CN102674589B - Treatment method of N-phosphonomethyl aminodiacetic acid wastewater - Google Patents
Treatment method of N-phosphonomethyl aminodiacetic acid wastewater Download PDFInfo
- Publication number
- CN102674589B CN102674589B CN2012101139328A CN201210113932A CN102674589B CN 102674589 B CN102674589 B CN 102674589B CN 2012101139328 A CN2012101139328 A CN 2012101139328A CN 201210113932 A CN201210113932 A CN 201210113932A CN 102674589 B CN102674589 B CN 102674589B
- Authority
- CN
- China
- Prior art keywords
- wastewater
- phosphonomethyl
- filtrate
- value
- chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a treatment method of N-phosphonomethyl aminodiacetic acid wastewater. the treatment method comprises the following steps: separating out iminodiacetonitrile from the N-phosphonomethyl aminodiacetic acid wastewater by an adsorption method; adding calcium hydroxide in the wastewater, controlling pH value of solution to be larger than 8.0, filtering and separating out organic calcium sediment; regulating the pH value of filtrate to be 3.0-4.0 by hydrochloric acid, then adding chloride and stirring, adding sodium hydroxide to control the pH value of solution to be 6.0-6.5, and continuously stirring, filtering and separating out the solid sediment; and finally, adjusting pH value of the separated filtrate to be 2.0-3.0 by hydrochloric acid, adsorbing the filtrate by activated aluminum oxide, thereby obtaining the completely treated N-Phosphonomethyl aminodiacetic acid wastewater. Based on a complexing principle, the problem that high-concentration sodium chloride in the wastewater influences the treatment of wastewater is solved, not only is the wastewater treatment problem in companies solved, the whole process of treatment is simplified, the cost is lowered and the feasibility is improved, but also the cost for the companies is saved and the competitiveness of the companies is improved.
Description
Technical field
The present invention relates to technical field of waste water processing, refer to especially a kind for the treatment of process of N-(phosphonomethyl) iminodiacetic acid wastewater.
Background technology
Glyphosate is one of weedicide that is most widely used at present, and pmida98 is one of intermediate of producing glyphosate.And while utilizing the IDA method to carry out the production of pmida98, need to use a large amount of hydrochloric acid and sodium hydroxide, thereby cause in its production process, discharged the waste water that contains in a large number high density chlorination sodium.And how effectively to reclaim pmida98 from the N-(phosphonomethyl) iminodiacetic acid wastewater that contains high density chlorination sodium, and make the waste water after processing reach emission request, be the technical problem that the sector is badly in need of solving at present.Present most of enterprise is generally to adopt the calcium oxide precipitator method, membrane filter method or distillation and concentration method etc. to the processing mode of N-(phosphonomethyl) iminodiacetic acid wastewater, and they all exist the some shortcomings part, as:
While (1) adopting the calcium oxide precipitation, generally the deposition rate of pmida98 in waste water is no more than 90%, the content of the Phosphorus From Wastewater after precipitation, carbon, nitrogen and COD(chemical oxygen demand (COD)) emission standard that requires that surpasses far away.
While (2) adopting membrane filter method,, although its treatment effect is better,, because its processing speed is slower, generally be difficult to realize the approximately requirement more than 100 tons of day output; Particularly used nanofiltration membrane can't be regenerated, so the cost that the method is processed is higher, and can't effectively reclaim the pmida98 in waste water, thereby easily causes the wasting of resources.
While (3) adopting the distillation and concentration method, the method faces too that processing speed is slow, and cost is higher, the problem of the pmida98 in can't efficient recovery waste water.
Therefore, due to the impact of high density chlorination sodium, the conventional precipitator method or ion exchange method etc. all are difficult to make the emission request that reaches of phosphorus, carbon, nitrogen and COD in waste water.
Summary of the invention
The purpose of this invention is to provide a kind of simple to operately, cost is low, the treatment process of the N-(phosphonomethyl) iminodiacetic acid wastewater that feasibility is large.
