CN205740597U - A kind of device strengthening iron-carbon micro-electrolysis Ozonation degrading nitrobenzene waste water - Google Patents
A kind of device strengthening iron-carbon micro-electrolysis Ozonation degrading nitrobenzene waste water Download PDFInfo
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Abstract
This utility model belongs to the technical field that treatment of Nitrobenzene waste water processes, it is specifically related to a kind of device strengthening iron-carbon micro-electrolysis Ozonation degrading nitrobenzene waste water, solve in prior art after iron-carbon micro-electrolysis bed longtime running, filler passivation inactivation, cell reaction is obstructed and catalyst is to the limited problem of the efficiency increase rate of ozone oxidation degrading waste water, first nitrobenzene waste water put to iron-carbon micro-electrolysis groove and be aided with ultrasound wave, making the Nitrobenzol of difficult degradation is degradable aniline by fast restore under ultrasonic/iron-carbon micro-electrolysis acts on jointly, simultaneously after cell reaction produce to Fe2+It is released in waste water；Deliver to waste water again hypergravity equipment fully reacts with ozone, remaining organic pollution in deep oxidation degrading waste water.This utility model makes the reaction rate of iron-carbon micro-electrolysis improve 6 ~ 10 times on the whole, makes free Fe in waste water simultaneously2+Concentration improves 5 ~ 8 times, drastically reduce the area the ozone usage of follow-up hypergravity Ozonation.
Description
Technical field
This utility model belongs to the technical field that treatment of Nitrobenzene waste water processes, and is specifically related to a kind of strengthening micro-electricity of ferrum carbon
The device of solution-Ozonation degrading nitrobenzene waste water, it uses ultrasonic technology, Fe-C Micro Electrolysis Method and Ozonation altogether
Same-action treatment of Nitrobenzene waste water.
Background technology
Iron-carbon micro-electrolysis technology is using waste iron filing and activated carbon granule as the filler of reactor, utilizes ferrum, oxidation of coal
The difference of reduction potential, makes both constitute countless small galvanic elements, the organic contamination in deoxidization, degradation waste water in the reactor
Thing.Reaction equation is as follows:
Anode:E(Fe/Fe2+)=0.44 V(formula 1)
Negative electrode:E(H+/H2)=0.00 V(formula 2)
In reaction, ferrum is as anode betatopic, and is transferred to carbon surface, by the H on its surface+The proton state that capture produces
[H].[H] is the reducing agent that a kind of activity is stronger, can effectively reduce the nitryl group on organic pollution, azo bond etc., thus
Destroy the rock-steady structure of the organic molecule of difficult degradation so that it is be prone to degraded.The most difficult oxidative degradation of Nitrobenzol, is because its benzene
Nitro on ring has strong electron attraction and makes phenyl ring be passivated.Iron-carbon micro-electrolysis rule can effectively by the nitro on Nitrobenzol also
Originally it was amido, activated phenyl ring so that it is be prone to degraded.Therefore iron-carbon micro-electrolysis technology is commonly used for the pre-place of nitrobenzene wastewater
Reason.But after iron-carbon micro-electrolysis bed longtime running, the iron oxides that ferrum carbon surface is easily generated is covered, electrolysis simultaneously produces
Ferrous coagulation is easily formed stable flocculate and is gradually deposited at filling surface, causes filler passivation inactivation, electrolysis
Reaction is obstructed, and causes iron-carbon micro-electrolysis bed to be difficult to long-term operation continuously.
The powerful energy of ultrasonic load, can cause liquid current stabilization, is widely used in all kinds of liquid-liquid, solid-liquid chemical reaction
Strengthening.For solid-liquid reaction system, strong microjet and shock wave energy produced by ultrasonic cavitation in the solution
Washing away the surface of solids, the reactivity site of the release surface of solids, the most ultrasonic liquid current stabilization caused exacerbates solid-liquid mixing
One-tenth degree thus improve chemical reaction rate.
