CN104773888A - Iron-carbon inner electrolysis-Fenton oxidation-electrolytic electrocatalytic oxidation combined wastewater treatment method and device - Google Patents
Iron-carbon inner electrolysis-Fenton oxidation-electrolytic electrocatalytic oxidation combined wastewater treatment method and device Download PDFInfo
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Abstract
The invention relates to an iron-carbon inner electrolysis-Fenton oxidation-electrolytic electrocatalytic oxidation combined wastewater treatment method and device. According to the invention, iron-carbon inner electrolysis-Fenton oxidation-electrolytic electrocatalytic oxidation is adopted. Wastewater is subjected to iron-carbon inner electrolysis in an iron-carbon inner electrolysis filling material tower, and is subjected to Fenton-method treatment, such that residual Fe<2+> in the solution obtained after iron-carbon inner electrolysis is subjected to a sufficient oxidation reaction; an electrolytic electrocatalytic oxidation reaction is carried out, such that heterocyclic organics in the wastewater are thoroughly decomposed. The method causes no secondary pollution. With the method, various organics in high-salt wastewater can be highly efficiently degraded, a COD removal rate can be higher than 75%, and biodegradable BOD5/CODcr is increased from 0.03 to higher than 0.3, such that biodegradability is substantially improved. Outlet water has the advantages of low salt content, low chromaticity and low ammonia nitrogen content.
Description
Technical field
The present invention relates to technical field of waste water processing, refer in particular to a kind of compounding method that application Iron carbon reduction-Fenton oxidation-electrolysis By Electrocatalytic Oxidation combination treatment contains pyridine, prussiate, alkanes, benzoquinones class, imidazolone, high salinity waste water.
Background technology
The waste water of the annual discharge of whole nation industry is about 100,000,000 t.It is high that waste water has organic concentration, and toxicity is large, and pollutant component is complicated, and recalcitrant substance is many, and water quality, the water yield often have the features such as fluctuation.That has wherein carried out processing accounts for 7% of total amount, processes up to standard only to account for processed 1%.These waste water enter rivers water body, directly cause environment total phosphorus, ammonia nitrogen etc. to exceed standard, make body eutrophication, phycophyta amount reproduction.Some contains the discharge of wastewater of riskiest pesticide and the compound such as phenol, cyanogen in addition, not only seriously destroys water ecology, and constitutes great threat to the living environment of the mankind.
The ultimate principle of Iron carbon reduction oxidation is that the Fe of low potential and the C of noble potential produce potential difference in waste water, and the waste water with certain electroconductibility serves as ionogen, forms countless small galvanic cells, creates electrode reaction, the series reaction caused thus.
Fenton method studies the most a kind of technique.Fenton reagent is by H
2o
2and Fe
2+a kind of strong oxidizer obtained after mixing.By under enough low pH condition (2 ~ 5), Fe
2+with H
2o
2effect, generates hydroxy radical qiao OH and the free radical reaction oxidation of organic compounds that carries out.
There is oxidizing reaction and negative electrode generation reduction reaction in pole, external electric field Xiayang, the reactive hydroxyl radical oxidation of organic compounds utilizing electrode to produce in the electrode of electrolysis By Electrocatalytic Oxidation mainly in electrolyzer, utilizes the dissolved oxygen reduction generation H in cathodic reduction water
2o
2, under the katalysis of ferrous ion, " Fenton-like " effect occurs, and organic pollutant in degrading waste water, can improve current efficiency greatly, reduce processing cost.
These three kinds of method of wastewater treatment are generally studied, but there are some shortcomings separately, limit the practical application of wastewater treatment.For the feature containing pyridine, prussiate, alkanes, benzoquinones class, imidazolone, high salinity waste water, adopt and Iron carbon reduction method, Fenton oxidation method and electrolysis By Electrocatalytic Oxidation three kinds of methods are together in series, learn from other's strong points to offset one's weaknesses, acting in conjunction, efficiently can process waste water.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, in conjunction with the character of waste water, method and the device of a kind of Iron carbon reduction-Fenton oxidation-electrolysis By Electrocatalytic Oxidation combination treatment waste water is provided, efficiently can processes used water difficult to degradate.
