CN101974032A - Method for recycling N-(Phosphonomethyl)iminodiaceticacid (PMIDA) in PMIDA production wastewater, application and special device - Google Patents
Method for recycling N-(Phosphonomethyl)iminodiaceticacid (PMIDA) in PMIDA production wastewater, application and special device Download PDFInfo
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- CN101974032A CN101974032A CN 201010510542 CN201010510542A CN101974032A CN 101974032 A CN101974032 A CN 101974032A CN 201010510542 CN201010510542 CN 201010510542 CN 201010510542 A CN201010510542 A CN 201010510542A CN 101974032 A CN101974032 A CN 101974032A
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Abstract
The invention relates to a method for recycling N-(Phosphonomethyl)iminodiaceticacid (PMIDA) in PMIDA production wastewater, an application and a special device. The method comprises the following steps: 1, regulating the weight content of the PMIDA in the PMIDA production wastewater, and then adding hydrogen peroxide to remove formaldehyde; 2, adding the processed wastewater into a neutralization kettle, regulating the pH value, adding the wastewater into a triple effect evaporation system, enabling the wastewater processed in the triple effect evaporation to enter into an evaporation kettle, and evaporating acid water so as to enter into a biochemical treatment system; 3, enabling primary mother liquor to enter into the evaporation kettle, adding hydrochloric acid to regulate the pH value, carrying out negative-pressure evaporation concentration, and carrying out solid-liquid separation, wherein the solid is industrial salt, and the liquid is PMIDA solution. The PMIDA solution prepared by the invention has the PMIDA content of about 13%, not only can resolve the problem of recycling the PMIDA, but also can treat the PMIDA and phosphorous acid in the wastewater, thereby reducing the phosphorus content of the wastewater and enabling wastewater discharge to accord with the national standard.
Description
Technical field
The present invention relates to reclaim in the pmida98 production technique waste water methods and applications and the specific equipment of pmida98.
Background technology
Pmida98 (N; N-oxalic acid amino methane phosphoric acid) be a kind of pure white look meal.
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 living weedicide, widespread use farming, 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 of the pmida98 of China's production at present is mainly two: one is glycine-dimethylphosphite method, this is that China develops technology the earliest, technology maturation is the operational path that present 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 present production pmida98 that we develop in recent years, and the product of its production is welcome by external user all, particularly ground such as the U.S., Europe.
It is main raw material that the applicant has adopted with diethanolamine, with phosphorus trichloride, the synthetic pmida98 of formaldehyde condensation reaction, as the disclosed a kind of preparation N of patent No. ZL00116540.2, the technology of N-oxalic acid amino methane phosphoric acid (pmida98).This production technique is a direct technology, has shortened reactions steps and reaction times, has simplified production technique and equipment, have simple to operate, reduce raw material variety, reduce investment outlay, reduce cost, reduce pollution characteristics.And pmida98 (N-phosphonomethyl iminodiethanoic acid) is the intermediate of herbicide glyphosate, and it also is the source region of severe processing wastewater in process of production, and the comprehensive utilization that how to improve technology and waste water is very important.
Chinese invention patent (application number: 200810124403.1 applyings date: 2008-07-01) disclose a kind of method that from produce the pmida98 mother liquor, reclaims pmida98,,, obtained clarified mother liquor through secondary filter with producing the pmida98 mother liquor of pmida98; Anionic ion-exchange resins adsorption column on the pmida98 clarified mother liquor, controlled temperature is 2-12BV/H at 5-30 ℃ with flow velocity, and pmida98 is adsorbed, and absorption effluent is gone wastewater treatment; Sodium hydroxide solution with 3-8% is a desorption liquid, and controlled temperature is to carry out desorption under the 1-4BV/H condition at 25-50 ℃ with flow velocity, and the desorption water outlet is the pmida98 sodium salt solution, through the recyclable pmida98 of acidification.
Chinese invention patent (application number: 200810212210.1 applyings date: 2008-09-05) disclose a kind of integrated conduct method of pmida98 mother liquor, adopt pmida98 and homologue thereof in the nanofiltration membrane concentrated mother liquor, the lateral enrichment dope removes to reclaim pmida98 in the film, sees through light fluid dewatering crystallization and obtains thick sodium-chlor.Thick sodium-chlor obtains refining sodium-chlor through handling, and can be directly used in the electrolysis production caustic soda.
