CN205740573U - The device of hypergravity reinforced nano Zero-valent Iron Ozone advanced treating nitrobenzene waste water - Google Patents
The device of hypergravity reinforced nano Zero-valent Iron Ozone advanced treating nitrobenzene waste water Download PDFInfo
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- CN205740573U CN205740573U CN201620455704.2U CN201620455704U CN205740573U CN 205740573 U CN205740573 U CN 205740573U CN 201620455704 U CN201620455704 U CN 201620455704U CN 205740573 U CN205740573 U CN 205740573U
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Abstract
This utility model belongs to the technical field of nitrobenzene wastewater treatment, a kind of device of hypergravity reinforced nano Zero-valent Iron Ozone advanced treating nitrobenzene waste water, solve current nano zero valence iron preparation process numerous and diverse, directly by the problems such as ozone utilization rate is the highest, consumption is big during ozonization nitrobenzene waste water.Rotary packed bed including percussion flow, rotary packed bed in set top, lower reaction zone, reaction zone, top is reactive liquid solution district, and lower reaction zone is gas liquid reaction district, arranges by liquid device between reaction zone, top and the bottom, and the top, lower reaction zone arranges gas outlet.Air inlet is connected with ozonator, and gas outlet is connected with exhaust gas processing device, and percussion flow device feed pipe III and feed pipe IV are connected with reservoir V and reservoir VI respectively.The utilization rate of this utility model nano zero valence iron is more abundant, improves ozone utilization rate and oxidation efficiency, is suitable for processing the biggest, to process task weight nitrobenzene waste water and processes.
Description
Technical field
This utility model belongs to the technical field of nitrobenzene wastewater treatment, is specifically related to a kind of hypergravity reinforced nano zeroth order
The device of ferrum-Ozone advanced treating nitrobenzene waste water.
Background technology
Nitrobenzene waste water is the waste water of a kind of extremely difficult degraded, owing to its source is wide, toxicity is big, has the most been listed in excellent by China
First control pollutant list.In recent years, the Controlling research of nitrobenzene waste water receives much attention.
It is big that nano zero valence iron (Nanoscaled Zerovalent Iron, NZVI) has specific surface area, and reactivity is high
Etc. feature, it has huge in waste water treatment fields such as the removal of heavy metal ion, organic wastewater degraded, underground water pollution reparations
Application potential.Research shows, the nitrobenzene compounds of difficult degradation can be reduced into the most raw by nano zero valence iron fast and efficiently
The amino benzenes compounds of thing degraded.But, in the applied research of existing nano zero valence iron, the preparation flow of nano zero valence iron is usual
For: under nitrogen protection, continuous stirring, dropwise add to containing in certain density soluble ferrite solution with certain speed
Enter strong reductant, then through repeatedly centrifugal or magnetic separation separating, washing, be finally dried or be saved in ethanol or acetone soln.On
Stating preparation process step numerous and diverse, condition is harsh, and inevitable part nanoparticle is oxidized during being dried and preserving
Inactivation.In the preparation process of nanoparticle, often there is incorporation time length (5～50 ms), mix in the reactor of tradition stirring-type
Close uneven, the unequal problem of particle size distribution, it is difficult to meet large batch of Production requirement.
Ozone is a kind of green, efficient, the oxidant of non-secondary pollution.The Oxidation of pollutant can be divided into by ozone
Direct oxidation effect with ozone molecule direct aggression pollutant and the hydroxyl radical free radical indirect aggression pollutant with catalysis generation
Indirect oxidation effect.Mineralization of organic material can be become little molecule thing with indirect oxidation effect by the direct oxidation of ozone effectively
Matter, thus improve the biodegradability of waste water.Base hydroxyl radical free radical is as a kind of Strong oxdiative group, it is possible to non-selectivity by waste water
In organic matter degradation become micromolecular compound.Document is reported, nano zero valence iron and Fe2+All can produce hydroxyl with catalysis ozone
Free, thus by contaminant degradation.But, the application of current ozonation technology exists the problems such as ozone poorly water-soluble.Right
In the nitrobenzene waste water of difficult degradation, directly carry out process with ozone and there is also the problems such as ozone utilization rate is the highest, ozone usage is big.
