CN105566382B - A kind of method that glyphosate mother solution recycles - Google Patents
A kind of method that glyphosate mother solution recycles Download PDFInfo
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- CN105566382B CN105566382B CN201510959822.7A CN201510959822A CN105566382B CN 105566382 B CN105566382 B CN 105566382B CN 201510959822 A CN201510959822 A CN 201510959822A CN 105566382 B CN105566382 B CN 105566382B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
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Abstract
The present invention relates to a kind of methods that glyphosate mother solution recycles, it is characterized in that：Glyphosate mother solution is after nano-filtration membrane equipment is handled, glyphosate in concentrate recycles, and film permeate passes through the reaction kettle stir process containing activated carbon, last millipore filter press filtration again, filter cake activated carbon returns to reaction kettle and repeats, and filter liquor may be used as industrial water or cleaning water.Using the method for the present invention, the rate of recovery of glyphosate is up to 90% or more.
Description
Technical field
The present invention relates to a kind of methods that glyphosate mother solution recycles, and grass is synthesized more particularly, to iminodiacetic acid (salt) acid system
The processing method of mother liquor after sweet phosphine technique extraction glyphosate powder.
Background technology
Glyphosate is also known as glyphosate, agriculture up to etc., English name glyphosate, entitled N- (phosphonomethyl) glycine of chemistry,
It is a kind of non-selective steriland herbicide by Monsanto Chemicals' development and production, there is wide spectrum, efficient, low toxicity, nothing
The characteristics of residual.The country's main production method of glyphosate has glycine method and iminodiacetic acid at present（IDA）Method, wherein
IDA methods, which prepare glyphosate, is gone back by hydrolyzing, being condensed into pmida, then by pmida oxidation using iminodiacetonitrile as raw material
Original is prepared into glyphosate.
During preparing glyphosate from N-phosphonomethyl aminodiacetic acid, one ton of glyphosate powder of production just has 5~6 tons of glyphosate mother solution, and grass is sweet
The glyphosate concentration of phosphine mother liquor is generally 1~5%, and previous glyphosate mother solution majority is the gyphosate solution for adding original powder to be configured to 10%
Sale.After low concentration gyphosate solution is prohibited, the gyphosate solution through 30% or more distillation and concentration compound concentration, product formaldehyde
The national standard of gyphosate solution is not met with heat storage index, final products are unqualified.Therefore glyphosate mother solution glyphosate
Recovery processing and the removal of formaldehyde become manufacturer's urgent need to solve the problem.Application No. is in 200810163281.7 patent
The method of open glyphosate mother solution glyphosate recycling, but need high temperature when this method glyphosate mother solution film process（50-80
℃）Film concentrates, and when extract powder needs freezing and crystallizing again（10 DEG C or less）, such one hot cold energy consumption is very big, and open skill
The rate of recovery of mother liquor glyphosate is not mentioned in art.Application No. is glyphosate mother is disclosed in 200910097423.9 patent
Liquid glyphosate recycles and the method for formaldehyde removal.Level Four film process, level-one are needed when the technology glyphosate mother solution film process
The dope glyphosate concentration of film concentration is low（2-7%）And filtrate cycle number is low（1-20 times）, need to be passed through ammonia Wu Luotuo be made
Product, such utilization rate of equipment and installations is low, and filtrate later process is of high cost.Application No. is disclose grass in 201212434885.6 patent
The method of sweet phosphine mother liquor glyphosate recycling and formaldehyde removal, the technology obtain solid slow-release urine by the way that industrial urea is added
Element removes formaldehyde to recycle glyphosate mother solution, which does not mention the specific of the recycling of glyphosate mother solution glyphosate
Data and clean-up performance.
Existing patented technology has equipment investment big, and high energy consumption, technique is cumbersome, the glyphosate recycling in glyphosate mother solution
For rate 80% or so, formaldehyde removal rate highest can reach 90%, the few disadvantage of the recycled number of mother liquor.Therefore, it is understanding
Certainly presently, there are problems for industry, and many researchs are also in process at present.
Invention content
The object of the present invention is to provide a kind of recovery methods of glyphosate mother solution, it is characterized in that：Glyphosate mother solution is by receiving
After the processing of filter membrane equipment, the glyphosate in concentrate recycles, and film permeate is stirred by the reaction kettle containing activated carbon again
Processing, last millipore filter press filtration, filter cake activated carbon return reaction kettle reuse, filter liquor may be used as industrial water or
Person's cleaning water.
The glyphosate mother solution is that the mother liquor after glyphosate powder is extracted in iminodiacetic acid (salt) acid system synthesizing glyphosate technique,
Glyphosate weight concentration is 1~5%.Wherein iminodiacetic acid (salt) acid system is using iminodiacetonitrile as raw material, by hydrolyzing, being condensed
It is prepared into glyphosate at pmida, then by pmida redox.
