CN105884092A - Method and device for degrading nitrobenzene waste water through reinforced iron-carbon micro-electrolysis-ozonation method - Google Patents
Method and device for degrading nitrobenzene waste water through reinforced iron-carbon micro-electrolysis-ozonation method Download PDFInfo
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- CN105884092A CN105884092A CN201610363467.1A CN201610363467A CN105884092A CN 105884092 A CN105884092 A CN 105884092A CN 201610363467 A CN201610363467 A CN 201610363467A CN 105884092 A CN105884092 A CN 105884092A
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- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000002351 wastewater Substances 0.000 title claims abstract description 101
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000006385 ozonation reaction Methods 0.000 title claims abstract description 39
- 230000000593 degrading effect Effects 0.000 title claims abstract description 24
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 81
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000002604 ultrasonography Methods 0.000 claims abstract description 24
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000015556 catabolic process Effects 0.000 claims abstract description 8
- 238000006731 degradation reaction Methods 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 51
- 239000007788 liquid Substances 0.000 claims description 48
- 239000007789 gas Substances 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 230000003647 oxidation Effects 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 24
- 238000005728 strengthening Methods 0.000 claims description 15
- 239000012530 fluid Substances 0.000 claims description 14
- 239000000498 cooling water Substances 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 230000036647 reaction Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 13
- 239000000945 filler Substances 0.000 abstract description 11
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910017112 Fe—C Inorganic materials 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 230000033558 biomineral tissue development Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- -1 phenyl ring Nitro Chemical class 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention belongs to the technical field of ozonation waste water treatment, and particularly relates to a method and device for degrading nitrobenzene waste water through a reinforced iron-carbon micro-electrolysis-ozonation method. The problems that in the prior art, after an iron-carbon micro-electrolysis bed operates for a long time, filler is passivated and inactivated, an electrolytic reaction is blocked, and the efficiency improving range of a catalyst to ozonation degradation of the waste water is limited are solved. Firstly, the nitrobenzene waste water is placed in an iron-carbon micro-electrolysis bath, ultrasonic waves are used for assisting, nitrobenzene hard to degrade is fast reduced into aniline easy to degrade under the common action of ultrasound/iron-carbon micro-electrolysis, and meanwhile Fe2+ is released into the waste water after the electrolytic reaction; then the waste water is fed into supergravity equipment to fully react with ozone, and residual organic pollutants in the waste water are deeply oxydatively degraded. The reaction rate of iron-carbon micro-electrolysis is overall increased by 6-10 times, meanwhile, the concentration of free Fe2+ in the waste water is increased by 5-8 times, and the use amount of the ozone in the subsequent supergravity-ozonation method is greatly reduced.
Description
Technical field
The invention belongs to the technical field that treatment of Nitrobenzene waste water processes, be specifically related to a kind of strengthening iron-carbon micro-electrolysis-smelly
The method and device of oxygen oxidizing process degrading nitrobenzene waste water, it uses ultrasonic technology, Fe-C Micro Electrolysis Method and Ozonation
Common effect 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 [H] that capture produces.
[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 destroys
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 on its phenyl ring
Nitro there is strong electron attraction and make phenyl ring be passivated.Nitro on Nitrobenzol can be effectively reduced to by iron-carbon micro-electrolysis rule
Amido, activates phenyl ring so that it is be prone to degraded.Therefore iron-carbon micro-electrolysis technology is commonly used for the pretreatment of nitrobenzene wastewater.So
And after iron-carbon micro-electrolysis bed longtime running, the iron oxides that ferrum carbon surface is easily generated is covered, it is electrolysed the bivalence of generation simultaneously
The coagulation of ferrum is easily formed stable flocculate and is gradually deposited at filling surface, causes filler passivation inactivation, cell reaction
It is obstructed, 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 the present invention is for iron-carbon micro-electrolysis bed longtime running in prior art, 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, it is provided that a kind of strengthening iron-carbon micro-electrolysis-
The method and device of Ozonation degrading nitrobenzene waste water.
The present invention adopts the following technical scheme that realization:
A kind of method strengthening iron-carbon micro-electrolysis-Ozonation degrading nitrobenzene waste water, it is characterised in that: step is as follows: (1)
First nitrobenzene waste water put to iron-carbon micro-electrolysis groove and be aided with ultrasound wave, making the Nitrobenzol of difficult degradation at ultrasonic/micro-electricity of ferrum carbon
Solving under common effect by fast restore is degradable aniline, produce after cell reaction simultaneously to Fe2+It is released in waste water；
(2) deliver to waste water 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.
