CN211111241U - Ozone is trace hydrogen peroxide solution catalytic unit in coordination - Google Patents
Ozone is trace hydrogen peroxide solution catalytic unit in coordination Download PDFInfo
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- CN211111241U CN211111241U CN201921937352.4U CN201921937352U CN211111241U CN 211111241 U CN211111241 U CN 211111241U CN 201921937352 U CN201921937352 U CN 201921937352U CN 211111241 U CN211111241 U CN 211111241U
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Abstract
The utility model discloses an ozone is trace hydrogen peroxide solution catalytic unit in coordination, including water inlet, intake pipe, gas-liquid buffer, the micropore aeration district that links to each other with the gas-liquid buffer, the catalytic reaction district that links to each other with the micropore aeration district and the tail gas absorption district and the outlet pipe that are linked together with the catalytic reaction district, the intake pipe includes the main intake pipe of being connected with the gas-liquid buffer and the pressure boost intake pipe that extends in the catalytic reaction district by the device extroversion, still be equipped with confined application of sample pipe in the pressure boost intake pipe, angle α between application of sample pipe and the pressure boost intake pipe is less than 90 degrees, the catalytic reaction district in the middle of set up with pressure boost intake pipe complex draft tube, micropore aeration district sets up micron pore path aeration board.
Description
Technical Field
The utility model belongs to the environmental protection field, more specifically say, relate to an ozone is trace hydrogen peroxide solution catalytic unit in coordination.
Background
Ozone is a high-efficiency strong oxidant, and has wide application in the field of wastewater treatment due to broad-spectrum reaction and mild reaction process. The catalytic ozonation technology is one of advanced oxidation technologies, can greatly reduce the selectivity of the ozonation process, improves the sewage treatment efficiency and the utilization rate of ozone, and has wide application in the field of deep degradation of difficultly-degraded wastewater. The catalytic ozonation is a novel ozonation method developed in recent years, wherein more intermediate products with strong oxidizing capacity, such as hydroxyl radical, are generated by ozone under the action of a catalyst to oxidize and decompose organic pollutants in water, the intermediate products have strong oxidizing capacity and no reaction selectivity, and high-stability and difficult-to-degrade organic matters which cannot be oxidized by ozone can be quickly oxidized and decomposed.
In order to improve the removal rate of refractory organic matters in wastewater, researches in recent years gradually turn to a synergistic catalytic system of ozone and hydrogen peroxide. The catalyst and ozone form a catalytic oxidation system to promote the ozone to decompose hydroxyl radicals, wherein hydrogen peroxide is added as an initiator to form the catalytic oxidation system with the ozone, so that the ozone can be promoted to decompose the hydroxyl radicals; meanwhile, as an oxidant, hydrogen peroxide is added into a reaction system, such as formed by active metal sites in a catalyst and alumina (M)n+the-Al) pi bond has strong electron-withdrawing capability, and is easy to generate a reaction system similar to Fenton to form a heterogeneous Fenton-like oxidation system, so that the decomposition of hydrogen peroxide is further promoted to generate hydroxyl radicalsThe compound is shown in the specification. The strong catalytic oxidation treatment is carried out on the wastewater, and the good removal effect is achieved on the organic matters which are high in stability and difficult to degrade in the wastewater.
The prior art of Chinese patent publication No. CN106882866A discloses a method for treating wastewater by hydrogen peroxide and ozone heterogeneous catalytic oxidation, which comprises the following steps: a. adding the wastewater into a reactor, adding a supported ozone catalytic oxidation heterogeneous catalyst, and adding a hydrogen peroxide solution for mixing; b. ozone is evenly introduced into the reactor in a micro-bubble form through a microporous titanium plate at the bottom of the reactor to carry out wastewater treatment reaction. The method for treating the wastewater by using the hydrogen peroxide and the ozone in the cooperation of heterogeneous catalytic oxidation generates more hydroxyl radicals, performs strong catalytic oxidation treatment on the wastewater, and has a good effect of removing high-stability and difficultly-degraded organic matters in the wastewater. According to the method, through the arrangement of the microporous titanium plate, ozone is uniformly introduced into the reactor in a microbubble form through the microporous titanium plate at the bottom of the reactor, so that three phases of ozone gas, hydrogen peroxide, wastewater and a catalyst are fully contacted, and the strong catalytic oxidation treatment of the wastewater is completed.
