CN104119379A - Process for extracting glyphosate raw powder from glyphosate mother liquid - Google Patents
Process for extracting glyphosate raw powder from glyphosate mother liquid Download PDFInfo
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- CN104119379A CN104119379A CN201410398478.4A CN201410398478A CN104119379A CN 104119379 A CN104119379 A CN 104119379A CN 201410398478 A CN201410398478 A CN 201410398478A CN 104119379 A CN104119379 A CN 104119379A
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- glyphosate
- mother liquor
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- membrane concentration
- mother
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- 239000005562 Glyphosate Substances 0.000 title claims abstract description 249
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 249
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 249
- 239000007788 liquid Substances 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 95
- 239000000843 powder Substances 0.000 title claims abstract description 49
- 239000012528 membrane Substances 0.000 claims abstract description 108
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 82
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004471 Glycine Substances 0.000 claims abstract description 17
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 16
- 239000012452 mother liquor Substances 0.000 claims description 140
- 238000001223 reverse osmosis Methods 0.000 claims description 45
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 40
- 239000010413 mother solution Substances 0.000 claims description 40
- 238000006460 hydrolysis reaction Methods 0.000 claims description 29
- 230000007062 hydrolysis Effects 0.000 claims description 28
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 15
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 11
- 238000010612 desalination reaction Methods 0.000 claims description 11
- 238000000909 electrodialysis Methods 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 11
- -1 continue hydrolysis Substances 0.000 claims description 10
- 238000002203 pretreatment Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003814 drug Substances 0.000 abstract description 3
- 108010009736 Protein Hydrolysates Proteins 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010129 solution processing Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011034 membrane dialysis Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a process for extracting glyphosate raw powder from a glyphosate mother liquid in order to solve the technical problems that glyphosate raw drugs cannot be directly extracted from the glyphosate mother liquid in the prior art. The process comprises the following steps: in glyphosate synthesis through a glycine process, adding the synthesized condensed liquid into excessive hydrochloric acid for hydrolyzing, adding a glyphosate concentrated mother liquid subjected to membrane concentration into the hydrolysate, continuously hydrolyzing, and extracting the glyphosate raw powder. The glyphosate in the concentrated mother liquid can be extracted by over 95 percent.
Description
Technical field
The present invention relates to glyphosate production field, be specifically related to a kind of technique of extracting the former powder of glyphosate from glyphosate mother solution.
Background technology
Glyphosate is the pesticide species of current global output maximum, and domestic glyphosate corporate boss will adopt IDA method and two kinds of production technique of glycine method.No matter which kind of technique, in glyphosate production, all can produce a large amount of waste water.Glycine method has raw material and is easy to get, and process costs is low, Atom economy advantages of higher and develop into the main flow technique of China.In this technique, 1 ton of glyphosate of every production will produce the glyphosate mother solution of 5 tons of left and right.Glyphosate mother solution is because glyphosate content is 1% left and right, and contains the salts such as a large amount of NaCl, is all that directly concentrated 10% aqua of making is sold in the past.In February, 2009, national Ministry of Industry and Information and the Ministry of Agriculture issue bulletin No. 1158, within 2010, work the gyphosate solution of forbidding production and selling 10%, the bottleneck that is treated as glyphosate production of glyphosate mother solution.Therefore, a kind of efficient glyphosate mother solution processing scheme of exploitation is extremely urgent.
At present, glyphosate mother solution processing is generally as offal treatment after extraction triethylamine.This treatment process not only additionally increases the processing cost of mother liquor, also can cause whole wastes of glyphosate in mother liquor.Therefore, developing a kind of mother liquor, to extract the method for glyphosate particularly important.Though contain a certain amount of glyphosate composition in glyphosate mother solution, but due to its existence form complexity in mother liquor, or directly attracted symbiosis to become macromolecular substance by other composition in mother liquor, or the reticulated structure being grouped into by other one-tenth wraps up, ordinary method cannot extract it with former medicine form.
As 200910114938.5, name is called the application for a patent for invention of " a kind of method that reclaims the former powder of glyphosate from glyphosate mother solution ", processing step is: (1) adds extraction agent triethylamine in glyphosphonic acid aqueous mother liquor, after stirring, and stratification; (2) glyphosate alkaline mother liquor is concentrated into glyphosate content 4-5%, crystallization, separates, and obtains glyphosate concentrated mother liquor; (3), under strong acid condition, sodium-chlor and other inorganic salt crystallizations, carry out solid-liquid separation, obtains filter cake and filtrate; (4) again through crystallization, filtration, the dry former powder of glyphosate that obtains.
