CN102702254B - Method for recycling N-(Phosphonomethyl) iminodiacetic acid from production process wastewater of N-(Phosphonomethyl) iminodiacetic acid to prepare glyphosate aqueous solution - Google Patents
Method for recycling N-(Phosphonomethyl) iminodiacetic acid from production process wastewater of N-(Phosphonomethyl) iminodiacetic acid to prepare glyphosate aqueous solution Download PDFInfo
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- CN102702254B CN102702254B CN201210181901.6A CN201210181901A CN102702254B CN 102702254 B CN102702254 B CN 102702254B CN 201210181901 A CN201210181901 A CN 201210181901A CN 102702254 B CN102702254 B CN 102702254B
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- phosphonomethyl
- pmida98
- iminodiacetic acid
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Abstract
The invention relates to a method for recycling N-(Phosphonomethyl) iminodiacetic acid from production process wastewater of N-(Phosphonomethyl) iminodiacetic acid, application thereof, and a special device. The method for recycling N-(Phosphonomethyl) iminodiacetic acid from production process wastewater of N-(Phosphonomethyl) iminodiacetic acid to prepare glyphosate aqueous solution comprises the steps as follows: 1), adjusting the weight content of N-(Phosphonomethyl) iminodiacetic acid in production process wastewater of N-(Phosphonomethyl) iminodiacetic acid , and then, adding hydrogen peroxide to remove formaldehyde; 2), pouring the treated wastewater into a neutralization reactor, adjusting the PH value, and then, pouring the treated wastewater with the adjusted PH value into a three-effect evaporation system; 3), pouring the material in an evaporation reactor into a centrifuge for centrifugation so as to obtain primary mother liquid; 4), pouring the primary mother liquid into the evaporation reactor, adjusting the PH value, treating the primary mother liquid with the adjusted PH value by negative-pressure evaporation and concentration, and then carrying out solid-liquid separation, thereby obtaining N-(Phosphonomethyl) iminodiacetic acid solution; 5), treating the N-(Phosphonomethyl) iminodiacetic acid solution by evaporation, concentration and desalination; and 6), pouring the treated N-(Phosphonomethyl) iminodiacetic acid solution into an oxidation reactor for producing glyphosate, adding hydrogen peroxide dropwise, pouring the oxidated solution into a reduction reactor after oxidization, and adding ferrous sulfate dropwise, thereby preparing a glyphosate agent. The method provided by the invention not only can solve the recycling problem of the N-(Phosphonomethyl) iminodiacetic acid, but also can treat the N-(Phosphonomethyl) iminodiacetic acid and phosphorous acid in wastewater, so that the content of phosphorus in the wastewater is reduced, and the wastewater discharge accords with national standards.
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 (5)
1. reclaim the method for preparing glyphosate from N-phosphonomethyl aminodiacetic acid aqua in pmida98 production technique waste water, it is characterized in that the method 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. the pmida98 solution of gained, carries out evaporation concentration desalination, and 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. reclaim the method for preparing glyphosate from N-phosphonomethyl aminodiacetic acid aqua in pmida98 production technique waste water according to claim 1, it is characterized in that: 1. step first adds soda ash and suitably regulate pH, then add hydrogen peroxide removing formaldehyde, the concentration of hydrogen peroxide is 27.5%.
3. reclaim the method for preparing glyphosate from N-phosphonomethyl aminodiacetic acid aqua in pmida98 production technique waste water according to claim 1, it is characterized in that: 2. step adopts soda ash and 32% ionic membrane caustic soda adjust ph.
4. reclaim the method for preparing glyphosate from N-phosphonomethyl aminodiacetic acid aqua in pmida98 production technique waste water according to claim 1, it is characterized in that: step 3. whizzer adopts twin-stage push-down whizzer.
5. reclaim the method for preparing glyphosate from N-phosphonomethyl aminodiacetic acid aqua in pmida98 production technique waste water according to claim 1, it is characterized in that: the temperature of step 4. negative pressure evaporation is 80 ~ 90 DEG C, and the time is 4 ~ 6 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210181901.6A CN102702254B (en) | 2010-10-18 | 2010-10-18 | Method for recycling N-(Phosphonomethyl) iminodiacetic acid from production process wastewater of N-(Phosphonomethyl) iminodiacetic acid to prepare glyphosate aqueous solution |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210181901.6A CN102702254B (en) | 2010-10-18 | 2010-10-18 | Method for recycling N-(Phosphonomethyl) iminodiacetic acid from production process wastewater of N-(Phosphonomethyl) iminodiacetic acid to prepare glyphosate aqueous solution |
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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| CN102702254A CN102702254A (en) | 2012-10-03 |
| CN102702254B true CN102702254B (en) | 2015-04-15 |
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| CN104522047B (en) * | 2014-12-15 | 2016-06-01 | 四川贝尔化工集团有限公司 | A kind of aqua compound method based on glyphosate mother solution purifying treatment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101691383A (en) * | 2009-09-28 | 2010-04-07 | 南京第一农药集团有限公司 | Method for processing PMIDA synthesis mother liquor |
| CN101696225A (en) * | 2009-10-29 | 2010-04-21 | 安徽华星化工股份有限公司 | Material recycling method in preparation of N-(Phosphonomethyl) iminodiacetic acid |
| CN101755831A (en) * | 2010-01-22 | 2010-06-30 | 广西自主化工有限公司 | Production method of glyphosate solution |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101691383A (en) * | 2009-09-28 | 2010-04-07 | 南京第一农药集团有限公司 | Method for processing PMIDA synthesis mother liquor |
| CN101696225A (en) * | 2009-10-29 | 2010-04-21 | 安徽华星化工股份有限公司 | Material recycling method in preparation of N-(Phosphonomethyl) iminodiacetic acid |
| CN101755831A (en) * | 2010-01-22 | 2010-06-30 | 广西自主化工有限公司 | Production method of glyphosate solution |
Non-Patent Citations (1)
| Title |
|---|
| "草甘膦的合成新工艺研究";郭建敏 等;《草甘膦的合成新工艺研究》;20090630;第37卷(第3期);第276-278页 * |
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