The prior art of Chinese patent publication No. CN104192981A discloses an activated carbon catalytic ozonation device and a sewage treatment process thereof, the device comprises a reaction tank, the reaction tank is sequentially divided into an upflow reaction zone, a downflow reaction zone and a separation zone from inside to outside through a guide cylinder, and the bottoms of the upflow reaction zone, the downflow reaction zone and the separation zone are communicated to form an activated carbon storage zone; the upflow reaction zone is internally provided with an ozone and water input device and is communicated with the top of the downflow reaction zone; an annular fluid director is arranged at the communicating position of the bottoms of the downflow reaction zone and the separation zone, at least one part of the bottom of the fluid director extends into the active carbon storage zone, and the part of the top of the fluid director, which is positioned below the separation zone, is provided with an inclined flow guide surface. The activated carbon catalytic ozonation device can enable activated carbon to be in a circulating fluidized state, increase the porosity of an activated carbon bed, and improve the catalytic reaction effect of ozone molecules and organic pollutants on the surface of the activated carbon, so that the catalytic ozonation capacity of the activated carbon is enhanced, the ozone utilization rate is improved, and the decontamination effect is improved.
The metal-loaded catalyst is used as an efficient ozone catalyst, the reaction process belongs to a gas-liquid-solid three-phase mixed reaction process, the reaction process is complex, the mass transfer rate can be improved through effective contact of the gas-liquid-solid three phases, the ozone reaction efficiency is improved, and the ozone oxidizability, the adsorption performance of the catalyst and the catalytic degradation performance can be effectively combined. Most of the current researches on the catalytic reaction of ozone are still focused on the preparation and improvement of the catalyst, the research on the reactor device is far from insufficient, and the current ozone reactor has the problems of low catalytic efficiency, low ozone utilization, difficulty in recycling the catalyst and the like, and is a factor for restricting the further development of the catalytic oxidation of ozone.
Disclosure of Invention
1. Problems to be solved
To the problem that improves current ozone and hydrogen peroxide solution concerted catalysis efficiency, the utility model provides an ozone is trace hydrogen peroxide solution catalytic unit and method in coordination, the device can effectively improve the mixing efficiency of ozone and hydrogen peroxide solution, further improves catalytic efficiency.
2. Technical scheme
In order to solve the above problem, the utility model discloses the technical scheme who adopts as follows:
a catalytic device for ozone and trace hydrogen peroxide comprises a water inlet, an air inlet pipe, a gas-liquid buffer area, a micropore aeration area connected with the gas-liquid buffer area, a catalytic reaction area connected with the micropore aeration area, a tail gas absorption area communicated with the catalytic reaction area and an water outlet pipe, wherein the air inlet pipe comprises a main air inlet pipe connected with the gas-liquid buffer area and a pressurizing air inlet pipe extending from the outside of the device to the inside of the catalytic reaction area, the pressurizing air inlet pipe is further provided with a closed sample adding pipe, the angle α between the sample adding pipe and the pressurizing air inlet pipe is smaller than 90 degrees, a guide cylinder matched with the pressurizing air inlet pipe is arranged in the middle of the catalytic reaction area, and the micropore aeration area is provided with a micron pore channel aeration plate.
The air inlet pipe comprises a main air inlet pipe and a pressurizing air inlet pipe, so that ozone enters in two ways, namely enters the catalytic reaction zone from the lower part of the catalytic reaction zone in a micro-bubble mode and enters from the inside of the catalytic reaction zone in a pressurizing airflow mode, and the catalyst and air water are fully and uniformly mixed through the matching of the guide cylinder and the air inlet pressure of the pressurizing air inlet pipe; simultaneously, set up the application of sample pipe on the pressure boost intake pipe, can make the hydrogen peroxide solution of adding change under the negative pressure of gas formation in the pressure boost intake pipe and get into the catalytic reaction district to gaseous stream drives down abundant and catalytic reaction district's interior gas, liquid, solid three-phase mixture, improves catalysis efficiency in coordination.
Besides the above-mentioned continuous water inlet and outlet mode, it also can adopt sequencing batch water inlet and outlet mode.