Technical scheme of the present invention is: the method for a kind of Iron carbon reduction-Fenton oxidation-electrolysis oxidation united with lime-plaster art breading waste water, adopt Iron carbon reduction-Fenton oxidation-electrolysis catalytic oxidation, waste water first carries out Iron carbon reduction and carries out the process of Fenton method again in Iron carbon reduction packing tower, to make after Iron carbon reduction remaining Fe in solution
2+obtain fully oxidized reaction, then carry out catalytic and oxidative electrolysis technology reaction the heterocycle organism in waste water is thoroughly decomposed.
The COD content of described waste water is that 31000-40000mg/L, BOD/COD are less than 0.1, containing pyridine, prussiate, alkanes, benzoquinones class, imidazolone organism.
Fill with the mixing of iron C catalyst particle in Iron carbon reduction packing tower; Described iron C catalyst volume ratio is 1:3-8.
In catalytic and oxidative electrolysis technology reaction, anode electrode adopts titanium base rare-earth oxide dopant material, and the rare earth oxide materials of doping is two or more arbitrary proportion doped and compounded in Ta, Bi, Pr.
Fenton reagent is by Fe
2+ion and H
2o
2composition.
Be applied to the device in the method for described Iron carbon reduction-Fenton oxidation-electrolysis By Electrocatalytic Oxidation combination treatment waste water, primarily of Iron carbon reduction packing tower, Fenton pond, electrolyzer, water outlet coagulative precipitation tank and outlet sump series connection.
Also be provided with aerating apparatus air pump, air pump is connected with Iron carbon reduction packing tower.
The reaction of described Iron carbon reduction-Fenton oxidation-electrolysis By Electrocatalytic Oxidation combination treatment waste water is all carried out under normal temperature, normal pressure.
Beneficial effect:
1. the invention discloses Iron carbon reduction-Fenton oxidation-electrolysis oxidation united with lime-plaster Technology process waste water method.
2. Iron carbon reduction-the Fenton oxidation developed-electrolysis oxidation united with lime-plaster Technology has efficient Degradation through coagulation-settlement process again, for macromole toxic organics, heterocyclic containing difficult degradation, the water treatment effect of high COD is outstanding, non-secondary pollution, water outlet COD clearance arrives more than 75%, BOD
5/ COD
crcan reach more than 0.3 from less than 0.1, biodegradability improves greatly.
3. operation feasible, whole reaction is all carried out under normal temperature, condition of normal pressure, economizes on resources, and the waste residue ferrous ion of generation can carry out recycle.
Accompanying drawing explanation
Fig. 1 is schematic flow sheet of the present invention.
Wherein, 1 is wastewater disposal basin, and 2 is air pump, and 3 is Iron carbon reduction packing tower, and 4 is Fenton pond, and 5 is electrolyzer, and 6 is water outlet coagulative precipitation tank, and 7 is outlet sump.
Embodiment
The method of Iron carbon reduction-Fenton oxidation of the present invention-electrolysis catalytic oxidation process waste water, waste water salinity is high, and containing pyridine, prussiate, alkanes, benzoquinones class, imidazolone organism, toxicity is large, colourity is high, COD is high, BOD/COD is low, and biodegradability is poor.Comprise Iron carbon reduction, Fenton oxidation and electrolysis catalytic oxidation three part composition, first waste water is carried out Inner electrolysis process, then carry out Fenton oxidation process, finally carry out electrolysis.
The composition complete process that three kinds of methods is together in series process waste water, can process the waste water containing such organic species multiple.Fe/C Inner electrolysis process, by the hydroxo complex effect of the corrosion reaction that caused by potential difference in galvanic interaction and iron, makes organism rupture, the effect such as open loop; Without the need to adding ferrous salt again, the Fe of generation
2+with the H added
2o
2form Fenton reagent, produce the hydroxyl radical free radical in a large number with Strong oxdiative ability, bring out chain reaction, pass through the metal oxide electrode that in electrolysis electrocatalysis process, catalytic performance is outstanding again, produce hydroxyl radical free radical or the superoxide radical with Strong oxdiative ability, active free radical and some organism generation electrochemical actions, can to the complete efficient degradation of such waste water
Add aerating apparatus continuous supplemental oxygen on the one hand in described equipment, oxidation of organic compounds, plays and stirs phase same-action on the other hand, avoiding iron filings to lump.
Inner electrolysis filler particles is mixed by the particulate matter of different iron-carbon ratio and forms; The negative electrode of electrolysis adopts stainless steel electrode, and anode adopts two or more rare-earth oxide doped and compounded materials such as titanium base Ta, Bi, Pr.
