottom temperature of the stripping tower in the stripping process is 105-115 ℃.
6. The method as claimed in claim 1, wherein the concentration treatment in step (5) is to concentrate the glyphosate mother liquor to COD > 50000mg/L and total phosphorus > 30000 mg/L.
7. The method according to claim 1, wherein the oxidation treatment in the step (6) is performed in an atmosphere of air or oxygen; the temperature of the oxidation treatment is 220-300 ℃, and the time is 30-90 min.
8. The method according to claim 1, wherein the temperature at the bottom of the rectification column in the rectification treatment in the step (7) is 65 to 120 ℃, and the pressure is-0.050 to 0.050 MPa.
9. The method according to claim 1, wherein the ammonium bicarbonate water mixture in the step (7) is a solution or a crystal slurry, and the mass content of ammonium bicarbonate in the ammonium bicarbonate water mixture is 10-50%.
10. The method according to claim 1, wherein the mass content of the ammonia water in the step (8) is more than or equal to 15%; the sodium carbonate mixture is an aqueous solution or crystal slurry, and the mass content of sodium carbonate in the sodium carbonate mixture is 20-70%.
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