NF membrane used in the nano-filtration membrane equipment is rolled film, and molecular cut off is 100~500Da, operating pressure
For 1.5~4.5Mpa, operating temperature is 15~50 DEG C.
It is needed in the nanofiltration process concentrate plus 1~10 tap water, the additive amount of each tap water penetrates for nanofiltration
0.5~10 times of liquid weight.
Activated carbon in the reaction kettle is commercially available activated carbon, additive amount account for film through total solution weight 1~
10%, specific surface area is 2000~3000 ㎡/g.
Solution reaction temperature in the reaction kettle is 20~90 DEG C, and the reaction time is 3~24 hours.
The millipore filter is equipped with filter stick, and the aperture of filter stick is 0.1~0.5 μm, and operating pressure 0.10~
0.50Mpa。
Glyphosate mother liquor of the present invention eliminates 95% or more formaldehyde after nanofiltration（Permeate is arrived）, after nanofiltration
Concentrate addition part original glyphosate powder can prepare 30% or more qualified gyphosate solution, and the rate of recovery of glyphosate is up to 90%
More than.For nanofiltration permeate liquid again after the processing such as activated carbon, formaldehyde is oxidized to carbon dioxide or formic acid, and the removal rate of formaldehyde reaches
99% or more.It is used directly for industrial water after permeate that treated in this way filtering, filter cake activated carbon can directly repeat to make
With, or mend the new activated carbon of point and reuse.
Method for processing mother solution of glyphosate of the present invention compared with prior art, has the advantages that following some：
（1）The present invention extracts the rate of recovery higher of glyphosate technicals from mother liquor, up to 90% or more.
（2）Activated carbon catalysis long lifespan used in the present invention, consumption is low, may be reused, and it is equivalent to remove formaldehyde to the end
It is burned when fruit is undesirable, green economy is pollution-free.
（3）The present invention solves the glyphosate solution recycled from glyphosate mother solution cannot prepare conjunction because the indexs such as formaldehyde are excessively high
The problem of 30% gyphosate solution of lattice.Glyphosate mother solution impurity after processing is few, and formaldehyde removal rate utilizes mother 95% or more
The gyphosate solution that liquid is prepared meets FAO standards, and permeate that treated is used directly for glyphosate production water, solves
The problem of glyphosate waste water processing, reduces the discharge of waste water, saves production cost.
Description of the drawings
Fig. 1 is present invention process flow chart.
Specific implementation mode
With reference to specific embodiment, the present invention is described in further detail, but right of the present invention be not limited to it is following
Example：
Embodiment 1
Fig. 1 is shown in embodiment technological process.Weigh the glyphosate that glyphosate concentration is 2.51%, concentration of formaldehyde is 35.41g/kg
Mother liquor 100kg pours into the hopper of nano-filtration membrane equipment, is 25m equipped with a nanofiltration area2Rolling NF membrane, open cycle
Pump adjusts pressure valve and pressure is adjusted to 1.8Mpa, controls 25 DEG C of temperature, and when permeate is gone out to 70kg, 50kg is added toward hopper
Tap water when permeate goes out 50kg again, then adds 50kg tap water, and repeatedly plus the water of 3 equivalent, permeate are taken in total
Going out 220kg, permeate concentration of formaldehyde is 15.50g/kg, and glyphosate concentration 0.096%, obtained concentrate is 30 kilograms,
Wherein content of formaldehyde is 4.3g/kg, and glyphosate content is 7.66%.Concentrate is extracted into surge-tank and original glyphosate powder and auxiliary agent is added
Prepare 30% gyphosate solution.So far the mother liquor glyphosate rate of recovery is 91.50%, and formaldehyde removal rate is 96.33%.
Above-mentioned permeate 220kg is poured into 500L reaction kettles, while activated carbon 5kg is added, and is heated while stirring, temperature control
60 DEG C are made as, the reaction time is 24 hours.The millipore filter that volume is 300L is discharged into after reaction.It is slowly pressurizeed with compressed air
To 0.2Mpa, until pressing dry.Finally obtain filter cake 11.5kg, filtered fluid 211.8kg.Filter cake is mainly the activity for having adsorbed permeate
Charcoal, can direct repeated application.Concentration of formaldehyde is 0.013g/kg to filtered fluid after testing, this ground beetle aldehyde removal rate is 99.92%.It crosses
Filtrate draws up industrial water of the head tank as synthesizing glyphosate when.It is final calculate the mother liquor glyphosate rate of recovery is
91.50%, formaldehyde removal rate is 96.33%*99.92%=96.25%.