Complete the device of the method for above-mentioned strengthening iron-carbon micro-electrolysis-Ozonation degrading nitrobenzene waste water, including ferrum
Carbon micro-electrolysis bed, iron-carbon micro-electrolysis bed is provided with inlet and liquid outlet, and inlet is connected by fluid flowmeter I and liquid pump I
Nitrobenzene waste water reservoir；Being provided with ultrasound wave vibration plate bottom iron-carbon micro-electrolysis bed, ultrasound wave vibration plate is connected with supersonic generator
Logical；Iron-carbon micro-electrolysis bed is wrapped up by chuck, and chuck is provided with water inlet and outlet, and is all connected with aqua storage tank, and passes through liquid
Pump II makes the cooling water in storage tank control by fluid flowmeter II at iron-carbon micro-electrolysis bed outer circulation flowing temperature control, cooling water flow velocity
System；The liquid outlet of iron-carbon micro-electrolysis bed is connected with reservoir；Rotary packed bed it be provided with inlet, liquid outlet, air inlet and go out
QI KOU, wherein inlet is connected with reservoir by fluid flowmeter III and liquid pump III, and liquid outlet is connected to reservoir；Rotate
Packed bed gas outlet is connected with device for absorbing tail gas, and air inlet is connected with ozonator gas outlet by gas flowmeter；Oxygen
Gas cylinder is connected with ozonator air inlet.
Hypergravity equipment of the present invention is published hypergravity swinging bed device, including filler bed, helical duct
The high-gravity rotating bed equipment (application reference number 91109255.2,200520100685) of the various ways such as formula, preferably rotary filling
Material bed hypergravity equipment.
Complete the device of the method for above-mentioned strengthening iron-carbon micro-electrolysis-Ozonation degrading nitrobenzene waste water, including ferrum
Carbon micro-electrolysis bed and rotary packed bed, iron-carbon micro-electrolysis bed is provided with inlet and liquid outlet, inlet by fluid flowmeter I with
And liquid pump I connects nitrobenzene waste water reservoir；Ultrasound wave vibration plate, ultrasound wave vibration plate and ultrasound wave it is provided with bottom iron-carbon micro-electrolysis bed
Generator is connected；Iron-carbon micro-electrolysis bed is wrapped up by chuck, and chuck is provided with water inlet and outlet, and all with aqua storage tank phase
Even, and making the cooling water in storage tank at iron-carbon micro-electrolysis bed outer circulation flowing temperature control by liquid pump II, cooling water flow velocity is by liquid
Flow meter II controls；The liquid outlet of iron-carbon micro-electrolysis bed is connected with reservoir；Rotary packed bed it is provided with inlet, liquid outlet, enters
QI KOU and gas outlet, wherein inlet is connected with reservoir by fluid flowmeter III and liquid pump III, and liquid outlet is connected to
Reservoir；Rotary packed bed gas outlet is connected with device for absorbing tail gas, and air inlet is gone out with ozonator by gas flowmeter
QI KOU connects；Oxygen cylinder is connected with ozonator air inlet, and exhaust gas processing device inner stuffing is activated carbon.
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 reaction
Carry out, the Fe that light electrolysis generates simultaneously2+Hydrolyzable generates the Fe (OH) with coagulation2With Fe (OH)3, formed in the solution
Stable flocculate, on the one hand this flocculate is gradually deposited at ferrum carbon filler surface, hinders iron-carbon micro-electrolysis electron transfer process,
On the other hand the Fe that part is free is carried away in absorption secretly2+, reduce Fe in solution2+Concentration, urging needed for causing follow-up Ozonation
Agent Fe2+Supply deficiency.All there is filler and be easily passivated inactivation in the most traditional iron-carbon micro-electrolysis bed, it is difficult to long-term operation continuously
Problem.The intervention of ultrasound wave then can release the problem that ferrum carbon filler is easily passivated.
The invention has the beneficial effects as follows: iron-carbon micro-electrolysis is combined by (1) with hypergravity-Ozonation two-stage process
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 ozone
Oxidizing process deep oxidation degrading waste water, on the other hand utilizes the Fe that micro-electrolysis reaction is generated2+Catalysis as Ozonation
Agent, it is achieved zero interpolation of catalyst needed for follow-up hypergravity-Ozonation；(2) after for ensureing that iron-carbon micro-electrolysis reaction can be
Continuous hypergravity-Ozonation provides enough catalyst Fes2+, and use intensified by ultrasonic wave iron-carbon micro-electrolysis to react, utilize super
The powerful energy field of sound wave, updates ferrum carbon filler surface continuously, it is ensured that iron-carbon micro-electrolysis high reaction rate, prevents flocculate simultaneously
Generate and reduce Fe2+Loss.(3) intervention of ultrasound wave makes the reaction rate of iron-carbon micro-electrolysis improve 6 ~ 10 on the whole
Times, make free Fe in waste water simultaneously2+Concentration improves 5 ~ 8 times, drastically reduce the area the smelly of follow-up hypergravity-Ozonation
Oxygen consumption.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
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, the present invention is described in further detail below in conjunction with the accompanying drawings.But present invention is not by following
Embodiment is limited to.
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.The present invention (1) first with iron-carbon micro-electrolysis can by nitrobenzene reduction be chemical property more
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 follow-up overweight
Power-Ozonation provides enough catalyst Fes2+, it is achieved catalyst Fe in hypergravity-Ozonation technical process 2+ 's
Zero adds, and reduces ozone usage.
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.
