CN102690287B - Device for preparing gyphosate solution by using N-phosphonomethyl aminodiacetic acid solution - Google Patents
Device for preparing gyphosate solution by using N-phosphonomethyl aminodiacetic acid solution Download PDFInfo
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- CN102690287B CN102690287B CN201210181903.5A CN201210181903A CN102690287B CN 102690287 B CN102690287 B CN 102690287B CN 201210181903 A CN201210181903 A CN 201210181903A CN 102690287 B CN102690287 B CN 102690287B
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- pmida98
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- gyphosate
- wastewater
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Abstract
The invention relates to a method for recovering N-phosphonomethyl aminodiacetic acid from wastewater generated in a process for producing N-phosphonomethyl aminodiacetic acid, and application and special equipment. A device for preparing a gyphosate solution by using the N-phosphonomethyl aminodiacetic acid solution comprises a wastewater tank, a wastewater neutralization kettle, a triple effect evaporation system, a first evaporation kettle, a centrifugal machine, a mother liquor tank, a second evaporation kettle, a suction filtration cylinder, a third evaporation kettle, a gyphosate oxidation pot, a reduction kettle, and a membrane separation facility which are sequentially connected through pipelines; and an acid water evaporation outlet of the first evaporation kettle is connected with a biochemical treatment system. By the device, the content of N-phosphonomethyl aminodiacetic acid in the obtained N-phosphonomethyl aminodiacetic acid solution is about 13 percent, and the N-phosphonomethyl aminodiacetic acid solution can be subsequently used conveniently; and the N-phosphonomethyl aminodiacetic acid can be recycled, and the N-phosphonomethyl aminodiacetic acid and phosphorous acid in the wastewater can be treated, so that the phosphorus content in the wastewater can be reduced, and the wastewater discharge meets the national standard.
Description
The present patent application is the patent No.: 201010510542.5, and patent name is: the methods and applications and the specific equipment that reclaim pmida98 in pmida98 production technique waste water, and the applying date is: the divisional application of the application for a patent for invention of 2010-10-18.
Technical field
The present invention relates to the methods and applications and the specific equipment that reclaim pmida98 in pmida98 production technique waste water.
Background technology
Pmida98 (N; N-oxalic acid amino methane phosphoric acid) be a kind of clean white powder thing.
Its molecular formula: C
5n
10nO
7p
Molecular structural formula:
Pmida98 is the main raw material of pesticide herbicide glyphosate.Glyphosate is the industries such as raw weedicide, widespread use agriculture, woods, industrial traffic of going out of a kind of efficient, low temperature, noresidue, broad spectrum, comprises the weeding on forest, rubber plantation, farmland, tea mulberry, orchard, sugarcane field and railway airport.
The operational path that current China produces pmida98 is mainly two: one for glycine-dimethyl phosphate method, this is that China develops technology the earliest, technology maturation is the operational path that current most of manufacturing enterprise adopts, and shortcoming is that environmental pollution is serious, needs high activated catalyst; Two is iminodiethanoic acid (IDA method), and this is the operational path of the current production pmida98 that we develop in recent years, and its product produced all is welcome by Foreign User, the particularly ground such as the U.S., Europe.
It is main raw material that applicant have employed with diethanolamine, and synthesize pmida98 with phosphorus trichloride, formaldehyde condensation reaction, disclosed in patent No. ZL00116540.2, one prepares N, the technique of N-oxalic acid amino methane phosphoric acid (pmida98).This production technique is direct technology, shortens reactions steps and reaction times, simplifies production technique and equipment, have simple to operate, reduce raw material variety, reduce investment outlay, reduce costs, the feature of decreasing pollution.And pmida98 (N-phosphonomethyl iminodiethanoic acid) is the intermediate of herbicide glyphosate, it is also the source region of severe processing wastewater in process of production, and how the comprehensive utilization of improving technique and waste water is very important.
Chinese invention patent (application number: 200810124403.1 applyings date: 2008-07-01) discloses a kind of from producing the method reclaiming pmida98 pmida98 mother liquor, by producing the pmida98 mother liquor of pmida98, through secondary filter, obtains clarified mother liquor; Anionic ion-exchange resins adsorption column on pmida98 clarified mother liquor, control temperature is 2-12BV/H at 5-30 DEG C and flow velocity, and pmida98 is adsorbed, and wastewater treatment is gone in absorption water outlet; With the sodium hydroxide solution of 3-8% for desorption liquid, control temperature carries out desorption under 25-50 DEG C and flow velocity are 1-4BV/H condition, and desorption water outlet is pmida98 sodium salt solution, through the recyclable pmida98 of acidification.