Chinese invention patent (application number: the 200910035810.X applying date: 2009-09-28) disclose a kind of treatment process of PMIDA synthesis mother liquor, this method at be to be that raw material adopts the acid mother liquid that is produced in the IDA path of preparing pmida98 technology with the iminodiacetonitrile, this mother liquor is regulated pH value through alkali and is obtained concentrated solution 6～11 after reverse osmosis membrane concentrates, and concentrated solution reclaims through infiltration evaporation and obtains formaldehyde.Adopt the inventive method can obtain mass percentage concentration at the pmida98 concentrated solution more than 9%, this pmida98 concentrated solution can directly be processed into the raw material of aqua sale or conduct production agricultural chemicals glyphosate.
Summary of the invention
In order to improve the comprehensive utilization of pmida98 production technique waste water, first purpose of the present invention provides the method that reclaims pmida98 in a kind of pmida98 production technique waste water, second purpose of the present invention provides a kind of method that adopts the pmida98 formulations prepared from solutions gyphosate solution of gained, the 3rd purpose of the present invention provides the device that reclaims pmida98 in a kind of pmida98 production technique waste water, and the 4th purpose of the present invention provides a kind of device of pmida98 formulations prepared from solutions gyphosate solution.
In order to realize first above-mentioned purpose, the present invention has adopted following technical scheme:
Reclaim the method for pmida98 in the pmida98 production technique waste water, this method comprises the steps: that 1. adjusting the pmida98 weight content at pmida98 production technique waste water is 0.7%-1.5%, adds hydrogen peroxide then, removes formaldehyde; 2. in the waste water of handling well being entered and still, regulating pH value is 4.5～6.0, enters the triple effect evaporation system then, enters evaporating kettle through the waste water of triple effect evaporation system, steams sour water and enters biochemical treatment system; 3. in the evaporating kettle material to enter whizzer centrifugal, solid is an Industrial Salt, time mother liquor of winning; 4. for the first time mother liquor enters evaporating kettle, after add hydrochloric acid and regulate pH value to 1.3～1.8, negative pressure evaporation concentrates, and carries out solid-liquid separation then, solid is an Industrial Salt, liquid is pmida98 solution.
As preferably, 1. above-mentioned step adds soda ash earlier and suitably regulates PH, adds hydrogen peroxide then and removes formaldehyde, and 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 above-mentioned step 4. temperature of negative pressure evaporation is 80～90 ℃, and the time is 4～6 hours.
In order to realize second above-mentioned purpose, the present invention has adopted following technical scheme:
Adopt the method for the pmida98 formulations prepared from solutions gyphosate solution of above-mentioned any one technical scheme gained, this method comprises the steps:
(1) the pmida98 solution of any one technical scheme gained carries out the evaporation concentration desalination, and pmida98 content reaches more than 15% to its mother liquor;
(2) enter in the production glyphosate stills for air blowing, drip hydrogen peroxide,, enter reduction kettle again, drip ferrous sulfate, can be made into gyphosate solution when oxidation finishes;
(3) again gyphosate solution is entered the membrane sepn facility, add glyphosate technicals, can be mixed with the gyphosate solution of desired concn by aqua in the gyphosate solution of membrane sepn.
In order to realize the 3rd above-mentioned purpose, the present invention has adopted following technical scheme:
Be used for the device that above-mentioned pmida98 production technique waste water reclaims pmida98, this device comprises in the wastewater disposal basin that is connected by pipeline successively, the waste water and still, triple effect evaporation system, first evaporating kettle, whizzer, mother liquor pond, second evaporating kettle and suction filtration tube; The sour water of 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 purpose, the present invention has adopted following technical scheme:
The device that is used for above-mentioned pmida98 formulations prepared from solutions gyphosate solution, this device comprise in the wastewater disposal basin that is connected by pipeline successively, the waste water and still, triple effect evaporation system, first evaporating kettle, whizzer, mother liquor pond, second evaporating kettle, suction filtration tube, the 3rd evaporating kettle, glyphosate stills for air blowing, reduction kettle and membrane sepn facility; The sour water of first evaporating kettle steams mouth and is connected with biochemical treatment system.
As preferably, above-mentioned whizzer adopts twin-stage push-down whizzer.
About 8.5 tons of the processing wastewater that 1 ton of pmida98 of every production produces, our company one is by optimizing technology; The 2nd, change the water idea, the reuse of washing water; The 3rd, handle back process water recycled, thereby make the processing wastewater amount descend 50%.Be one ton of pmida98 of present every production, about 4 tons of the wastewater flow rate of generation.To produce 30 tons every day is example, 120 tons of the processing wastewaters of its generation.Mother liquor about 9 tons is arranged in these 120 tons of wastewater treatment process, account for about 9% of total wastewater flow rate.