Preferably, the angle between the sampling pipe and the supercharging air inlet pipe is not less than 30 degrees and not more than α degrees and not more than 60 degrees, because the gas pressure in the supercharging air inlet pipe is large, the angle arranged between the sampling pipe and the supercharging air inlet pipe can directly influence the mixing efficiency of the hydrogen peroxide and the ozone, and the hydrogen peroxide can be rapidly and fully mixed with the ozone under the action of negative pressure within the angle range of 30 degrees to 60 degrees, so that the efficiency of the synergetic catalysis is improved.
Preferably, the tail end of the supercharging air inlet pipe is positioned on the same straight line with the sampling pipe. Under the condition, the added hydrogen peroxide is more fully mixed in gas, liquid and solid phases.
Preferably, the intake pressure ratio of the main intake pipe to the supercharged intake pipe satisfies: (5-50): 1. When the pressure of the main air inlet pipe and the pressure of the pressurizing air inlet pipe are in the ratio range, the catalyst in the catalytic reaction area moves upwards along the inner wall of the guide cylinder under the action of the lower microporous airflow and the upper pressurizing pipe airflow, and then descends after reaching the upper end of the guide cylinder, so that hydrogen peroxide added from the sample adding port is more fully mixed with the catalyst under the drive of the ozone airflow, and the catalytic efficiency is improved.
Preferably, the size of the pore of the micron pore aeration plate is gradually reduced along the radial direction from the periphery to the center, and the micron pore aeration plate is matched with the guide cylinder and the pressurizing air inlet pipe to form an ascending area, a descending area, an advection I area and an advection II area. The micron pore channel aeration plate is arranged to enable an advection area to form an advection I area and an advection II area, airflow of the advection I area above the periphery (large pores) of the micron pore channel aeration plate is larger than airflow of the advection II area in the central area (small pores) of the micron pore channel aeration plate, when the micron pore channel aeration plate is used with a guide cylinder in a matching mode, a catalyst in the advection II area enters an ascending area along the guide cylinder under the action of airflow of a pressurizing air inlet pipe, then the catalyst falls into the advection I area through a descending area and then easily enters the advection II area, and then the catalyst enters the ascending area through the advection II area to enable three phases of.
Preferably, the pore size of the microporous aeration plate is linearly reduced or stepwise reduced from the periphery to the center.
Preferably, the pore size of the micron pore aeration plate is 20-500 μm. The pore size setting can form bubbles with different sizes in the convection air flow to cause the asymmetric balance of the air pressure of the space around the bubbles, thereby realizing the specific air flow orbit of the air flow in a certain form in the guide shell and realizing the reflux state of the catalyst and the gas-liquid.
Preferably, the height of the guide cylinder in the catalytic reaction zone and the aperture reduction mode of the micron pore aeration plate are adjusted according to the filling height of the catalyst, the gas pressure of the supercharging gas inlet pipe and the gas pressure of the main gas inlet pipe, so that the catalyst flows from the advection I zone to the advection II zone in the advection zone.
Preferably, the height h of the lower end of the guide shell from the micron pore channel aeration plate1The height h of the lower end of the pressurizing air inlet pipe from the micron pore channel aeration plate2The relationship with the height h of the catalytic reaction zone filled with catalyst is: h is2:h＝1:(0.5～4)，h1:h＝1:(0.6～8)。
Preferably, the volume ratio of the guide shell to the catalytic reaction zone is 1 (4-8), the diameter of the guide shell is 1/4-4/5 of the diameter of the catalytic reaction zone, and the guide shell is arranged according to the size change of the catalyst.
Preferably, the draft tube is made of inorganic glass or organic glass and is transparent.
Preferably, the thickness of the micron pore channel aeration plate is 2-4 cm.
Preferably, the height-diameter ratio of the catalytic reaction zone is (2-8): 1.
Preferably, the tail gas absorption area introduces gas flow into a tail gas absorption tower/tank/pool/barrel through a top conduit, the tail gas absorption tower/tank/pool/barrel is provided with a closed water sealing device and a suck-back prevention device, and tail gas is absorbed and discharged through reaction.