High-gravity technology (High Gravity Technology, Higee) as a kind of novel process intensification technology,
There is incorporation time short, the advantage such as mix homogeneously.High-gravity technology utilizes the packed bed simulation super gravity field of high speed rotating, is filling out
During material high speed rotating liquid had broken, shear, the effect such as tear, greatly increase alternate contact area, acceleration
Boundary renewal rate, thus it is greatly improved phase boundary mass transfer rate, strengthen micro mixing.The most biphase to liquid-liquid, or
Microcosmic mixing between gas-liquid two-phase flow, mass transfer, reaction, cross_flow rotating packed bed all has conventional agitator incomparable
Advantage.
Summary of the invention
Numerous and diverse for current nano zero valence iron preparation process, be difficult to amplify, directly use ozonization nitrobenzene waste water time smelly
The problems such as coefficient of oxygen utilization is the highest, consumption is big, this utility model aim to provide a kind of can serialization, be easy to through engineering approaches amplify overweight
The device of power reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water.
For achieving the above object, the technical solution adopted in the utility model is:
The device of a kind of hypergravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water, including percussion flow-rotation
Turning packed bed, Impinging Stream-Rotating Packed Bed includes percussion flow device and rotary packed bed, and rotary packed bed shell is provided with feed liquor
Mouth, liquid outlet, air inlet and gas outlet, percussion flow device from top inlet enter rotary packed bed, rotary packed bed in set
Reaction zone, top and lower reaction zone, reaction zone, top is for containing ferrous iron salt nitrobenzene waste water solution and KBH4Or NaBH4Aqueous solution
Liquid-liquid reactions district, lower reaction zone is the gas-liquid reaction district containing aniline waste water Yu ozone, and upper and lower part sets in reaction zone respectively
Putting coaxial filler rotor, arrange by liquid device between reaction zone, top and the bottom, the top, lower reaction zone arranges gas outlet, air inlet
Mouth is connected with ozonator by gas flowmeter, and ozonator connects oxygen cylinder；Gas outlet is with exhaust gas processing device even
Connect,
Percussion flow device is that bottom has to nozzle III, the feed pipe III of nozzle IV and feed pipe IV, feed pipe III He
Feed pipe IV is contained ferrous iron salt nitrobenzene waste water solution reservoir V by pump IV and pump V with storing and stores KBH respectively4Or
NaBH4The reservoir VI of aqueous solution connects, and is respectively equipped with fluid flow between feed pipe III and feed pipe IV and pump IV and pump V
Meter III and effusion meter IV, liquid outlet is located at bottom Impinging Stream-Rotating Packed Bed III, and leads to reservoir VII.
Described is taper liquid-receiving plate by liquid device, is circular flat disk, square position is evenly equipped with some bottom taper liquid-receiving plate
Liquid distributing hole, taper liquid-receiving plate outer is connected with revolving bed shell.
Described taper liquid-receiving plate inclination angle is 5 °～45 °, described taper liquid-receiving plate bottom circular square position percent opening be 30%～
60%。
Having for inclined-plane inside the filler rotor in gas-liquid reaction district, inclined-plane is provided with angled with inclined-plane some with holes
Swash plate.
The filler rotor medial slope in gas-liquid reaction district and vertical design angle are 15 °～45 °, and swash plate with holes is with oblique
Face design angle 60 °～90 °.