Chinese invention patent (application number: 200810212210.1 applyings date: 2008-09-05) discloses a kind of integrated conduct method of pmida98 mother liquor, adopt the pmida98 in nanofiltration membrane concentrated mother liquor and homologue thereof, in film, lateral enrichment dope goes to reclaim pmida98, obtains thick sodium-chlor through light fluid dewatering crystallization.Thick sodium-chlor obtains refining sodium-chlor through process, can be directly used in electrolysis production caustic soda.
Chinese invention patent (application number: the 200910035810.X applying date: 2009-09-28) discloses a kind for the treatment of process of PMIDA synthesis mother liquor, the method for be for raw material adopts IDA route to prepare the acid mother liquid produced in pmida98 technique with iminodiacetonitrile, this mother liquor regulates pH value to concentrate through reverse osmosis membrane after 6 ~ 11 through alkali and obtains concentrated solution, and concentrated solution reclaims through infiltration evaporation and obtains formaldehyde.Adopt the inventive method can obtain the pmida98 concentrated solution of mass percentage concentration more than 9%, this pmida98 concentrated solution directly can be processed into aqua sale or the raw material as production agricultural chemicals glyphosate.
Summary of the invention
In order to improve the comprehensive utilization of pmida98 production technique waste water, first object of the present invention is to provide a kind of method reclaiming pmida98 in pmida98 production technique waste water, second object of the present invention is to provide a kind of method adopting the pmida98 solution of gained to prepare gyphosate solution, 3rd object of the present invention is to provide the device reclaiming pmida98 in a kind of pmida98 production technique waste water, and the 4th object of the present invention is to provide the device that a kind of pmida98 solution prepares gyphosate solution.
In order to realize first above-mentioned object, present invention employs following technical scheme:
Reclaim the method for pmida98 in pmida98 production technique waste water, the method comprises the following steps: that 1. adjusting pmida98 weight content at pmida98 production technique waste water is 0.7%-1.5%, then adds hydrogen peroxide, removing formaldehyde; 2. in being entered by the waste water handled well and still, regulate pH value to be 4.5 ~ 6.0, then enter triple effect evaporation system, the waste water through triple effect evaporation system enters evaporating kettle, steams sour water and enters biochemical treatment system; 3. in evaporating kettle, material enters centrifuge, and solid is Industrial Salt, obtains first time mother liquor; 4. first time mother liquor enter evaporating kettle, after add hydrochloric acid regulate pH value to 1.3 ~ 1.8, negative pressure evaporation concentrate, then carry out solid-liquid separation, solid is Industrial Salt, and liquid is pmida98 solution.
As preferably, 1. above-mentioned step first adds soda ash and suitably regulates PH, and then add hydrogen peroxide removing formaldehyde, the concentration of hydrogen peroxide is 27.5%.
As preferably, 2. above-mentioned step adopts soda ash and 32% ionic membrane caustic soda to regulate pH value.
As preferably, above-mentioned step 3. whizzer adopts twin-stage push-down whizzer.
As preferably, the temperature of above-mentioned step 4. negative pressure evaporation is 80 ~ 90 DEG C, and the time is 4 ~ 6 hours.
In order to realize second above-mentioned object, present invention employs following technical scheme:
Adopt the pmida98 solution of any one technical scheme gained above-mentioned to prepare the method for gyphosate solution, the method comprises the following steps:
(1) the pmida98 solution of any one technical scheme gained, carries out evaporation concentration desalination, and to its mother liquor, pmida98 content reaches more than 15%;
(2) enter in production glyphosate still, drip hydrogen peroxide, when oxidation terminates, then enter reduction kettle, drip ferrous sulfate, can be made into gyphosate solution;
(3) again gyphosate solution is entered membrane sepn facility, add glyphosate technicals by aqua in the gyphosate solution of membrane sepn, the gyphosate solution of desired concn can be mixed with.
In order to realize the 3rd above-mentioned object, present invention employs following technical scheme:
For reclaiming the device of pmida98 in above-mentioned pmida98 production technique waste water, this device comprise be connected by pipeline successively wastewater disposal basin, waste water neutralize still, triple effect evaporation system, the first evaporating kettle, whizzer, mother liquor pond, the second evaporating kettle and suction filtration cylinder; The sour water of the first evaporating kettle steams mouth and is connected with biochemical treatment system.