Hypergravity-ozone high grade oxidation technology is a kind of emerging wastewater processing technology, utilizes rotary packed bed construction
Elevated Gravity, strengthening ozone is transferred to the mass transport process of liquid phase, is effectively increased concentration of ozone in liquid phase and oxygen from gas phase
Change efficiency.The oxidation mechanism of ozonization method is direct oxidation and indirect oxidation, and the former utilizes ozone direct oxidation to degrade organic point
Son, has selectivity to effective object, and the latter then utilizes ozone selfdecomposition reaction in aqueous produce OH and aoxidize
Pollutant in degrading waste water, react comparatively fast and to effective object non-selectivity.Therefore, improve ozone and generate OH in the solution
Ability can improve the efficiency of ozone oxidation equally.Obviously high-gravity technology only accelerates the ozone mass transfer rate to liquid phase,
But do not accelerate ozone and generate the reaction rate of OH in the solution.
Homogeneous catalysis Ozonation is to add metal ion catalyst in the solution, and catalysis ozone decomposes, and accelerates OH
Generating rate, thus improve ozone oxidation degradation of organic waste water efficiency.Conventional catalyst is Fe2+, anti-for radical chain
The initiator answered, accelerates ozone and generates the speed of OH.But ozone is dissolved in the mass transport process of liquid phase, by liquid film controlling, pass
Matter is slow, and the addition of catalyst can not accelerate the mass transport process of ozone, the therefore catalyst effect to ozone oxidation degrading waste water
Rate, especially degrading high concentration organic wastewater, increase rate is limited.
Summary of the invention
After this utility model is for iron-carbon micro-electrolysis bed longtime running in prior art, filler passivation inactivation, cell reaction
It is obstructed and catalyst is to the limited problem of the efficiency increase rate of ozone oxidation degrading waste water, it is provided that a kind of strengthening micro-electricity of ferrum carbon
The device of solution-Ozonation degrading nitrobenzene waste water.
This utility model adopts the following technical scheme that realization:
The device of strengthening iron-carbon micro-electrolysis-Ozonation degrading nitrobenzene waste water, including iron-carbon micro-electrolysis bed, ferrum carbon is micro-
Bed electrolysis is provided with inlet and liquid outlet, and inlet connects nitrobenzene waste water reservoir by fluid flowmeter I and liquid pump I；
Being provided with ultrasound wave vibration plate bottom iron-carbon micro-electrolysis bed, ultrasound wave vibration plate is connected with supersonic generator；Iron-carbon micro-electrolysis bed quilt
Chuck is wrapped up, and chuck is provided with water inlet and outlet, and is all connected with aqua storage tank, and is made the cooling in storage tank by liquid pump II
Water is controlled by fluid flowmeter II at iron-carbon micro-electrolysis bed outer circulation flowing temperature control, cooling water flow velocity；Going out of iron-carbon micro-electrolysis bed
Liquid mouth is connected with reservoir；Rotary packed bed being provided with inlet, liquid outlet, air inlet and gas outlet, wherein inlet passes through
Fluid flowmeter III and liquid pump III are connected with reservoir, and liquid outlet is connected to reservoir；Rotary packed bed gas outlet and tail gas
Absorption plant connects, and air inlet is connected with ozonator gas outlet by gas flowmeter；Oxygen cylinder enters with ozonator
QI KOU connects.
The method of strengthening iron-carbon micro-electrolysis-Ozonation degrading nitrobenzene waste water, step is as follows: (1) is first by Nitrobenzol
Waste water is put to iron-carbon micro-electrolysis groove and is aided with ultrasound wave, makes the Nitrobenzol of difficult degradation jointly act at ultrasonic/iron-carbon micro-electrolysis
Lower is degradable aniline by fast restore, simultaneously after cell reaction produce to Fe2+It is released in waste water；(2) by waste water
Deliver to hypergravity equipment fully reacts with ozone, remaining organic pollution in deep oxidation degrading waste water.
In nitrobenzene waste water, the concentration of Nitrobenzol is less than or equal to 500 mg/L, through ultrasonic/iron-carbon micro-electrolysis processed waste water
Middle remaining nitro phenenyl concentration is less than or equal to 50 mg/L, and after hypergravity-Ozonation processes, Pollutants in Wastewater mineralization rate reaches
To more than 90%, and Nitrobenzol zero remains.Nitrobenzene waste water initial pH acid or alkali regulate to 2 ~ 4；Constitute the ferrum of light electrolysis electrode
Consider to be worth doing with quality of activated carbon ratio as 1:3 ~ 3:1；Iron filings mass concentration is 10 g/L ~ 30 g/L.
