Wastewater multi-effect catalytic oxidation treatment device
By designing a multi-effect catalytic oxidation treatment device combining hydrogen peroxide and ozone, and using ultrasonic accelerated reactions, the problems of low efficiency and high cost in treating high-concentration organic wastewater are solved, and efficient, low-cost and long-life wastewater treatment effects are achieved.
Patent Information
- Application Number
- CN202421550336.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-03
- Publication Date
- 2025-04-25
- Estimated Expiration
- 2034-07-03
AI Technical Summary
The existing Fenton catalytic oxidation and ozone catalytic oxidation processes have their own advantages and disadvantages when treating high-concentration organic wastewater, and lack a treatment device that has both high efficiency, low cost and long life.
A wastewater multi-effect catalytic oxidation treatment device is designed, including a catalytic reactor, hydrogen peroxide storage tank, ultrasonic generator, exhaust gas destroyer and ozone generator. Through a multi-effect catalytic oxidation technology combining hydrogen peroxide and ozone, ultrasonic waves are used to accelerate the reaction mass transfer efficiency to avoid ineffective decomposition of oxidants.
It realizes efficient oxidation and degradation of high-concentration organic wastewater, reduces treatment costs, extends the service life of the catalyst, and improves the treatment depth.
Smart Images
Figure CN222795305U_ABST
Abstract
Description
Technical Field
[0001] The utility model relates to the technical field of wastewater treatment devices, in particular to a wastewater multi-effect catalytic oxidation treatment device. Background Art
[0002] Most of the industrial wastewater generated by the chemical industry contains difficult-to-degrade organic matter. Refractory organic matter has large molecular weight, high toxicity, and complex structural components. The degradation effect of general microorganisms on it is minimal. Therefore, physical and chemical methods are often used for pretreatment before biochemical treatment to improve the biodegradability of water.
[0003] Both Fenton catalytic oxidation and ozone catalytic oxidation use solid-phase catalysts to catalyze oxidants to produce free radicals to oxidize organic matter in wastewater, and neither produces secondary pollution. Both are new green oxidation processes, but each has its own advantages and disadvantages in the treatment of wastewater containing high concentrations of organic matter.
[0004] For Fenton catalytic oxidation, the advantage is that the amount of oxidant (hydrogen peroxide) required to be added when treating high-concentration organic wastewater is less than that of ozone. The disadvantage is that hydrogen peroxide cannot be added in unlimited quantities. This is because organic acids are easily produced during the catalytic oxidation of organic matter by hydrogen peroxide. Organic acids react with the catalytic components (transition metal oxides) in the solid-phase catalyst, resulting in the loss of effective components and thus the deactivation of the catalyst. Therefore, for the Fenton catalytic oxidation process, no matter how high the organic content in the treated wastewater is, the amount of oxidant hydrogen peroxide added cannot exceed a certain limit, otherwise the catalyst loses its function after the catalytic components of the catalyst are dissolved.
[0005] For ozone catalytic oxidation, the advantage is that the pH of the reaction process always remains in a neutral environment, the components of the catalyst are not lost, and the catalyst will not be deactivated. The disadvantage is that the amount of ozone required to treat high-concentration organic wastewater is relatively large, resulting in high treatment costs. At the same time, the investment cost of the ozone generator is also very high, and the half-life of ozone in wastewater is only about 20 minutes at normal temperature and pressure. The mass transfer efficiency of the ozone catalytic oxidation process is relatively slow, resulting in a large amount of ozone being ineffectively decomposed into oxygen and unable to form hydroxyl radicals to oxidize organic matter, resulting in low treatment efficiency of the ozone catalytic oxidation process for treating high-organic wastewater.
[0006] Therefore, it is necessary to study a wastewater treatment device that can combine the advantages of Fenton catalytic oxidation and ozone catalytic oxidation devices while avoiding their disadvantages. Utility Model Content
[0007] The technical problem to be solved by the utility model is to provide a wastewater multi-effect catalytic oxidation treatment device which has the characteristics of high efficiency, low cost and long life when treating high-concentration organic wastewater.
