CN102992515A - Method for treating highly saline atrazine production waste water - Google Patents
Method for treating highly saline atrazine production waste water Download PDFInfo
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- CN102992515A CN102992515A CN2012104793126A CN201210479312A CN102992515A CN 102992515 A CN102992515 A CN 102992515A CN 2012104793126 A CN2012104793126 A CN 2012104793126A CN 201210479312 A CN201210479312 A CN 201210479312A CN 102992515 A CN102992515 A CN 102992515A
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Abstract
A method for treating highly saline atrazine production waste water is mainly applied to treating wastewater generated in an atrazine production process and mainly comprises the steps of reaction, precipitation, filtering, nanofiltration, active carbon absorption and the like, wherein one or more of compounds A, B and C are added to the waste water to remove most organic matters in the waste water through reaction and precipitation at first; secondly, TOC (total organic carbon) in the waste water is reduced to about 500 mg/L through nanofiltration; and then the TOC in the waste water is absorbed through active carbon absorption so as to be reduced below 10 mg/L; therefore, COD (chemical oxygen demand) is 30-40 mg/L; as a result, the waste water can be emitted as reaching the standard or used as chemical saline for the chlor-alkali industry. The active carbon saturated in absorption can be recycled by using acids, bases or organic solvents; and the recycled active carbon can be reused.
Description
Technical field
The invention belongs to field of fine chemical, relate to a kind for the treatment of process of atrazine waste water, the treatment process of the high slat-containing wastewater that especially produces in the atrazine production process.
Background technology
Atrazine also is G-30027, and atrazine is sweet sorghum, sugarcane, Chinese sorghum, corn planting weedicide.The production technique of atrazine is that cyanuric chloride and Isopropylamine and ethamine react, and steam distillation after reaction finishes obtains the product atrazine.1 ton of atrazine of every production produces 2.5 tons of waste water approximately, contain unreacted raw material, intermediates, atrazine and hydrolysate thereof, NaCl and NaOH etc. in the waste water, COD reaches about 6000mg/L, if these waste water directly discharge, can produce very large harm to environment, therefore must process.
Contain NaCl 10-15% in the atrazine production wastewater, be byproduct of reaction, therefore can not process with biochemical method simply.The industrial method that all adopts multiple-effect evaporation, the water of evaporation still contains organism, goes biochemical treatment again; The salt of crystallization is processed business processes as danger is useless by special hazardous chemical, and the processing costs of this salt is about 3000 yuan per ton, so processing cost is very high, converts, and the processing costs of waste water per ton is 400-500 unit.
Zhao Chun etc. (CN101734821B) propose the technique of neutralization, aluminum chloride and polyacrylamide coagulation, sand filtration, reduction vaporization, charcoal absorption, but the waste residue amount that this technique produces is a lot, comprise the waste residue of coagulation and the sodium-chlor that salts out, it is useless to be danger, and processing costs is still very high; Zheng Zheng etc. (CN100465100C) propose to adopt high-frequency voltage to process atrazine waste water, and voltage 8000-12000V can process the waste water of atrazine-containing 18-200mg/L, and this method energy consumption is large, is not suitable for suitability for industrialized production; Cheng Di etc. (CN102107999B) have proposed the technique that air scavenging ethamine and Isopropylamine, acid out reclaim atrazine, but actual atrazine production wastewater is atrazine-containing not only, main atrazine-containing is produced by product and hydrolysate, atrazine content is not high, therefore adopting the water COD after this art breading is 2000-3000mg/L, does not still reach emission standard; Active carbon powder and activated carbon fiber can planar water in micro-atrazine proved by a lot of documents, such as Tang Dengyong etc.