It is super that device based on above-mentioned hypergravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water completes
Gravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water method: containing ferrous iron salt nitrobenzene waste water solution and
KBH4Or NaBH4Aqueous solution respectively by pump pump IV and pump V after fluid flowmeter III and effusion meter IV measure from feed pipe III He
Percussion flow device squeezed into by feed pipe IV, sprays laggard row at a high speed through the nozzle III of percussion flow device and nozzle IV and the most quickly touches
Hitting, mix, react, the filler rotor II of the high speed rotating of liquid entrance subsequently carries out secondary deep hybrid reaction；Liquid-liquid is biphase mixed
Close after reaction completes and become containing aniline waste water, got rid of to revolving bed outer casing inner wall containing aniline waste water, under gravity along inwall
It flow to by liquid device, liquid distributing hole redistribute on filler rotor III inner band hole deviation plate；Containing aniline waste water at the work of centrifugal force
Being thrown under with in filler rotor III and throw away from inside to outside, ozone is entered by air inlet, with containing aniline waste water at filler rotor
Adverse current or cross-flow contact is carried out in III；After completing mass transfer between vapor-liquid two phases, reaction, ozone tail gas is discharged from gas outlet, after degraded
Waste water be then expelled to reservoir VII by liquid outlet.
The reaction equation preparing nano zero valence iron is:
The reaction equation of nano zero valence iron reduction Nitrobenzol is:
Nano zero valence iron and Fe2+Catalysis ozone produces the reaction equation of hydroxyl radical free radical:
The concentration of described nitrobenzene waste water is 50～500 mg L-1, in described soluble ferrite nitrobenzene waste water solution
Ferrous concentration is the concentration of Nitrobenzol in nitrobenzene waste water 20～30 times；Described KBH4Or NaBH4The concentration of aqueous solution is institute
Select concentration ferrous in soluble ferrite nitrobenzene waste water solution 2～4 times, described gas phase ozone concentration is 10～100
mg·L-1, the described ratio containing aniline waste water with ozone volume flow is 500～2000 L m-3, described soluble ferrite is
Ferrous chloride, ferrous nitrate or ferrous sulfate, the described original ph containing ferrous salt nitrobenzene waste water solution is 2.0～9.0.
Nano zero valence iron reduction is combined, first by the nitrobenzene reduction Cheng Yi of difficult degradation by this utility model with ozone oxidation
The Fe produced during the aniline of degraded, recycling nano zero valence iron and nano zero valence iron reduction Nitrobenzol2+Catalysis ozone produces
Aniline is degraded by hydroxyl radical free radical, thus realizes the advanced treating of p-nitrophenyl waste water.Reduction and oxidizing process are all super
Carry out under the strengthening of gravity installation.Cross_flow rotating packed bed is utilized to mix mass transfer feature fast and efficiently, to nano zero valence iron
Reduction and ozone oxidation process are strengthened, it is achieved that quick, efficient, serialization nano zero valence iron-Ozonation degree of depth
Treatment of Nitrobenzene waste water.Utilizing this law treatment of Nitrobenzene waste water, technique is simple, with low cost, rapidly and efficiently.
The beneficial effects of the utility model are:
1, high-gravity technology is used to prepare nano zero valence iron synchronization process nitrobenzene waste water online, it is to avoid traditional stirring
Device feeds in the way of " dropping ", and the most uniformly, the most fully, method is easy and simple to handle in reaction in mixing, can serialization run.
2, high-gravity technology is used to prepare nano zero valence iron synchronization process nitrobenzene waste water online, at nano zero valence iron
Preparation process realizes the reduction of p-nitrophenyl waste water, shorten the response time, it is to avoid in traditional method, nano zero-valence is iron
Washing during Bei, separate, be dried, numerous and diverse operation such as storage, change multistep is a step, greatly simplifies preparation and uses step
Suddenly；Changing the crystalline form (as shown in Figure 3) when nano zero valence iron reacts with nitrobenzene waste water, nano zero valence iron crystal grain is becoming
In core initial stage and growth course i.e. with Nitrobenzol generation reduction reaction, it is to avoid in conventional method, nano zero valence iron is with large grained
State is reacted with Nitrobenzol, and the utilization rate of nano zero valence iron is more abundant, during conventional nano Zero-valent Iron reduction Nitrobenzol, and nano zero-valence
The dose concentration of ferrum is 100～200 times of the concentration of Nitrobenzol in nitrobenzene waste water, is converted into nano zero valence iron in this method
Dose concentration is 20～30 times of the concentration of Nitrobenzol in nitrobenzene waste water.