[0008] The utility model discloses a wastewater multi-effect catalytic oxidation treatment device, comprising a catalytic reactor, a hydrogen peroxide storage tank, an ultrasonic generator, a tail gas destroyer and an ozone generator; a catalytic oxidation reaction section is arranged in the middle of the catalytic reactor, an overflow weir is arranged above the catalytic oxidation reaction section, a support plate is arranged below the catalytic oxidation reaction section, titanium aeration disks are distributed on the upper surface of the support plate, and the titanium aeration disks are connected to the ozone generator; the upper and lower ends of the catalytic oxidation reaction section are wire meshes, a wire mesh inner cylinder body of the same height is arranged in the middle, a common catalyst is filled between the outer wall of the catalytic oxidation reaction section and the wire mesh inner cylinder body, an ultrasonic probe is arranged inside the wire mesh inner cylinder body, and the ultrasonic probe is connected to the ultrasonic generator; the bottom water inlet of the catalytic reactor is connected to the water inlet pipeline and the hydrogen peroxide storage tank, the overflow weir water outlet is connected to the water outlet pipe, and the top gas outlet is connected to the tail gas destroyer.
[0009] Preferably, a hydrogen peroxide dosing pump is provided on the pipeline connecting the hydrogen peroxide storage tank and the bottom water inlet of the catalytic reactor. The hydrogen peroxide storage tank is made of opaque material, and the hydrogen peroxide dosing pump is a metering pump, which can control the amount of hydrogen peroxide added at any time.
[0010] Preferably, a water inlet pump and a flow meter are provided on the water inlet pipeline.
[0011] Preferably, the catalytic reactor is a cylindrical structure with a height-to-diameter ratio of 4-6:1, and the outer wall is made of stainless steel or other corrosion-resistant materials.
[0012] Preferably, the wire mesh inner cylinder structure has a diameter that is 1 / 4-1 / 2 of the diameter of the outer cylinder of the catalytic reactor.
[0013] Preferably, the mesh inner cylinder and mesh have apertures smaller than the particle size of the common catalyst, so that wastewater can pass through but the common catalyst cannot. The mesh inner cylinder and mesh are made of stainless steel or other corrosion-resistant materials.
[0014] Preferably, the common catalyst is a cylindrical structure with a diameter of 4-6 cm and a length of 2-4 cm. It can use coal-made columnar activated carbon with an iodine value ≥ 800 as a carrier, and load metal oxides of four components of manganese, copper, iron and cobalt as catalytic components. The content of the catalytic components (calculated as oxides) is 1.0-5.0% of the total mass of the carrier.
[0015] Preferably, the number of the ultrasonic probes is 1-5, and during operation, the ultrasonic density is maintained at 0.5-5.0w / cm 2 between.
[0016] Preferably, the ozone generator uses air as a gas source, the ozone concentration is 120-150 mg / L, the outlet pressure is 0.1 MPa, and the molar ratio of ozone dosage to COD removal is generally maintained at 1:1.
[0017] The working process of the wastewater multi-effect catalytic oxidation treatment device is as follows:
[0018] The wastewater to be treated is pressurized by the water inlet pump and then enters the bottom of the catalytic reactor through the flow meter. At the same time, the hydrogen peroxide in the hydrogen peroxide storage tank is metered by the hydrogen peroxide dosing pump and quantitatively mixed into the water inlet pipeline and enters the bottom of the catalytic reactor with the water inlet. The wastewater mixed with hydrogen peroxide rises from the bottom of the catalytic reactor and gradually immerses the common catalyst and ultrasonic probe. The ozone generated by the ozone generator is released through the titanium aeration plate through the pipeline. A small part of the ozone dissolves into the wastewater and enters the common catalyst bed to participate in the catalytic reaction. Another part of the undissolved ozone forms bubbles to stir and mix the wastewater. Ozone and hydrogen peroxide are used to treat the wastewater under the action of the common catalyst. The organic matter in the wastewater is oxidized and degraded. At the same time, the sound wave vibration generated by the ultrasonic probe accelerates the mass transfer efficiency of the catalytic reaction, effectively shortens the reaction time and avoids the ineffective decomposition of the oxidant, thereby improving the reaction efficiency. At the same time, the addition of ultrasound also has a cleaning effect on the mesopore blockage of the public catalyst by the colloid in the wastewater, so the addition of ultrasound avoids the service life of the public catalyst from being reduced due to blockage. The treated wastewater overflows from the outlet pipe through the overflow weir set at the upper end of the catalytic reactor, and the reacted gas (oxygen and a small amount of ozone) enters the exhaust gas destroyer through the outlet for treatment and then is discharged.