This patented method is desalination under strong acid condition, although the salinity outside the inorganic salt solubility range such as sodium-chlor can be removed, the inorganic salt in solubility range still exist in mother liquor in a large number; Although and method can, by the proposition of glyphosate powder, due to the existence of inorganic salt, can only propose the glyphosate of 20-30%, and former opaque amount obviously decline.
201010186170.5, name is called the application for a patent for invention of " a kind of method that reclaims the former powder of glyphosate from glyphosate mother solution ", and recovery method step is: (1) adds hydrochloric acid in the glyphosate alkaline mother liquor of glycine method recovery triethylamine; (2) mother liquor step (1) being obtained is concentrated into glyphosate content 8-10%, obtains filter cake and filtrate; (3) after filtrate decrease temperature crystalline step (2) being obtained, filter, obtain filter cake and filtrate; (4) filtrate is applied mechanically to lower batch of removal process.Due to glyphosate existence form complexity in mother liquor, only by adding crystal water, and do not provide energy, the glyphosate molecule in mother liquor cannot be separated out by mass crystallization; , in mother liquor, contain salt meanwhile, in a small amount of glyphosate of separating out, will contain a large amount of salinities, affect the quality of glyphosate.Therefore the method cannot reach glyphosate mother solution and efficiently puies forward powder object.
Summary of the invention
The technical barrier that cannot directly extract from glyphosate mother solution glyphosate technicals in order to solve prior art, the invention provides a kind of technique of extracting the former powder of glyphosate from glyphosate mother solution, can efficiently glyphosate in mother liquor be proposed with the form of former powder.
In order to realize foregoing invention object, its concrete technical scheme is as follows:
A kind of technique of extracting the former powder of glyphosate from glyphosate mother solution, it is characterized in that: in glyphosate by using glycine is synthetic, by the synthetic condensated liquid obtaining, add excessive hydrochloric acid hydrolysis, in hydrolytic process, glyphosate membrane concentration mother liquor is joined in hydrolyzed solution, continue hydrolysis, extract the former powder of glyphosate.
In producing glyphosate by using glycine technique, hydrolytic process can be by methyl alcohol, and the distillations such as moisture are gone out, and glyphosate composition can not be distilled away.Put forward powder scheme for this, because concentrated mother liquor add-on is less, through the pyrogenic distillation of hydrolytic process, the mother liquor amount obtaining is certain substantially, and glyphosate content also can only be in some specific scopes.In the time that in mother liquor, glyphosate content exceedes this scope, the glyphosate of the concentrated mother liquor adding will separate out with the production material of the form of former medicine and normal process simultaneously.
In glyphosate concentrated mother liquor of the present invention, by mass, containing glyphosate 5-20%, salinity 0.1-2%, pH=0.1-3.0.Save process energy consumption, control the salt content of glyphosate technicals, alleviate environmental protection pressure.
Describedly add excessive hydrochloric acid to refer to, the amount that adds hydrochloric acid be condensated liquid be hydrolyzed required hydrochloric acid content 1.05-3.0 doubly.Suitably add hydrochloric acid and be to add concentrated mother liquor in hydrolyzed solution, former hydrolyzed solution is diluted, now in hydrolyzed solution, concentration of hydrochloric acid reduces, and affects hydrolysis efficiency, finally will affect former powder yield.
In the time that hydrolysis temperature reaches 50-110 DEG C, add glyphosate mother solution.Be conducive to reduce energy consumption, increase safety coefficient.
The concentrated mother liquor amount adding is 0.1-3.0t/1t glyphosate output, and the glyphosate in mother liquor can at utmost extract with the production material hydrolysis of normal process.Mother liquor add-on is excessive, reticulated structure and part that the energy providing in temperature range for hydrolysis can only partially open glyphosate in parcel mother liquor disconnect symbiosis macromolecular substance, glyphosate in mother liquor can only be separated out by partial crystallization, and mother liquor glyphosate extraction yield decreases.