Embodiment 2
Fig. 1 is shown in embodiment technological process.Weigh the glyphosate that glyphosate concentration is 3.02%, concentration of formaldehyde is 32.70g/kg
Mother liquor 100kg pours into the hopper of nano-filtration membrane equipment, is 25m equipped with a nanofiltration area2Rolling NF membrane, open cycle
Pump adjusts pressure valve and pressure is adjusted to 3.0Mpa, controls 30 DEG C of temperature, and when permeate is gone out to 70kg, 50kg is added toward hopper
Tap water when permeate goes out 50kg again, then adds 50kg tap water, and repeatedly plus the water of 3 equivalent, permeate are taken in total
Going out 220kg, permeate concentration of formaldehyde is 14.28g/kg, and glyphosate concentration 0.13%, obtained concentrate is 30 kilograms,
Middle content of formaldehyde is 4.26g/kg, and glyphosate content is 9.10%.Concentrate is extracted into surge-tank addition original glyphosate powder and auxiliary agent is matched
The gyphosate solution of system 30%.So far the mother liquor glyphosate rate of recovery is 90.4%, and formaldehyde removal rate is 96.08%.
Above-mentioned permeate 220kg is poured into 500L reaction kettles, while activated carbon 15kg is added, and is heated while stirring, temperature
Control is 40 DEG C, and the reaction time is 10 hours.The millipore filter that volume is 300L is discharged into after reaction.Slowly added with compressed air
It is depressed into 0.25Mpa, until pressing dry.Finally obtain filter cake 32.3kg, filtered fluid 201.7kg.Filter cake has mainly adsorbed permeate
Activated carbon, can direct repeated application.Concentration of formaldehyde is 0.12g/kg to filtered fluid after testing, this ground beetle aldehyde removal rate is
99.23%.Filtered fluid draws up industrial water of the head tank as synthesizing glyphosate when.It is final to calculate to obtain the recycling of mother liquor glyphosate
Rate is 90.4%, and formaldehyde removal rate is 96.08%*99.23%=95.34%.
Embodiment 3
Fig. 1 is shown in embodiment technological process.Weigh the glyphosate that glyphosate concentration is 1.87%, concentration of formaldehyde is 33.16g/kg
Mother liquor 100kg pours into the hopper of nano-filtration membrane equipment, is 25m equipped with a nanofiltration area2Rolling NF membrane, open cycle
Pump adjusts pressure valve and pressure is adjusted to 4.0Mpa, controls 40 DEG C of temperature, and when permeate is gone out to 70kg, 50kg is added toward hopper
Tap water when permeate goes out 50kg again, then adds 50kg tap water, and repeatedly plus the water of 4 equivalent, permeate are taken in total
Going out 270kg, permeate concentration of formaldehyde is 11.77g/kg, and glyphosate concentration 0.069%, obtained concentrate is 30 kilograms,
Wherein content of formaldehyde is 4.6g/kg, and glyphosate content is 5.61%.Concentrate is extracted into surge-tank and original glyphosate powder and auxiliary agent is added
Prepare 30% gyphosate solution.So far the mother liquor glyphosate rate of recovery is 90%, and formaldehyde removal rate is 95.84%.
Above-mentioned permeate 270kg is poured into 500L reaction kettles, while activated carbon 22kg is added, and is heated while stirring, temperature
Control is 90 DEG C, and the reaction time is 3 hours.The millipore filter that volume is 300L is discharged into after reaction.Slowly added with compressed air
It is depressed into 0.2Mpa, until pressing dry.Finally obtain filter cake 46.2kg, filtered fluid 243.6kg.Filter cake is mainly the work for having adsorbed permeate
Property charcoal, can direct repeated application.Formaldehyde is 0.061g/kg to filtered fluid after testing, this ground beetle aldehyde removal rate is 99.53%.Filtering
Liquid draws up industrial water of the head tank as synthesizing glyphosate when.It is final calculate the mother liquor glyphosate rate of recovery is 90%, formaldehyde
Removal rate is 95.84%*99.53%=95.39%.
Embodiment 4
Fig. 1 is shown in embodiment technological process.Weigh the glyphosate that glyphosate concentration is 3.22%, concentration of formaldehyde is 34.63g/kg
Mother liquor 100kg pours into the hopper of nano-filtration membrane equipment, is 25m equipped with a nanofiltration area2Rolling NF membrane, open cycle
Pump adjusts pressure valve and pressure is adjusted to 4.5Mpa, controls temperature 50 C, and when permeate is gone out to 70kg, 50kg is added toward hopper
Tap water when permeate goes out 50kg again, then adds 50kg tap water, and repeatedly plus the water of 5 equivalent, permeate are taken in total
Going out 320kg, permeate concentration of formaldehyde is 10.48g/kg, and glyphosate concentration 0.1%, obtained concentrate is 30 kilograms,
Middle content of formaldehyde is 3.64g/kg, and glyphosate content is 9.67%.Concentrate is extracted into the gyphosate solution that surge-tank prepares 30%.Extremely
This mother liquor glyphosate rate of recovery is 90.09%, and formaldehyde removal rate is 96.84%.