[0019] Compared with the prior art, the utility model has the following beneficial effects:
[0020] (1) The utility model of the wastewater multi-effect catalytic oxidation treatment device is provided with a wire mesh inner cylinder and an ultrasonic probe inside the catalytic reactor, which not only enhances the mass transfer efficiency of the catalytic oxidation reaction and shortens the reaction time, but also avoids the ineffective decomposition of the oxidant and improves the reaction efficiency. At the same time, it also plays a cleaning role on the mesopore blockage of the public catalyst by the colloid in the wastewater, thereby improving the service life of the public catalyst;
[0021] (2) The wastewater multi-effect catalytic oxidation treatment device of the utility model is provided with a hydrogen peroxide addition system and an ozone addition system. The addition of hydrogen peroxide can reduce the investment cost and operation cost of the ozone generator; the addition of ozone can avoid the damage to the life of the catalyst caused by excessive addition of hydrogen peroxide, thereby ensuring the service life of the catalyst while ensuring the treatment effect;
[0022] (3) The wastewater multi-effect catalytic oxidation treatment device of the utility model has a simple structure and obvious effect. Under the action of the common catalyst of multiple metal oxide components, the multi-effect oxidation efficiency of hydrogen peroxide, ozone and ultrasound is higher, and the depth of wastewater treatment is deeper. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 This is a schematic diagram of the structure of the utility model wastewater multi-effect catalytic oxidation treatment device;
[0024] In the figure: 1. water inlet pipeline; 2. water inlet pump; 3. flow meter; 4. titanium aeration plate; 5. catalytic oxidation reaction section; 6. wire mesh inner cylinder; 7. ultrasonic probe; 8. common catalyst; 9. hydrogen peroxide storage tank; 10. hydrogen peroxide dosing pump; 11. ultrasonic generator; 12. tail gas destroyer; 13. ozone generator; 14. water outlet pipe; 15. overflow weir; 16. wire mesh; 17. support plate; 18. catalytic reactor. DETAILED DESCRIPTION
[0025] The specific implementation methods of the present invention will be described in detail below. In order to avoid too many unnecessary details, the well-known structures or functions will not be described in detail in the following embodiments. Unless otherwise defined, the technical and scientific terms used in the following embodiments have the same meanings as those generally understood by those skilled in the art to which the present invention belongs.
[0026] Example 1
[0027] like Figure 1 As shown, the wastewater multi-effect catalytic oxidation treatment device described in the utility model comprises a catalytic reactor 18, a hydrogen peroxide storage tank 9, an ultrasonic generator 11, a tail gas destroyer 12 and an ozone generator 13; a catalytic oxidation reaction section 5 is arranged in the middle of the catalytic reactor 18, an overflow weir 15 is arranged above the catalytic oxidation reaction section 5, and a support plate 17 is arranged below, and a titanium aeration disk 4 is distributed on the upper surface of the support plate 17, and the titanium aeration disk 4 is connected to the ozone generator 13; the upper and lower ends of the catalytic oxidation reaction section 5 are wire meshes 16, and a wire mesh inner cylinder 6 of the same height is arranged in the middle, and a common catalyst 8 is filled between the outer wall of the catalytic oxidation reaction section 5 and the wire mesh inner cylinder 6, and an ultrasonic probe 7 is arranged inside the wire mesh inner cylinder 6, and the ultrasonic probe 7 is connected to the ultrasonic generator 11; the bottom water inlet of the catalytic reactor 18 is connected to the water inlet pipeline 1 and the hydrogen peroxide storage tank 9, the water outlet of the overflow weir 15 is connected to the water outlet pipe 14, and the top gas outlet is connected to the tail gas destroyer 12.
