CN102249376A - Method for realizing recycling of aniline waste water and zero release through electropolymerization - Google Patents
Method for realizing recycling of aniline waste water and zero release through electropolymerization Download PDFInfo
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- CN102249376A CN102249376A CN 201110131660 CN201110131660A CN102249376A CN 102249376 A CN102249376 A CN 102249376A CN 201110131660 CN201110131660 CN 201110131660 CN 201110131660 A CN201110131660 A CN 201110131660A CN 102249376 A CN102249376 A CN 102249376A
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- aniline
- waste water
- electropolymerization
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- aniline waste
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Abstract
The invention discloses a method for realizing recycling of aniline waste water and zero release through electropolymerization and relates to the field of treatment of industrial sewage and the field of electrochemical synthesis of polyaniline. The invention discloses the method for realizing recycling of the aniline waste water and zero release through electropolymerization by using a stainless steel electrode and a titanium-based lead dioxide electrode; by the continuous polymerization and film formation of aniline on a stainless steel anode, the aniline components in waste water can be consumed, finally the aniline waste water is not toxic, and the formed film of aniline polymer can be collected as a product; and an appropriate amount of residual aniline waste water can be used as the make-up water of boiler recirculating water, and has the effect of biocide, and the zero release of the aniline waste water can be realized. Compared with the conventional electro-catalysis method, the method for treating the aniline waste water through electropolymerization has the advantages that: current efficiency is greatly improved, the aniline is sufficiently recycled, and the low-cost treatment and zero release of the aniline waste water are realized finally.
Description
Technical field
The present invention relates to the industrial sewage process field,, realize that the nothing of aniline waste water poisons processing and zero release based on the electric polymerization reaction of aniline.The present invention relates to the electrochemical synthesis field of polyaniline, the aniline physical resources in the waste water are turned to polymerization product.
Background technology
Aniline waste water is the focus that the field of environment protection investigators pay close attention to as common high toxicity, the organic wastewater with difficult degradation thereby of industrial trades such as pharmacy, chemical industry always.The processing of aniline waste water at first should realize the removal and the recycling of aniline, secondly should realize wastewater zero discharge as much as possible, to reach the purpose of conserve water resource and water resources recycling.
More typical aniline waste water treatment technology comprises biological process, absorption method, and chemical oxidization method etc., but most methods can not effectively realize the resource utilization of aniline waste water and the zero release of waste water.Gu Longmei etc. have reported in waste water and to have added formaldehyde and Tai-Ace S 150 carries out polycondensation that handle the technology of para-totuidine waste water, polymkeric substance is separated out the back and added the polyacrylamide precipitation, carries out flocculation treatment by iron carbon method again.Though this chemical oxidation method is finished the processing of amino benzene analog waste water, need the heavy addition chemical agent.(Gu Longmei. para-totuidine wastewater treatment equipment [P]. Chinese patent, 201020262547.2011-3-2.) use biological process to handle the Huang Jingsheng report of the method for aniline waste water by Sinopec, use Taiwan H.S.B high definition bacterium, with oil of mirbane (100mg/L), aniline (500mg/L), the oil of mirbane of the about 1500/L of COD, aniline waste water carries out biochemical treatment, realize qualified discharge, the objectionable impurities degraded relies on microorganism fully and carries out (Huang Jingsheng, Yu Fang etc. the full biochemical processing method [P] of nitrobenzene waste water or aniline waste water or its composite waste. Chinese patent, 200410065840.2005-07-27.), but this kind method treatment time is longer, and can not realize resource recycling.Research Institute of Nanjing Chemical Industry Group has been reported and has been used oil of mirbane to handle the technology of aniline waste water, with Aniline Production raw material oil of mirbane is solvent, and aniline waste water is extracted in the oil of mirbane again, drops into the Aniline Production flow process, the waste water of nitrobenzene-containing is as the thick oil of mirbane alkali cleaning water in the oil of mirbane production.(Liu Han etc. nitrobenzene extraction method for treating aniline wastewater [P]. Chinese patent, 200410064922.2005-03-30.) though this method has realized the processing fully of aniline waste water, but mainly can only be applicable to the waste water that produces in the special Aniline Production flow process, the aniline waste water that produces for other industrial circles can not guarantee to be suitable for.Chinese Academy of Sciences's treating aniline waste water by absorption-low temperature dry method that coalification is used, with aniline waste water by the fixed-bed reactor of absorption-catalyzer are housed, make that aniline concentration is lower than 5mg/L in the waste water of absorption back, absorption finishes the back at temperature of reaction 100-400 ℃, reaction 1-10h, charge into oxidizing gas, catalyzed oxidation aniline, and use this reactor repeatedly.This method needs fairly large reactor, catalyzer, heating unit etc.(Liu Zhenyu, Li Bingzheng. a kind of method for the treatment of aniline waste water by absorption-low temperature dry method [P]. Chinese patent, 200810054832.2010-06-02.) these aniline waste water treatment processs, maybe need to add the more chemical substance that adds, or only can be applicable to the recycling of specific aniline waste water.