The utility model also provides a method for adopting above-mentioned ozone in coordination with trace hydrogen peroxide solution catalytic unit to handle waste water, including following step:
1) the wastewater enters a gas-liquid buffer area through a water inlet pipe, ozone is introduced into the gas-liquid buffer area by opening a main air inlet valve, and the catalyst is filled when the wastewater containing ozone enters a catalytic reaction area through a micropore aeration area;
2) after the catalyst is filled, a pressurizing air inlet valve is opened, and hydrogen peroxide is added from the sample adding port by using an injector;
3) hydrogen peroxide enters the pressurizing air inlet pipe along the sample adding pipe, and the gas-liquid-solid three phases are uniformly mixed under the drive of the ozone airflow;
4) controlling the hydraulic retention time of the catalytic reaction area, and enabling the treated water to flow out through a water outlet.
Preferably, the hydraulic retention time in the step 4) is 5-100 min.
Preferably, the adding mass of the hydrogen peroxide in the step 2) is 0.01-0.2 per mill of the mass of the wastewater. The hydrogen peroxide assists the catalytic oxidation process of the ozone, and the generation of hydroxyl radicals in the spontaneous reaction process of the hydrogen peroxide is utilized to promote the reaction process of the ozone hydroxyl radicals, reduce the excessive consumption of easily degradable organic matters on the ozone, improve the ozone utilization rate in the reaction process, and form a double oxidation coupling center to accelerate the mineralization and decomposition of the organic matters.
Preferably, the ozone is derived from oxygen passing through an ozone generator, the concentration of the ozone is set to be 10-80%, and the source of the ozone is an oxygen cylinder or liquid oxygen.
Preferably, a water inlet pump is arranged on the water inlet pipe, and the water inlet pump is a peristaltic pump or a diaphragm metering pump.
Preferably, the wastewater enters the main body of the reaction device from the water inlet, and the water inlet mode can be continuous flow water inlet or intermittent water inlet; the treated water is discharged from the first water outlet or the second water outlet, and the position of the first water outlet or the second water outlet can be changed according to the water quantity.
Preferably, the size of the catalyst is 0.5-6 mm, and the adding proportion of the catalyst is 5-50% of the volume of the catalytic reaction zone.
3. Advantageous effects
Compared with the prior art, the beneficial effects of the utility model are that:
(1) the utility model discloses a set up confined application of sample pipe in the pressure boost intake pipe, introduced the supplementary ozone catalysis process of hydrogen peroxide solution, can make the hydrogen peroxide solution of adding change under the negative pressure that the gas formation in the pressure boost intake pipe gets into the catalytic reaction district, and fully mix with gas, liquid, solid three-phase in the catalytic reaction district under the air current drives, improved the formation rate of hydroxyl free radical, increased reaction efficiency, also improved the concerted catalysis efficiency;
(2) the utility model discloses well micron pore aeration board is along radially reducing gradually from the pore size at periphery to center, cooperates the structure and the air current pressure boost pipeline of draft tube, makes catalyst descend to the advection district after rising along the draft tube, can flow from advection I district to advection II district under the condition that does not use the divertor, and this setting has effectively increased three-phase backward flow efficiency and gas-liquid-solid contact rate, has improved the utilization ratio and the three-phase mass transfer effect of ozone;
(3) the device of the utility model can adjust the height of the draft tube in the catalytic reaction zone and the aperture reduction mode of the micron pore aeration plate according to the catalyst filling height, the gas pressure of the supercharging gas inlet pipe and the gas pressure of the main gas inlet pipe during actual treatment, so that the catalyst flows from the advection I zone to the advection II zone in the advection zone;
(4) the utility model discloses an adopt ozone in coordination with trace hydrogen peroxide solution catalytic unit to handle technology of waste water, opening main intake pipe valve and letting in ozone to the gas-liquid buffer, the waste water that contains ozone just begins to load the catalyst when micropore aeration district gets into the catalytic reaction zone, makes the catalyst be in under the state that flows all the time, can realize the solid three-phase intensive mixing of gas-liquid rapidly, is favorable to improving ozone machine hydrogen peroxide solution efficiency in coordination with catalysis more.
