CN208916893U - A kind of catalytic ozonation stirring reactor - Google Patents
A kind of catalytic ozonation stirring reactor Download PDFInfo
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- CN208916893U CN208916893U CN201820966494.2U CN201820966494U CN208916893U CN 208916893 U CN208916893 U CN 208916893U CN 201820966494 U CN201820966494 U CN 201820966494U CN 208916893 U CN208916893 U CN 208916893U
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Abstract
The utility model belongs to organic chemical waste water process field, and in particular to be to be transformed to traditional ozone reactor, obtain it is a kind of handle wastewater from chemical industry novel, efficient ozone catalysis oxidation stirring reactor.By being transformed to ozone reactor internal structure and (such as setting guide shell, increasing agitating device), to improve the ozone residence time；Meanwhile being combined ozone and the catalytic filler of load " active carbon+Nanoscale Iron (mixture of nano zero valence iron and nano iron oxide) ", ozone utilization rate is improved, to reduce process energy consumption and processing cost.
Description
Technical field
The technology belongs to organic chemical waste water process field, and in particular to be to be transformed to traditional ozone reactor,
Obtain a kind of processing the novel of wastewater from chemical industry, efficient ozone catalysis oxidation stirring reactor and sewage water treatment method.
Background technique
With China's expanding economy, organic chemical industry's industry has become the mainstay industry in China.It is big in chemical products
A large amount of waste water can be generated simultaneously during amount production, these waste water are removed containing the pollution such as general inorganic compound, heavy metal
Beyond the region of objective existence, the also characteristic organic pollutants usually containing the characteristics such as high toxicity, teratogenesis, carcinogenic, mutagenesis, such as Polychlorinated biphenyls, polycyclic
Aromatic hydrocarbons, phenolic compound, bromide fire retardant, dyestuff etc., therefore waste water has that complicated component, toxicity is high, the spies such as difficult
Point[1-3].Since the most difficulty of these characteristic organic pollutants is biodegradable, and there is stronger biotic recovery, has to environment
There is lasting pollution capacity, if with receiving water body is drained into certain prestige will be constituted to aquatile, animals and plants even human health
The side of body.
This kind of organic chemical waste water cannot be effectively treated in traditional biodegradation technique, and water outlet still has higher biology poison
Property (organic pollutant is not degraded effectively or mineralising)[4].Reaction rate is fast, treatment efficiency is good because having for high-level oxidation technology
The features such as, have become the important means for handling organic chemical waste water difficult to degrade, mainly includes Photocatalyst, Fenton examination
Agent oxidation technology, ozonation technology etc.[5-7].Ozonation technology is because it is obvious with treatment effect, is easy to engineering construction, just
In promote and apply the advantages that, be widely used in handling organic chemical waste water difficult to degrade[8].However, due to ozonation technology
There are the deficiencies of gas-liquid mass transfer effect difference, and leading to ozonation technology, energy consumption is high, with high costs, limit its it is further promote and
Using[9].And two key factors for influencing ozone reactor gas-liquid mass transfer effect are when including that incipient bubble size and gas stop
Between[10,11].Incipient bubble size determines the contact area of gas-liquid mass transfer, and bubble is smaller, and gas liquid interfacial area is bigger, more has
Conducive to haptoreaction；The residence time of gas determines the time of gas-liquid mass transfer contact, and the time of contact the long more is conducive to react.
Currently, existing experts and scholars are transformed ozonation aerated mode, ozone mass transfer effect can be effectively improved, is such as being passed
Microporous aeration disc is installed in system ozone reactor bottom, ozone transfer efficiency can be promoted to 22% or so from 8%；And use microbubble
Generator carries out the reactor ozone transfer efficiency of microbubble aeration up to 60-70% or so[12,13].But only rely on change ozone
Aeration mode can't fundamentally solve the problems, such as that ozone mass transfer effect is poor, need further from the internal structure of ozone reactor
It is transformed to improve the ozone residence time.