In step (1), the frequency of ultrasound wave is 20 ~ 40 kHz, ultrasonic power 4 ~ 8 kW.
Entering the waste water of hypergravity equipment in step (2) is 0.5 ~ 2.5 L/L with the liquid-gas ratio of ozone, and ozone concentration is 50
~ 100 mg/L, hypergravity equipment rotating speed is 400 ~ 800 rpm.
Step (1) is ultrasonic-and the iron-carbon micro-electrolysis treatment of Nitrobenzene waste water time is 30 ~ 45min, and reaction temperature controls in room
Temperature, step (2) hypergravity-ozone Oxidation Treatment time is 20 ~ 40 min.
Hypergravity equipment described in the utility model is published hypergravity swinging bed device, including filler bed, spiral
The high-gravity rotating bed equipment (application reference number 91109255.2,200520100685) of the various ways such as channel-type, preferably revolves
Turn filler bed hypergravity equipment.
Traditional hypergravity-Ozonation mainly utilizes the feature of hypergravity equipment intensification mass transfer, greatly improves molten
The ozone concentration dissolved in liquid, but do not accelerate ozone and generate the reaction rate of OH, when therefore actual waste water processes, often need
Add catalyst Fe2+, catalysis ozone decomposes, and accelerates the generating rate of OH, makes full use of the ozone dissolved in solution, improves
Oxidation efficiency.Additionally, for the nitrobenzene wastewater of stable chemical nature, direct hypergravity-Ozonation is difficult to quickly
By degradable, the longest, thus add energy consumption.But iron-carbon micro-electrolysis and two sections of works of hypergravity-Ozonation
Skill combination process nitrobenzene wastewater time, on the one hand available iron carbon micro-electrolysis by the nitrobenzene reduction of difficult degradation for being prone to by oxygen
Change the aniline of degraded, shorten the operation time of hypergravity-Ozonation, reduce ozone usage, on the other hand iron-carbon micro-electrolysis
Produced Fe2+Can directly be released in waste water, accelerate ozone decomposed as catalyst and produce OH, reaction mechanism such as formula 3 ~ 6
Shown in.
(formula 3)
(formula 4)
(formula 5)
(formula 6)
(formula 7)
When traditional Fe-C Micro Electrolysis Method directly processes waste water, iron surface is easily formed oxide layer, hinders iron-carbon micro-electrolysis anti-
The carrying out answered, the Fe that light electrolysis generates simultaneously2+Hydrolyzable generates the Fe (OH) with coagulation2With Fe (OH)3, in the solution
Forming stable flocculate, on the one hand this flocculate is gradually deposited at ferrum carbon filler surface, hinders iron-carbon micro-electrolysis electron transmission
Process, on the other hand the Fe that part is free is carried away in absorption secretly2+, reduce Fe in solution2+Concentration, causes follow-up Ozonation institute
The catalyst Fe needed2+Supply deficiency.All there is filler and be easily passivated inactivation in the most traditional iron-carbon micro-electrolysis bed, it is difficult to the most continuous
The problem run.The intervention of ultrasound wave then can release the problem that ferrum carbon filler is easily passivated.
The beneficial effects of the utility model are: (1) is by iron-carbon micro-electrolysis and hypergravity-Ozonation two-stage process combination
Getting up and process for nitrobenzene waste water, the most first using Fe-C Micro Electrolysis Method is aniline by nitrobenzene reduction, it is simple to follow-up
Ozonation deep oxidation degrading waste water, on the other hand utilizes the Fe that micro-electrolysis reaction is generated2+As Ozonation
Catalyst, it is achieved zero interpolation of catalyst needed for follow-up hypergravity-Ozonation；(2) for ensureing iron-carbon micro-electrolysis reaction energy
Enough catalyst Fes are provided for follow-up hypergravity-Ozonation2+, and use intensified by ultrasonic wave iron-carbon micro-electrolysis to react, profit
With the powerful energy field of ultrasound wave, update ferrum carbon filler surface continuously, it is ensured that iron-carbon micro-electrolysis high reaction rate, prevent flocculation simultaneously
The generation of thing reduces Fe2+Loss.(3) intervention of ultrasound wave make the reaction rate of iron-carbon micro-electrolysis improve 6 on the whole ~
10 times, make free Fe in waste water simultaneously2+Concentration improves 5 ~ 8 times, drastically reduce the area follow-up hypergravity-Ozonation
Ozone usage.