Embodiment 1
1. be that the waste water that 32000mg/L, BOD/COD are less than 0.1 is squeezed in Inner electrolysis packing tower by air pump by initial for 1L COD content, filler uses the composite grain thing that homemade iron carbon volume ratio is 1:1, and regulate pH to 2.5, aeration, after being disposed; Through Fenton pond, add 20g H
2o
2solution, regulates pH to 2 to carry out oxidizing reaction, after completion of the reaction; Enter electrolyzer and carry out electrolytic oxidation, electrolytic anode material adopts the base and doped Pr metal oxide materials of titanium oneself made, and preparation method is with reference to Z.He, C.Huang, Q.Wang, Z.Jiang, J.Chen, S.Song, Int.J.Electrochem.Sci.6 (2011) 4341 – 4354..Control current density, electrolysis voltage, regulates electrolysis process, is disposed; Regulate pH to 8.5, be disposed through water outlet coagulative precipitation tank coagulation-settlement process and discharge through outlet sump.The COD content of water outlet is 9000mg/L, COD clearance be 71.8%, BOD/COD is 0.35.
Embodiment 2
Be that the waste water that 33000mg/L, BOD/COD are less than 0.1 is squeezed in Inner electrolysis packing tower by air pump by initial for 1L COD content, filler uses the composite grain thing that homemade iron carbon volume ratio is 1:2.5, and regulate pH to 2.5, aeration, after being disposed; Through Fenton oxidation process, add 20g H
2o
2solution, regulates pH to 3, after completion of the reaction; Carry out electrolysis, electrolytic anode material adopts the base and doped Bi metal oxide materials of titanium oneself made, preparation method with reference to C.A.Mart í nez-Huitle, E.Brillas, Appl.Catal.B:Environ.87 (2009) 105 – 145..Control current density, electrolysis voltage, regulates electrolysis process, is disposed; Regulate pH to 8, coagulation-settlement process is disposed.The COD content of water outlet is 8200mg/L, COD clearance be 75.2%, BOD/COD is 0.38.
Embodiment 3
Be that the waste water that 34000mg/L, BOD/COD are less than 0.1 is squeezed in Inner electrolysis packing tower by air pump by initial for 1L COD content, filler uses the composite grain thing that homemade iron carbon volume ratio is 1:5, and regulate pH to 2.5, aeration, after being disposed; Through Fenton oxidation process, add 20g H
2o
2solution, regulates pH to 6, after completion of the reaction; Carry out electrolysis, electrolytic anode material adopts the base and doped Ta metal oxide of titanium, the Pr metal oxide materials that oneself make, preparation method with reference to G.Chen, Sep.Purif.Technol.38 (2004) 11 – 41., Ta metal oxide and Pr metal oxide mass ratio be 2:1.Control current density, electrolysis voltage, regulates electrolysis process, is disposed; Regulate pH to 8.5, coagulation-settlement process is disposed.The COD content of water outlet is 7400mg/L, COD clearance be 78.2%, BOD/COD is 0.48.
Embodiment 4
Be that the waste water that 35000mg/L, BOD/COD are less than 0.1 is squeezed in Inner electrolysis packing tower by air pump by initial for 1L COD content, filler uses the composite grain thing that homemade iron carbon volume ratio is 1:5, and regulate pH to 2.5, aeration, after being disposed; Through Fenton oxidation process, add 10g H
2o
2solution, regulates pH to 3, after completion of the reaction; Carry out electrolysis, electrolytic anode material adopts the base and doped Ta metal oxide materials of titanium oneself made, preparation method with reference to C.A.Mart í nez-Huitle, S.Ferro, Chem.Soc.Rev.35 (2006) 1324 – 1340..Control current density, electrolysis voltage, regulates electrolysis process, is disposed; Regulate pH to 12, coagulation-settlement process is disposed.The COD content of water outlet is 8200mg/L, COD clearance be 76.6%, BOD/COD is 0.37.
Embodiment 5
Be that the waste water that 36000mg/L, BOD/COD are less than 0.1 is squeezed in Inner electrolysis packing tower by air pump by initial for 1L COD content, filler uses the composite grain thing that homemade iron carbon volume ratio is 1:1.5, and regulate pH to 2.5, aeration, after being disposed; Through Fenton oxidation process, add 100g H
2o
2solution, regulates pH to 3, after completion of the reaction; Carry out electrolysis, electrolytic anode material adopts the base and doped Ta metal oxide of titanium, Pr metal oxide, the Bi metal oxide that oneself make, preparation method is with reference to M.Panizza, G.Cerisola, Chem.Rev.109 (2009) 6541 – 6569., doping mass ratio corresponding to three is 4:2:3 [3-5].Control current density, electrolysis voltage, regulates electrolysis process, is disposed; Regulate pH to 8.5, coagulation-settlement process is disposed.The COD content of water outlet is 6800mg/L, COD clearance be 81.1%, BOD/COD is 0.48.