In addition, such as CN107331526A discloses a kind of manifold type film ozone catalytic reaction dress for handling organic wastewater
It sets.It include level-one preatreating reactors, second level preatreating reactors, Membrane catalysis main reactor, membrane catalytic reactor monitoring with
Intelligence control system, Membrane cleaning system；It is characterized in that the level-one preatreating reactors include: variable speed blender,
Pass in and out water ga(u)ge, thermometer and pH probe；Second level preatreating reactors includes: the multi-medium filtering for including filtrate quartz sand
Device；Membrane catalysis main reactor includes: active carbon treatment region and catalysis membrane module area, is furthermore furnished with vacuum pump, water inlet and import/exhaust
System；Membrane cleaning system includes: backwashing pump, metering pump and 1 clean water tank and 2 medicine tins.The reaction unit process flow
More complex, quartz sand need to consume more backwashing waters in more medium filter, close when being catalyzed membrane module higher cost and high temperature
Envelope problem needs further to be solved always.
CN205061658U discloses a kind of O3 catalytic oxidation reaction unit for wastewater treatment, including catalysis oxidation
Reactor, aeration component, gas flowmeter, ozone generator, three phase separator and separation water circulator, separation water circulator with
By pipeline connection, three phase separator passes through connection water pipe connection with water circulator is separated for catalyst oxidation reactor bottom；Using
Supported Manganese, copper active carbon be catalyst filling, improve ozone Oxidation Treatment effect.But it is loaded on catalyst filling
Enter in reactor if manganese, copper are lost, be easy to cause heavy metal pollution；In addition, catalytic amount filler is mounted on ozone hair
In raw device, catalysis is carried out to the ozone of generation in advance and generates more free radicals, catalysis oxygen is then entered by gas flowmeter
Change reactor, free radical loss is more in this process, and decontamination efficiency weakens significantly.
CN206529326U discloses a kind of multi-stage, efficient catalytic ozonation recirculation reactor, including one stage catalyzing oxidation
Reactor, suction ventilator, stirring motor, cycle of ozone pipe and stirring blade, the ozone generator are connected to gas-water mixing zone
Side, it is anti-that the baffle is embedded in one stage catalyzing oxidation reactor, second level catalyst oxidation reactor and three-level catalysis oxidation respectively
The side of device is answered, the inner cavity of the collecting hood is inlaid with suction ventilator, and one end of the cycle of ozone pipe is both connected to collecting hood
Top, the lower end of the stirring motor is equipped with stirring blade, and the outlet pipe is connected to the outer of three-level catalyst oxidation reactor
Side, the control switch are embedded on the outer wall of ozone generator.Relative to column ozone reactor, which has land occupation
The disadvantages of area is big, attended operation is difficult.
Summary of the invention
In view of deficiency existing for existing ozone reactor, the purpose of this utility model is that by ozone reactor inside
Structure is transformed and (such as setting guide shell, increases agitating device), to improve the ozone residence time；Meanwhile it by ozone and loading
The catalytic filler of " active carbon+Nanoscale Iron (mixture of nano zero valence iron and nano iron oxide) " is combined, and improves ozone
Utilization rate, the utility model provide novel, the efficient ozone catalysis oxidation stirring reactor of one kind and sewage water treatment method.
The utility model is achieved through the following technical solutions:
A kind of novel, efficient ozone catalysis oxidation stirring reactor, the ozone reactor are from bottom to top divided into two-stage:
First order reaction zone includes aerator and guide shell；
Second level reaction zone includes supporting layer, catalytic filler and agitating device；
Wherein, the ozone that ozone generator (1) generates carries out the ozone catalytic oxygen after gas flowmeter (2) adjust gas velocity
Change in stirring reactor (4)；
In first order reaction zone, aerator (3) is located at ozone reactor bottom, preferably microbubble aerator,
Ozone reactor bottom is aerated using aerator (3), and sewage such as organic chemical waste water is through flow pump (5) and valve (6)
Into reactor (4), air-liquid is pre-mixed here, is then sufficiently mixed through guide shell (7) and interior circulation, is extended
The air-liquid haptoreaction time；
In the reaction zone of the second level, the supporting layer (8) that ozone and waste water are passed through positioned at first order reaction zone top enters filling
The reaction zone of catalytic filler (9)；Meanwhile making positioned at the electric device of reactor head (11) drive three-level blender (10) smelly
Oxygen, waste water and catalytic filler are sufficiently mixed, deep contact catalysis oxidation, exhaust, effluent.
It is preferred that the waste water enters subsequent work from the slave water outlet (13) for being located at reactor top after two-stage catalytic oxidation
In skill；The exhaust gas processing device (12) that exhaust gas enters positioned at reactor top is handled.