As preferably, above-mentioned whizzer adopts twin-stage push-down whizzer.
In order to realize the 4th above-mentioned object, present invention employs following technical scheme:
Prepare the device of gyphosate solution for above-mentioned pmida98 solution, this device comprise be connected by pipeline successively wastewater disposal basin, waste water neutralize still, triple effect evaporation system, the first evaporating kettle, whizzer, mother liquor pond, the second evaporating kettle, suction filtration cylinder, the 3rd evaporating kettle, glyphosate still, reduction kettle and membrane sepn facility; The sour water of the first evaporating kettle steams mouth and is connected with biochemical treatment system.
As preferably, above-mentioned whizzer adopts twin-stage push-down whizzer.
Often produce the processing wastewater about 8.5 tons that 1 ton of pmida98 produces, our company one passes through Optimization Technology; Two is transformation water ideas, the reuse of washing water; Three is process water recycleds after process, thus makes the Waste water yield decline 50%.Namely often one ton of pmida98 is produced now, the wastewater flow rate of generation about 4 tons.To produce 30 tons every day, its processing wastewater 120 tons produced.In these 120 tons of wastewater treatment process, there is the mother liquor of about 9 tons, account for about 9% of total wastewater flow rate.
The present invention is owing to adopting above-mentioned technical scheme, and obtained pmida98 solution pmida98 content about 13%, can so that follow-up use; The present invention both can solve pmida98 reuse, can administer pmida98 in waste water, phosphorous acid again, thus the phosphorus content in waste water is declined, and discharge of wastewater meets national standard.
Accompanying drawing explanation
Fig. 1 is integrated artistic schema of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is made a detailed explanation.
Reclaim the method for preparing glyphosate from N-phosphonomethyl aminodiacetic acid aqua in pmida98 production technique waste water as shown in Figure 1, the method comprises the following steps:
(1) in wastewater disposal basin, waste water PH is about-0.1, and pmida98 content, at 0.7%-1.5%, adds soda ash and suitably regulates PH, then drips the hydrogen peroxide of 27.5%, and object is removing formaldehyde.
(2) in being entered by this waste water and still, regulate pH value (controls about PH=5), enter triple effect evaporation system with 98% content soda ash and 32% ionic membrane caustic soda, the waste water of triple effect through evaporating enters evaporating kettle (20m
3), steam sour water and enter biochemical treatment system.
(3) in still, material (filter cake) enters twin-stage push-down whizzer, and solid is Industrial Salt, entrusts the unified process of Deqing Salt Company, and filtrate is first time mother liquor, pmida98 content about 10%.
(4) mother liquor enters 10m for the first time
3evaporating kettle, after add 31% hydrochloric acid and regulate PH to 1.3-1.8, concentrated about 5 hours of negative pressure evaporation, temperature, at 80-90 DEG C, then carries out solid-liquid separation, and solid is Industrial Salt, and liquid be mother liquor (i.e. pmida98 solution) for the second time, its pmida98 content about 13%.
(5) again second time mother liquor is carried out evaporation concentration desalination, to mother liquor, pmida98 content reaches about 15%.
(6) enter in production glyphosate still, drip 27.5% hydrogen peroxide, when oxidation terminates, then enter reduction kettle, drip ferrous sulfate, can be made into about 4%-5% gyphosate solution.
(6) enter membrane sepn facility again, can about 10% be reached by membrane sepn concentration, this gyphosate solution is added glyphosate technicals, 30% gyphosate solution can be mixed with.
As shown in Figure 1, this above-mentioned device comprise be connected by pipeline successively wastewater disposal basin, waste water neutralize still, triple effect evaporation system, the first evaporating kettle, twin-stage push-down whizzer, mother liquor pond, the second evaporating kettle, suction filtration cylinder, the 3rd evaporating kettle, glyphosate still, reduction kettle and membrane sepn facility; The sour water of the first evaporating kettle steams mouth and is connected with biochemical treatment system.