For achieving the above object, solution of the present invention is:
A kind for the treatment of process of N-(phosphonomethyl) iminodiacetic acid wastewater, concrete steps are:
1), adopt absorption method to isolate iminodiacetonitrile N-(phosphonomethyl) iminodiacetic acid wastewater;
2), add calcium hydroxide, control the pH value of solution greater than 8.0, filter to isolate the organic calcium throw out;
3), with step 2) in the filtrate that obtains be 3.0-4.0 with hydrochloric acid conditioning solution pH value, then add chlorate to stir, add afterwards sodium hydroxide that the pH value of solution is adjusted to 6.0-6.5, continue stirring, filter to isolate fixedly throw out;
4), be 2.0-3.0 with the filtrate in step 3) with the salt acid for adjusting pH value, and by activated alumina, adsorb, thus the N-(phosphonomethyl) iminodiacetic acid wastewater after being processed fully.
Described step 2) after in, isolated organic calcium throw out dissolves with hydrochloric acid again, then by macroporous adsorbent resin, carry out fractionation by adsorption, filtrate is acid calcium chloride filtrate; And then utilize sodium hydroxide to carry out wash-out to resin, must contain the solution of pmida98 sodium.
After in described step 3), isolated fixedly throw out dissolves with hydrochloric acid, then by macroporous adsorbent resin, carry out fractionation by adsorption, filtrate is acid iron(ic) chloride filtrate; And then utilize sodium hydroxide to carry out wash-out to resin, must contain the solution of pmida98 sodium.
Described step 2) need to stir 1 hour after adding hydrochloric acid in.
Absorption method in described step 1) is absorption with macroporous adsorbent resin.
Chlorate in described step 3) is iron(ic) chloride, nickelous chloride, cupric chloride or zinc chloride.
after adopting such scheme, as seen the present invention systematically analyzes existing relative merits to the N-(phosphonomethyl) iminodiacetic acid wastewater treatment process, for containing the characteristics of the sodium-chlor of high density in hot N-(phosphonomethyl) iminodiacetic acid wastewater, pmida98 carries out on the basis of fully reclaiming in to waste water, based on complex scheme, utilize transition metal ion the pmida98 in waste water to be identified and further formed the title complex of transition metal ion-pmida98, and then the pH value by regulator solution, the title complex of transition metal ion-pmida98 is separated with the form of precipitation, thereby solved the impact that Coal Gas Washing Cycling Water sodium-chlor is processed N-(phosphonomethyl) iminodiacetic acid wastewater, and make the content of the Phosphorus From Wastewater after processing fully be about 1mg/L, the content of carbon is about 50mg/L, the content of nitrogen is about 10mg/L, COD is about 90mg/L.
This invention not only can solve the waste water handling problem that enterprise faces, and the whole flow operations that order is processed is simple, and cost is lower, and feasibility is larger, and can save cost for enterprise, improves the competitive power of enterprise.
Embodiment
The present invention has disclosed a kind for the treatment of process of N-(phosphonomethyl) iminodiacetic acid wastewater, its concrete operation step:
1), the henna N-(phosphonomethyl) iminodiacetic acid wastewater of 10L is adsorbed by macroporous adsorbent resin, obtain clear solution;
2), then add 0.5 kg of hydrogen calcium oxide, control the pH value of solution greater than 8.0, stirred 1 hour, filter, isolate the organic calcium throw out;
3) and then the filtrate that obtains with the pH value that hydrochloric acid is adjusted to solution, be about 3.0-4.0, add again 0.05 kilogram of iron(ic) chloride (or nickelous chloride, or cupric chloride, or zinc chloride), stir half an hour under room temperature, and then with sodium hydroxide, the pH value of solution is adjusted to 6.0-6.5, continue to stir half an hour, filter, isolate the brown color solid precipitation;
4), again filtrate is about 2.0-3.0 with the salt acid for adjusting pH value finally, and by activated alumina, adsorb, thus the N-(phosphonomethyl) iminodiacetic acid wastewater after being processed fully.
In final filtrate, the content of each material is as follows: the content of phosphorus is about 1mg/L; The content of carbon is about 50mg/L; The content of nitrogen is about 10mg/L; COD is about 90mg/L.
And step 2) in the organic calcium throw out in the separating and recycle of pmida98 and calcium chloride: after the organic calcium throw out is dissolved with hydrochloric acid, then by macroporous adsorbent resin, filtrate is acid calcium chloride filtrate; And then utilize 5% sodium hydroxide to carry out wash-out to resin, must contain the solution of pmida98 sodium.