Use the removal efficient height of electrochemical oxidation method to aniline waste water, processing speed is fast, and cost and medicament input amount descend to some extent, but still face problems such as processing cost height, complex process, are difficult to large-scale application.The method of aniline, oil of mirbane in the use electrolytic process degrading waste water of Nanjing University's report, use titanium base ruthenium or ti-lead dioxide anode and have the electrolyzer that cationic exchange membrane is separated, aniline waste water carries out dc electrolysis in the antianode chamber, and cathode compartment adds NaOH solution.This method is still used strong alkali solution and is used expensive catalyticing anode material, and handling for aniline waste water makes troubles.(Zhao Yuming. aniline in a kind of electrolytic process degrading waste water is or/and the method for oil of mirbane [P]. Chinese patent, 200610040664.2008-05-21.) Institutes Of Technology Of Tianjin reported the method for using microbiological fuel cell to handle aniline waste water, use electrode materialss such as carbon, vitrescence carbon, negative electrode uses the platinum plating catalyzer, use anaerobic sludge to start microbiological fuel cell, and just like you more anode glucose be converted to aniline, glucose mixing solutions, in order to consume the aniline pollutent.This method is also just brought the corresponding lifting of complex process degree in conjunction with biological and two kinds of processing means of electrochemistry.(Zhang Jiaqi. the method [P] of a kind of microbiological fuel cell and processing aniline waste water thereof. Chinese patent, 201010262015.2010-12-22.)
In the treating processes of the catalytic oxidation of aniline waste water, the electrochemical polymerization phenomenon of aniline on anode is of common occurrence, is deposited on anode surface and has hindered the catalyzed oxidation process greatly.Aniline category matter can be at various electrode surfaces, fast even polymerization film formation, therefore by the aniline electric polymerization reaction, aniline category matter polymerization in the waste water is deposited on the plate, low cost, less energy-consumption processing aniline waste water will be very likely realized, and the zero release of the recycling and the waste water of aniline waste water can be realized.This patent just proposes and has invented a kind of method that aniline waste water is realized aniline waste water resource utilization and zero release by the electropolymerization film forming.
Summary of the invention
The present invention seeks to utilize the electropolymerization film process of aniline on anode, use 304,321 stainless steel anodes, titanium base tindioxide anode carries out electrochemical treatment to aniline waste water.On the basis that the electrochemical polymerization reaction of aniline is controlled, utilize the film forming continuous growth of aniline polymerization, consume the aniline composition in the waste water, finally make aniline waste water thoroughly do not had the processing of poisoning.