(CN101698665B) technique of the neutralization of proposition diluted alkaline, carbon fiber adsorption and catalytic combustion, Mathanol regenerating, the example that provides is the experimental result of atrazine-containing and the aqueous solution of sodium-chlor of in proportion preparation, this and actual production difference are very large, the solubleness of atrazine in water only has 33mg/L, and the actual production waste water COD is 6000mg/L, the about 2000-3000mg/L of TOC, obviously the major portion of organic carbon (TOC) is not atrazine, so this technique practical value is little; Shen Rongming (Zhejiang University's Master's thesis, 2007) has studied ozone oxidation and Mn
2+, Cu
2+, Fe
2+The degradation technique of the simulated wastewater in O3 catalytic oxidation laboratory and actual production waste water, the result shows the simulated wastewater oxidative degradation successful to the laboratory, and the factory effluent of reality is not had effect substantially, document does not provide reason; (China Environmental Science, 2005,25 (1): 92-95) studied the technique of dechlorination degradation of atrazine by foam nickel/iron powder, be only applicable to contain the waste water of micro-atrazine such as Wei Hong; (Harbin University of Commerce's journal (natural science edition) 2008,24 (6): 667-671) reported the research of micro-atrazine in the absorbent charcoal loading titanium dioxide catalyst degradation water such as Cao Lianqiu; Xin Chengyou (Shandong University's Master's thesis, 2004) studied bacterium HB-5 and be immobilized in the soil pollution reparation and the application of atrazine production wastewater in processing, but experiment only limits to the water sample of laboratory preparation, only divide atrazine content in the bleed, do not consider other organism, the report of industrial application is not arranged yet.
External research focuses mostly on aspect the removal and degraded of in water micro-atrazine, such as Kearney; (USP5,011,599) such as Philip C. discloses a kind of first ozone oxidation, the technical process of atrazine-containing waste water is processed in microbiological deterioration again; Sadowsky etc. (USP6,369,299) disclose a kind of transgenic plant of the triazine ring of can degrading; Hrsak etc. (USP7,658,850) disclose a kind of mixt bacteria of can degrade atrazine and other triazine ring compounds; Achintya N.Bezbaruah (Journalof Environmental Science and Health Part B, 2009,44:518-524) etc. studied the technique of Nanoscale Iron catalyzed degradation lower concentration atrazine; Selma Mededovic etc. (Ind.Eng.Chem.Res., 2007,46:2702-2709) studied the technique of electricimpulse degraded atrazine; (the Weed Science such as Jasbir Singh, 1998,46:381-388) studied the reinforcement of iron ion to atrazine degraded in water content and the soil, (Aquatic Sciences, 2003, the 65:359-366) rule of research ultraviolet degradation atrazine such as Charles M.Sharpless, etc., these researchs all are the micro-atrazines that adopts in the various technology degradation water, but COD does not reduce in the water, and the water after the processing still can not directly discharge.(the Bull Environ Contam Toxicol such as Rajendra Kumar Sharma, 2008,80:461-464) studied the absorption to lower concentration atrazine (COD) of charcoal, flying dust, coconut charcoal, sawdust, coconut fiber and bagasse charcoal, if this technology is directly used in high-concentration waste water, then because the sorbent material consumption is too large, cause processing cost very high.
From paper or the patent of having delivered, the atrazine method of wastewater treatment mainly contains charcoal absorption, electrochemical oxidation, ozone oxidation, catalyzed oxidation, biological degradation etc., but these technology all are not suitable for industrial production because of various reasons, therefore existing production equipment all adopts the method for multiple-effect evaporation to carry out preliminary treatment, cost is very high, the waste residue that produces still need be processed by danger is useless, and processing costs is very high.
Summary of the invention
Characteristics according to atrazine production wastewater, the present invention proposes the treatment process of the high saliferous factory effluent of a kind of atrazine, by reaction, filtration, nanofiltration, charcoal absorption the organism in the atrazine waste water to be removed, make waste water after processing, reach the requirement of chlor-alkali plant salt solution, perhaps reach discharging standards.
Foregoing treatment process, preferred scheme is that described reaction refers to that the high saliferous factory effluent of atrazine at first advances reactor, adds compd A, B, C in waste water, be hydrolyzed with the organism in the waste water, complex reaction makes it form precipitation, removes the part organic carbon in the waste water.