3, use high-gravity technology to enhance ozone mass transfer in water, and utilize nano zero valence iron reduction Nitrobenzol process
Nano zero valence iron and Fe produced by2+Carry out O3 catalytic oxidation, while without additional agent, improve ozone and utilize
Rate and oxidation efficiency, significantly reduce processing cost.
4, using super-gravity device, equipment volume is little, installation is simple, start-stop car convenient, can serialization run, and is suitable for processing
Batch is big, process the nitrobenzene waste water process of task weight.
5, by biphase for liquid-liquid be sufficiently mixed reaction after carry out vapor-liquid two phases reaction immediately and be integrated in same table apparatus, real
Existing Integrated design, the equipment that effectively reduces takes up an area space.Bottom filler rotor medial slope design, is conducive to accepting to fill from by liquid
Put the liquid being distributed as liquid re-distributor.Utilize this utility model device can realize the mixing of two strands of initial materials
Dosing, carries out absorbing the process intensification of reaction subsequently.Can also realize first carrying out the hybrid reaction of initial material, then carry out gas-
The process intensification of the mass transfer reaction that liquid two is alternate.
Accompanying drawing explanation
Fig. 1 is this utility model structural representation.
In figure: 29-reservoir V；30-pump IV；31-fluid flowmeter III；32-Impinging Stream-Rotating Packed Bed III；33-stores up
Liquid bath VI；34-pump V；35-fluid flowmeter IV；36-motor III；37-reservoir VII；38-oxygen cylinder；39-ozonator；
40-gas flowmeter；41-exhaust gas processing device.
Fig. 2 is the percussion flow-rotation of another kind of hypergravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water
Packed bed apparatus main body figure.
In figure: 42-inlet；43-feed pipe III；44-feed pipe IV；45-nozzle III；46-nozzle IV；47-shell；
48-gas outlet；49-air inlet；50-liquid outlet；51-rotary shaft；52-swash plate with holes；53-filler rotor III；54-is filled by liquid
Put；55-impingement region；56-filler rotor II.
Fig. 3 is a kind of hypergravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water described in the utility model
Nano zero valence iron in course of reaction and the transmission electron microscope pattern comparison diagram of the nano zero valence iron in conventional method course of reaction.
In figure: a-gravity Method；B-conventional method.
Detailed description of the invention
With detailed description of the invention, this utility model is described in further details below in conjunction with the accompanying drawings, but in this utility model
Hold and do not limited to by following embodiment.
The device of a kind of hypergravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water, including percussion flow-rotation
Turning packed bed, Impinging Stream-Rotating Packed Bed includes percussion flow device and rotary packed bed, and rotary packed bed shell is provided with feed liquor
Mouth, liquid outlet, air inlet and gas outlet, percussion flow device from top inlet enter rotary packed bed, rotary packed bed in set
Reaction zone, top and lower reaction zone, reaction zone, top is for containing ferrous iron salt nitrobenzene waste water solution and KBH4Or NaBH4Aqueous solution
Liquid-liquid reactions district, lower reaction zone is the gas-liquid reaction district containing aniline waste water Yu ozone, and upper and lower part sets in reaction zone respectively
Putting coaxial filler rotor, arrange by liquid device between reaction zone, top and the bottom, the top, lower reaction zone arranges gas outlet, air inlet
Mouth is connected with ozonator by gas flowmeter, and ozonator connects oxygen cylinder；Gas outlet is with exhaust gas processing device even
Connect,
Percussion flow device is that bottom has to nozzle III, the feed pipe III of nozzle IV and feed pipe IV, feed pipe III He
Feed pipe IV is contained ferrous iron salt nitrobenzene waste water solution reservoir V by pump IV and pump V with storing and stores KBH respectively4Or
NaBH4The reservoir VI of aqueous solution connects, and is respectively equipped with fluid flow between feed pipe III and feed pipe IV and pump IV and pump V
Meter III and effusion meter IV, liquid outlet is located at bottom Impinging Stream-Rotating Packed Bed III, and leads to reservoir VII.