For achieving the above object, the present invention takes following technical scheme: be the aniline waste water of 10～1000mg/L in concentration, add the ionogen sodium sulfate concentration and make sodium sulfate reach 0.05～0.2mol/L, make the specific conductivity of waste water reach 5～20mS/cm, pH is controlled at 4～10.Use dc supply that waste water is handled, working electrode is a stainless steel electrode, the titanium electrode, and the titanium-based oxide electrode, platinum electrode or Graphite Electrodes, the working electrode area is 5cm with pending liquor capacity ratio
2: 1cm
3～1cm
2: 5cm
3Using the operating voltage of dc supply is 2.5～5V, and the adjusting working current density is 1～10A/m
2, carry out the lasting processing of 0.1～12h.
Water outlet aniline concentration is less than 10mg/L, and chemical oxygen demand (COD) (COD) emission concentration is lower than 100mg/L.
Waste water after the processing contains the minor amounts of aniline material, but reuse is the boiler recirculated cooling water, realizes the zero release of waste water.
Embodiment
Embodiment 1
Select the pending aniline waste water 100ml of 100mg/L concentration for use, the setting operating voltage is 3.2V, regulates the ionogen sodium sulfate concentration and makes it to reach 0.1mol/L, and conductivity of waste water reaches 10mS/cm, and pH is 7, and the adjusting working current density is 5A/m
2, the working electrode area is 5cm with pending liquor capacity ratio
2: 1cm
3, behind electrochemical treatment 12h, aniline electropolymerization film forming product integral body comes off, and means that aniline is removed from water substantially.Aniline concentration becomes the 7mg/L chemical oxygen demand (COD) by 100mg/L, and to become COD by 250mg/L be 53mg/L.Handle 100mg/L aniline waste water power consumption 4.03kwh per ton.Working electrode is 304 stainless steels.
Embodiment 2
Select the pending aniline waste water 20ml of 20mg/L concentration for use, the setting operating voltage is 4.0V, regulates the ionogen sodium sulfate concentration and makes it to reach 0.1mol/L, and conductivity of waste water reaches 10mS/cm, and pH is 4, and the adjusting working current density is 8A/m
2, the working electrode area is 2cm with pending liquor capacity ratio
2: 1cm
3, behind electrochemical treatment 0.1h, aniline electropolymerization film forming product integral body comes off, and means that aniline is removed from water substantially.Aniline concentration becomes 4mg/L by 20mg/L, and it is 15mg/L that chemical oxygen demand (COD) becomes COD by 50mg/L.Handle 20mg/L aniline waste water power consumption 0.52kwh per ton.Working electrode is 304 stainless steels.
Embodiment 3
Select the pending aniline waste water 100ml of 20mg/L concentration for use, the setting operating voltage is 2.5V, regulates the ionogen sodium sulfate concentration and makes it to reach 0.1mol/L, and conductivity of waste water reaches 10mS/cm, and pH is 10, and the adjusting working current density is 4.5A/m
2, the working electrode area is 2cm with pending liquor capacity ratio
2: 1cm
3, behind electrochemical treatment 12h, aniline electropolymerization film forming product integral body comes off, and means that aniline is removed from water substantially.Aniline concentration becomes 3mg/L by 20mg/L, and it is 9.8mg/L that chemical oxygen demand (COD) becomes COD by 50mg/L.Handle 20mg/L aniline waste water power consumption 0.59kwh per ton.Working electrode is 321 stainless steels.
Embodiment 4
Select the pending aniline waste water 1000ml of 400mg/L concentration for use, the setting operating voltage is 4.5V, regulates the ionogen sodium sulfate concentration and makes it to reach 0.05mol/L, and conductivity of waste water reaches 5mS/cm, and pH is 7, and the adjusting working current density is 9A/m
2, the working electrode area is 1cm with pending liquor capacity ratio
2: 1cm
3, behind electrochemical treatment 12h, aniline electropolymerization film forming product integral body comes off, and means that aniline is removed from water substantially.Aniline concentration becomes 8mg/L by 400mg/L, and it is 26mg/L that chemical oxygen demand (COD) becomes COD by 1000mg/L.Handle 400mg/L aniline waste water power consumption 17.12kwh per ton.Working electrode is the industrially pure titanium electrode.