Accompanying drawing explanation
Fig. 1 is schematic diagram of the present utility model.
In figure: 1-nitrobenzene waste water reservoir；2-liquid pump I；3-fluid flowmeter I；4-fluid flowmeter II；5-liquid pump
Ⅱ；6-aqua storage tank；7-ferrum carbon filler bed；8-ultrasound wave vibration plate；9-chuck；10-supersonic generator；11-reservoir；12-revolves
Turn packed bed；13-fluid flowmeter III；14-liquid pump III；15-gas flowmeter；16-device for absorbing tail gas；17-ozone occurs
Device；18-oxygen cylinder.
Detailed description of the invention
With case study on implementation, this utility model is described in further detail below in conjunction with the accompanying drawings.But this utility model content is also
Do not limited to by following embodiment.
The device of strengthening iron-carbon micro-electrolysis-Ozonation degrading nitrobenzene waste water, including iron-carbon micro-electrolysis bed 7, ferrum carbon
Light electrolysis bed 7 is provided with inlet and liquid outlet, and inlet connects nitrobenzene waste water by fluid flowmeter I 3 and liquid pump I 2 and stores up
Liquid bath 1；Being provided with ultrasound wave vibration plate 8 bottom iron-carbon micro-electrolysis bed 7, ultrasound wave vibration plate 8 is connected with supersonic generator 10；Ferrum carbon
Light electrolysis bed 7 is wrapped up by chuck 9, and chuck 9 is provided with water inlet and outlet, and is all connected with aqua storage tank 6, and by liquid pump II
5 make the cooling water in storage tank control by fluid flowmeter II 4 at iron-carbon micro-electrolysis bed 7 outer circulation flowing temperature control, cooling water flow velocity；
The liquid outlet of iron-carbon micro-electrolysis bed 7 is connected with reservoir 11；Rotary packed bed 12 be provided with inlet, liquid outlet, air inlet and
Gas outlet, wherein inlet is connected with reservoir 11 by fluid flowmeter III 13 and liquid pump III 14, and liquid outlet is connected to storage
Liquid bath 11；Rotary packed bed 8 gas outlets are connected with device for absorbing tail gas 16, and air inlet is occurred with ozone by gas flowmeter 15
Device 17 gas outlet connects；Oxygen cylinder 18 is connected with ozonator 17 air inlet.
The method of strengthening iron-carbon micro-electrolysis-Ozonation degrading nitrobenzene waste water, step is as follows: (1) is first by Nitrobenzol
Waste water is put to iron-carbon micro-electrolysis groove and is aided with ultrasound wave, makes the Nitrobenzol of difficult degradation jointly act at ultrasonic/iron-carbon micro-electrolysis
Lower is degradable aniline by fast restore, simultaneously after cell reaction produce to Fe2+It is released in waste water；(2) by waste water
Deliver to hypergravity equipment fully reacts with ozone, remaining organic pollution in deep oxidation degrading waste water.In nitrobenzene waste water
The concentration of Nitrobenzol is less than or equal to 500 mg/L, and after ultrasonic/iron-carbon micro-electrolysis deals with, in waste water, remaining nitro phenenyl concentration is little
In equal to 50 mg/L, supersonic frequency is 20 ~ 40kHz, and power is 4 ~ 8 kW.Iron filings mass concentration 10 g/L ~ 30 g/L, is constituted
The iron filings of light electrolysis electrode and quality of activated carbon are than for 1:3 ~ 3:1；Initial pH on wastewater acid or alkali regulate to 2 ~ 4；Ozone oxidation
The stage of reaction, in hypergravity equipment, waste water is 0.5 ~ 2.5 L/L with the liquid-gas ratio of ozone, and ozone concentration is 50 ~ 100 mg/L, super
Gravimetric devices rotating speed is 400 ~ 800 rpm.Nitrobenzene reduction can be first chemical property with iron-carbon micro-electrolysis by this utility model (1)
The most active aniline, then carry out ozone deep oxidation degraded；(2) iron-carbon micro-electrolysis is that Ozonation provides catalyst
Fe2+, improve ozone oxidation efficiency；(3) free Fe during ultrasonic intervention ensure that light electrolysis water outlet2+Higher concentration, for rear
Continuous hypergravity-Ozonation provides enough catalyst Fes2+, it is achieved catalyst in hypergravity-Ozonation technical process
Fe 2+ Zero interpolation, and reduce ozone usage.