Drawings
FIG. 1 is a schematic view of the catalytic device of the present invention, in which ozone is cooperated with trace hydrogen peroxide solution;
in the figure:
100. a water inlet pipe; 110. a water inlet;
200. an air inlet pipe; 210. a main air inlet pipe; 211. a primary air intake valve; 220. a supercharging air inlet pipe; 221. a boost intake valve; 230. a sample adding pipe; 240. a sample addition port; 250. the tail end of the supercharging air inlet pipe; 260. a pressurized air outlet; 270. an air inlet;
300. a gas-liquid buffer zone;
400. a microporous aeration zone; 410. a micron pore aeration plate;
500. a catalytic reaction zone; 510. a draft tube; 520. a guide shell bearing plate; 530. a rise region; 540. a descending zone; 550. a advection area; 551. an advection I zone; 552. advection II area; 560. a catalyst loading port; 570. a catalyst;
600. a tail gas absorption zone; 610. a tail gas absorption pipe; 620. a liquid seal device;
700. a water outlet pipe; 710. a first water outlet; 720. a second water outlet.
Detailed Description
The present invention will be further described with reference to the following specific embodiments.
A catalytic device for ozone and trace hydrogen peroxide comprises a water inlet 110, an air inlet pipe 200, a gas-liquid buffer area 300, a micropore aeration area 400 connected with the gas-liquid buffer area 300, a catalytic reaction area 500 connected with the micropore aeration area 400, a tail gas absorption area 600 communicated with the catalytic reaction area 500 and a water outlet pipe 700, wherein the air inlet pipe 200 comprises a main air inlet pipe 210 connected with the gas-liquid buffer area and a pressurizing air inlet pipe 220 extending from the outside of the device to the inside of the catalytic reaction area 500, the pressurizing air inlet pipe is further provided with a closed sample adding pipe, an angle α between the sample adding pipe and the pressurizing air inlet pipe is smaller than 90 degrees, a guide cylinder 510 matched with the pressurizing air inlet pipe 220 is arranged in the middle of the catalytic reaction area 500, the micropore aeration area 400 is provided with a micron pore aeration plate 410, the pore size of the micron aeration plate 410 is gradually reduced from the periphery to the center, the micron pore plate 410 is matched with the guide cylinder 510 and the pressurizing air inlet pipe 220 to form an ascending area 530, a descending area.
The micron pore aeration plate 410 is arranged to enable the advection area 550 to form an advection I area 551 and an advection II area 552, the airflow of the advection I area 551 above the periphery (large pore) of the micron pore aeration plate 410 is larger than the airflow of the advection II area 552 in the central area (small pore) of the micron pore aeration plate 410, when the micron pore aeration plate is matched with the guide cylinder 510 for use, the catalyst in the advection II area 552 enters the ascending area 530 along the guide cylinder 510 under the action of the airflow of the pressurized air inlet pipe 220, then falls into the advection I area 551 through the descending area 540, enters the advection II area 552 under the action of the atmospheric flow, and then enters the ascending area 530 through the advection II area 552, so that the gas, the liquid and the solid phases are effectively.
The COD concentration of the initial wastewater used in the following examples is 120-350 mg/L.
Example 1
As shown in fig. 1, in the present embodiment, a closed sample adding pipe 230 is disposed on the supercharged air intake pipe 220, an angle α between the sample adding pipe 230 and the supercharged air intake pipe 220 is 45 degrees, and the end of the supercharged air intake pipe 220 and the sample adding pipe 230 are located on the same straight line.
In the embodiment, the size of the pore of the micron pore aeration plate 410 is linearly reduced from 200 μm to 50 μm from the periphery to the center;
the thickness of the micron pore aeration plate 410 is set to be 2 cm;
the height-diameter ratio of the reactor is selected to be 4:1, the volume ratio of the guide shell 510 to the catalytic reaction zone 500 is 1:4, and the diameter of the guide shell 510 is 4/5 of the diameter of the catalytic reaction zone;
the height h of the lower end of the guide shell 510 from the micron pore aeration plate1The height h of the lower end of the pressurizing air inlet pipe 220 from the micron pore aeration plate 4102The relationship to the 570 height h of the catalytic reaction zone 500 loaded with catalyst is: h is2:h＝1:2，h1:h＝1:1。
The method for treating the wastewater by adopting the ozone and trace hydrogen peroxide synergistic catalysis device comprises the following steps:
1) the wastewater enters the gas-liquid buffer zone 300 through the water inlet pipe 100, the valve of the main air inlet pipe 210 is opened to introduce ozone (the concentration of ozone accounts for 40%) into the gas-liquid buffer zone 300, and when the wastewater containing ozone enters the catalytic reaction zone 500 through the microporous aeration zone 400, the catalyst 570 starts to be filled;
2) after the catalyst 570 is filled, the valve of the supercharged air inlet pipe 220 is opened, and the air inlet pressure ratio of the main air inlet pipe 210 to the supercharged air inlet pipe 220 is 5: 1; adding hydrogen peroxide (the addition amount is 0.05 per mill of the wastewater) from the sample adding port 240 by using an injector;
3) the uniformly mixed gas-liquid-solid three phases flow from the advection II area 552 to the rising area 530 and the falling area 540, then fall into the advection I area 551, enter the advection II area 552 under the action of atmospheric flow of the advection I area 551, and then enter the rising area 530 from the advection II area 552;
4) controlling the 500-water retention time of the catalytic reaction zone to be 60min, and enabling the treated water to flow out through a water outlet.