Glyphosate membrane concentration technique of the present invention is: the glyphosate original nut liquid after separation triethylamine is through pre-treatment, remove solid insoluble impurity in original nut liquid, mother liquid obtained through the processing of first-stage reverse osmosis film, one-level membrane concentration mother liquor enters the processing of two-pass reverse osmosis film after acidifying, the secondary membrane concentration mother liquor obtaining enters the desalination of three-stage electrodialysis exchange membrane after acidifying, film is processed to the one-level, secondary, the three grades of light liquid that produce to be merged, through level Four reverse osmosis membrane, it is concentrated that gained level Four membrane concentration liquid returns to the circulation of one-level film; The light liquid that level Four film produces does biochemical treatment, reclaims three grades of membrane concentration mother liquors and obtains glyphosate concentrated mother liquor.
Preferably, in three grades of described EDBM processes, by adding NaCl or NH in the light liquid of water management
4the concentration of Cl is 1-9%.Measure NaCl or the NH of three grades of membrane concentration liquid by timing
4the content of Cl, controls NaCl or NH
4the concentration of Cl, in the scope of 1-9%, can obtain the concentrated mother liquor finished product of least loss amount.
Preferably, the concentrated ratio of described first-stage reverse osmosis film is 1-5 times, and the concentrated ratio of two-pass reverse osmosis film is 1-5 times, can farthest retain the recovery of glyphosate in mother liquor.Described concentrated ratio is mother liquor after concentrated and the concentration ratio before charging.
Preferably, the pH after described one-level membrane concentration mother liquor acidifying is 2.0-5.0, is beneficial to follow-up secondary membrane reverse osmosis and concentrates and three grades of films exchange desalting treatment.
Preferably, the pH after described secondary membrane concentration mother liquor acidifying is 0.1-3.0, is beneficial to three grades of follow-up film exchange desalting treatment.
Preferably, the glyphosate content of described one-level membrane concentration mother liquor is 2-6%, and the glyphosate content of secondary membrane concentration mother liquor is 4-8%, and the glyphosate content of three grades of membrane concentration mother liquors is 5-20%.The concentration control of films at different levels is the losses in order to reduce effective constituent in mother liquor, makes mother liquor obtain farthest effectively utilizing.
Beneficial effect of the present invention is:
1, the scheme of the former powder of glyphosate mother solution extraction glyphosate in the present invention, adopt the extraction process combining with the hydrolysis process of conventional glyphosate production, glyphosate mother solution after concentration is joined in hydrolyzed solution, there is hydrolysis reaction with together with the production material of normal process, can extract more than 95% glyphosate in concentrated mother liquor.
2, whole process program of the present invention has been made important breakthrough in the glyphosate recovery problem of glyphosate mother solution, can not only fundamentally solve environmental issue in glyphosate by using glycine production, also improve the yield of glyphosate dry powder, indirectly expanded the production capacity of enterprise.In package, the mother liquor that glyphosate production produces can digest by carrying powder, and enterprise more can increase benefit in alleviating environmental protection pressure.
3, the present invention strictly controls the index of glyphosate concentrated mother liquor, and containing glyphosate 5-20%, salinity 0.1-2%, pH=0.1-3.0, can save process energy consumption, can control again the salt content of glyphosate technicals, alleviates environmental protection pressure.
4, technique of the present invention, in the time that hydrolysis temperature reaches 50-110 DEG C, adds glyphosate mother solution.If concentrated mother liquor adds too early, the hydrolyzation material generation side reaction of composition and normal process in meeting generation concentrated mother liquor, cause the reduction of glyphosate powder yield, and temperature is too low, open the reticulated structure of glyphosate in parcel mother liquor and disconnect the required energy shortage of symbiosis macromolecular substance, glyphosate in mother liquor cannot crystallization, can not reach mother liquor and put forward powder object; On the other hand, hydrolytic process is a persistently overheating process, while starting to be hydrolyzed, hydrolyzation material has occupied more than 70% volume of hydrolysis kettle, hydrolysis kettle liquid level can go up and reduce with temperature, concentrated mother liquor adds too early, and the potential safety hazard of run at high level can occur, so will inevitably cause larger impact to producing; Hydrolytic process is also the process of a distillation simultaneously, and concentrated mother liquor adds too early, and concentrated mother liquor can heat up with the condensated liquid of normal process, and energy consumption can increase too much.Therefore, strictly control the time point that concentrated mother liquor adds, be not only conducive to reduce energy consumption, also help increase safety coefficient.
5, the concentrated mother liquor amount that technique of the present invention adds is 0.1-3.0t/1t glyphosate output, and 1t glyphosate output adds the concentrated mother liquor of 0.1-3.0t.Because mother liquor add-on is excessive, reticulated structure and part that the energy providing in temperature range for hydrolysis can only partially open glyphosate in parcel mother liquor disconnect symbiosis macromolecular substance, glyphosate in mother liquor can only be separated out by partial crystallization, and mother liquor glyphosate is put forward a point rate and decreased.Therefore,, within the scope of this, the glyphosate in concentrated mother liquor can at utmost extract with the production material hydrolysis of normal process.