Foregoing treatment process, preferred scheme is, described compd A is tricyanic acid, cyanuramide, cyanurodiamide, trimeric cyanamide, Surchlor GR 60 or trichloroisocyanuric acid etc., and described compd B is hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid etc.; Described Compound C is diatomite, perlite, acidic white earth etc.
Foregoing treatment process, preferred scheme are that the high saliferous factory effluent of atrazine after described filtration refers to react is removed in the waste water and precipitated through centrifugal, filtration.
Foregoing treatment process, preferred scheme is that the waste water after described nanofiltration refers to filter removes nanofiltration membrane separation, and the TOC in the waste water is further reduced.
Foregoing treatment process, preferred scheme are, the nanofiltration membrane molecular weight cut-off 150-1000 of employing (preferred 150-300).
Foregoing treatment process, preferred scheme are that described charcoal absorption refers to that the waste water after the nanofiltration adsorbs with gac (being preferably Powdered Activated Carbon), and waste water reaches the requirement of chlor-alkali plant salt solution after the absorption, perhaps reaches discharging standards.
Foregoing treatment process, preferred scheme is, with used regeneration of activated carbon.
Foregoing treatment process, preferred scheme is that regeneration of activated carbon liquid send the filter progress circular treatment.
Thus, the treatment process of the high saliferous factory effluent of atrazine that the present invention proposes mainly may further comprise the steps:
(1) reaction: atrazine production wastewater at first advances reactor, adds compd A, B, C in waste water, is hydrolyzed with organism in the waste water, the reaction such as complexing precipitates its formation, removes the part organic carbon in the waste water.
(2) filter: waste water is removed in the waste water and is precipitated through centrifugal, filtration behind the reaction precipitation.
(3) nanofiltration: the waste water after the filtration removes nanofiltration membrane separation, and the TOC in the waste water is down to about 500mg/L.
(4) charcoal absorption: the waste water charcoal absorption after the nanofiltration, the TOC of waste water is down to below the 10mg/L after the absorption, and COD30-40mg/L can qualified discharge or use as the change salt solution of chlor-alkali industry.
(5) regeneration of activated carbon: adsorbed organic gac and regenerated with acid, alkali, organic solvent etc.
(6) regenerated liquid is processed: regeneration of activated carbon liquid adds reactant A, B, C postprecipitation, send filter progress again.
Treatment process provided by the invention, waste water mainly for the treatment of the generation of atrazine production process, mainly comprise: the operations such as reaction, precipitation, filtration, nanofiltration, charcoal absorption, at first add compd A in the waste water, B, C remove most of organism in the waste water by reaction precipitation, then with nanofiltration the TOC in the waste water is down to about 500mg/L, use again charcoal absorption, the TOC of waste water is reduced to below the 10mg/L after the absorption, COD30-40mg/L can qualified discharge or use as the change salt solution of chlor-alkali industry.Adsorbing saturated gac can regenerate with acid, alkali or organic solvent etc., and the gac after the regeneration can be reused.
Compared with prior art, technical superiority of the present invention is embodied in:
1, the water COD after the processing is down to below the 60mg/L, reaches discharging standards;
2, adopt reaction-nanofiltration-absorbing process, simple to operate, save evaporization process, energy consumption is low, and processing costs is 30 yuan/tons, compares with former technique and reduces by 90%;
3, the Halite water TOC＜10mg/L after the processing reaches the requirement of the change salt solution of chlor-alkali production, can be used as salt solution, and NaCl and water are recycled utilization.
Description of drawings
Fig. 1 is the process flow diagram of the high saliferous production wastewater treatment of atrazine of the present invention, among the figure: the 1-atrazine production wastewater; 2-regeneration of activated carbon liquid; 3-chemical A/B/C adds entrance; The 4-reactor; 5-reactor pump; The 6-strainer; 7-comes inherent filtration intermediate water tank rework solution; 8-by-product fire retardant; 9-filters intermediate water tank; 10-nanofiltration intake pump; 11-filtered water recycle pump; 12-intermediate water tank backwater; The 13-accurate filter; The 14-high-pressure pump; The 15-nanofiltration device; 16-nanofiltration intermediate water tank; 17-gac conveying pump; The 18-activated carbon adsorber; 19-charcoal absorption water out; 20-regeneration alkali lye; 21-cleaning water; The 22-regenerated liquid.