Nitrobenzene waste water in reservoir 1 is squeezed in iron-carbon micro-electrolysis bed 7 by liquid pump I 2, opens supersonic generator simultaneously
10, it is launched high-frequency electrical energy and changes into ultrasound wave through ultrasound wave vibration plate 8 and reach in iron-carbon micro-electrolysis bed 7, with iron-carbon micro-electrolysis
Common effect treatment of Nitrobenzene waste water.Owing to the wastewater temperature after ul-trasonic irradiation is higher, the therefore temperature of iron-carbon micro-electrolysis bed
By the cooling water control of circulation in chuck 9, i.e. open liquid pump II 5, the cooling water in aqua storage tank 6 is squeezed in chuck 9, the coldest
But water flows back to, aqua storage tank 6, so recycle from the low level liquid outlet of chuck again.Nitrobenzene waste water is micro-through ultrasonic/ferrum carbon
After electrolysis 30 ~ 45 min, all inject in reservoirs 11, liquid pump III 14 squeeze into rotary packed bed 12, carry out hypergravity-
Ozone oxidation advanced treating.Oxygen in oxygen cylinder 18 enters ozonator 17 and generates ozone, and ozone is through gas flowmeter 15
Entering rotary packed bed 12, it is concurrent with ozone counter current contacting that the waste water in reservoir 11 enters rotary packed bed 12 through liquid pump III 14
Raw reaction, reacted waste water flows back into reservoir 11 again to be continued to be delivered in rotary packed bed 12 by liquid pump III 14, at circulation
Reason.Hypergravity-ozonation technology process time is 20 ~ 40 min.
Embodiment 1: utilize Fig. 1 shown device flow chart, processes nitrobenzene-containing waste water.In waste water, the initial benzene concentration of nitro is
300 mg/L, pH value is 2.In light electrolysis groove, waste iron filing concentration is 20g/L, and ferrum carbon mass ratio is 3:1, ultrasonic power output
For 8kW, frequency is 40 KHz, and chuck China and foreign countries circulating cooling water flow velocity is 60L/h.By 1m3Nitrobenzene waste water inject light electrolysis
After reacting 30 min in groove, the Nitrobenzol of 99% is reduced to aniline, and the Fe-C Micro Electrolysis Method that reaction rate is more traditional improves 7
Times, and Fe free in waste water2+Concentration improves 6.2 times.After light electrolysis completes, waste water is carried out hypergravity-ozone oxidation deep
Degree degraded, rotary packed bed rotating speed is 200 rpm, and waste water and ozone liquid-gas ratio are 1.5 L/L, and ozone concentration is 80 mg/L, super
Gravimetric devices rotating speed is 800 rpm, and after reaction 30min, pollutant mineralization rate reaches 97%；And do not use ultrasound wave to directly utilize
Light electrolysis-hypergravity-Ozonation processes waste water, under the conditions of and same operation constant in treating capacity, reaches same treatment
During effect, the process time lengthening of waste water 5 times, the consumption of ozone adds 3 times.