6, the membrane treatment process of glyphosate mother solution of the present invention adopts reverse osmosis membrane and electrodialysis exchange membrane to concentrate the glyphosate concentrated mother liquor that obtains glyphosate content 5-20%, can retain the sweet phosphine of increasing more than more than 95% glyphosate and 95% in original nut liquid, salinity is removed more than 99%, and other removal of impurity is more than 95%.This scheme equipment routine, simple to operate, in the concentrated mother liquor obtaining, the loss of glyphosate is little.
Embodiment
Below in conjunction with embodiment, essentiality content of the present invention is described in further detail.
Embodiment 1
A kind of technique of extracting the former powder of glyphosate from glyphosate mother solution, in glyphosate by using glycine is synthetic, by the synthetic condensated liquid obtaining, add excessive hydrochloric acid hydrolysis, in hydrolytic process, glyphosate concentrated mother liquor after membrane concentration is joined in hydrolyzed solution, continue hydrolysis, extract the former powder of glyphosate.
Embodiment 2
A kind of technique of extracting the former powder of glyphosate from glyphosate mother solution, in glyphosate by using glycine is synthetic, by the synthetic condensated liquid obtaining, add excessive hydrochloric acid hydrolysis, in hydrolytic process, glyphosate concentrated mother liquor after membrane concentration is joined in hydrolyzed solution, continue hydrolysis, extract the former powder of glyphosate.
In described glyphosate concentrated mother liquor, by mass, containing glyphosate 5%, salinity 0.1%, pH=3.
Embodiment 3
A kind of technique of extracting the former powder of glyphosate from glyphosate mother solution, in glyphosate by using glycine is synthetic, by the synthetic condensated liquid obtaining, add excessive hydrochloric acid hydrolysis, in hydrolytic process, glyphosate concentrated mother liquor after membrane concentration is joined in hydrolyzed solution, continue hydrolysis, extract the former powder of glyphosate.
In described glyphosate concentrated mother liquor, by mass, containing glyphosate 20%, salinity 2%, pH=0.1.
Describedly add excessive hydrochloric acid to refer to, the amount that adds hydrochloric acid is 3 times that condensated liquid is hydrolyzed required hydrochloric acid content.
Embodiment 4
A kind of technique of extracting the former powder of glyphosate from glyphosate mother solution, in glyphosate by using glycine is synthetic, by the synthetic condensated liquid obtaining, add excessive hydrochloric acid hydrolysis, in hydrolytic process, glyphosate concentrated mother liquor after membrane concentration is joined in hydrolyzed solution, continue hydrolysis, extract the former powder of glyphosate.
In described glyphosate concentrated mother liquor, by mass, containing glyphosate 10%, salinity 1%, pH=1.
Describedly add excessive hydrochloric acid to refer to, the amount that adds hydrochloric acid is 1.05 times that condensated liquid is hydrolyzed required hydrochloric acid content.
In the time that hydrolysis temperature reaches 50 DEG C, add glyphosate concentrated mother liquor.
Embodiment 5
A kind of technique of extracting the former powder of glyphosate from glyphosate mother solution, in glyphosate by using glycine is synthetic, by the synthetic condensated liquid obtaining, add excessive hydrochloric acid hydrolysis, in hydrolytic process, glyphosate concentrated mother liquor after membrane concentration is joined in hydrolyzed solution, continue hydrolysis, extract the former powder of glyphosate.
In described glyphosate concentrated mother liquor, by mass, containing glyphosate 8%, salinity 1.5%, pH=3.
Describedly add excessive hydrochloric acid to refer to, the amount that adds hydrochloric acid is 2 times that condensated liquid is hydrolyzed required hydrochloric acid content.
In the time that hydrolysis temperature reaches 110 DEG C, add glyphosate concentrated mother liquor.
The amount of the described glyphosate concentrated mother liquor adding is 2t/1t glyphosate output.
Embodiment 6
A kind of technique of extracting the former powder of glyphosate from glyphosate mother solution, in glyphosate by using glycine is synthetic, by the synthetic condensated liquid obtaining, add excessive hydrochloric acid hydrolysis, in hydrolytic process, glyphosate concentrated mother liquor after membrane concentration is joined in hydrolyzed solution, continue hydrolysis, extract the former powder of glyphosate.