Described is taper liquid-receiving plate by liquid device, is circular flat disk, square position is evenly equipped with some bottom taper liquid-receiving plate
Liquid distributing hole, taper liquid-receiving plate outer is connected with revolving bed shell.
Described taper liquid-receiving plate inclination angle is 5 °～45 °, described taper liquid-receiving plate bottom circular square position percent opening be 30%～
60%。
Having for inclined-plane inside the filler rotor in gas-liquid reaction district, inclined-plane is provided with angled with inclined-plane some with holes
Swash plate.
The filler rotor medial slope in gas-liquid reaction district and vertical design angle are 15 °～45 °, and swash plate with holes is with oblique
Face design angle 60 °～90 °.
Utilizing the processing method that this utility model completes, processing at 20 DEG C containing initial concentration is 250 mg L-1Nitro
Benzene waste water.By FeSO4·7H2O is dissolved in the nitrobenzene waste water in reservoir V 29, prepares Fe2+Concentration is nitro phenenyl concentration
25 times containing FeSO4Nitrobenzene waste water solution, regulating initial pH is 4.0；With tap water by NaBH4It is dissolved in reservoir VI 33,
It is made into NaBH4Concentration is containing FeSO4Fe in nitrobenzene waste water solution2+The NaBH of 3 times of concentration4Aqueous solution.Containing FeSO4Nitrobenzol
Waste water solution and NaBH4Aqueous solution is measured through fluid flowmeter III 31 and fluid flowmeter IV 35 by pump IV 30 and pump V 34 respectively
After, squeeze into percussion flow device from feed pipe III 43 and feed pipe IV 44, through nozzle III 45 and nozzle IV 46 spray of percussion flow device
After going out, two strands of liquid are with 20 m s-1Shock initial velocity carry out first Fast Collision, mix, react, liquid enters 1000 subsequently
The filler rotor II 56 of rpm carries out secondary deep hybrid reaction；Liquid-liquid two-phase mixtures becomes containing aniline waste water after having reacted,
Got rid of to revolving bed shell 47 inwall containing aniline waste water, flow to by liquid device 54 along inwall under gravity, by liquid distributing hole again
It is distributed on filler rotor III 53 inner band hole deviation plate 52；Filler rotor III it is thrown under the influence of centrifugal force containing aniline waste water
In 53 and throw away from inside to outside, the ozone oxidation entered by air inlet 49 in the filler rotor III 53 of 1000 rpm, ozone
Flow is 50 L h-1, gas phase ozone concentration is 40 mg L-1, liquid-gas ratio is 1000 L m-3, after reaction, ozone tail gas from
Gas outlet 48 is discharged, and the waste water after degraded is then expelled to reservoir VII 37 by liquid outlet 50.After single reaction, take from liquid outlet 50
Sample detects, and Nitrobenzol clearance 99%, COD clearance reaches 71%.