Embodiment 2: utilize Fig. 1 shown device flow chart, processes nitrobenzene-containing waste water.The initial benzene concentration of nitro in waste water
For, 500 mg/L, pH value is 2.5.In light electrolysis groove, waste iron filing concentration is 30 g/L, and ferrum carbon mass ratio is 1:3, and ultrasound wave is defeated
Going out power is 6 kW, and frequency is 20 KHz, and chuck China and foreign countries circulating cooling water flow velocity is 45 L/h.By 1m3Nitrobenzene waste water note
After reacting 45 min in electrolysis bath in a subtle way, the Nitrobenzol of 96% is reduced to aniline, the Fe-C Micro Electrolysis Method that reaction rate is more traditional
Improve 10 times, and Fe free in waste water2+Concentration improves 8 times.After light electrolysis completes, waste water is carried out hypergravity-ozone
Oxidation depth is degraded, and rotary packed bed rotating speed is 200 rpm, and waste water and ozone liquid-gas ratio are 0.5 L/L, and ozone concentration is 100
Mg/L, hypergravity equipment rotating speed is 400 rpm, and after reacting 40 min, pollutant mineralization rate reaches 95%；And do not use ultrasound wave
Directly utilize light electrolysis-hypergravity-Ozonation and process waste water, under the conditions of and same operation constant in treating capacity, reach
During same treatment effect, the process time lengthening of waste water 6 times, the consumption of ozone adds 4 times.
Embodiment 3: utilize Fig. 1 shown device flow chart, processes nitrobenzene-containing waste water.In waste water, the initial benzene concentration of nitro is
100 mg/L, pH value is 4.In light electrolysis groove, waste iron filing concentration is 10 g/L, and ferrum carbon mass ratio is 1:1, ultrasonic power output
Being 4 kW, frequency is 30 KHz, and chuck China and foreign countries circulating cooling water flow velocity is 30 L/h.By 1m3Nitrobenzene waste water inject micro-electricity
Solving after reacting 40 min in groove, the Nitrobenzol of 99% is reduced to aniline, and the Fe-C Micro Electrolysis Method that reaction rate is more traditional improves
6 times, and Fe free in waste water2+Concentration improves 5 times.After light electrolysis completes, waste water is carried out hypergravity-ozone oxidation degree of depth
Degraded, rotary packed bed rotating speed is 600 rpm, and waste water and ozone liquid-gas ratio are 2.5 L/L, and ozone concentration is 50 mg/L, overweight
Power equipment rotating speed is 800 rpm, and after reacting 20 min, pollutant mineralization rate reaches 98%；And it is micro-not use ultrasound wave to directly utilize
Electrolysis-hypergravity-Ozonation processes waste water, under the conditions of and same operation constant in treating capacity, reaches same treatment effect
Time really, the process time lengthening of waste water 4 times, the consumption of ozone adds 3 times.
Claims (1)
1. the device strengthening iron-carbon micro-electrolysis-Ozonation degrading nitrobenzene waste water, it is characterised in that: include that ferrum carbon is micro-
Bed electrolysis (7), iron-carbon micro-electrolysis bed (7) is provided with inlet and liquid outlet, and inlet passes through fluid flowmeter I (3) and liquid pump I
(2) nitrobenzene waste water reservoir (1) is connected；Iron-carbon micro-electrolysis bed (7) bottom is provided with ultrasound wave vibration plate (8), ultrasound wave vibration plate (8)
It is connected with supersonic generator (10)；Iron-carbon micro-electrolysis bed (7) is wrapped up by chuck (9), and chuck (9) is provided with water inlet and goes out
The mouth of a river, and be all connected with aqua storage tank (6), and make the cooling water in storage tank follow outside iron-carbon micro-electrolysis bed (7) by liquid pump II (5)
Circulation moves temperature control, and cooling water flow velocity is controlled by fluid flowmeter II (4)；The liquid outlet of iron-carbon micro-electrolysis bed (7) and reservoir
(11) it is connected；Rotary packed bed (12) are provided with inlet, liquid outlet, air inlet and gas outlet, and wherein inlet passes through liquid
Effusion meter III (13) and liquid pump III (14) are connected with reservoir (11), and liquid outlet is connected to reservoir (11)；Rotary packed bed
(8) gas outlet is connected with device for absorbing tail gas (16), and air inlet is given vent to anger with ozonator (17) by gas flowmeter (15)
Mouth connects；Oxygen cylinder (18) is connected with ozonator (17) air inlet.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112499754A (en) * | 2020-12-01 | 2021-03-16 | 张家港市五湖新材料技术开发有限公司 | Nitrogenous wastewater treatment system |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112499754A (en) * | 2020-12-01 | 2021-03-16 | 张家港市五湖新材料技术开发有限公司 | Nitrogenous wastewater treatment system |
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