In described glyphosate concentrated mother liquor, by mass, containing glyphosate 15%, salinity 0.8%, pH=1.2.
Describedly add excessive hydrochloric acid to refer to, the amount that adds hydrochloric acid is 1.1 times that condensated liquid is hydrolyzed required hydrochloric acid content.
In the time that hydrolysis temperature reaches 90 DEG C, add glyphosate concentrated mother liquor.
The amount of the described glyphosate concentrated mother liquor adding is 0.1t/1t glyphosate output.
Embodiment 7
A kind of technique of extracting the former powder of glyphosate from glyphosate mother solution, in glyphosate by using glycine is synthetic, by the synthetic condensated liquid obtaining, add excessive hydrochloric acid hydrolysis, in hydrolytic process, glyphosate concentrated mother liquor after membrane concentration is joined in hydrolyzed solution, continue hydrolysis, extract the former powder of glyphosate.
In described glyphosate concentrated mother liquor, by mass, containing glyphosate 12%, salinity 0.8%, pH=2.2.
Describedly add excessive hydrochloric acid to refer to, the amount that adds hydrochloric acid is 2.8 times that condensated liquid is hydrolyzed required hydrochloric acid content.
In the time that hydrolysis temperature reaches 80 DEG C, add glyphosate concentrated mother liquor.
The amount of the described glyphosate concentrated mother liquor adding is 3t/1t glyphosate output.
Embodiment 8
A kind of technique of extracting the former powder of glyphosate from glyphosate mother solution, in glyphosate by using glycine is synthetic, by the synthetic condensated liquid obtaining, add excessive hydrochloric acid hydrolysis, in hydrolytic process, glyphosate concentrated mother liquor after membrane concentration is joined in hydrolyzed solution, continue hydrolysis, extract the former powder of glyphosate.
In described glyphosate concentrated mother liquor, by mass, containing glyphosate 16%, NaCl 1.2%, pH=0.5.
Describedly add excessive hydrochloric acid to refer to, the amount that adds hydrochloric acid is 1.5 times that condensated liquid is hydrolyzed required hydrochloric acid content.
In the time that hydrolysis temperature reaches 60 DEG C, add glyphosate concentrated mother liquor.
The amount of the described glyphosate concentrated mother liquor adding is 1.2 t/1t glyphosate output.
Embodiment 9
Glyphosate membrane concentration technique of the present invention is: the glyphosate original nut liquid after separation triethylamine is through pre-treatment, remove solid insoluble impurity in original nut liquid, mother liquid obtained through the processing of first-stage reverse osmosis film, one-level membrane concentration mother liquor enters the processing of two-pass reverse osmosis film after acidifying, the secondary membrane concentration mother liquor obtaining enters the desalination of three-stage electrodialysis exchange membrane after acidifying, film is processed to the one-level, secondary, the three grades of light liquid that produce to be merged, through level Four reverse osmosis membrane, it is concentrated that gained level Four membrane concentration liquid returns to the circulation of one-level film; The light liquid that level Four film produces does biochemical treatment, reclaims three grades of membrane concentration mother liquors and obtains glyphosate concentrated mother liquor.
Described glyphosate original nut liquid separates the glyphosate mother solution after triethylamine.
Embodiment 10
Glyphosate membrane concentration technique of the present invention is: the glyphosate original nut liquid after separation triethylamine is through pre-treatment, remove solid insoluble impurity in original nut liquid, mother liquid obtained through the processing of first-stage reverse osmosis film, one-level membrane concentration mother liquor enters the processing of two-pass reverse osmosis film after acidifying, the secondary membrane concentration mother liquor obtaining enters the desalination of three-stage electrodialysis exchange membrane after acidifying, film is processed to the one-level, secondary, the three grades of light liquid that produce to be merged, through level Four reverse osmosis membrane, it is concentrated that gained level Four membrane concentration liquid returns to the circulation of one-level film; The light liquid that level Four film produces does biochemical treatment, reclaims three grades of membrane concentration mother liquors and obtains glyphosate concentrated mother liquor.
In three grades of described EDBM processes, be 1% by adding the concentration of NaCl in the light liquid of water management.