It can be from being set to first order reaction zone and second level reaction zone thief hatch (14) is sampled in preferred process
Carry out coherent detection.Meanwhile air-liquid admixture can be in due course from the observation panel for being set to first order reaction zone in the reactor
(15) it is observed.
The utility model provides a kind of using aforementioned novel, efficient ozone catalysis oxidation stirring reactor sewage
(such as wastewater from chemical industry) processing method, comprising the following steps:
The ozone that ozone generator generates enters reactor, preferably reaction column, reactor bottom setting through gas flowmeter
Microbubble aerator, i.e. starting microbubble is aerated at the beginning for reaction, and ozone bubbles are fog-like, increase ozone bubbles and pollution
Effective contact area of object；When starting aeration, most of ozone gas enters guide shell, and the gas velocity in guide shell is greater than its surrounding
Gas velocity results in intermediate fluid density in this way and becomes smaller, forms density contrast, pressure difference, thus make air-liquid when flowing out guide shell to
Surrounding, downwards diffusion, air-liquid flow direction；In the order reaction area, ozone and waste water are acted on through guide shell to be formed interior circulation and disturbs
Stream, contact oxidation time extend, and pollutant obtains fully degraded or mineralising；
The supporting layer that ozone and waste water pass through positioned at first order reaction zone top, which enters second level reaction zone and is filled with catalysis, to be filled out
The reaction zone of material；Meanwhile three-level blender is driven to fill ozone, waste water and catalytic filler positioned at the electric device of reactor head
Divide mixing, deep contact catalysis oxidation, exhaust, effluent.
It is preferred that microbubble outlet velocity interval is 0.5~1.0L/min.
Be first to be flowed up from guide shell bottom it is preferred that as illustrated by the arrows in fig. 1, air-liquid flow direction is consistent, then to
Outside, it flows downward to form circulation.Maximum possible extends the contact oxidation time, and pollutant obtains fully degraded or mine
Change.
It is preferred that annular space ratio is 0.8~1.0 after most of ozone gas enters guide shell, on the one hand controlling the parameter can protect
The most of ozone through microbubble aeration of card enters inside guide shell；On the other hand guide shell is made to form enough pressure differences, just
It is recycled in being formed in air-liquid mixing.
Ozone and waste water enter through supporting layer is filled with the reaction zone of catalytic filler, which is " active carbon+nanometer
The lightweight of iron (mixture of nano zero valence iron and nano iron oxide) ", compound catalytic filler, wherein nano zero valence iron and nanometer
The quality of iron oxide is 1:1~3:1 than range.
Preferably through modified aforementioned catalytic agent filler, variety classes, difference are added on the basis of customary preparation methods
Surfactant (such as sodium carboxymethylcellulose, the ionic liquid and PBTCA water treatment agent) conduct of concentration, different amounts is modified
Modified catalyst is obtained after agent.
Preferred catalytic packing material size range is 3mm~5mm, and preferably the filler specific gravity range is 0.75~0.95, in the ratio
Filler in weight range can be suspended in reaction zone.Catalyst filling in the utility model has large specific surface area, absorption
The characteristics such as ability is strong, reactivity is high, the hydroxyl of catalyst surface promote ozone decompose generate more hydroxyl radical free radicals (
OH), the pollutant for being adsorbed on filler surface is made thoroughly to be degraded or mineralising；Meanwhile the nano zero valence iron in composite catalyzing filler
It can inhibit the generation of ozonisation by-product (such as inorganic byproduct bromate), reduce risk of toxicity.
The air-liquid residence time that the utility model catalytic ozonation stirs stranding formula reactor is 1h.
The preferred embodiment of aforementioned processing methods is, three-grade electric agitating device is arranged in ozone reactor, by stirring make gas,
Liquid is uniformly mixed admittedly, comes into full contact with oxidation.The starting stirring when air-liquid is full of reaction column of three-grade electric agitating device, preferably
Mixing speed range be 6.0~7.5r/s, continue mixing time be consistent with the air-liquid residence time.
Since individual ozone oxidation has certain selectivity, often has and aoxidize halfway problem, therefore, first
Grade is individually on the basis of ozone oxidation reaction, and in the second level, reaction zone generates more OH, no choosing using catalyst ozone
Selecting property, exhaustive oxidation or even mineralising pollutant and its intermediate product, control out aquatic toxicity.