The separating of pmida98 and iron(ic) chloride in brown color solid precipitation in another step 3): after the brown color solid precipitation is dissolved with hydrochloric acid, then by macroporous adsorbent resin, filtrate is acid iron(ic) chloride filtrate; And then utilize 5% sodium hydroxide to carry out wash-out to resin, must contain the solution of pmida98 sodium.
this shows, the present invention systematically analyzes existing relative merits to the N-(phosphonomethyl) iminodiacetic acid wastewater treatment process, for containing the characteristics of the sodium-chlor of high density in hot N-(phosphonomethyl) iminodiacetic acid wastewater, pmida98 carries out on the basis of fully reclaiming in to waste water, based on complex scheme, utilize transition metal ion the pmida98 in waste water to be identified and further formed the title complex of transition metal ion-pmida98, and then the pH value by regulator solution, the title complex of transition metal ion-pmida98 is separated with the form of precipitation, thereby solved the impact that Coal Gas Washing Cycling Water sodium-chlor is processed N-(phosphonomethyl) iminodiacetic acid wastewater, and make the content of the Phosphorus From Wastewater after processing fully be about 1mg/L, the content of carbon is about 50mg/L, the content of nitrogen is about 10mg/L, COD is about 90mg/L.
In a word, the present invention utilizes iron(ic) chloride (or nickelous chloride, or cupric chloride, or zinc chloride) to carry out the complex-precipitation technology to pmida98 a small amount of in waste water.
This invention not only can solve the waste water handling problem that enterprise faces, and the whole flow operations that order is processed is simple, and cost is lower, and feasibility is larger, and can save cost for enterprise, improves the competitive power of enterprise.
Claims (4)
1. the treatment process of a N-(phosphonomethyl) iminodiacetic acid wastewater, concrete steps are:
1), adopt absorption method to isolate iminodiacetonitrile N-(phosphonomethyl) iminodiacetic acid wastewater;
2), add calcium hydroxide, control the pH value of solution greater than 8.0, filter to isolate the organic calcium throw out;
3), with step 2) in the filtrate that obtains be 3.0-4.0 with hydrochloric acid conditioning solution pH value, then add chlorate to stir, add afterwards sodium hydroxide that the pH value of solution is adjusted to 6.0-6.5, continue stirring, filter to isolate fixedly throw out; Described chlorate is iron(ic) chloride, nickelous chloride, cupric chloride or zinc chloride;
4), be 2.0-3.0 with the filtrate in step 3) with the salt acid for adjusting pH value, and by activated alumina, adsorb, thus the N-(phosphonomethyl) iminodiacetic acid wastewater after being processed fully.
2. the treatment process of N-(phosphonomethyl) iminodiacetic acid wastewater as claimed in claim 1, it is characterized in that: after described step 2), isolated organic calcium throw out dissolves with hydrochloric acid again, carry out fractionation by adsorption by macroporous adsorbent resin again, filtrate is acid calcium chloride filtrate; And then utilize sodium hydroxide to carry out wash-out to resin, must contain the solution of pmida98 sodium.
3. the treatment process of N-(phosphonomethyl) iminodiacetic acid wastewater as claimed in claim 1 is characterized in that: after in described step 3), isolated fixedly throw out dissolves with hydrochloric acid, then by macroporous adsorbent resin, carry out fractionation by adsorption, filtrate is acid iron(ic) chloride filtrate; And then utilize sodium hydroxide to carry out wash-out to resin, must contain the solution of pmida98 sodium.