Embodiment 11
Glyphosate membrane concentration technique of the present invention is: the glyphosate original nut liquid after separation triethylamine is through pre-treatment, remove solid insoluble impurity in original nut liquid, mother liquid obtained through the processing of first-stage reverse osmosis film, one-level membrane concentration mother liquor enters the processing of two-pass reverse osmosis film after acidifying, the secondary membrane concentration mother liquor obtaining enters the desalination of three-stage electrodialysis exchange membrane after acidifying, film is processed to the one-level, secondary, the three grades of light liquid that produce to be merged, through level Four reverse osmosis membrane, it is concentrated that gained level Four membrane concentration liquid returns to the circulation of one-level film; The light liquid that level Four film produces does biochemical treatment, reclaims three grades of membrane concentration mother liquors and obtains glyphosate concentrated mother liquor.
In three grades of described EDBM processes, be 9% by adding the concentration of NaCl in the light liquid of water management.
The concentrated ratio of described first-stage reverse osmosis film is 1 times, and the concentrated ratio of two-pass reverse osmosis film is 1 times.
Embodiment 12
Glyphosate membrane concentration technique of the present invention is: the glyphosate original nut liquid after separation triethylamine is through pre-treatment, remove solid insoluble impurity in original nut liquid, mother liquid obtained through the processing of first-stage reverse osmosis film, one-level membrane concentration mother liquor enters the processing of two-pass reverse osmosis film after acidifying, the secondary membrane concentration mother liquor obtaining enters the desalination of three-stage electrodialysis exchange membrane after acidifying, film is processed to the one-level, secondary, the three grades of light liquid that produce to be merged, through level Four reverse osmosis membrane, it is concentrated that gained level Four membrane concentration liquid returns to the circulation of one-level film; The light liquid that level Four film produces does biochemical treatment, reclaims three grades of membrane concentration mother liquors and obtains glyphosate concentrated mother liquor.
In three grades of described EDBM processes, be 5% by adding the concentration of NaCl in the light liquid of water management.
The concentrated ratio of described first-stage reverse osmosis film is 5 times, and the concentrated ratio of two-pass reverse osmosis film is 5 times.
PH after described one-level membrane concentration mother liquor acidifying is 2.0, and the pH after the acidifying of secondary membrane concentration mother liquor is 0.1.
Embodiment 13
Glyphosate membrane concentration technique of the present invention is: the glyphosate original nut liquid after separation triethylamine is through pre-treatment, remove solid insoluble impurity in original nut liquid, mother liquid obtained through the processing of first-stage reverse osmosis film, one-level membrane concentration mother liquor enters the processing of two-pass reverse osmosis film after acidifying, the secondary membrane concentration mother liquor obtaining enters the desalination of three-stage electrodialysis exchange membrane after acidifying, film is processed to the one-level, secondary, the three grades of light liquid that produce to be merged, through level Four reverse osmosis membrane, it is concentrated that gained level Four membrane concentration liquid returns to the circulation of one-level film; The light liquid that level Four film produces does biochemical treatment, reclaims three grades of membrane concentration mother liquors and obtains glyphosate concentrated mother liquor.
In three grades of described EDBM processes, by adding NH in the light liquid of water management
4the concentration of Cl is 2%.
The concentrated ratio of described first-stage reverse osmosis film is 2 times, and the concentrated ratio of two-pass reverse osmosis film is 2 times.
PH after described one-level membrane concentration mother liquor acidifying is 5.0, and the pH after the acidifying of secondary membrane concentration mother liquor is 2.0.
The glyphosate content of described one-level membrane concentration mother liquor is 2%, and the glyphosate content of secondary membrane concentration mother liquor is that the glyphosate content of 4%, three grade of membrane concentration mother liquor is 5%.
Embodiment 14
Glyphosate membrane concentration technique of the present invention is: the glyphosate original nut liquid after separation triethylamine is through pre-treatment, remove solid insoluble impurity in original nut liquid, mother liquid obtained through the processing of first-stage reverse osmosis film, one-level membrane concentration mother liquor enters the processing of two-pass reverse osmosis film after acidifying, the secondary membrane concentration mother liquor obtaining enters the desalination of three-stage electrodialysis exchange membrane after acidifying, film is processed to the one-level, secondary, the three grades of light liquid that produce to be merged, through level Four reverse osmosis membrane, it is concentrated that gained level Four membrane concentration liquid returns to the circulation of one-level film; The light liquid that level Four film produces does biochemical treatment, reclaims three grades of membrane concentration mother liquors and obtains glyphosate concentrated mother liquor.
In three grades of described EDBM processes, by adding NH in the light liquid of water management
4the concentration of Cl is 6%.