Embodiment 5
Select the pending aniline waste water 300ml of 800mg/L concentration for use, the setting operating voltage is 5V, regulates the ionogen sodium sulfate concentration and makes it to reach 0.2mol/L, and conductivity of waste water reaches 20mS/cm, and pH is 7, and the adjusting working current density is 10A/m
2, the working electrode area is 1cm with pending liquor capacity ratio
2: 2cm
3, behind electrochemical treatment 8h, aniline electropolymerization film forming product integral body comes off, and means that aniline is removed from water substantially.Aniline concentration becomes 7mg/L by 800mg/L, and it is 72mg/L that chemical oxygen demand (COD) becomes COD by 2000mg/L.Handle 8000mg/L aniline waste water power consumption 35.05kwh per ton.Working electrode is 321 stainless steels.
Embodiment 6
Select the pending aniline waste water 300ml of 750mg/L concentration for use, the setting operating voltage is 2.5V, regulates the ionogen sodium sulfate concentration and makes it to reach 0.1mol/L, and conductivity of waste water reaches 10mS/cm, and pH is 7, and the adjusting working current density is 1A/m
2, the working electrode area is 1cm with pending liquor capacity ratio
2: 5cm
3, behind electrochemical treatment 12h, aniline electropolymerization film forming product integral body comes off, and means that aniline is removed from water substantially.Aniline concentration becomes 6mg/L by 750mg/L, and it is 44mg/L that chemical oxygen demand (COD) becomes COD by 1880mg/L.Handle 750mg/L aniline waste water power consumption 22.89kwh per ton.Working electrode is the industrially pure titanium electrode.
Embodiment 7
Select the pending aniline waste water 200ml of 200mg/L concentration for use, the setting operating voltage is 4V, regulates the ionogen sodium sulfate concentration and makes it to reach 0.1mol/L, and conductivity of waste water reaches 10mS/cm, and pH is 7, and the adjusting working current density is 8A/m
2, the working electrode area is 1cm with pending liquor capacity ratio
2: 5cm
3, behind electrochemical treatment 6h, aniline electropolymerization film forming product integral body comes off, and means that aniline is removed from water substantially.Aniline concentration becomes 5.5mg/L by 200mg/L, and it is 34mg/L that chemical oxygen demand (COD) becomes COD by 500mg/L.Handle 200mg/L aniline waste water power consumption 7.33kwh per ton.Working electrode is a titanium base stannic oxide electrode.
Embodiment 8
Select the pending aniline waste water 100ml of 100mg/L concentration for use, the setting operating voltage is 5V, regulates the ionogen sodium sulfate concentration and makes it to reach 0.1mol/L, and conductivity of waste water reaches 10mS/cm, and pH is 7, and the adjusting working current density is 10A/m
2, the working electrode area is 5cm with pending liquor capacity ratio
2: 1cm
3, behind electrochemical treatment 4h, aniline electropolymerization film forming product integral body comes off, and means that aniline is removed from water substantially.Aniline concentration becomes 4mg/L by 100mg/L, and it is 42mg/L that chemical oxygen demand (COD) becomes COD by 500mg/L.Handle 100mg/L aniline waste water power consumption 7.67kwh per ton.Working electrode is a titanium base stannic oxide electrode.
Claims (1)
1. realize it is characterized in that the method for aniline waste water resource utilization and zero release by electropolymerization for one kind:
In concentration is the aniline waste water of 10～1000mg/L, adds the ionogen sodium sulfate concentration and makes sodium sulfate reach 0.05～0.2mol/L, makes the specific conductivity of waste water reach 5～20mS/cm, and pH is controlled at 4～10; Use dc supply that waste water is handled, working electrode is a stainless steel electrode, the titanium electrode, and the titanium-based oxide electrode, platinum electrode or Graphite Electrodes, the working electrode area is 5cm with pending liquor capacity ratio
2: 1cm
3～1cm
2: 5cm
3Using the operating voltage of dc supply is 2.5～5V, and the adjusting working current density is 1～10A/m
2, carry out the lasting processing of 0.1～12h.