Specific implementation method
Describe technical scheme of the present invention in detail below in conjunction with embodiment and accompanying drawing, but protection domain is not limited to this.
The high saliferous factory effluent that embodiment 1 atrazine is produced, saltiness 12%, TOC 6000mg/L, COD 16200mg/L, waste water at first advances reactor, to wherein adding the compound tricyanic acid, sulfuric acid and diatomite are hydrolyzed with organism in the waste water, the reactions such as complexing make it form precipitation, remove by filter the precipitation in the waste water, processed waste water TOC is 1800mg/L, COD5100mg/L carries out nanofiltration separation with the DK nanofiltration membrane again, waste water TOC 500mg/L after the nanofiltration, COD 1260mg/L, then waste water adsorbs with Powdered Activated Carbon, waste water TOC 8.3mg/L after the absorption, COD 22mg/L.
The treatment process of 2 one kinds of high saliferous factory effluents of atrazine of embodiment, by reaction, filtration, nanofiltration, charcoal absorption the organism in the atrazine waste water to be removed, make waste water after processing, reach the requirement of chlor-alkali plant salt solution, perhaps reach discharging standards.
Fig. 1 is the process flow diagram of the high saliferous production wastewater treatment of atrazine of the present invention; utilize this technique from the atrazine production technique, to take out high saliferous factory effluent; saltiness 15%; TOC 6500mg/L; COD 17500mg/L; at first advance reactor; in waste water, add the compound cyanuramide; hydrochloric acid; perlite; be hydrolyzed with the organism in the waste water; the reactions such as complexing make it form precipitation; remove by filter the precipitation in the waste water, waste water TOC is 2200mg/L behind the reaction precipitation, COD 5960mg/L; advance again nanofiltration membrane NF270 and carry out nanofiltration separation; waste water TOC 600mg/L after the nanofiltration, COD1650mg/L, then waste water adsorbs with granulated active carbon; waste water TOC 9.6mg/L after the absorption, COD 27mg/L.
The saturated gac of absorption is regenerated with NaOH, regenerated liquid TOC 15000mg/L, COD 40100mg/L, add compound trimeric cyanamide, phosphoric acid, acidic white earth, reaction precipitation, solution TOC 2300mg/L after filtering, COD 6300mg/L, pass through nanofiltration, charcoal absorption, TOC reduces to 10mg/L again, COD 29mg/L.
The recycling of gac after the regeneration is used for the waste water of adsorption treatment TOC 800mg/L, COD 2100mg/L, the waste water TOC 10mg/L after the adsorption treatment, COD 27mg/L.
Claims (10)
1. the treatment process of the high saliferous factory effluent of atrazine, it is characterized in that, by reaction, filtration, nanofiltration, charcoal absorption, the organism in the atrazine waste water is removed, make waste water after processing, reach the requirement of chlor-alkali plant salt solution, perhaps reach discharging standards.
2. treatment process according to claim 1, it is characterized in that, described reaction refers to that the high saliferous factory effluent of atrazine at first advances reactor, in waste water, add compd A, B, C, be hydrolyzed with the organism in the waste water, complex reaction makes it form precipitation, removes the part organic carbon in the waste water.
3. treatment process according to claim 2, it is characterized in that, described compd A is tricyanic acid, cyanuramide, cyanurodiamide, trimeric cyanamide, Surchlor GR 60 or trichloroisocyanuric acid etc., and described compd B is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid etc.; Described Compound C is diatomite, perlite or acidic white earth etc.
4. treatment process according to claim 1 is characterized in that, the high saliferous factory effluent of atrazine after described filtration refers to react is removed in the waste water and precipitated through centrifugal, filtration.
5. treatment process according to claim 1 is characterized in that, the waste water after described nanofiltration refers to filter removes nanofiltration membrane separation, and the TOC in the waste water is further reduced.