[0028] A hydrogen peroxide dosing pump 10 is provided on the pipeline connecting the hydrogen peroxide storage tank 9 and the bottom water inlet of the catalytic reactor 18. The hydrogen peroxide storage tank 9 is made of opaque material, and the hydrogen peroxide dosing pump 10 is a metering pump, which can control the amount of hydrogen peroxide added at any time.
[0029] The water inlet pipeline 1 is provided with a water inlet pump 2 and a flow meter 3 .
[0030] The catalytic reactor 18 is a cylindrical structure with a height-to-diameter ratio of 4-6:1, and the outer wall is made of stainless steel or other corrosion-resistant materials.
[0031] The wire mesh inner cylinder 6 is a cylindrical structure, and its diameter is 1 / 4-1 / 2 of the diameter of the outer cylinder of the catalytic reactor 18.
[0032] The pore size of the wire mesh inner cylinder 6 and the wire mesh 16 is smaller than the particle size of the public catalyst 8, so that waste water can pass through but the public catalyst 8 cannot pass through. The wire mesh inner cylinder 6 and the wire mesh 16 are made of stainless steel or other corrosion-resistant materials.
[0033] The common catalyst 8 is a cylindrical structure with a diameter of 4-6 cm and a length of 2-4 cm. It can use a coal-made columnar activated carbon with an iodine value ≥ 800 as a carrier, and loads metal oxides of four components of manganese, copper, iron and cobalt as catalytic components. The content of the catalytic components (calculated as oxides) is 1.0-5.0% of the total mass of the carrier.
[0034] The number of the ultrasonic probes 7 is 1-5, and in this embodiment, there is 1. During operation, the ultrasonic density is maintained at 0.5-5.0w / cm 2 between.
[0035] The ozone generator 13 uses air as a gas source, the ozone concentration is 120-150 mg / L, the outlet pressure is 0.1 MPa, and the molar ratio of ozone dosage to COD removal is generally maintained at 1:1.
[0036] The working process of the wastewater multi-effect catalytic oxidation treatment device is as follows:
[0037] The wastewater to be treated is pressurized by the water inlet pump 2 and then enters the bottom of the catalytic reactor 18 through the flowmeter 3. At the same time, the hydrogen peroxide in the hydrogen peroxide storage tank 9 is metered by the hydrogen peroxide dosing pump 10 and quantitatively mixed into the water inlet pipeline and enters the bottom of the catalytic reactor 18 with the water inlet. The wastewater mixed with hydrogen peroxide rises from the bottom of the catalytic reactor 18 and gradually immerses the common catalyst 8 and the ultrasonic probe 7. The ozone generated by the ozone generator 13 is released through the titanium aeration plate 4 through the pipeline. A small part of the ozone dissolves into the wastewater and enters the bed of the common catalyst 8 to participate in the catalytic reaction. Another part of the undissolved ozone forms bubbles to stir and mix the wastewater. Ozone and hydrogen peroxide are mixed in the common catalyst 8. Under the action, the organic matter in the wastewater is oxidized and degraded. At the same time, the sound wave vibration generated by the ultrasonic probe 7 accelerates the mass transfer efficiency of the catalytic reaction, effectively shortens the reaction time and avoids the ineffective decomposition of the oxidant, thereby improving the reaction efficiency; at the same time, the addition of ultrasound also has a cleaning effect on the mesopore blockage of the public catalyst 8 by the colloid in the wastewater, so the addition of ultrasound avoids the service life of the public catalyst 8 from being reduced due to blockage; the treated wastewater overflows from the outlet pipe 14 through the overflow weir 15 arranged at the upper end of the catalytic reactor 18, and the reacted gas (oxygen and a small amount of ozone) enters the exhaust gas destroyer 12 through the outlet for treatment and then discharged.