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| CN 201110131660 CN102249376B (en) | 2011-05-20 | 2011-05-20 | Method for realizing recycling of aniline waste water and zero release through electropolymerization |
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| CN 201110131660 CN102249376B (en) | 2011-05-20 | 2011-05-20 | Method for realizing recycling of aniline waste water and zero release through electropolymerization |
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| CN102249376B CN102249376B (en) | 2012-12-12 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017118A (en) * | 2017-06-15 | 2018-05-11 | 武汉科技大学 | A kind of method based on electrochemical modification method processing cationic dyes waste water |
| CN108083519A (en) * | 2017-12-27 | 2018-05-29 | 黄山学院 | A kind of method of rhodamine B degradation waste water |
| CN109179585A (en) * | 2018-09-17 | 2019-01-11 | 浙江树人学院 | A method of degradation crystal violet waste water |
| CN110872145A (en) * | 2018-08-29 | 2020-03-10 | 华中科技大学 | Method for removing organic matters by electrochemical cooperation with hydrogen peroxide |
| CN113044931A (en) * | 2021-03-23 | 2021-06-29 | 南京环保产业创新中心有限公司 | Treatment device for nitroaromatic wastewater, and cathode preparation method and application thereof |
| CN113135827A (en) * | 2021-04-29 | 2021-07-20 | 中国石油化工股份有限公司 | Method for continuously and stably recovering aniline in aniline wastewater |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244878A (en) * | 2008-02-25 | 2008-08-20 | 南京大学 | Treatment for wastewater in para-nitraniline production and method for resource recovery and use |
| CN101264996A (en) * | 2008-04-15 | 2008-09-17 | 中国科学院山西煤炭化学研究所 | Method for treating aniline waste water by absorption-low temperature dry method |
| CN101570371A (en) * | 2009-06-12 | 2009-11-04 | 东华大学 | Pretreatment process method and device for removing aniline in wastewater through potassium ferrate |
-
2011
- 2011-05-20 CN CN 201110131660 patent/CN102249376B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244878A (en) * | 2008-02-25 | 2008-08-20 | 南京大学 | Treatment for wastewater in para-nitraniline production and method for resource recovery and use |
| CN101264996A (en) * | 2008-04-15 | 2008-09-17 | 中国科学院山西煤炭化学研究所 | Method for treating aniline waste water by absorption-low temperature dry method |
| CN101570371A (en) * | 2009-06-12 | 2009-11-04 | 东华大学 | Pretreatment process method and device for removing aniline in wastewater through potassium ferrate |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017118A (en) * | 2017-06-15 | 2018-05-11 | 武汉科技大学 | A kind of method based on electrochemical modification method processing cationic dyes waste water |
| CN108083519A (en) * | 2017-12-27 | 2018-05-29 | 黄山学院 | A kind of method of rhodamine B degradation waste water |
| CN110872145A (en) * | 2018-08-29 | 2020-03-10 | 华中科技大学 | Method for removing organic matters by electrochemical cooperation with hydrogen peroxide |
| CN109179585A (en) * | 2018-09-17 | 2019-01-11 | 浙江树人学院 | A method of degradation crystal violet waste water |
| CN109179585B (en) * | 2018-09-17 | 2021-08-20 | 浙江树人学院 | Method for degrading methyl violet wastewater |
| CN113044931A (en) * | 2021-03-23 | 2021-06-29 | 南京环保产业创新中心有限公司 | Treatment device for nitroaromatic wastewater, and cathode preparation method and application thereof |
| CN113135827A (en) * | 2021-04-29 | 2021-07-20 | 中国石油化工股份有限公司 | Method for continuously and stably recovering aniline in aniline wastewater |
| CN113135827B (en) * | 2021-04-29 | 2023-04-28 | 中国石油化工股份有限公司 | Method for continuously and stably recycling aniline in aniline wastewater |
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