For the water inlet mode, a continuous water inlet mode can be adopted, a conduit is arranged from the water inlet 110, and the wastewater is pumped into the gas-liquid buffer area 300 through a peristaltic pump or a diaphragm metering pump;
the ozone is guided by the ozone generator through the air inlet pipe 200 and enters the gas-liquid buffer zone 300 through the main air inlet pipe 210; the gas-liquid is mixed for the first time in the gas-liquid buffer zone 300; the uniformly mixed gas-liquid rises with the water flow and reaches the micro-porous aeration plate 410, and after passing through the micro-porous aeration plate 410, the ozone is split into bubbles with smaller size and relatively more quantity; a large amount of tiny bubbles carry the wastewater to generate an ozone catalytic oxidation reaction in the catalytic reaction zone 500, and the guide cylinder 510 arranged at the part can better guide the catalyst, ozone molecules and wastewater to gas, liquid and solid phases so as to be more fully mixed; adding 0.05 thousandth of hydrogen peroxide from the sample inlet 240 according to the mass proportion of the wastewater, sealing the sample inlet 240 by adopting a rubber sealing plug, adding the hydrogen peroxide by adopting an injector during sample addition, and supplementing the process of forming hydroxyl radicals with ozone to further promote the deep degradation of organic matters; after the reaction, the wastewater can be discharged out of the device through the first water outlet 710 or the second water outlet 720, and after the reaction, the redundant gas is absorbed through the tail gas absorption area 600, so that no ozone is discharged in the tail gas.
The size of the catalyst 570 is 1-2 mm, and the loading amount is 20% of that of the catalytic reaction zone 500;
the process set according to the scheme is used for deeply treating the effluent of the centralized secondary sedimentation tank of a certain chemical plant, and when the volume of a treated water sample is set to be 1L, the removal rate of COD (chemical oxygen demand) reaches 65.1% when the ozone is subjected to catalytic reaction for 1 h.
Comparative example 1
The other conditions are the same as the embodiment 1, a reactor with the guide shell 510, the supercharging air inlet pipe 220 and the hydrogen peroxide sample adding pipe 230 is not arranged, the pore size of the micron pore aeration plate 410 is uniform and 500 mu m, namely, only ozone is adopted for catalytic treatment from the lower part, when the hydrogen peroxide is not added, the COD removal rate is 25.3 percent when the ozone is subjected to catalytic reaction for 1 hour,
comparative example 2
The other conditions are the same as the embodiment 1, a reactor with a guide shell 510, a pressurized air inlet pipe 220 and a uniform pore size of the micron pore aeration plate 410 is arranged, namely, the main air inlet pipe 210 is combined with the pressurized air inlet pipe 220 and the guide shell 510, a hydrogen peroxide solution sample adding pipe 230 is not arranged, when the hydrogen peroxide solution is not added, the conventional ozone catalytic oxidation is carried out by adopting the reactor, and the COD removal rate is 35.7% when the ozone catalytic reaction is carried out for 1 hour.
Comparative example 3
The other conditions are the same as those of the embodiment 1, only hydrogen peroxide is additionally added, and the COD removal rate reaches 56.9 percent when the ozone is subjected to catalytic reaction for 1 hour.
Comparative example 4
The other conditions are the same as the example 1, but the pore size of the micron pore aeration plate 410 is uniform 500 μm, ozone catalytic oxidation is adopted, hydrogen peroxide with the volume of 0.5 per mill of the water sample is added, and the COD removal rate reaches 62.7% after the ozone catalytic reaction is carried out for 1 hour.