By the above solution, Ozone Gas Mass Transfer Efficiency can be effectively improved, so that ozone and pollutant is sufficiently met Xie Fanying, mentions
The degradation rate and salinity of high pollution object, are effectively reduced the bio-toxicity of water outlet；Because of the raising of ozone utilization rate, keep this practical
Novel reactor can reduce ozone dosage under same treatment effect, to reduce process energy consumption and processing cost.
Compared with traditional ozone reactor, the utility model is had the advantage that
(1) react more efficient, more thorough.In the utility model technique, ozone reactor is divided into two-stage, and the first order is led
Flow cartridge makes air-liquid form interior circulation in reactor, and the catalytic filler and agitating device of the second level make reaction zone form stirring-type
Catalysis oxidation, gas, liquid, solid three-phase come into full contact with reaction, and it is anti-that two-stage reaction area effectively extends contact of the ozone with pollutant
Between seasonable, the haptoreaction area of ozone and pollutant is increased, Ozone Gas Mass Transfer Efficiency and utilization rate effectively improve, and react higher
It imitates, more thoroughly.
(2) ozone dosage can be reduced, reagent cost is reduced.The utility model reactor effectively increases ozone utilization
Therefore rate can reduce ozone dosage under same treatment effect, to reduce process energy consumption and processing cost.
(3) it is discharged safer.In the utility model technique, pollutant obtains efficient, thorough degradation, degradation rate and mine
Change degree effectively improves, so that the bio-toxicity in reaction process is effectively controlled.Meanwhile because smelly under same treatment effect
Oxygen dosage is reduced, and (characteristic organic pollutants such as tetrabromobisphenol A ozonisation is also easy to produce ozonisation by-product in electronics industry waste water
Inorganic byproduct bromate) it is well controlled, be conducive to the control to waste water genetoxic.
Detailed description of the invention
The present invention will be further described with reference to the accompanying drawing.
Fig. 1 is novel, efficient ozone reactor plan view of the utility model；Wherein, 1- ozone generator；2- gas stream
Meter；3- microbubble aerator；4- catalytic ozonation stirring reactor；5- water pump；6- valve；7- guide shell；8- is held
Hold in the palm layer；9- catalytic filler；10- three-level agitating device；11- electric device；12- exhaust gas processing device；13- water outlet；14- sampling
Mouthful；15- observation panel；16- deflector.
Fig. 2 is traditional reactor and the utility model reactor to COD, TOC, TBBPA treatment effect figure.
Fig. 3 is traditional reactor and the utility model reactor under the conditions of COD, TOC, TBBPA removal rate are 100%
Need ozone dosage comparison diagram.
Fig. 4 is to be discharged acute, chronic bio-toxicity comparison diagram after traditional reactor and the utility model reactor reaction.
Specific embodiment
The utility model is described in further detail below with reference to embodiment and attached drawing, but the embodiment party of utility model
Formula is without being limited thereto.
Embodiment 1
A kind of novel, efficient ozone catalysis oxidation stirring reactor, the ozone reactor are from bottom to top divided into two-stage:
First order reaction zone includes aerator and guide shell；
Second level reaction zone includes supporting layer, catalytic filler and agitating device；
Wherein, the ozone that ozone generator (1) generates carries out the ozone catalytic oxygen after gas flowmeter (2) adjust gas velocity
Change in stirring reactor (4)；
In first order reaction zone, aerator (3) is located at ozone reactor bottom, preferably microbubble aerator,
Ozone reactor bottom is aerated using aerator (3), and organic chemical waste water enters anti-through flow pump (5) and valve (6)
Device (4) are answered, air-liquid is pre-mixed here, is then sufficiently mixed through guide shell (7) and interior circulation, extension air-liquid connect
Touch the reaction time；
In the reaction zone of the second level, the supporting layer (8) that ozone and waste water are passed through positioned at first order reaction zone top enters filling
The reaction zone of catalytic filler (9)；Meanwhile making positioned at the electric device of reactor head (11) drive three-level blender (10) smelly
Oxygen, waste water and catalytic filler are sufficiently mixed, deep contact catalysis oxidation, exhaust, effluent.