The present invention is owing to adopt above-mentioned technical scheme, and prepared pmida98 solution pmida98 content is about 13%, can be so that follow-up use; The present invention both can solve the pmida98 reuse, can administer pmida98 in the waste water, phosphorous acid again, thereby the phosphorus content in the waste water is descended, and discharge of wastewater meets national standard.
Description of drawings
Fig. 1 is an 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 that pmida98 prepares gyphosate solution in the pmida98 production technique waste water as shown in Figure 1, this method comprises the steps:
(1) waste water PH is about-0.1 in wastewater disposal basin, and pmida98 content adds soda ash and suitably regulates PH at 0.7%-1.5%, drips 27.5% hydrogen peroxide again, and purpose is to remove formaldehyde.
(2) this waste water is entered in and still, regulate pH value (about control PH=5) with 98% content soda ash and 32% ionic membrane caustic soda, enter the triple effect evaporation system, triple effect enters evaporating kettle (20m through the waste water of evaporation
3), steam sour water and enter biochemical treatment system.
(3) material (filter cake) enters twin-stage push-down whizzer in the still, and solid is an Industrial Salt, entrusts the unified processing of Deqing Salt Company, and filtrate is the mother liquor first time, 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, negative pressure evaporation concentrates about 5 hours, temperature is carried out solid-liquid separation then at 80-90 ℃, solid is an Industrial Salt, liquid is mother liquor (being pmida98 solution) for the second time, its pmida98 content about 13%.
(5) more for the second time mother liquor carry out the evaporation concentration desalination, pmida98 content reaches about 15% to the mother liquor.
(6) enter in the production glyphosate stills for air blowing, drip 27.5% hydrogen peroxide,, enter reduction kettle again, drip ferrous sulfate, can be made into about 4%-5% gyphosate solution when oxidation finishes.
(6) enter the membrane sepn facility again, can reach about 10%, this gyphosate solution is added glyphosate technicals, can be mixed with 30% gyphosate solution by membrane sepn concentration.
As shown in Figure 1, above-mentioned this device comprises in the wastewater disposal basin that is connected by pipeline successively, the waste water and still, triple effect evaporation system, first evaporating kettle, twin-stage push-down whizzer, mother liquor pond, second evaporating kettle, suction filtration tube, the 3rd evaporating kettle, glyphosate stills for air blowing, reduction kettle and membrane sepn facility; The sour water of first evaporating kettle steams mouth and is connected with biochemical treatment system.
Claims (10)
1. reclaim the method for pmida98 in the pmida98 production technique waste water, it is characterized in that this method comprises the steps: that 1. adjusting the pmida98 weight content at pmida98 production technique waste water is 0.7%-1.5%, add hydrogen peroxide then, remove formaldehyde; 2. in the waste water of handling well being entered and still, regulating pH value is 4.5～6.0, enters the triple effect evaporation system then, enters evaporating kettle through the waste water of triple effect evaporation system, steams sour water and enters biochemical treatment system; 3. in the evaporating kettle material to enter whizzer centrifugal, solid is an Industrial Salt, time mother liquor of winning; 4. for the first time mother liquor enters evaporating kettle, after add hydrochloric acid and regulate pH value to 1.3～1.8, negative pressure evaporation concentrates, and carries out solid-liquid separation then, solid is an Industrial Salt, liquid is pmida98 solution.
2. reclaim the method for pmida98 in the pmida98 production technique waste water according to claim 1, it is characterized in that: 1. step adds soda ash earlier and suitably regulates PH, adds hydrogen peroxide then and removes formaldehyde, and the concentration of hydrogen peroxide is 27.5%.
3. reclaim the method for pmida98 in the 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 to regulate pH value.
4. reclaim the method for pmida98 in the 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 pmida98 in the pmida98 production technique waste water according to claim 1, it is characterized in that: the step 4. temperature of negative pressure evaporation is 80～90 ℃, and the time is 4～6 hours.