[0038] Take a coal chemical wastewater as an example. The COD of the wastewater before treatment is 230mg / L and the water volume is 200m 3 / h, the wastewater multi-effect catalytic oxidation treatment device of the utility model is used for treatment, the catalytic reactor 18 is 10m high and 2.5m in diameter, and the outer wall material is 304 stainless steel; the wire mesh inner cylinder 6 is a perforated 316L stainless steel with a hole diameter of 2mm and a diameter of 1m; the wire mesh 16 has a hole diameter of 2mm; an ultrasonic probe 7 is set, and the ultrasonic density is 5.0w / cm 2 ; The public catalyst 8 uses coal-made columnar activated carbon with an iodine value of 800 as a carrier, and carries metal oxides of four components of manganese, copper, iron and cobalt as catalytic components. The content of the catalytic component (in terms of oxides) is 5.0% of the total mass of the carrier. The activated carbon carrier has a diameter of 3 cm and a length of 4 cm; the added ozone concentration is 120 mg / L, the outlet pressure is 0.1 MPa, the ozone dosage is 40 kg per hour, the 27.5% concentration hydrogen peroxide is added at a concentration of 0.2% (volume ratio), and the effluent COD is 30 mg / L.
[0039] The above description is only a preferred embodiment of the utility model and is not intended to limit the utility model. Although the utility model is described in detail with reference to the above embodiments, those skilled in the art can still modify the technical solutions recorded in the above embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the utility model shall be included in the protection scope of the utility model.
Claims
1. A wastewater multi-effect catalytic oxidation treatment device, characterized by: The invention comprises a catalytic reactor (18), a hydrogen peroxide storage tank (9), an ultrasonic generator (11), an exhaust gas destroyer (12) and an ozone generator (13); a catalytic oxidation reaction section (5) is provided in the middle of the catalytic reactor (18); an overflow weir (15) is provided above the catalytic oxidation reaction section (5); a support plate (17) is provided below the catalytic oxidation reaction section (5); a titanium aeration disk (4) is distributed on the upper surface of the support plate (17); the titanium aeration disk (4) is connected to the ozone generator (13); the upper and lower ends of the catalytic oxidation reaction section (5) are wire rods. A mesh (16) is provided in the middle with a wire mesh inner cylinder (6) of the same height, a common catalyst (8) is filled between the outer wall of the catalytic oxidation reaction section (5) and the wire mesh inner cylinder (6), an ultrasonic probe (7) is provided inside the wire mesh inner cylinder (6), and the ultrasonic probe (7) is connected to an ultrasonic generator (11); the bottom water inlet of the catalytic reactor (18) is connected to a water inlet pipeline (1) and a hydrogen peroxide storage tank (9), the water outlet of the overflow weir (15) is connected to a water outlet pipe (14), and the top gas outlet is connected to a tail gas destroyer (12).
2. The wastewater multi-effect catalytic oxidation treatment device according to claim 1, characterized in that: A hydrogen peroxide dosing pump (10) is provided on the pipeline communicating between the hydrogen peroxide storage tank (9) and the bottom water inlet of the catalytic reactor (18).
3. The wastewater multi-effect catalytic oxidation treatment device according to claim 1, characterized in that: The water inlet pipeline (1) is provided with a water inlet pump (2) and a flow meter (3).
4. The wastewater multi-effect catalytic oxidation treatment device according to claim 1, characterized in that: The catalytic reactor (18) is a cylindrical structure with a height-to-diameter ratio of 4-6:
1.
5. The wastewater multi-effect catalytic oxidation treatment device according to claim 4, characterized in that: The wire mesh inner cylinder (6) is a cylindrical structure, and its diameter is 1 / 4-1 / 2 of the diameter of the outer cylinder of the catalytic reactor (18).
6. The wastewater multi-effect catalytic oxidation treatment device according to claim 1, characterized in that: The pore size of the wire mesh inner cylinder (6) and the wire mesh (16) is smaller than the particle size of the common catalyst (8).
7. The wastewater multi-effect catalytic oxidation treatment device according to claim 6, characterized in that: The common catalyst (8) is a cylindrical structure with a diameter of 4-6 cm and a length of 2-4 cm.
8. The wastewater multi-effect catalytic oxidation treatment device according to claim 1, characterized in that: The number of the ultrasonic probes (7) is 1-5.