Shown in concrete technology flow chart 1, the nitrobenzene waste water in reservoir 1 is squeezed in iron-carbon micro-electrolysis bed 7 by liquid pump I 2,
Opening supersonic generator 10, it is launched high-frequency electrical energy and changes into ultrasound wave through ultrasound wave vibration plate 8 and reach the micro-electricity of ferrum carbon simultaneously
Solve in bed 7, jointly act on treatment of Nitrobenzene waste water with iron-carbon micro-electrolysis.Owing to the wastewater temperature after ul-trasonic irradiation is higher, because of
The temperature of this iron-carbon micro-electrolysis bed, by the cooling water control of circulation in chuck 9, i.e. opens liquid pump II 5, by the cooling in aqua storage tank 6
Water is squeezed in chuck 9, and cooling water flows back to, aqua storage tank 6, so recycle from the low level liquid outlet of chuck again subsequently.Nitro
Benzene waste water, after ultrasonic/iron-carbon micro-electrolysis effect 30 ~ 45 min, all injects in reservoir 11, liquid pump III 14 squeezes into rotation
Packed bed 12, carries out hypergravity-ozone oxidation advanced treating.Oxygen in oxygen cylinder 18 enters ozonator 17 and generates smelly
Oxygen, ozone enters rotary packed bed 12 through gas flowmeter 15, and the waste water in reservoir 11 enters through liquid pump III 14 and rotates filler
Bed 12 and ozone counter current contacting reacting, reacted waste water flows back into reservoir 11 again to be continued to be delivered to by liquid pump III 14
In rotary packed bed 12, circular treatment.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 (6)
1. the method strengthening iron-carbon micro-electrolysis-Ozonation degrading nitrobenzene waste water, it is characterised in that: step is as follows:
(1) first being put to iron-carbon micro-electrolysis groove by nitrobenzene waste water and be aided with ultrasound wave, the Nitrobenzol making difficult degradation is micro-at ultrasonic/ferrum carbon
Be degradable aniline by fast restore under the common effect of electrolysis, produce after cell reaction simultaneously to Fe2+It is released into waste water
In；(2) deliver to waste water hypergravity equipment fully reacts with ozone, remaining organic pollution in deep oxidation degrading waste water.
A kind of method strengthening iron-carbon micro-electrolysis-Ozonation degrading nitrobenzene waste water the most according to claim 1, its
It is characterised by: nitrobenzene waste water concentration is less than or equal to 500 mg/L, remaining nitro in ultrasonic/iron-carbon micro-electrolysis processed waste water
Benzene concentration regulates to 2 ~ 4 less than or equal to 50 mg/L, nitrobenzene waste water initial pH acid or alkali；Constitute the iron filings of light electrolysis electrode
With quality of activated carbon than for 1:3 ~ 3:1；Iron filings mass concentration is 10 g/L ~ 30 g/L.
A kind of side strengthening iron-carbon micro-electrolysis-Ozonation degrading nitrobenzene waste water the most according to claim 1 and 2
Method, it is characterised in that: in step (1), the frequency of ultrasound wave is 20 ~ 40 kHz, ultrasonic power 4 ~ 8 kW.
A kind of method strengthening iron-carbon micro-electrolysis-Ozonation degrading nitrobenzene waste water the most according to claim 3, its
It is characterised by: entering the waste water of hypergravity equipment in step (2) with the liquid-gas ratio of ozone is 0.5 ~ 2.5 L/L, and ozone concentration is
50 ~ 100 mg/L, hypergravity equipment rotating speed is 400 ~ 800 rpm.
A kind of method strengthening iron-carbon micro-electrolysis-Ozonation degrading nitrobenzene waste water the most according to claim 4, its
It being characterised by: 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.
6. one kind completes a kind of iron-carbon micro-electrolysis-Ozonation degrading nitrobenzene waste water strengthened as claimed in claim 5
The device of method, it is characterised in that: include that iron-carbon micro-electrolysis bed (7), iron-carbon micro-electrolysis bed (7) are provided with inlet and liquid outlet,
Inlet connects nitrobenzene waste water reservoir (1) by fluid flowmeter I (3) and liquid pump I (2)；Iron-carbon micro-electrolysis bed (7) end
Portion is provided with ultrasound wave vibration plate (8), and ultrasound wave vibration plate (8) is connected with supersonic generator (10)；Iron-carbon micro-electrolysis bed (7) is pressed from both sides
Set (9) is wrapped up, and chuck (9) is provided with water inlet and outlet, and is all connected with aqua storage tank (6), and makes storage by liquid pump II (5)
Cooling water in groove is controlled 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) are provided with inlet, liquid outlet, air inlet
Mouth and gas outlet, wherein inlet is connected with reservoir (11) by fluid flowmeter III (13) and liquid pump III (14), goes out
Liquid mouth is connected to reservoir (11)；Rotary packed bed (8) gas outlet is connected with device for absorbing tail gas (16), and air inlet passes through gas
Effusion meter (15) is connected with ozonator (17) gas outlet；Oxygen cylinder (18) is connected with ozonator (17) air inlet.
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