Wherein, the waste water enters subsequent work from the slave water outlet (13) for being located at reactor top after two-stage catalytic oxidation
In skill；The exhaust gas processing device (12) that exhaust gas enters positioned at reactor top is handled.
Wherein, it can be carried out from first order reaction zone and second level reaction zone thief hatch (14) is set in the reaction process
Sampling carries out coherent detection；Meanwhile air-liquid admixture can be in due course from being set to first order reaction zone in the reactor
Mouth (15) is observed.
Embodiment 2
(such waste water contains a large amount of inorganic and organic pollutants, as bromide fire retardant tetrabromo is double by taking electronics industry waste water as an example
Phenol A), through water analysis, in the actual waste water condition of water quality be respectively pH 2.5~4, COD 385mg/L, TOC 125mg/L,
TBBPA 1mg/L, acute toxicity 45TU, chronic toxicity 87TU are reacted using traditional column ozone reactor with the utility model
Device handles such industrial wastewater.
Wastewater treatment is carried out using the device of embodiment 1, wherein ozone dosage 4mg/L, wastewater pH 3.0, temperature
It is 30 DEG C, reaction time 1h,
The ozone that ozone generator generates enters reactor through gas flowmeter, and reactor bottom is arranged microbubble and is aerated dress
It sets, i.e. starting microbubble aeration, microbubble outlet speed are 0.8L/min at the beginning for reaction, and ozone bubbles are fog-like, increase
Effective contact area of ozone bubbles and pollutant；When starting aeration, most of ozone gas enters guide shell, and annular space ratio is
0.85, the gas velocity in guide shell is greater than its surrounding gas velocity, results in intermediate fluid density in this way and becomes smaller, and forms density contrast, pressure
Power is poor, so that air-liquid be made to spread around, downwards when flowing out guide shell, air-liquid flow direction, air-liquid flow direction is consistent,
Be first flowed up from guide shell bottom, then outward, flow downward to form circulation；In first order reaction zone, ozone and useless
Water acts on forming interior circulation flow-disturbing through guide shell, and the contact oxidation time extends, and pollutant obtains fully degraded or mineralising；
The supporting layer that ozone and waste water pass through positioned at first order reaction zone top, which enters second level reaction zone and is filled with catalysis, to be filled out
The reaction zone of material；Meanwhile three-level blender is driven to fill ozone, waste water and catalytic filler positioned at the electric device of reactor head
Divide mixing, deep contact catalysis oxidation, exhaust, effluent；
The catalytic filler is the lightweight of " active carbon+Nanoscale Iron ", compound catalytic filler, i.e. nano zero valence iron and nanometer
The mixture of iron oxide, wherein nano zero valence iron and the mass ratio of nano iron oxide are 2:1, partial size 4mm, preferably the filler ratio
Weight is 0.90.
The air-liquid residence time that catalytic ozonation stirs stranding formula reactor is 1h.
The mixing speed of three-grade electric agitating device is 6.5r/s.
It is as a result as follows using the specific removal effect of aforementioned processing methods:
Specific effect is shown in attached drawing 1, and traditional ozone reactor is to the waste water under identical ozone dosage and condition of water quality
The removal rate of COD, TOC and TBBPA are respectively 53%, 35% and 60%, and the utility model ozone reactor is by three indexs
Removal rate is improved to 98%, 85% and 100%, and pollutant obtains even mineralising of effectively degrading.
Specific effect is shown in attached drawing 2, when COD, TOC, TBBPA removal rate are 100%, compared to traditional reactor, originally
Utility model reactor ozone dosage can reduce 54.17%, 60.59%, 51.76%, and reagent cost is greatly saved.
Specific effect is shown in attached drawing 3, and under identical ozone dosage and condition of water quality, traditional reactor is discharged acute and chronic
Toxicity is still up to 13.5TU, 20.75TU, and the acute toxicity of the utility model ozone reactor water outlet it is up to standard (for 0.75TU,
Standard of drainage is < 1.0TU), chronic toxicity control is in 1.5TU hereinafter, acute and chronic bio-toxicity is significantly controlled.
