CN102674638A - Device for recycling N-Phosphonomethyl aminodiacetic acid from waste water in N-Phosphonomethyl aminodiacetic acid production process - Google Patents
Device for recycling N-Phosphonomethyl aminodiacetic acid from waste water in N-Phosphonomethyl aminodiacetic acid production process Download PDFInfo
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- CN102674638A CN102674638A CN2012101819020A CN201210181902A CN102674638A CN 102674638 A CN102674638 A CN 102674638A CN 2012101819020 A CN2012101819020 A CN 2012101819020A CN 201210181902 A CN201210181902 A CN 201210181902A CN 102674638 A CN102674638 A CN 102674638A
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- waste water
- pmida98
- aminodiacetic acid
- phosphonomethyl aminodiacetic
- acid
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Abstract
The invention relates to a method, application and a device for recycling N-Phosphonomethyl aminodiacetic acid from waste water in an N-Phosphonomethyl aminodiacetic acid production process. The device comprises a waste water tank, a waste water neutralization kettle, a triple effect evaporation system, a first evaporation kettle, a centrifugal machine, a mother liquid tank, a second evaporation kettle and a suction filtration cylinder, wherein an acid water steam outlet of the first evaporation kettle is connected with a biochemical treatment system. Due to the adoption of the device, the content of N-Phosphonomethyl aminodiacetic acid in prepared N-Phosphonomethyl aminodiacetic acid solution is about 13%, so that the subsequent use of the N-Phosphonomethyl aminodiacetic acid can be facilitated. The problem in recycling the N-Phosphonomethyl aminodiacetic acid can be solved, N-Phosphonomethyl aminodiacetic acid and phosphorous acid in the waste water can be treated, so that the phosphorus content in the waste water is reduced, and the discharged waste water can accord with national standards.
Description
Application of the present invention is that the patent No. is: 201010510542.5, and patent name is: reclaim the methods and applications and the specific equipment of pmida98 in the pmida98 production technique waste water, the applying date is: the dividing an application of the application for a patent for invention of 2010-10-18.
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 62 IPA Salt.Glyphosate 62 IPA Salt is the living weedicide that goes out of a kind of efficient, low temperature, noresidue, broad spectrum, and industries such as widespread use farming, woods, industrial traffic comprise 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 glycocoll-dimethylphosphite method; This is China's exploitation 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.
The applicant has adopted and has used diethylolamine to be main raw material, with phosphorus trichloride, the synthetic pmida98 of formaldehyde condensation reaction, like 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 step 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 midbody of herbicide glyphosate, and it also is the source region of severe spent process water in process of production, and the comprehensive utilization that how to improve technology and waste water is very important.
(application number: 200810124403.1 applyings date: 2008-07-01) disclose a kind of method that from produce the pmida98 mother liquor, reclaims pmida98, the pmida98 mother liquor with producing pmida98 through secondary filter, obtains clarified mother liquor to Chinese invention patent; 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 nf 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 directly be used for 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; What this method was directed against is to be that raw material adopts the acid mother liquid that is produced in the IDA path of preparing pmida98 technology with the NSC 263496; This mother liquor is regulated pH value through alkali and is obtained liquid concentrator 6～11 after reverse osmosis membrane concentrates, and liquid concentrator reclaims through infiltration evaporation and obtains formaldehyde.Adopt the inventive method can obtain mass percentage concentration at the pmida98 liquid concentrator more than 9%, this pmida98 liquid concentrator can directly be processed into the raw material of aqua sale or conduct production agricultural chemicals Glyphosate 62 IPA Salt.
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 technical scheme below the present invention has adopted:
Reclaim the method for pmida98 in the pmida98 production technique waste water, this method comprises the steps: to be 0.7%-1.5% at pmida98 production technique waste water adjustment pmida98 weight content 1., adds ydrogen peroxide 50 then, removes formaldehyde; 2. in the waste water handled well being got into and still, regulating pH value is 4.5～6.0, gets into the triple effect evaporation system then, gets into evaporating kettle through the waste water of triple effect evaporation system, steams sour water and gets into biochemical treatment system; 3. material entering whizzer is centrifugal in the evaporating kettle, and solid is an Industrial Salt, time mother liquor of winning; 4. for the first time mother liquor gets into 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 ydrogen peroxide 50 then and removes formaldehyde, and the concentration of ydrogen peroxide 50 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 technical scheme below the present invention has adopted:
Adopt the method for the pmida98 formulations prepared from solutions gyphosate solution of above-mentioned any technical scheme gained, this method comprises the steps:
(1) the pmida98 solution of any technical scheme gained carries out the evaporation concentration desalination, and pmida98 content reaches more than 15% to its mother liquor;
(2) get in the production Glyphosate 62 IPA Salt stills for air blowing, drip ydrogen peroxide 50,, get into reduction kettle again, drip ferrous sulfate, can be made into gyphosate solution when oxidation finishes;
(3) again gyphosate solution is got into the membrane sepn facility, add glyphosate technicals, can be mixed with the gyphosate solution of desired concn through aqua in the gyphosate solution of membrane sepn.