The concentrated ratio of described first-stage reverse osmosis film is 3 times, and the concentrated ratio of two-pass reverse osmosis film is 3 times.
PH after described one-level membrane concentration mother liquor acidifying is 3, and the pH after the acidifying of secondary membrane concentration mother liquor is 1.
The glyphosate content of described one-level membrane concentration mother liquor is 6%, and the glyphosate content of secondary membrane concentration mother liquor is that the glyphosate content of 8%, three grade of membrane concentration mother liquor is 20%.
Embodiment 15
Glyphosate membrane concentration technique of the present invention is: the glyphosate original nut liquid after separation triethylamine is through pre-treatment, remove solid insoluble impurity in original nut liquid, mother liquid obtained through the processing of first-stage reverse osmosis film, one-level membrane concentration mother liquor enters the processing of two-pass reverse osmosis film after acidifying, the secondary membrane concentration mother liquor obtaining enters the desalination of three-stage electrodialysis exchange membrane after acidifying, film is processed to the one-level, secondary, the three grades of light liquid that produce to be merged, through level Four reverse osmosis membrane, it is concentrated that gained level Four membrane concentration liquid returns to the circulation of one-level film; The light liquid that level Four film produces does biochemical treatment, reclaims three grades of membrane concentration mother liquors and obtains glyphosate concentrated mother liquor.
In three grades of described EDBM processes, be 3% by adding the concentration of NaCl in the light liquid of water management.
The concentrated ratio of described first-stage reverse osmosis film is 2 times, and the concentrated ratio of two-pass reverse osmosis film is 2 times.
PH after described one-level membrane concentration mother liquor acidifying is 2.5, and the pH after the acidifying of secondary membrane concentration mother liquor is 1.5.
The glyphosate content of described one-level membrane concentration mother liquor is 3%, and the glyphosate content of secondary membrane concentration mother liquor is that the glyphosate content of 6%, three grade of membrane concentration mother liquor is 10%.
Embodiment 16
Extract glyphosate mother solution after triethylamines through three-stage filtration pre-treatment by 10 tons, remove solid insoluble impurity in original nut liquid, mother liquid obtained through the processing of first-stage reverse osmosis film, add again hydrochloric acid and adjust pH=2.73, enter the processing of two-pass reverse osmosis film, the secondary membrane concentration mother liquor obtaining, adds hydrochloric acid fine setting pH=1.77, enter the desalination of three-stage electrodialysis exchange membrane, obtain product glyphosate concentrated mother liquor.The total interception rate of glyphosate is 96.3%, glyphosate content 5.26% in final glyphosate concentrated mother liquor, salts contg 0.92%.
Embodiment 17
According to glycine method synthesizing glyphosate, two parts of raw materials that take equal in quality synthesize after condensated liquid under identical conditions, and portion completes follow-up hydrolysis by normal process, and crystallization is filtered, dry, obtains glyphosate technicals.Another part adds 340g hydrochloric acid hydrolysis, continues by normal process to complete hydrolysis after adding concentrated mother liquor 200g of the present invention while being warming up to 80 DEG C, and crystallization, filters, the dry glyphosate technicals that obtains.
Normal process obtains glyphosate technicals 109.5g, and content is 95.6%, obtains glyphosate technicals 120.3g after adding mother liquor, and content is 95.2%, and it is 97.6% that gelled acid mother liquor is put forward powder rate.
Claims (10)
1. one kind is extracted the technique of the former powder of glyphosate from glyphosate mother solution, it is characterized in that: in glyphosate by using glycine is synthetic, by the synthetic condensated liquid obtaining, add excessive hydrochloric acid hydrolysis, in hydrolytic process, glyphosate concentrated mother liquor after membrane concentration is joined in hydrolyzed solution, continue hydrolysis, extract the former powder of glyphosate.
2. a kind of technique of extracting the former powder of glyphosate from glyphosate mother solution according to claim 1, is characterized in that: in described glyphosate concentrated mother liquor, by mass, and containing glyphosate 5-20%, salinity 0.1-2%, pH=0.1-3.0.
3. a kind of technique of extracting the former powder of glyphosate from glyphosate mother solution according to claim 1, is characterized in that: described in add excessive hydrochloric acid to refer to, the amount that adds hydrochloric acid be condensated liquid be hydrolyzed required hydrochloric acid content 1.05-3.0 doubly.