Control effect of the 1 the utility model ozone reactor of table to ozonisation by-product bromate
Referring to the specific effect of subordinate list 1, when tetrabromobisphenol A concentration is 1.0mg/L in waste water, it is in ozone dosage range
Under the conditions of 1.0-20.0 mg/L, traditional ozone reactor generates bromate amount and increases to 100.5 μ g/L from 7.6 μ g/L, and this reality
With in novel ozone reactor without bromate generate.
Above-described embodiment is the preferable embodiment of the utility model, but the embodiments of the present invention is not by above-mentioned
The limitation of embodiment, it is made under other any spiritual essence and principles without departing from the utility model to change, modify, replacing
In generation, simplifies combination, should be equivalent substitute mode, is included within the protection scope of the utility model.
Claims (5)
1. a kind of catalytic ozonation stirring reactor, which is characterized in that the reactor is from bottom to top divided into two-stage:
First order reaction zone includes aerator and guide shell；
Second level reaction zone includes supporting layer, catalytic filler and agitating device；
Wherein, the ozone that ozone generator (1) generates carries out the catalytic ozonation after gas flowmeter (2) adjust gas velocity and stirs
It mixes in formula reactor (4)；
In first order reaction zone, aerator (3) is located at reactor bottom, is microbubble aerator, and reactor bottom is adopted
It is aerated with aerator (3), organic chemical waste water enters reactor (4) through flow pump (5) and valve (6), and air-liquid is herein
Place is pre-mixed, and is then sufficiently mixed through guide shell (7) and interior circulation, and the air-liquid haptoreaction time is extended；
In the reaction zone of the second level, ozone and waste water are filled with through supporting layer (8) entrance positioned at first order reaction zone top and urge
Change the reaction zone of filler (9)；Meanwhile positioned at the electric device of reactor head (11) drive three-level blender (10) make ozone,
Waste water and catalytic filler are sufficiently mixed, deep contact catalysis oxidation, exhaust, effluent.
2. reactor according to claim 1, which is characterized in that the waste water is after two-stage catalytic oxidation from positioned at reaction
The slave water outlet (13) on device top enters in subsequent technique.
3. reactor according to claim 1, which is characterized in that the vent gas treatment that exhaust gas enters positioned at reactor top fills
(12) are set to be handled.
4. reactor according to claim 1, which is characterized in that from being set to first order reaction zone and second level reaction zone
Thief hatch (14) is sampled carry out coherent detection.
5. reactor according to claim 1, which is characterized in that air-liquid admixture can be in due course from setting in the reactor
The observation panel (15) for being placed in first order reaction zone is observed.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108557985A (en) * | 2018-06-22 | 2018-09-21 | 哈尔滨工业大学（深圳） | A kind of catalytic ozonation stirring reactor and sewage water treatment method |
| CN111620434A (en) * | 2020-06-08 | 2020-09-04 | 中国石油化工股份有限公司 | Wastewater treatment device and method and application thereof |
| CN113354141A (en) * | 2021-06-01 | 2021-09-07 | 广西北投环保水务集团有限公司 | Negative-pressure ozone-sludge-based activated carbon catalytic oxidation sewage treatment device and treatment process thereof |
| CN110668552B (en) * | 2019-11-11 | 2023-05-26 | 南京大学盐城环保技术与工程研究院 | Ozone synergistic micro hydrogen peroxide catalytic device and method |
-
2018
- 2018-06-22 CN CN201820966494.2U patent/CN208916893U/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108557985A (en) * | 2018-06-22 | 2018-09-21 | 哈尔滨工业大学（深圳） | A kind of catalytic ozonation stirring reactor and sewage water treatment method |
| CN110668552B (en) * | 2019-11-11 | 2023-05-26 | 南京大学盐城环保技术与工程研究院 | Ozone synergistic micro hydrogen peroxide catalytic device and method |
| CN111620434A (en) * | 2020-06-08 | 2020-09-04 | 中国石油化工股份有限公司 | Wastewater treatment device and method and application thereof |
| CN113354141A (en) * | 2021-06-01 | 2021-09-07 | 广西北投环保水务集团有限公司 | Negative-pressure ozone-sludge-based activated carbon catalytic oxidation sewage treatment device and treatment process thereof |
| CN113354141B (en) * | 2021-06-01 | 2022-06-10 | 广西北投环保水务集团有限公司 | Negative-pressure ozone-sludge-based activated carbon catalytic oxidation sewage treatment device and treatment process thereof |
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