Example 2
In this embodiment, as shown in fig. 1, a closed sample adding pipe 230 is disposed on the supercharged air intake pipe 220, an angle α between the sample adding pipe 230 and the supercharged air intake pipe 220 is 60 degrees, and the end of the supercharged air intake pipe 220 and the sample adding pipe 230 are located on the same straight line.
In the embodiment, the sizes of the pore channels of the micron pore channel aeration plate 410 are reduced in a step-like manner, the pore channel of the area corresponding to the advection I area 551 is 500 micrometers, and the pore channel of the area corresponding to the advection II area 552 is 100 micrometers;
the thickness of the micron pore channel aeration plate is set to be 3 cm;
the height-diameter ratio of the reactor is selected to be 8:1, the volume ratio of the guide shell to the catalytic reaction zone is 1:6, and the diameter of the guide shell is 1/2 of that of the catalytic reaction zone;
the height h of the lower end of the guide cylinder from the micron pore channel aeration plate1The height h of the lower end of the pressurizing air inlet pipe from the micron pore channel aeration plate2The relationship with the height h of the catalytic reaction zone filled with catalyst is: h is2:h＝1:0.5，h1:h＝1:0.6。
The air inlet pressure ratio of the main air inlet pipe to the supercharging air inlet pipe is 20: 1.
The method for treating the wastewater by adopting the ozone and trace hydrogen peroxide synergistic catalysis device comprises the following steps:
1) the wastewater enters the gas-liquid buffer zone 300 through the water inlet pipe 100, ozone (with the concentration of 80%) is introduced into the gas-liquid buffer zone 300 by opening the valve of the main air inlet pipe 210, and the catalyst begins to be filled when the wastewater containing ozone enters the catalytic reaction zone 500 through the microporous aeration zone 400;
2) after the catalyst is filled, a valve of a pressurizing air inlet pipe 220 is opened, and hydrogen peroxide (the addition amount is 0.2 per mill of the mass of the wastewater) is added from a sample adding port 240 by using an injector;
3) the uniformly mixed gas-liquid-solid three phases flow from the advection II area 552 to the rising area 530 and the falling area 540, then fall into the advection I area 551, enter the advection II area 552 under the action of atmospheric flow of the advection I area 551, and then enter the rising area 530 from the advection II area 552;
4) controlling the hydraulic retention time of the reaction zone to be 5min, and enabling the treated water to flow out through a water outlet.
The size of the catalyst is 2-4 mm, and the loading amount is 25% of that of the catalytic reaction zone;
the process set according to the scheme is used for carrying out advanced treatment on effluent of the centralized secondary sedimentation tank of a certain chemical plant, and when the volume of a treated water sample is set to be 10L, the removal rate of COD (chemical oxygen demand) reaches 58.2% when the ozone is subjected to catalytic reaction for 1 h.
Example 3
In this embodiment, a closed sample adding pipe 230 is disposed on the supercharged air inlet pipe 220, an angle α between the sample adding pipe 230 and the supercharged air inlet pipe 220 is 30 degrees, and the end of the supercharged air inlet pipe 220 and the sample adding pipe 230 are located on the same straight line.
In the embodiment, the sizes of the pore channels of the micron pore channel aeration plate 410 are reduced in a step-like manner, the pore channel of the area corresponding to the advection I area 551 is 100 micrometers, and the pore channel of the area corresponding to the advection II area 552 is 20 micrometers;
the thickness of the micron pore channel aeration plate is set to be 4 cm;
the height-diameter ratio of the reactor is selected to be 2:1, the volume ratio of the guide shell to the catalytic reaction zone is 1:8, and the diameter of the guide shell is 1/4 of that of the catalytic reaction zone;
the height h of the lower end of the guide cylinder from the micron pore channel aeration plate1The height h of the lower end of the pressurizing air inlet pipe from the micron pore channel aeration plate2The relationship with the height h of the catalytic reaction zone filled with catalyst is: h is2:h＝1:4，h1:h＝1:8。
The air inlet pressure ratio of the main air inlet pipe to the supercharging air inlet pipe is 50: 1.