Claims (5)
1. the device of hypergravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water, it is characterised in that: include
Impinging Stream-Rotating Packed Bed, Impinging Stream-Rotating Packed Bed includes percussion flow device and rotary packed bed, rotary packed bed shell
Being provided with inlet, liquid outlet, air inlet and gas outlet, percussion flow device enters rotary packed bed from top inlet, rotary filling
Setting reaction zone, top and lower reaction zone in material bed, reaction zone, top is for containing ferrous iron salt nitrobenzene waste water solution and KBH4Or
NaBH4The liquid-liquid reactions district of aqueous solution, lower reaction zone is the gas-liquid reaction district containing aniline waste water Yu ozone, and upper and lower part is anti-
Being respectively provided with coaxial filler rotor in answering district, arrange by liquid device between reaction zone, top and the bottom, the top, lower reaction zone sets
Putting gas outlet, air inlet is connected with ozonator by gas flowmeter, and ozonator connects oxygen cylinder；Gas outlet and tail
Flash Gas Compression Skid System connects,
Percussion flow device is that bottom has to nozzle III, the feed pipe III of nozzle IV and feed pipe IV, feed pipe III and charging
Pipe IV is contained ferrous iron salt nitrobenzene waste water solution reservoir V by pump IV and pump V with storing and stores KBH respectively4Or NaBH4
The reservoir VI of aqueous solution connects, be respectively equipped with between feed pipe III and feed pipe IV and pump IV and pump V fluid flowmeter III and
Effusion meter IV, liquid outlet is located at bottom Impinging Stream-Rotating Packed Bed III, and leads to reservoir VII.
The device of hypergravity reinforced nano Zero-valent Iron the most according to claim 1-Ozone advanced treating nitrobenzene waste water,
It is characterized in that: described is taper liquid-receiving plate by liquid device, is circular flat disk, if being evenly equipped with on square position bottom taper liquid-receiving plate
Dry liquid distributing hole, taper liquid-receiving plate outer is connected with revolving bed shell.
The device of hypergravity reinforced nano Zero-valent Iron the most according to claim 2-Ozone advanced treating nitrobenzene waste water,
It is characterized in that described taper liquid-receiving plate inclination angle is 5 °～45 °, described taper liquid-receiving plate bottom circular square position percent opening be 30%～
60%。
4. according to the hypergravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water described in claim 1 or 2 or 3
Device, it is characterised in that having for inclined-plane inside the filler rotor in gas-liquid reaction district, inclined-plane is provided with angled with inclined-plane
Some swash plates with holes.
The device of hypergravity reinforced nano Zero-valent Iron the most according to claim 4-Ozone advanced treating nitrobenzene waste water,
It is characterized in that the filler rotor medial slope in gas-liquid reaction district and vertical design angle are 15 °～45 °, swash plate with holes with
Inclined design angle 60 °～90 °.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105858965A (en) * | 2016-05-18 | 2016-08-17 | 中北大学 | Method and device for deep treatment on nitrobenzene wastewater by using supergravity intensifying nano zero-valent iron-ozone method |
| CN108675487A (en) * | 2018-04-18 | 2018-10-19 | 中北大学 | Hypergravity strengthening extraction-catalysis O3/H2O2Handle the method and device of high nitrobenzene waste water |
| CN112408565A (en) * | 2020-11-16 | 2021-02-26 | 昆明理工大学 | Method and device for extracting rare precious metals from salt-containing wastewater |
-
2016
- 2016-05-18 CN CN201620455704.2U patent/CN205740573U/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105858965A (en) * | 2016-05-18 | 2016-08-17 | 中北大学 | Method and device for deep treatment on nitrobenzene wastewater by using supergravity intensifying nano zero-valent iron-ozone method |
| CN105858965B (en) * | 2016-05-18 | 2023-04-14 | 中北大学 | Method and device for advanced treatment of nitrobenzene wastewater by supergravity-enhanced nano zero-valent iron-ozone method |
| CN108675487A (en) * | 2018-04-18 | 2018-10-19 | 中北大学 | Hypergravity strengthening extraction-catalysis O3/H2O2Handle the method and device of high nitrobenzene waste water |
| CN108675487B (en) * | 2018-04-18 | 2021-08-17 | 中北大学 | Supergravity enhanced extraction-catalysis of O3/H2O2Method and device for treating high-concentration nitrobenzene wastewater |
| CN112408565A (en) * | 2020-11-16 | 2021-02-26 | 昆明理工大学 | Method and device for extracting rare precious metals from salt-containing wastewater |
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