4. a kind of technique of extracting the former powder of glyphosate from glyphosate mother solution according to claim 1, is characterized in that: in the time that hydrolysis temperature reaches 50-110 DEG C, add glyphosate concentrated mother liquor.
5. a kind of technique of extracting the former powder of glyphosate from glyphosate mother solution according to claim 1, is characterized in that: described in the amount of the glyphosate concentrated mother liquor that adds be 0.1-3.0t/1t glyphosate output.
6. a kind of technique of extracting the former powder of glyphosate from glyphosate mother solution according to claim 1, it is characterized in that: described glyphosate membrane concentration technique is: the glyphosate original nut liquid after separation triethylamine is through pre-treatment, remove solid insoluble impurity in original nut liquid, mother liquid obtained through the processing of first-stage reverse osmosis film, one-level membrane concentration mother liquor enters the processing of two-pass reverse osmosis film after acidifying, the secondary membrane concentration mother liquor obtaining enters the desalination of three-stage electrodialysis exchange membrane after acidifying, film is processed to the one-level producing, secondary, three grades of light liquid merge, through level Four reverse osmosis membrane, it is concentrated that gained level Four membrane concentration liquid returns to the circulation of one-level film, the light liquid that level Four film produces does biochemical treatment, reclaims three grades of membrane concentration mother liquors and obtains glyphosate concentrated mother liquor.
7. a kind of technique of extracting the former powder of glyphosate from glyphosate mother solution according to claim 6, is characterized in that: in three grades of described EDBM processes, by adding NaCl or NH in the light liquid of water management
4the concentration of Cl is 1-9%.
8. a kind of technique of extracting the former powder of glyphosate from glyphosate mother solution according to claim 6, is characterized in that: the concentrated ratio of described first-stage reverse osmosis film is 1-5 times, and the concentrated ratio of two-pass reverse osmosis film is 1-5 times.
9. a kind of technique of extracting the former powder of glyphosate from glyphosate mother solution according to claim 6, is characterized in that: the PH after described one-level membrane concentration mother liquor acidifying is 2.0-5.0, and the pH after the acidifying of secondary membrane concentration mother liquor is 0.1-3.0.
10. a kind of technique of extracting the former powder of glyphosate from glyphosate mother solution according to claim 6, it is characterized in that: the glyphosate content of described one-level membrane concentration mother liquor is 2-6%, the glyphosate content of secondary membrane concentration mother liquor is 4-8%, and the glyphosate content of three grades of membrane concentration mother liquors is 5-20%.
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| CN106565550A (en) * | 2016-11-02 | 2017-04-19 | 河北美邦工程科技股份有限公司 | Method for concentrating and dewatering camphor sulfonic acid solution in production process of L-phenylglycine |
| CN113072580A (en) * | 2021-04-19 | 2021-07-06 | 浙江新安化工集团股份有限公司 | Method for recovering glyphosate from glyphosate acid mother liquor by glycine method |
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| CN101659673A (en) * | 2009-09-24 | 2010-03-03 | 南京工业大学 | Treatment process for recycling glyphosate mother liquor |
| CN101817844A (en) * | 2009-10-16 | 2010-09-01 | 杭州深瑞水务有限公司 | Method for treating glyphosate mother solution by integrated membrane separation process |
| CN103949160A (en) * | 2013-06-24 | 2014-07-30 | 浙江赛特膜技术有限公司 | Method and apparatus for resourceful treatment of glyphosate mother liquor by bipolar membrane electrodialysis integrated nanofiltration and reverse osmosis technology |
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| CN101659673A (en) * | 2009-09-24 | 2010-03-03 | 南京工业大学 | Treatment process for recycling glyphosate mother liquor |
| CN101817844A (en) * | 2009-10-16 | 2010-09-01 | 杭州深瑞水务有限公司 | Method for treating glyphosate mother solution by integrated membrane separation process |
| CN103949160A (en) * | 2013-06-24 | 2014-07-30 | 浙江赛特膜技术有限公司 | Method and apparatus for resourceful treatment of glyphosate mother liquor by bipolar membrane electrodialysis integrated nanofiltration and reverse osmosis technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106565550A (en) * | 2016-11-02 | 2017-04-19 | 河北美邦工程科技股份有限公司 | Method for concentrating and dewatering camphor sulfonic acid solution in production process of L-phenylglycine |
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| CN113072580A (en) * | 2021-04-19 | 2021-07-06 | 浙江新安化工集团股份有限公司 | Method for recovering glyphosate from glyphosate acid mother liquor by glycine method |
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