The method for treating the wastewater by adopting the ozone and trace hydrogen peroxide synergistic catalysis device comprises the following steps:
1) the wastewater enters the gas-liquid buffer zone 300 through the water inlet pipe 100, the valve of the main air inlet pipe 210 is opened to introduce ozone (with the concentration of 10%) into the gas-liquid buffer zone 300, and when the wastewater containing ozone enters the catalytic reaction zone 500 through the microporous aeration zone 400, the catalyst starts to be filled;
2) after the catalyst is filled, a valve of a pressurizing air inlet pipe 220 is opened, and hydrogen peroxide (the addition amount is 0.01 per mill of the mass of the wastewater) is added from a sample adding port 240 by using an injector;
3) the uniformly mixed gas-liquid-solid three phases flow from the advection II area 552 to the rising area 530 and the falling area 540, then fall into the advection I area 551, enter the advection II area 552 under the action of atmospheric flow of the advection I area 551, and then enter the rising area 530 from the advection II area 552;
4) controlling the hydraulic retention time of the reaction zone to be 100min, and enabling the treated water to flow out through a water outlet.
The size of the catalyst is selected to be 2-6 mm, and the loading amount is 25% of that of the catalytic reaction zone;
the process set according to the scheme is used for carrying out advanced treatment on effluent of the centralized secondary sedimentation tank of a certain chemical plant, and when the volume of a treated water sample is set to be 5L, the removal rate of COD (chemical oxygen demand) reaches 55.1% when the ozone is subjected to catalytic reaction for 1 hour.
The above embodiment is only the preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above embodiment, for example, the angle α between the sampling tube 230 and the supercharging inlet tube 220 can also be other values between 0-90 °, or the combination of various forms of the scheme in embodiments 1-3, and any other changes, modifications, substitutions and combinations that do not depart from the spirit and principle of the present invention should be equivalent alternatives, all within the protection scope of the present invention.
Claims (7)
1. The ozone-trace hydrogen peroxide synergistic catalytic device is characterized by comprising an air inlet pipe (200), a gas-liquid buffer area (300), a micropore aeration area (400) connected with the gas-liquid buffer area (300) and a catalytic reaction area (500) connected with the micropore aeration area (400), wherein the air inlet pipe (200) comprises a main air inlet pipe (210) connected with the gas-liquid buffer area (300) and a pressurizing air inlet pipe (220) extending from the outside of the device to the inside of the catalytic reaction area (500), a closed sample adding pipe (230) is arranged on the pressurizing air inlet pipe (220), an angle α between the sample adding pipe (230) and the pressurizing air inlet pipe (220) is smaller than 90 degrees, a guide cylinder (510) matched with the pressurizing air inlet pipe (220) is arranged in the middle of the catalytic reaction area (500), and a micron pore channel aeration plate (410) is arranged in the micropore aeration area (400).
2. The ozone-assisted trace hydrogen peroxide solution catalytic device as claimed in claim 1, wherein an angle between the sample adding pipe (230) and the pressurized air inlet pipe (220) is 30 degrees to α degrees and 60 degrees.
3. The ozone and trace hydrogen peroxide synergistic catalysis device as claimed in claim 2, wherein the tail end of the pressurized air inlet pipe (220) and the sample adding pipe (230) are located on the same straight line.
4. The ozone and trace hydrogen peroxide synergistic catalysis device as claimed in claim 1, wherein the air inlet pressure ratio of the main air inlet pipe (210) to the supercharging air inlet pipe (220) is (5-50): 1.
5. The ozone-assisted trace hydrogen peroxide solution catalytic device according to claim 1, wherein the pore size of the micron pore aeration plate (410) is gradually reduced along the radial direction from the periphery to the center, and the micron pore aeration plate, the guide cylinder (510) and the pressurized air inlet pipe (220) are matched to form an ascending area (530), a descending area (540), an advection I area (551) and an advection II area (552), and the advection I area (551) and the advection II area (552) form an advection area (550).
6. The ozone and trace hydrogen peroxide synergistic catalysis device as claimed in claim 5, wherein the pore size of the micron pore aeration plate (410) is 20-500 μm.
7. The ozone-cooperated micro hydrogen peroxide solution catalytic device as claimed in claim 5 or 6, wherein the height of the guide cylinder (510) in the catalytic reaction zone (500) and the aperture reduction mode of the micron pore aeration plate (410) are adjusted according to the catalyst loading height, the gas pressure of the pressurized gas inlet pipe (220) and the gas pressure of the main gas inlet pipe (210), so that the catalyst flows from the advection I zone (551) to the advection II zone (552) in the advection zone (550).
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