4., as the treatment process of claim 1,2 or 3 described N-(phosphonomethyl) iminodiacetic acid wastewaters, it is characterized in that: the absorption method in described step 1) is absorption with macroporous adsorbent resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101139328A CN102674589B (en) | 2012-04-18 | 2012-04-18 | Treatment method of N-phosphonomethyl aminodiacetic acid wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101139328A CN102674589B (en) | 2012-04-18 | 2012-04-18 | Treatment method of N-phosphonomethyl aminodiacetic acid wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102674589A CN102674589A (en) | 2012-09-19 |
| CN102674589B true CN102674589B (en) | 2013-11-13 |
Family
ID=46807230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101139328A Expired - Fee Related CN102674589B (en) | 2012-04-18 | 2012-04-18 | Treatment method of N-phosphonomethyl aminodiacetic acid wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102674589B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351070B (en) * | 2013-07-26 | 2015-05-06 | 闽南师范大学 | Method for treating glyphosate waste water |
| CN103601319B (en) * | 2013-11-22 | 2014-11-26 | 无锡合众信息科技有限公司 | Pmida wastewater treatment device |
| CN105440074B (en) * | 2014-09-30 | 2018-05-22 | 北京紫光英力化工技术有限公司 | A kind of method that pmida Recycling Mother Solution is applied mechanically |
| CN105524107B (en) * | 2014-09-30 | 2017-12-29 | 北京紫光英力化工技术有限公司 | A kind of PMIDA clean manufacturing and accessory substance novel process for recycling |
| CN107902796A (en) * | 2017-11-17 | 2018-04-13 | 闽南师范大学 | Pig-farm wastewater advanced treatment process |
| CN114031239B (en) * | 2022-01-10 | 2022-04-08 | 中南大学 | Method for separating multiple metals in plasma fused soot elution wastewater |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7828976B2 (en) * | 2007-06-22 | 2010-11-09 | I. Kruger, Inc. | Method of removing phosphorus from wastewater |
| CN101974032B (en) * | 2010-10-18 | 2012-10-03 | 浙江拜克开普化工有限公司 | Method for recycling N-(Phosphonomethyl)iminodiaceticacid (PMIDA) in PMIDA production wastewater, application and special device |
| CN102115281B (en) * | 2011-01-18 | 2012-07-04 | 中国中化股份有限公司 | Method for pretreating wastewater generated in production of N-(Phosphonomethyl) iminodiaceticacid (PMIDA) |
-
2012
- 2012-04-18 CN CN2012101139328A patent/CN102674589B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102674589A (en) | 2012-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102674589B (en) | Treatment method of N-phosphonomethyl aminodiacetic acid wastewater | |
| CN104163519B (en) | The process for purification of effluent brine in a kind of glyphosate production | |
| CN106048217B (en) | The comprehensive reutilization method of oxide powder and zinc | |
| CN102936070A (en) | Method for treating mercury-containing wastewater during PVC (Polyvinyle Chloride) production through two-step process | |
| CN107902855B (en) | Recovery process of waste zinc ions in viscose fiber production | |
| CN110980866A (en) | Method for deeply removing zinc-nickel alloy electroplating wastewater | |
| CN110117043B (en) | Method for removing heavy metal ions in wastewater by using ion exchange resin and regeneration method of resin | |
| CN101421193A (en) | An effluent treatment process | |
| CN103936189A (en) | Processing method for recovery processing of high ammonia nitrogen wastewater | |
| EP2376389B1 (en) | Perchlorate removal from concentrated salt solutions using amphoteric ion-exchange resins | |
| CN110981013A (en) | Method for treating waste liquid after extraction of thiamine | |
| JP2005193167A (en) | Drainage purification method and purification method | |
| CN110983070B (en) | Method for preparing refined nickel sulfate from copper electrolyte decoppered liquid | |
| Rodriguez-Freire et al. | Technologies for fractionation of wastewater and resource recovery | |
| CN103351070B (en) | Method for treating glyphosate waste water | |
| WO2012143394A1 (en) | Method for recovery of thallium from an aqueous solution | |
| CN107381705B (en) | Method for separating and recovering multiple cationic heavy metals in water through phase change regulation | |
| CN105712569A (en) | Deep processing method of selenium containing wastewater | |
| JP4164681B2 (en) | How to recover phosphorus | |
| CN1328250C (en) | Effluent treating and resource recovering process for refining step of 2B acid production | |
| US20180119298A1 (en) | Iodide removal from brine using ion retardation resins | |
| CN114768752A (en) | Fly ash loaded hydrotalcite-like compound composite adsorbent, preparation method and application | |
| CN104692447B (en) | Etching waste liquor and wiring board mud are processed the method for preparing basic copper chloride simultaneously | |
| CN109897967B (en) | Method for separating and recovering zinc from complex chloride system | |
| CN108101260B (en) | Method for treating lithium cobaltate production wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 363000 Fujian County, Zhangzhou city before the straight street, No. 36 Applicant after: Minnan Normal University Address before: 363000 Fujian County, Zhangzhou city before the straight street, No. 36 Applicant before: Minnan Normal University |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: ZHANGZHOU NORMAL COLLEGE TO: MINNAN NORMAL UNIVERSITY |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131113 Termination date: 20160418 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |