CN105858965A - Method and device for deep treatment on nitrobenzene wastewater by using supergravity intensifying nano zero-valent iron-ozone method - Google Patents

Method and device for deep treatment on nitrobenzene wastewater by using supergravity intensifying nano zero-valent iron-ozone method Download PDF

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CN105858965A
CN105858965A CN201610328715.9A CN201610328715A CN105858965A CN 105858965 A CN105858965 A CN 105858965A CN 201610328715 A CN201610328715 A CN 201610328715A CN 105858965 A CN105858965 A CN 105858965A
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waste water
liquid
ozone
packed bed
iii
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CN105858965B (en
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焦纬洲
刘有智
高璟
罗莹
申红艳
栗秀萍
祁贵生
袁志国
张巧玲
俸志荣
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North University of China
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • 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
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • 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
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/002—Construction details of the apparatus
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/78—Details relating to ozone treatment devices
    • C02F2201/782—Ozone generators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention belongs to the technical field of nitrobenzene wastewater treatment, particularly relates to a method and a device for deep treatment on nitrobenzene wastewater by using a supergravity intensifying nano zero-valent iron-ozone method, and aims to solve the problems that the conventional nano zero-valent iron is complex in preparation process, the utilization rate of ozone is low and the amount is large when ozone is adopted to treat nitrobenzene wastewater, and the like. The method comprises the following steps: enabling a ferrous salt containing nitrobenzene wastewater solution and a KBH4 or NaBH4 solution to react in an impinging stream-rotating packed bed so as to obtain aniline-containing wastewater; enabling the aniline-containing wastewater to react with ozone in the rotating packed bed. The device comprises the impinging stream-rotating packed bed, wherein an upper reaction zone and a lower reaction zone are arranged inside the impinging stream-rotating packed bed; the upper reaction zone is a liquid-liquid reaction zone; the lower reaction zone is a gas-liquid reaction area; a liquid receiving device is arranged between the upper reaction zone and the lower reaction zone; a gas outlet is formed in the upmost part of the lower reaction zone. By adopting the method and the device, the nano zero-valent iron is relatively sufficiently utilized, the utilization rate of ozone is increased, the oxidation efficiency of ozone is improved, and the method and the device are applicable to nitrobenzene wastewater treatment which is large in treatment volume and heavy in treatment task.

Description

The method of hypergravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water And device
Technical field
The invention belongs to the technical field of nitrobenzene wastewater treatment, be specifically related to a kind of hypergravity reinforced nano Zero-valent Iron- The method and device of 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, it is desirable to provide a kind of can serialization, be easy to through engineering approaches amplify hypergravity strong The method changing nano zero valence iron-Ozone advanced treating nitrobenzene waste water.
For achieving the above object, the technical solution used in the present invention is:
The method of hypergravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water, comprises the steps:
1), first by soluble ferrite it is dissolved in nitrobenzene waste water, is made into containing ferrous iron salt nitrobenzene waste water solution；
2), KBH is taken4Or NaBH4Aqueous solution；
3), containing ferrous iron salt nitrobenzene waste water solution and KBH4Or NaBH4Two strands of liquid of aqueous solution are at Impinging Stream-Rotating Packed Bed Interior collision, mix, react, while preparing nano zero valence iron, nitrobenzene reduction is become aniline, is formed containing aniline waste water；
4), containing aniline waste water in rotary packed bed, carry out adverse current with ozone or cross-flow contacts, carry out oxidative degradation, degraded Rear waste water is discharged, and ozone tail gas is discharged.
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, the described soluble ferrite nitrobenzene waste water solution Central Asia The concentration of ferrum is 20～30 times of the concentration of Nitrobenzol in nitrobenzene waste water；Described KBH4Or NaBH4The concentration of aqueous solution is selected 2～4 times of concentration ferrous in soluble ferrite nitrobenzene waste water solution, 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 chlorination Ferrous iron, ferrous nitrate or ferrous sulfate, the described original ph containing ferrous salt nitrobenzene waste water solution is 2.0～9.0.
Described containing ferrous iron salt nitrobenzene waste water solution and KBH4Or NaBH4Two strands of liquid of aqueous solution are equal-volume fluid, two The shock initial velocity of stock equal-volume fluid is 1～25 m s-1.The rotating speed of described super-gravity device is at 100～3000 rpm.Described Reaction temperature is 10～30 DEG C.
Complete the device of the method for above-mentioned hypergravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water, Including Impinging Stream-Rotating Packed Bed I and rotary packed bed II, Impinging Stream-Rotating Packed Bed I includes percussion flow device and rotary filling Material bed I, percussion flow device includes that bottom has and distinguishes to feed pipe I and feed pipe II, feed pipe I and the feed pipe II of nozzle It is connected with reservoir I and reservoir II by pump I and pump II, between feed pipe I and feed pipe II and pump I and pump II, is designed with liquid Flowmeter body, arranges liquid outlet, and leads to reservoir III bottom Impinging Stream-Rotating Packed Bed；Rotary packed bed II and reservoir Connected by pump III and fluid flowmeter III between III；The air inlet of rotary packed bed II passes through gas flowmeter and ozonator phase Even, ozonator connects oxygen cylinder；The gas outlet of rotary packed bed II is connected with exhaust gas processing device, liquid outlet connects liquid storage Groove IV.
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 I and pump II after fluid flowmeter I and flow meter II measure from feed pipe I, feed pipe II squeezes in Impinging Stream-Rotating Packed Bed, and two strands of liquid collide in Impinging Stream-Rotating Packed Bed, mix, react, in preparation While nano zero valence iron, nitrobenzene reduction is become aniline, be thrown out of containing aniline waste water subsequently and enter reservoir III；Give up containing aniline Water is squeezed into by pump III and is carried out with the ozone produced by ozonator in rotary packed bed II countercurrently or cross-flow contacts, and carries out oxygen Changing degradation reaction, after degraded, waste water enters reservoir IV, and ozone tail gas is expelled to exhaust gas processing device.
Another kind completes the method for described hypergravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water Device, including Impinging Stream-Rotating Packed Bed, Impinging Stream-Rotating Packed Bed includes percussion flow device and rotary packed bed, rotary filling Material bed shell is provided with inlet, liquid outlet, air inlet and gas outlet, and percussion flow device enters from top inlet and rotates filler 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 NaBH4The liquid-liquid reactions district of aqueous solution, lower reaction zone is the gas-liquid reaction district containing aniline waste water Yu ozone, upper, Being respectively provided with coaxial filler rotor in lower reaction zone, arrange by liquid device between reaction zone, top and the bottom, lower reaction zone is It is provided above gas outlet.
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 °, and described taper is subject to Liquid plate bottom circular square position percent opening is 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.Medial slope and vertical design angle are 15 °～45 °, swash plate with holes and inclined design angle 60 °～90 °.
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 connected with reservoir V and reservoir VI by pump IV and pump V respectively, feed pipe III and feed pipe IV and pump IV and Being respectively equipped with fluid flowmeter III and effusion meter IV between pump V, liquid outlet is located at bottom Impinging Stream-Rotating Packed Bed III, and leads to To reservoir VII；Air inlet is connected with ozonator by gas flowmeter, and ozonator connects oxygen cylinder；Gas outlet with Exhaust gas processing device connects.
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.
Nano zero valence iron reduction is combined by the present invention with ozone oxidation, first the nitrobenzene reduction of difficult degradation is become degradable Aniline, recycling nano zero valence iron and nano zero valence iron reduction Nitrobenzol during produce Fe2+Catalysis ozone produces hydroxyl Radical pair aniline is degraded, thus realizes the advanced treating of p-nitrophenyl waste water.Reduction and oxidizing process are all at hypergravity Carry out under the strengthening of device.Utilize cross_flow rotating packed bed to mix mass transfer feature fast and efficiently, nano zero valence iron is reduced And ozone oxidation process strengthened, it is achieved that quickly, efficiently, serialization nano zero valence iron-Ozonation advanced treating Nitrobenzene waste water.Utilizing this law treatment of Nitrobenzene waste water, technique is simple, with low cost, rapidly and efficiently.
The invention has the beneficial effects as follows:
1, use high-gravity technology to prepare nano zero valence iron synchronization process nitrobenzene waste water online, it is to avoid conventional agitator with The mode " dripped " feeds, 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 5) 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.The mixing utilizing apparatus of the present invention can realize two strands of initial materials is joined Liquid, carries out absorbing the process intensification of reaction subsequently.Can also realize first carrying out the hybrid reaction of initial material, then carry out solution-air The process intensification of two alternate mass transfer reactions.
Accompanying drawing explanation
Fig. 1 is the work of a kind of hypergravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water of the present invention Process flow figure.
In figure: 1-reservoir I；2-pump I；3-fluid flowmeter I；4-Impinging Stream-Rotating Packed Bed I；5-reservoir II；6- Pump II；7-fluid flowmeter II；8-motor I；9-reservoir III；10-pump III；11-fluid flowmeter III；12-is rotary packed bed Ⅱ；13-reservoir IV；14-motor II；15-oxygen cylinder；16-ozonator；17-gas flowmeter；18-vent gas treatment fills Put.
Fig. 2 is hitting of a kind of hypergravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water of the present invention Hit stream-rotary packed bed apparatus main body figure.
In figure: 19-impingement region；20-nozzle I；21-nozzle II；22-filler rotor I；23-feed pipe I；24-feed pipe Ⅱ；25-inlet；26-shell；27-liquid outlet；28-rotary shaft.
Fig. 3 is another kind of hypergravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water of the present invention Process chart.
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. 4 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. 5 is a kind of hypergravity reinforced nano Zero-valent Iron of the present invention-Ozone advanced treating nitrobenzene waste water reaction During nano zero valence iron and conventional method course of reaction in the transmission electron microscope pattern comparison diagram of nano zero valence iron.
In figure: a-gravity Method；B-conventional method.
Detailed description of the invention
With detailed description of the invention, the present invention is described in further details below in conjunction with the accompanying drawings, but present invention is not subject to Following embodiment is limited to.
The method of hypergravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water, it is characterised in that: include as Lower step:
1), first by soluble ferrite it is dissolved in nitrobenzene waste water, is made into containing ferrous iron salt nitrobenzene waste water solution；
2), KBH is taken4Or NaBH4Aqueous solution；
3), containing ferrous iron salt nitrobenzene waste water solution and KBH4Or NaBH4Two strands of liquid of aqueous solution are at Impinging Stream-Rotating Packed Bed Interior collision, mix, react, while preparing nano zero valence iron, nitrobenzene reduction is become aniline, is formed containing aniline waste water；
4), containing aniline waste water in rotary packed bed, carry out adverse current with ozone or cross-flow contacts, carry out oxidative degradation, degraded Rear waste water is discharged, and ozone tail gas is discharged.
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.Institute State containing ferrous iron salt nitrobenzene waste water solution and KBH4Or NaBH4Two strands of liquid of aqueous solution are equal-volume fluid, two strands of equal-volume streams The shock initial velocity of body is 1～25 m s-1.The rotating speed of described super-gravity device is at 100～3000 rpm.Described reaction temperature is 10～30 DEG C.
Embodiment 1-6, utilizes technological process shown in Fig. 1, treatment of Nitrobenzene waste water.Described device includes percussion flow-rotation Packed bed I and rotary packed bed II, Impinging Stream-Rotating Packed Bed I includes percussion flow device and rotary packed bed I, and percussion flow fills Put to have bottom including and pass through pump I and pump II respectively to feed pipe I and feed pipe II, feed pipe I and the feed pipe II of nozzle It is connected with reservoir I and reservoir II, between feed pipe I and feed pipe II and pump I and pump II, is designed with fluid flowmeter, clash into Stream-rotary packed bed bottom arranges liquid outlet, and leads to reservoir III；By pump III and liquid between rotary packed bed II and reservoir III Flowmeter body III connects；The air inlet of rotary packed bed II is connected with ozonator by gas flowmeter, ozonator Connect oxygen cylinder；The gas outlet of rotary packed bed II is connected with exhaust gas processing device, liquid outlet connects reservoir IV.Described as follows In embodiment, rotary packed bed is that adverse current is rotary packed bed.
Soluble ferrite is dissolved in the nitrobenzene waste water in reservoir I 1, is configured to certain density containing ferrous salt Nitrobenzene waste water, regulating initial pH is 2.0～9.0；With tap water by KBH4Or NaBH4It is dissolved in reservoir II 5, is made into one Determine the NaBH of concentration4Aqueous solution.Two strands of liquid respectively by pump I 2 and pump II 6 after fluid flowmeter I 3 and flow meter II 7 measure, Spray from nozzle I 20 and the nozzle II 21 of feed pipe I 23 and feed pipe II 24, impingement region 19 carry out first Fast Collision, Mixing, reaction.Subsequently, liquid is radially entered into by introversion and extroversion in the filler rotor I 22 of high speed rotating, carries out secondary deep equal Even mixing, reaction.Then liquid is thrown out of, and flow to liquid outlet 27 along rotary packed bed shell 26 inwall, enters reservoir III 9. In waste water in reservoir III 9 is squeezed into rotary packed bed II 12 by pump III 10 after fluid flowmeter III 11 measures, in nanometer zero Valency ferrum and Fe2+Catalysis under, count through gas flowmeter 17 with from ozonator 16 in the filler rotor I 22 of high speed rotating Ozone contact reaction after amount, after reaction, waste water enters reservoir IV 13, and tail gas is discharged into exhaust gas processing device from gas outlet 18.Waste water in reservoir IV 13 can be circulated process in being squeezed into rotary packed bed 12 again by pump III 10.
Embodiment 1:
Utilizing technological process shown in Fig. 1, processing at 15 DEG C containing initial concentration is 250 mg L-1Nitrobenzene waste water.By sulphuric acid Ferrous (FeSO4·7H2O) it is dissolved in the nitrobenzene waste water in reservoir I 1, prepares Fe2+Concentration is 25 times of nitro phenenyl concentration Containing FeSO4Nitrobenzene waste water solution, regulating initial pH is 9.0；With tap water by NaBH4It is dissolved in reservoir II 5, is made into NaBH4Concentration is containing FeSO4Fe in nitrobenzene waste water solution2+The NaBH of 3 times of concentration4Aqueous solution.Two strands of liquid are with 15 m s-1Shock initial velocity carry out first Fast Collision at impingement region 19, mix, react, then going through rotating speed is filling out of 100 rpm Material rotor I 22 carries out secondary deep uniformly mix, react.Liquid enters reservoir III 9 afterwards.Waste water in reservoir III 9 In being squeezed into rotary packed bed II 12 by pump III 10 after fluid flowmeter III 11 measures, by ozone oxygen in the filler of 100 rpm Changing, ozone flow is 75 L h-1, gas phase ozone concentration is 50 mg L-1, liquid-gas ratio is 1500 L m-3, waste water after reaction Enter reservoir IV 13.
Sample analysis from reservoir III 9, after nano zero valence iron reduction, Nitrobenzol clearance reaches 96%, and COD clearance reaches 5%；Sample analysis from reservoir IV 13, Nitrobenzol clearance 99%, COD clearance reaches 70%.Compare with traditional method, this Bright treatment effeciency is high, and the process time significantly shortens, and ozone usage substantially reduces.
Embodiment 2:
Utilizing technological process shown in Fig. 1, processing at 30 DEG C containing initial concentration is 50 mg L-1Nitrobenzene waste water.By chlorination Ferrous (FeCl2) it is dissolved in the nitrobenzene waste water in reservoir I 1, prepare Fe2+Concentration is containing of 20 times of nitro phenenyl concentration FeCl2Nitrobenzene waste water solution, regulating initial pH is 7.0；Preparation KBH4Concentration is by being joined containing FeCl2In nitrobenzene waste water solution Fe2+The KBH that concentration is 2.5 times4Aqueous solution is placed in reservoir II 5.Two strands of liquid are with 25 m s-1Shock initial velocity at rotating speed be Reservoir III 9 is entered after reaction in the Impinging Stream-Rotating Packed Bed I 4 of 1200 rpm.Waste water in reservoir III 9 is by pump III 10 In squeezing into rotary packed bed II 12, by ozone oxidation in the filler of 1200 rpm, ozone flow is 40 L h-1, gas phase ozone Concentration is 10 mg L-1, liquid-gas ratio is 2000 L m-3, after reaction, waste water enters reservoir IV 13.After single reaction, from storage Sample analysis in liquid bath III 9, after nano zero valence iron reduction, Nitrobenzol clearance reaches 98%, and COD clearance reaches 7%；From reservoir IV Sample analysis in 13, Nitrobenzol clearance 100%, COD clearance reaches 75%.
Embodiment 3:
Utilizing technological process shown in Fig. 1, processing at 20 DEG C containing initial concentration is 500 mg L-1Nitrobenzene waste water.By FeCl2 It is dissolved in the nitrobenzene waste water in reservoir I 1, prepares Fe2+Concentration be 30 times of nitro phenenyl concentration containing FeCl2Nitrobenzene waste water Solution, regulating initial pH is 2.0；Preparation KBH4Concentration is by being joined containing FeCl2Fe in nitrobenzene waste water solution2+The KBH that concentration is 3 times4 Aqueous solution is placed in reservoir II 5.Two strands of liquid are with 1 m s-1Clash into initial velocity in percussion flow-rotation that rotating speed is 1000 rpm Reservoir III 9 is entered after reacting in turning packed bed I 4.Waste water in reservoir III 9 is squeezed into rotary packed bed II 12 by pump III 10 In, by ozone oxidation in the filler of 1000 rpm, ozone flow is 75 L h-1, gas phase ozone concentration is 100 mg L-1, Liquid-gas ratio is 500 L m-3, after reaction, waste water enters reservoir IV 13.Afterwards, the waste water in reservoir IV 13 is by pump III 10 dozens In entering rotary packed bed II 12, circular response 5min, Nitrobenzol clearance 99%, COD clearance reaches 94%.
Embodiment 4:
Utilizing technological process shown in Fig. 1, processing at 10 DEG C containing initial concentration is 400 mg L-1Nitrobenzene waste water.By FeCl2 It is dissolved in the nitrobenzene waste water in reservoir I 1, prepares Fe2+Concentration be 25 times of nitro phenenyl concentration containing FeCl2Nitrobenzene waste water Solution, regulating initial pH is 4.0；Preparation NaBH4Concentration is by being joined containing FeCl2Fe in nitrobenzene waste water solution2+Concentration 4 times NaBH4Aqueous solution is placed in reservoir II 5.Two strands of liquid are with 10 m s-1Clash into initial velocity at the shock that rotating speed is 3000 rpm Reservoir III 9 is entered after reaction in stream-rotary packed bed I 4.Waste water in reservoir III 9 is squeezed into rotary packed bed by pump III 10 In II 12, by ozone oxidation in the filler of 3000 rpm, ozone flow is 50 L h-1, gas phase ozone concentration is 60 mg L-1, liquid-gas ratio is 1000 L m-3, after reaction, waste water enters reservoir IV 13.Afterwards, the waste water in reservoir IV 13 is by pump III 10 squeeze into rotary packed bed II 12, circular response 10min, and Nitrobenzol clearance 99%, COD clearance reaches 97%.
Embodiment 5:
Utilizing technological process shown in Fig. 1, processing at 25 DEG C containing initial concentration is 300 mg L-1Nitrobenzene waste water.Will FeSO4·7H2O is dissolved in the nitrobenzene waste water in reservoir I 1, prepares Fe2+Concentration be 25 times of nitro phenenyl concentration containing FeSO4 Nitrobenzene waste water solution, regulating initial pH is 7.0；With tap water by NaBH4It is dissolved in reservoir II 5, is made into NaBH4Concentration For containing FeSO4Fe in nitrobenzene waste water solution2+The NaBH of 2.5 times of concentration4Aqueous solution.Two strands of liquid are with 20 m s-1Shock Initial velocity enters reservoir III 9 after reacting in the Impinging Stream-Rotating Packed Bed I 4 that rotating speed is 100 rpm.Giving up in reservoir III 9 In water is squeezed into rotary packed bed II 12 by pump III 10, by ozone oxidation in the filler of 100 rpm, ozone flow is 65 L h-1, gas phase ozone concentration is 40 mg L-1, liquid-gas ratio is 1500 L m-3, after reaction, waste water enters reservoir IV 13.Single is anti- Ying Hou, Nitrobenzol clearance 99%, COD clearance reaches 79%.
Embodiment 6:
Utilizing technological process shown in Fig. 1, processing at 20 DEG C containing initial concentration is 200 mg L-1Nitrobenzene waste water.Will FeSO4·7H2O is dissolved in the nitrobenzene waste water in reservoir I 1, prepares Fe2+Concentration be 20 times of nitro phenenyl concentration containing FeSO4 Nitrobenzene waste water solution, regulating initial pH is 5.0；With tap water by NaBH4It is dissolved in reservoir II 5, is made into NaBH4Concentration For containing FeSO4Fe in nitrobenzene waste water solution2+The NaBH of 2.5 times of concentration4Aqueous solution.Two strands of liquid are with 5 m s-1Shock Initial velocity enters reservoir III 9 after reacting in the Impinging Stream-Rotating Packed Bed I 4 that rotating speed is 1200 rpm.In reservoir III 9 In waste water is squeezed into rotary packed bed II 12 by pump III 10, by ozone oxidation in the filler of 1200 rpm, ozone flow is 55 L·h-1, gas phase ozone concentration is 30 mg L-1, liquid-gas ratio is 1000 L m-3, after reaction, waste water enters reservoir IV 13.Single After secondary response, Nitrobenzol clearance 99%, COD clearance reaches 68%.
Embodiment 7 utilizes technological process shown in Fig. 3, described device to include Impinging Stream-Rotating Packed Bed, percussion flow-rotation Packed bed includes percussion flow device and rotary packed bed, and rotary packed bed shell is provided with inlet, liquid outlet, air inlet and gives vent to anger Mouthful, 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 NaBH4The liquid-liquid reactions district of aqueous solution, bottom is reacted District is the gas-liquid reaction district containing aniline waste water Yu ozone, is respectively provided with coaxial filler rotor, up and down in reaction zone, upper and lower part Arranging by liquid device between reaction zone, portion, the top, lower reaction zone arranges gas outlet.
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 °, and described taper is subject to Liquid plate bottom circular square position percent opening is 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.Medial slope and vertical design angle are 15 °～45 °, swash plate with holes and inclined design angle 60 °～90 °.
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 connected with reservoir V and reservoir VI by pump IV and pump V respectively, feed pipe III and feed pipe IV and pump IV and Being respectively equipped with fluid flowmeter III and effusion meter IV between pump V, liquid outlet is located at bottom Impinging Stream-Rotating Packed Bed III, and leads to To reservoir VII；Air inlet is connected with ozonator by gas flowmeter, and ozonator connects oxygen cylinder；Gas outlet with Exhaust gas processing device connects.
Containing ferrous iron salt nitrobenzene waste water solution and KBH4Or NaBH4Aqueous solution respectively by pump pump IV and pump V through liquid stream Percussion flow device is squeezed into from feed pipe III and feed pipe IV, through the nozzle III of percussion flow device after gauge III and effusion meter IV metering Spray at a high speed the first Fast Collision of laggard row with nozzle IV, mix, react, the filler rotor II of the high speed rotating of liquid entrance subsequently Carry out secondary deep hybrid reaction；Liquid-liquid two-phase mixtures becomes after having reacted containing aniline waste water, is got rid of to rotation containing aniline waste water Rotated bed outer casing inner wall, flow to by liquid device, liquid distributing hole redistribute filler rotor III inner band along inwall under gravity On hole deviation plate；Being thrown under the influence of centrifugal force in filler rotor III containing aniline waste water and throw away from inside to outside, ozone is by entering QI KOU enters, and carries out adverse current with containing aniline waste water or cross-flow contacts in filler rotor III；Complete mass transfer between vapor-liquid two phases, anti- Ying Hou, ozone tail gas is from gas outlet discharge, and the waste water after degraded is then expelled to reservoir VII by liquid outlet.
Embodiment 7:
Utilizing technological process shown in Fig. 3, processing at 20 DEG C containing initial concentration is 250 mg L-1Nitrobenzene waste water.Will FeSO4·7H2O is dissolved in the nitrobenzene waste water in reservoir V 29, prepares Fe2+Concentration is containing of 25 times of nitro phenenyl concentration FeSO4Nitrobenzene waste water solution, regulating initial pH is 4.0；With tap water by NaBH4It is dissolved in reservoir VI 33, is made into NaBH4Concentration is containing FeSO4Fe in nitrobenzene waste water solution2+The NaBH of 3 times of concentration4Aqueous solution.Containing FeSO4Nitrobenzene waste water Solution and NaBH4Aqueous solution respectively by pump IV 30 and pump V 34 after fluid flowmeter III 31 and fluid flowmeter IV 35 measure, Percussion flow device is squeezed into, through nozzle III 45 and nozzle IV 46 ejection of percussion flow device from feed pipe III 43 and feed pipe IV 44 After, 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 (14)

1. the method for hypergravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water, it is characterised in that: include Following steps:
1), first by soluble ferrite it is dissolved in nitrobenzene waste water, is made into containing ferrous iron salt nitrobenzene waste water solution；
2), KBH is taken4Or NaBH4Aqueous solution；
3), containing ferrous iron salt nitrobenzene waste water solution and KBH4Or NaBH4Two strands of liquid of aqueous solution are at Impinging Stream-Rotating Packed Bed Interior collision, mix, react, while preparing nano zero valence iron, nitrobenzene reduction is become aniline, is formed containing aniline waste water；
4), containing aniline waste water in rotary packed bed, carry out adverse current with ozone or cross-flow contacts, carry out oxidative degradation, degraded Rear waste water is discharged, and ozone tail gas is discharged.
The method of hypergravity reinforced nano Zero-valent Iron the most according to claim 1-Ozone advanced treating nitrobenzene waste water, It is characterized in that: the concentration of described nitrobenzene waste water is 50～500 mg L-1；Described soluble ferrite nitrobenzene waste water is molten Ferrous in liquid concentration is the concentration of Nitrobenzol in nitrobenzene waste water 20～30 times；Described KBH4Or NaBH4The concentration of aqueous solution For 2～4 times of concentration ferrous in selected soluble ferrite nitrobenzene waste water solution, described gas phase ozone concentration be 10～ 100 mg·L-1, the described ratio containing aniline waste water with ozone volume flow is 500～2000 L m-3；Described solubility is ferrous Salt is ferrous chloride, ferrous nitrate or ferrous sulfate, the described original ph containing ferrous salt nitrobenzene waste water solution be 2.0～ 9.0。
The side of hypergravity reinforced nano Zero-valent Iron the most according to claim 1 and 2-Ozone advanced treating nitrobenzene waste water Method, it is characterised in that: described containing ferrous iron salt nitrobenzene waste water solution and KBH4Or NaBH4Two strands of liquid of aqueous solution are equal-volume Fluid, the shock initial velocity of two strands of equal-volume fluids is 1～25 m s-1。
4. the rotating speed of super-gravity device described in is at 100～3000 rpm.
5. reaction temperature described in is 10～30 DEG C.
6. one kind completes hypergravity reinforced nano Zero-valent Iron as claimed in claim 3-Ozone advanced treating nitrobenzene waste water The device of method, it is characterised in that: include Impinging Stream-Rotating Packed Bed I and rotary packed bed II, percussion flow-rotation filler Bed I includes percussion flow device and rotary packed bed I, and percussion flow device includes that bottom has to the feed pipe I of nozzle and charging Pipe II, feed pipe I and feed pipe II are connected with reservoir I and reservoir II by pump I and pump II respectively, feed pipe I and charging It is designed with fluid flowmeter between pipe II and pump I and pump II, liquid outlet is set bottom Impinging Stream-Rotating Packed Bed, and leads to storage Liquid bath III；It is connected by pump III and fluid flowmeter III between rotary packed bed II with reservoir III；The air inlet of rotary packed bed II Being connected with ozonator by gas flowmeter, ozonator connects oxygen cylinder；The gas outlet of rotary packed bed II and tail Flash Gas Compression Skid System connects, liquid outlet connects reservoir IV.
7. one kind based on the hypergravity reinforced nano Zero-valent Iron described in claim 4-Ozone advanced treating nitrobenzene waste water The hypergravity reinforced nano Zero-valent Iron that device completes-Ozone advanced treating nitrobenzene waste water method, it is characterised in that: containing ferrous iron Iron salt nitrobenzene waste water solution and KBH4Or NaBH4Aqueous solution respectively by pump I and pump II through fluid flowmeter I and flow meter II meter Squeezing in Impinging Stream-Rotating Packed Bed I from feed pipe I and feed pipe II after amount, two strands of liquid are at Impinging Stream-Rotating Packed Bed I Interior collision, mix, react, while preparing nano zero valence iron, nitrobenzene reduction is become aniline, got rid of containing aniline waste water subsequently Go out to enter reservoir III；Carry out with the ozone produced by ozonator in being squeezed into rotary packed bed II containing aniline waste water by pump III Adverse current or cross-flow contact, carry out oxidative degradation, and after degraded, waste water enters reservoir IV, and ozone tail gas is expelled to vent gas treatment Device.
8. one kind completes hypergravity reinforced nano Zero-valent Iron as claimed in claim 3-Ozone advanced treating nitrobenzene waste water The device of method, it is characterised in that: include that Impinging Stream-Rotating Packed Bed, Impinging Stream-Rotating Packed Bed include percussion flow device With rotary packed bed, rotary packed bed shell is provided with inlet, liquid outlet, air inlet and gas outlet, and percussion flow device is from top Inlet enter rotary packed bed, rotary packed bed in set reaction zone, top and lower reaction zone, reaction zone, top for containing ferrous iron Iron salt nitrobenzene waste water solution and KBH4Or NaBH4The liquid-liquid reactions district of aqueous solution, lower reaction zone is with smelly containing aniline waste water The gas-liquid reaction district of oxygen, is respectively provided with coaxial filler rotor in reaction zone, upper and lower part, arrange and be subject between reaction zone, top and the bottom Liquid device, the top, lower reaction zone arranges gas outlet.
The device of hypergravity reinforced nano Zero-valent Iron the most according to claim 6-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 dress of hypergravity reinforced nano Zero-valent Iron the most according to claim 7-Ozone advanced treating nitrobenzene waste water Putting, it is characterised in that described taper liquid-receiving plate inclination angle is 5 °～45 °, described taper liquid-receiving plate bottom circular square position percent opening is 30%～60%.
11. according to the hypergravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water described in claim 6 or 7 or 8 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 dress of 12. hypergravity reinforced nano Zero-valent Iron according to claim 9-Ozone advanced treating nitrobenzene waste water Put, it is characterised in that the filler rotor medial slope in gas-liquid reaction district and vertical design angle are 15 °～45 °, band hole deviation Plate (52) and inclined design angle 60 °～90 °.
The dress of 13. hypergravity reinforced nano Zero-valent Iron according to claim 10-Ozone advanced treating nitrobenzene waste water Put, it is characterised in that 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 feed pipe IV be connected with reservoir V and reservoir VI by pump IV and pump V respectively, feed pipe III and feed pipe IV and pump Being respectively equipped with fluid flowmeter III and effusion meter IV between IV and pump V, liquid outlet is located at bottom Impinging Stream-Rotating Packed Bed III, And lead to reservoir VII；Air inlet is connected with ozonator by gas flowmeter, and ozonator connects oxygen cylinder；Give vent to anger Mouth is connected with exhaust gas processing device.
14. 1 kinds based on the hypergravity reinforced nano Zero-valent Iron described in claim 11-Ozone advanced treating nitrobenzene waste water Hypergravity reinforced nano Zero-valent Iron-Ozone advanced treating nitrobenzene waste water method of completing of device, it is characterised in that: containing Asia Ferrum iron salt nitrobenzene waste water solution and KBH4Or NaBH4Aqueous solution respectively by pump pump IV and pump V through fluid flowmeter III and flow Percussion flow device is squeezed into from feed pipe III and feed pipe IV, through nozzle III and nozzle IV high speed of percussion flow device after meter IV metering Carrying out first Fast Collision after ejection, mix, react, liquid enters the filler rotor II of high speed rotating and carries out secondary deep subsequently Hybrid reaction；Liquid-liquid two-phase mixtures becomes after having reacted containing aniline waste water, is got rid of to revolving bed shell containing aniline waste water Wall, flow to by liquid device, liquid distributing hole redistribute on filler rotor III inner band hole deviation plate along inwall under gravity；Contain Aniline waste water is thrown under the influence of centrifugal force in filler rotor III and throws away from inside to outside, and ozone is entered by air inlet, with In filler rotor III, adverse current or cross-flow contact is carried out containing aniline waste water；After completing mass transfer between vapor-liquid two phases, reaction, ozone tail Gas is discharged from gas outlet, and the waste water after degraded is then expelled to reservoir VII by liquid outlet.
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