Above-mentioned permeate 320kg is poured into 500L reaction kettles, while activated carbon 30kg is added, and is heated while stirring, temperature
Control is 40 DEG C, and the reaction time is 18 hours.The millipore filter that volume is 300L is discharged into after reaction at twice.Use compressed air
It slowly is forced into 0.2Mpa, until pressing dry.Finally obtain filter cake 65.7kg, filtered fluid 281.5kg.Filter cake has mainly adsorbed transmission
The activated carbon of liquid, can direct repeated application.Formaldehyde is 0.025g/kg to filtered fluid after testing, this ground beetle aldehyde removal rate is
99.79%.Filtered fluid draws up industrial water of the head tank as synthesizing glyphosate when.It is final to calculate to obtain the recycling of mother liquor glyphosate
Rate is 90.09%, and formaldehyde removal rate is 96.84%*99.79%=96.64%.
Claims (1)
1. a kind of method that glyphosate mother solution recycles, it is characterized in that：Weigh that glyphosate concentration is 3.22%, concentration of formaldehyde is
The glyphosate mother solution 100kg of 34.63g/kg, pours into the hopper of nano-filtration membrane equipment, is 25m equipped with a nanofiltration area2Volume
Formula NF membrane opens circulating pump, adjusts pressure valve and pressure is adjusted to 4.5MPa, control temperature 50 C, permeate goes out to 70kg
When, 50kg tap water is added toward hopper, when permeate goes out 50kg again, then adds 50kg tap water, adds 5 equivalent repeatedly
Water, permeate takes out 320kg in total, and permeate concentration of formaldehyde is 10.48g/kg, and glyphosate concentration 0.1% is obtained
Concentrate is 30 kilograms, and wherein content of formaldehyde is 3.64g/kg, and glyphosate content is 9.67%；Concentrate is extracted into surge-tank preparation
30% gyphosate solution；So far the mother liquor glyphosate rate of recovery is 90.09%, and formaldehyde removal rate is 96.84%；
Above-mentioned permeate 320kg is poured into 500L reaction kettles, while activated carbon 30kg is added, and is heated while stirring, temperature control
It it is 40 DEG C, the reaction time is 18 hours；The millipore filter that volume is 300L is discharged into after reaction at twice；It is slow with compressed air
It is forced into 0.2 MPa, until pressing dry；Finally obtain filter cake 65.7kg, filtered fluid 281.5kg；Filter cake has mainly adsorbed permeate
Activated carbon, can direct repeated application；Formaldehyde is 0.025g/kg to filtered fluid after testing, this ground beetle aldehyde removal rate is 99.79%；
Filtered fluid draws up industrial water of the head tank as synthesizing glyphosate when；It is final calculate the mother liquor glyphosate rate of recovery is
90.09%, formaldehyde removal rate is 96.84% × 99. 79%=96.64%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525351A (en) * | 2009-04-01 | 2009-09-09 | 杭州天创净水设备有限公司 | Treatment process of glyphosate mother liquor |
| CN101531677A (en) * | 2009-04-16 | 2009-09-16 | 捷马化工股份有限公司 | Method for preparing glyphosate |
| CN101648755A (en) * | 2009-08-20 | 2010-02-17 | 杭州天创净水设备有限公司 | Glyphosate waste water low-discharging and mother liquor recycling method |
| CN103012474A (en) * | 2012-12-31 | 2013-04-03 | 浙江金帆达生化股份有限公司 | Cyclic production method of glyphosate |
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2015
- 2015-12-21 CN CN201510959822.7A patent/CN105566382B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525351A (en) * | 2009-04-01 | 2009-09-09 | 杭州天创净水设备有限公司 | Treatment process of glyphosate mother liquor |
| CN101531677A (en) * | 2009-04-16 | 2009-09-16 | 捷马化工股份有限公司 | Method for preparing glyphosate |
| CN101648755A (en) * | 2009-08-20 | 2010-02-17 | 杭州天创净水设备有限公司 | Glyphosate waste water low-discharging and mother liquor recycling method |
| CN103012474A (en) * | 2012-12-31 | 2013-04-03 | 浙江金帆达生化股份有限公司 | Cyclic production method of glyphosate |
Non-Patent Citations (1)
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