In order to realize the 3rd above-mentioned purpose, the technical scheme below the present invention has adopted:
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 through 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 technical scheme below the present invention has adopted:
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 through 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 62 IPA Salt 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 spent process water that 1 ton of pmida98 of every production produces, our company one is through optimizing technology; The 2nd, change the water idea, the reuse of washing water; The 3rd, handle back process water recycled, thereby make the spent process water 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 spent process waters of its generation.In these 120 tons of wastewater treatment process, the mother liquor about 9 tons is arranged, 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 made the phosphorus content in the waste water descend the discharge of wastewater National standard.
Description of drawings
Fig. 1 is an integrated artistic schema of the present invention.
Embodiment
Do a detailed explanation below in conjunction with the accompanying drawing specific embodiments of the invention.
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% ydrogen peroxide 50 again, and purpose is to remove formaldehyde.
(2) this waste water is got in and still, regulate pH value (about control PH=5) with 98% content soda ash and 32% ionic membrane caustic soda, get into the triple effect evaporation system, triple effect is through the waste water entering evaporating kettle (20m of evaporation
3), steam sour water and get into biochemical treatment system.
(3) material (filter cake) gets into twin-stage push-down whizzer in the still, and solid is an Industrial Salt, entrusts Deqing Salt Company Unified Treatment, and filtrating is the mother liquor first time, pmida98 content about 10%.
(4) mother liquor gets into 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) get in the production Glyphosate 62 IPA Salt stills for air blowing, drip 27.5% ydrogen peroxide 50,, get into reduction kettle again, drip ferrous sulfate, can be made into about 4%-5% gyphosate solution when oxidation finishes.
(6) get into the membrane sepn facility again, can reach about 10%, this gyphosate solution is added glyphosate technicals, can be mixed with 30% gyphosate solution through membrane sepn concentration.
As shown in Figure 1, this above-mentioned device comprises in the wastewater disposal basin that is connected through 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 62 IPA Salt 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 (2)
1. reclaim the device of pmida98 in the pmida98 production technique waste water, it is characterized in that: this device comprises in the wastewater disposal basin that is connected through 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.
2. reclaim the device of pmida98 in the pmida98 production technique waste water according to claim 1, it is characterized in that: whizzer adopts twin-stage push-down whizzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210181902 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210181902 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 |
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 |
Publications (2)
| Publication Number | Publication Date |
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| CN102674638A true CN102674638A (en) | 2012-09-19 |
| CN102674638B CN102674638B (en) | 2013-09-11 |
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| CN 201210181902 Expired - Fee Related 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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591424A (en) * | 2014-03-14 | 2015-05-06 | 山东潍坊润丰化工股份有限公司 | IDA method glyphosate wastewater resource treatment method |
| CN105060616A (en) * | 2015-07-21 | 2015-11-18 | 浙江荣凯科技发展股份有限公司 | Waste water purification treatment system |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5077431A (en) * | 1990-06-25 | 1991-12-31 | Monsanto Company | Peroxide process for producing n-phosphonomethylglycine |
| US20020148786A1 (en) * | 2001-04-13 | 2002-10-17 | Phillips Scott G. | Removal and recovery of chloride from phosphonomethyliminodiacetic acid process brine |
| CN101314607A (en) * | 2008-07-01 | 2008-12-03 | 南京大学 | Method for recycling glyphosine from mother solution for preparing glyphosine |
| 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 |
-
2010
- 2010-10-18 CN CN 201210181902 patent/CN102674638B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5077431A (en) * | 1990-06-25 | 1991-12-31 | Monsanto Company | Peroxide process for producing n-phosphonomethylglycine |
| US20020148786A1 (en) * | 2001-04-13 | 2002-10-17 | Phillips Scott G. | Removal and recovery of chloride from phosphonomethyliminodiacetic acid process brine |
| CN101314607A (en) * | 2008-07-01 | 2008-12-03 | 南京大学 | Method for recycling glyphosine from mother solution for preparing glyphosine |
| 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 (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591424A (en) * | 2014-03-14 | 2015-05-06 | 山东潍坊润丰化工股份有限公司 | IDA method glyphosate wastewater resource treatment method |
| CN104591424B (en) * | 2014-03-14 | 2017-05-10 | 山东潍坊润丰化工股份有限公司 | IDA method glyphosate wastewater resource treatment method |
| CN105060616A (en) * | 2015-07-21 | 2015-11-18 | 浙江荣凯科技发展股份有限公司 | Waste water purification treatment system |
| CN105060616B (en) * | 2015-07-21 | 2017-03-01 | 浙江荣凯科技发展股份有限公司 | Waste water purifying treatment system |
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