6. treatment process according to claim 5 is characterized in that, the nanofiltration membrane molecular weight cut-off 150-1000 of employing, (preferred 150-300).
7. treatment process according to claim 1 is characterized in that, described charcoal absorption refers to the waste water charcoal absorption after the nanofiltration, and waste water reaches the requirement of chlor-alkali plant salt solution after the absorption, perhaps reaches discharging standards.
8. treatment process according to claim 1 is characterized in that, with used regeneration of activated carbon.
9. treatment process according to claim 8 is characterized in that, regeneration of activated carbon liquid send the filter progress circular treatment.
10. treatment process according to claim 1 is characterized in that, gac is granulated active carbon and Powdered Activated Carbon.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104606839A (en) * | 2014-12-19 | 2015-05-13 | 马恩剑 | A method of degrading pesticide residues and heavy metals in traditional Chinese medicines |
| CN112955245A (en) * | 2018-10-30 | 2021-06-11 | 巴斯夫欧洲公司 | Removal of aluminum salts, HCl, NaCl and organic by-products from strongly alkaline DIOPAT suspensions by means of alkaline stable nanofiltration and then separation of salts and by-products by means of ultrafiltration after neutralization of the DIOPAT solution |
| CN113614288A (en) * | 2019-03-13 | 2021-11-05 | 科思创知识产权两合公司 | Post-treatment and reuse method of salt-containing process water |
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| CN101445289A (en) * | 2009-01-04 | 2009-06-03 | 南京信息工程大学 | Method for removing atrazine from drinking water |
| CN101628226A (en) * | 2008-07-15 | 2010-01-20 | 周奇迪 | Filter medium for removing pesticide in water and preparation method thereof |
| CN101698665A (en) * | 2009-10-30 | 2010-04-28 | 南京信息工程大学 | Method for treating atrazine waste water and recycling resources |
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Patent Citations (5)
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| US20050056598A1 (en) * | 2003-06-06 | 2005-03-17 | Chowdhury Ajit K. | Method for treating recalcitrant organic compounds |
| CN101050000A (en) * | 2007-05-16 | 2007-10-10 | 南京大学 | Method for removing atranex in water |
| CN101628226A (en) * | 2008-07-15 | 2010-01-20 | 周奇迪 | Filter medium for removing pesticide in water and preparation method thereof |
| CN101445289A (en) * | 2009-01-04 | 2009-06-03 | 南京信息工程大学 | Method for removing atrazine from drinking water |
| CN101698665A (en) * | 2009-10-30 | 2010-04-28 | 南京信息工程大学 | Method for treating atrazine waste water and recycling resources |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104606839A (en) * | 2014-12-19 | 2015-05-13 | 马恩剑 | A method of degrading pesticide residues and heavy metals in traditional Chinese medicines |
| CN104606839B (en) * | 2014-12-19 | 2017-06-16 | 马恩剑 | Degraded Chinese medicine pesticide residue, the method for heavy metal |
| CN112955245A (en) * | 2018-10-30 | 2021-06-11 | 巴斯夫欧洲公司 | Removal of aluminum salts, HCl, NaCl and organic by-products from strongly alkaline DIOPAT suspensions by means of alkaline stable nanofiltration and then separation of salts and by-products by means of ultrafiltration after neutralization of the DIOPAT solution |
| CN112955245B (en) * | 2018-10-30 | 2023-10-20 | 巴斯夫欧洲公司 | Removal of aluminum salts, HCl, naCl, and organic byproducts from a strongly basic diopta suspension |
| US11904279B2 (en) | 2018-10-30 | 2024-02-20 | Basf Se | Removal of Al-salts, HCl, NaCl and organic by-product from strong alkaline DIOPAT suspension by means of alkaline stable nanofiltration followed by separation of salts and byproducts after neutralization of DIOPAT solution by means of ultrafiltration |
| CN113614288A (en) * | 2019-03-13 | 2021-11-05 | 科思创知识产权两合公司 | Post-treatment and reuse method of salt-containing process water |
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