The method of wastewater treatment of a kind of three-diemsnional electrode and the coupling of electric class Fenton
Technical field
The present invention relates to a kind of electro-chemical water treatment technology, particularly relate to the method for wastewater treatment of a kind of three-diemsnional electrode and the coupling of electric class Fenton.
Background technology
Electrochemical oxidation process is a kind of high-level oxidation technology that development in recent years is got up, and it can pass through the direct degradation of organic substances of anodic reaction, or produces OH, O by electrode reaction
3The oxygenant degradation of organic substances of one class, this method have need not add pharmaceutical chemicals, does not produce secondary pollution, can carry out simple operation and other advantages at normal temperatures and pressures.The three-diemsnional electrode method in the electrochemical process particularly, more much bigger than the electrode specific surface of ordinary two dimensional electrode method, mass transfer velocity and speed of response are fast, current efficiency and spatiotemporal efficiency height, energy consumption is low, can effectively improve the biodegradability of waste water, thereby makes its research have very significant values with application.But, it is found that at research process, the limited amount of the hydroxyl radical free radical that simple three-diemsnional electrode method produces in reaction process, organic ability is subjected to certain limitation in purifying waste water, in order to remedy above-mentioned deficiency, be necessary that the amount of the hydroxyl radical free radical that produces in the further enhancing system reaches the purpose that organic clearance is significantly improved with three-diemsnional electrode method and other technology coupling coupling.
Summary of the invention
The object of the present invention is to provide the method for wastewater treatment of a kind of three-diemsnional electrode and the coupling of electric class Fenton, make the hydrogen peroxide of generation generate hydroxyl free, HO by chemical reaction by adding ferrous ion and ferric ion
2, O
2Reaction, effectively solve the three-diemsnional electrode method and handle the not high problem of organic removal rate in the waste water.
The objective of the invention is to be achieved through the following technical solutions:
The method of wastewater treatment of a kind of three-diemsnional electrode and the coupling of electric class Fenton, its described method comprises the steps: that with in the pending waste water injecting reactor control reaction conditions is as follows: the pH value is 3.0~3.5, and electrolysis voltage is 12~15V, aeration intensity is 600~700L/h, Na
2SO
4It is 1.2g/L that ionogen adds concentration, and reaction beginning back adds concentration in 3 D electrode reactor be 0.9~1.1mmol/L Fe
2+Solution, concentration are 5~8mmol/L Fe
3+Solution generates hydroxyl free, HO by electric class Fenton's reaction
2, O
2After, quiet heavy back water outlet.
The method of wastewater treatment of described a kind of three-diemsnional electrode and the coupling of electric class Fenton, its described reactor bottom are provided with the aerating apparatus that granule electrode is suspended and reaction oxygen is provided.
Advantage of the present invention and effect are:
1. this method can make the hydrogen peroxide of negative electrode and the generation of granule electrode surface be utilized effectively, and reaction and electric class Fenton (Fenton) method that inside reactor can carry out the electrocatalysis generation OH of three-diemsnional electrode simultaneously produce OH, HO
2, O
2Reaction, reached the purpose that realizes multiple function at an inside reactor, improved the economy and the practicality of technology.
2. this technological operation is simple, is applicable to the processing of the hardly degraded organic substance of different concns and different qualities, and organic clearance can be largely increased.
Description of drawings
Accompanying drawing 1 is the process flow sheet that waste water is handled in three-diemsnional electrode and electric class Fenton process coupling.
Embodiment
For the amount that solves the hydroxyl radical free radical that produces in the three-diemsnional electrode method reaction process limited, the problem that the hydrogen peroxide that produces can not effectively utilize, the present invention makes the hydrogen peroxide of generation generate hydroxyl free, HO by chemical reaction by adding ferrous ion and ferric ion
2, O
2Reaction (promptly take place electric Fenton-like reaction).This method provides the method for wastewater treatment of a kind of three-diemsnional electrode method and electric class Fenton (Fenton) coupling, efficiently solves the three-diemsnional electrode method and handles the not high problem of organic removal rate in the waste water.In order to address the above problem, the present invention adopts following technical scheme that the method for wastewater treatment of a kind of three-diemsnional electrode method and electric Fenton-like coupling is provided: the O that the bottom aerating apparatus provides
2On negative electrode and granule electrode surface, react and produce H
2O
2, H
2O
2With the Fe that adds
2+React and generate OH.See reaction formula (1), (2).In system, add Fe
3+The time, can add the carrying out of fast response (3) and (4), thereby accelerate the amount of hydroxyl radical free radical in the whole system.
Fe
2++H
2O
2→Fe
3++·OH+OH
- (1)
·OH+Fe
2+→Fe
3++OH
- (2)
Fe
3++H
2O
2→Fe
2++HO
2·+H
+ (3)
HO
2·+Fe
3+→Fe
2++O
2·+H
+ (4)
And when adding Fe
3+When concentration is bigger than normal, though still can be favourable to reaction (3) and (4), Fe at this moment
3+Inhibition for reaction (1) and (2) strengthens, and especially reaction (1) is directly determining the generation of Fenton reagent OH, therefore when adding Fe
3+It greater than favourable influence, finally showed as the restraining effect to the Fenton reaction to the disadvantageous effect of Fenton reagent oxidation reaction when concentration was bigger than normal.So, will be in the reaction process to Fe
2+And Fe
3+Dosage control, and guarantee to be reflected under the corresponding conditions and carry out.In the reaction, in reaction system, add the used granule electrode of three-diemsnional electrode method, regulate the pH value, add Na with sulfuric acid or sodium hydroxide
2SO
4Supporting electrolyte, the control of respective reaction condition is as follows: the pH value is 3.0~3.5, and electrolysis voltage is 12~15V, and aeration intensity is 600~700L/h, Na
2SO
4It is 1.2g/L that ionogen adds concentration, and reaction beginning back adds concentration in system be 0.9~1.1mmol/L Fe
2+Solution, concentration are 5~8mmol/L Fe
3+Solution generates hydroxyl free, HO by electric class Fenton's reaction
2, O
2After, quiet heavy back water outlet gets final product.