Claims (2)
1. pmida98 solution prepares the device of gyphosate solution, it is characterized in that: this device comprise be connected by pipeline successively wastewater disposal basin, waste water neutralize still, triple effect evaporation system, the first evaporating kettle, whizzer, mother liquor pond, the second evaporating kettle, suction filtration cylinder, the 3rd evaporating kettle, glyphosate still, reduction kettle and membrane sepn facility; The sour water of the first evaporating kettle steams mouth and is connected with biochemical treatment system;
The method that above-mentioned device adopts comprises the following steps:
1. adjusting pmida98 weight content at pmida98 production technique waste water is 0.7%-1.5%, then adds hydrogen peroxide, removing formaldehyde;
2. in being entered by the waste water handled well and still, adjust ph is 4.5 ~ 6.0, then enters triple effect evaporation system, and the waste water through triple effect evaporation system enters evaporating kettle, steams sour water and enters biochemical treatment system;
3. in evaporating kettle, material enters centrifuge, and solid is Industrial Salt, obtains first time mother liquor;
4. mother liquor enters evaporating kettle, rear salt adding acid for adjusting pH value to 1.3 ~ 1.8 for the first time, and negative pressure evaporation concentrates, and then carry out solid-liquid separation, solid is Industrial Salt, and liquid is pmida98 solution;
5. by the pmida98 solution of gained, carry out evaporation concentration desalination, to its mother liquor, pmida98 content reaches more than 15%;
6. enter and produce in glyphosate still, drip hydrogen peroxide, when oxidation terminates, then enter reduction kettle, drip ferrous sulfate, can be made into gyphosate solution;
7. again gyphosate solution is entered membrane sepn facility, add glyphosate technicals by aqua in the gyphosate solution of membrane sepn, the gyphosate solution of desired concn can be mixed with.
2. pmida98 solution according to claim 1 prepares the device of gyphosate solution, it is characterized in that: whizzer adopts twin-stage push-down whizzer.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010510542A CN101974032B (en) | 2010-10-18 | 2010-10-18 | Method for recycling N-(Phosphonomethyl)iminodiaceticacid (PMIDA) in PMIDA production wastewater, application and special device |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010510542A Division CN101974032B (en) | 2010-10-18 | 2010-10-18 | Method for recycling N-(Phosphonomethyl)iminodiaceticacid (PMIDA) in PMIDA production wastewater, application and special device |
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| Publication Number | Publication Date |
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| CN102690287A CN102690287A (en) | 2012-09-26 |
| CN102690287B true CN102690287B (en) | 2015-07-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010510542A Expired - Fee Related CN101974032B (en) | 2010-10-18 | 2010-10-18 | Method for recycling N-(Phosphonomethyl)iminodiaceticacid (PMIDA) in PMIDA production wastewater, application and special device |
| CN201210181903.5A Expired - Fee Related CN102690287B (en) | 2010-10-18 | 2010-10-18 | Device for preparing gyphosate solution by using N-phosphonomethyl aminodiacetic acid solution |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010510542A Expired - Fee Related CN101974032B (en) | 2010-10-18 | 2010-10-18 | Method for recycling N-(Phosphonomethyl)iminodiaceticacid (PMIDA) in PMIDA production wastewater, application and special device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102674589B (en) * | 2012-04-18 | 2013-11-13 | 闽南师范大学 | Treatment method of N-phosphonomethyl aminodiacetic acid wastewater |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1563021A (en) * | 2004-04-02 | 2005-01-12 | 安徽氯碱化工集团有限责任公司 | Preparation technique for synthesizing glyphosate through dehydrogenation oxidation process for diethanolamine |
| CN1775786A (en) * | 2005-11-28 | 2006-05-24 | 徐寅初 | Method for separating and concentrating glyphosate stock solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250141B (en) * | 2000-05-22 | 2014-10-01 | 孟山都技术有限责任公司 | Reaction systems for making n-(phosphonomethyl)glycine compounds |
| CN101428935B (en) * | 2008-11-28 | 2010-07-21 | 四川贝尔实业有限责任公司 | Treatment process for wastewater from N-(Phosphonomethyl)iminodiacetic acid production |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1563021A (en) * | 2004-04-02 | 2005-01-12 | 安徽氯碱化工集团有限责任公司 | Preparation technique for synthesizing glyphosate through dehydrogenation oxidation process for diethanolamine |
| CN1775786A (en) * | 2005-11-28 | 2006-05-24 | 徐寅初 | Method for separating and concentrating glyphosate stock solution |
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| Publication number | Publication date |
|---|---|
| CN101974032B (en) | 2012-10-03 |
| CN102690287A (en) | 2012-09-26 |
| CN101974032A (en) | 2011-02-16 |
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