6. adopt the method for the pmida98 formulations prepared from solutions gyphosate solution of any claim gained of claim 1～5, it is characterized in that this method comprises the steps:
(1) the pmida98 solution of any claim gained of claim 1～5 carries out the evaporation concentration desalination, and pmida98 content reaches more than 15% to its mother liquor;
(2) enter in the production glyphosate stills for air blowing, drip hydrogen peroxide,, enter reduction kettle again, drip ferrous sulfate, can be made into gyphosate solution when oxidation finishes;
(3) again gyphosate solution is entered the membrane sepn facility, add glyphosate technicals, can be mixed with the gyphosate solution of desired concn by aqua in the gyphosate solution of membrane sepn.
7. be used for the device that the described pmida98 production technique of claim 1 waste water reclaims pmida98, it is characterized in that: this device comprises in the wastewater disposal basin that is connected by pipeline successively, the waste water and still, triple effect evaporation system, first evaporating kettle, whizzer, mother liquor pond, second evaporating kettle and suction filtration tube; The sour water of first evaporating kettle steams mouth and is connected with biochemical treatment system.
8. reclaim the device of pmida98 in the pmida98 production technique waste water according to claim 7, it is characterized in that: whizzer adopts twin-stage push-down whizzer.
9. be used for the device of the described pmida98 formulations prepared from solutions of claim 6 gyphosate solution, it is characterized in that: this device comprises in the wastewater disposal basin that is connected by pipeline successively, the waste water and still, triple effect evaporation system, first evaporating kettle, whizzer, mother liquor pond, second evaporating kettle, suction filtration tube, the 3rd evaporating kettle, glyphosate stills for air blowing, reduction kettle and membrane sepn facility; The sour water of first evaporating kettle steams mouth and is connected with biochemical treatment system.
10. the device of pmida98 formulations prepared from solutions gyphosate solution according to claim 10 is characterized in that: whizzer adopts twin-stage push-down whizzer.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210181903.5A CN102690287B (en) | 2010-10-18 | 2010-10-18 | Device for preparing gyphosate solution by using N-phosphonomethyl aminodiacetic acid solution |
| CN201010510542A CN101974032B (en) | 2010-10-18 | 2010-10-18 | Method for recycling N-(Phosphonomethyl)iminodiaceticacid (PMIDA) in PMIDA production wastewater, application and special device |
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 Child Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210181901.6A Division 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 |
| CN201210181903.5A Division CN102690287B (en) | 2010-10-18 | 2010-10-18 | Device for preparing gyphosate solution by using N-phosphonomethyl aminodiacetic acid solution |
| CN 201210181902 Division CN102674638B (en) | 2010-10-18 | 2010-10-18 | Device for recycling N-Phosphonomethyl aminodiacetic acid from waste water in N-Phosphonomethyl aminodiacetic acid production process |
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| Publication Number | Publication Date |
|---|---|
| CN101974032A true CN101974032A (en) | 2011-02-16 |
| CN101974032B CN101974032B (en) | 2012-10-03 |
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| 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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| 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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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674589A (en) * | 2012-04-18 | 2012-09-19 | 漳州师范学院 | Treatment method of N-phosphonomethyl aminodiacetic acid wastewater |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001092272A2 (en) * | 2000-05-22 | 2001-12-06 | Monsanto Technology Llc | Reaction systems for making n-(phosphonomethyl)glycine compounds |
| CN101428935A (en) * | 2008-11-28 | 2009-05-13 | 四川贝尔实业有限责任公司 | Treatment process for wastewater from N-(Phosphonomethyl)iminodiacetic acid production |
Family Cites Families (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 |
| CN1775786B (en) * | 2005-11-28 | 2011-01-19 | 杭州天创净水设备有限公司 | Method for separating and concentrating glyphosate stock solution |
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2010
- 2010-10-18 CN CN201010510542A patent/CN101974032B/en not_active Expired - Fee Related
- 2010-10-18 CN CN201210181903.5A patent/CN102690287B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001092272A2 (en) * | 2000-05-22 | 2001-12-06 | Monsanto Technology Llc | Reaction systems for making n-(phosphonomethyl)glycine compounds |
| CN101428935A (en) * | 2008-11-28 | 2009-05-13 | 四川贝尔实业有限责任公司 | Treatment process for wastewater from N-(Phosphonomethyl)iminodiacetic acid production |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674589A (en) * | 2012-04-18 | 2012-09-19 | 漳州师范学院 | Treatment method of N-phosphonomethyl aminodiacetic acid wastewater |
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| Publication number | Publication date |
|---|---|
| CN102690287B (en) | 2015-07-08 |
| CN101974032B (en) | 2012-10-03 |
| CN102690287A (en) | 2012-09-26 |
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