Claims (7)
1. the method for Iron carbon reduction-Fenton oxidation-electrolysis oxidation united with lime-plaster art breading waste water, it is characterized in that: adopt Iron carbon reduction-Fenton oxidation-electrolysis catalytic oxidation, waste water first carries out Iron carbon reduction and carries out the process of Fenton method again in Iron carbon reduction packing tower, to make after Iron carbon reduction remaining Fe in solution
2+obtain fully oxidized reaction, then carry out catalytic and oxidative electrolysis technology reaction the heterocycle organism in waste water is thoroughly decomposed.
2. the method for Iron carbon reduction-Fenton oxidation-electrolysis By Electrocatalytic Oxidation combination treatment waste water as claimed in claim 1, it is characterized in that: the COD content of described waste water is 31000-40000mg/L, BOD/COD is less than 0.1, containing pyridine, prussiate, alkanes, benzoquinones class, imidazolone organism.
3. the method for Iron carbon reduction-Fenton oxidation-electrolysis By Electrocatalytic Oxidation combination treatment waste water as claimed in claim 1, is characterized in that: be fill with the mixing of iron C catalyst particle in Iron carbon reduction packing tower; Described iron C catalyst volume ratio is 1:3-8.
4. the method for Iron carbon reduction-Fenton oxidation-electrolysis By Electrocatalytic Oxidation combination treatment waste water as claimed in claim 1, it is characterized in that: in catalytic and oxidative electrolysis technology reaction, anode electrode adopts titanium base rare-earth oxide dopant material, and the rare earth oxide materials of doping is two or more arbitrary proportion doped and compounded in Ta, Bi, Pr.
5. the method for Iron carbon reduction-Fenton oxidation-electrolysis By Electrocatalytic Oxidation combination treatment waste water as claimed in claim 1, is characterized in that: Fenton reagent is by Fe
2+ion and H
2o
2composition.
6. be applied to the device in the method for the arbitrary described Iron carbon reduction-Fenton oxidation-electrolysis By Electrocatalytic Oxidation combination treatment waste water of claim 1 ~ 5, it is characterized in that: primarily of Iron carbon reduction packing tower, Fenton pond, electrolyzer, water outlet coagulative precipitation tank and outlet sump series connection.
7. be applied to the device in the method for Iron carbon reduction-Fenton oxidation-electrolysis By Electrocatalytic Oxidation combination treatment waste water as claimed in claim 6, it is characterized in that: be also provided with aerating apparatus air pump, air pump is connected with Iron carbon reduction packing tower.
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| CN107827293A (en) * | 2017-11-08 | 2018-03-23 | 伍立洁 | The handling process of highly salt containing organic waste water caused by a kind of marine products processing process |
| CN107963761A (en) * | 2017-11-29 | 2018-04-27 | 烟台海威斯特膜科技有限公司 | A kind of Zero discharging system and method for high salt cyanide wastewater |
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| CN107265764B (en) * | 2017-07-01 | 2021-07-06 | 山东龙安泰环保科技有限公司 | Method for treating landfill leachate to reach standard and directly discharging |
| CN107827293A (en) * | 2017-11-08 | 2018-03-23 | 伍立洁 | The handling process of highly salt containing organic waste water caused by a kind of marine products processing process |
| CN107963761A (en) * | 2017-11-29 | 2018-04-27 | 烟台海威斯特膜科技有限公司 | A kind of Zero discharging system and method for high salt cyanide wastewater |
| CN108726740A (en) * | 2018-06-11 | 2018-11-02 | 山东龙安泰环保科技有限公司 | A kind of high sodium chloride waste water Zero discharge treatment method |
| CN109607890A (en) * | 2018-12-24 | 2019-04-12 | 安徽国星生物化学有限公司 | A kind of pyridine pretreatment method for wastewater |
| CN113582464A (en) * | 2021-08-17 | 2021-11-02 | 华北理工大学 | Advanced treatment device for micro-polluted water |
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Application publication date: 20150715 |