A wastewater deep treatment system and process for ozone catalytic oxidation and degassing

Abstract

The present invention relates to the field of advanced wastewater treatment and zero-emission technologies, specifically to a system and process for advanced wastewater treatment using ozone catalytic oxidation and degassing. The wastewater treatment system of the present invention comprises an ozone catalytic oxidation system and an activated carbon degassing system. The advanced wastewater treatment process comprises the following steps: conveying wastewater to an ozone catalytic oxidation tank, where ozone is dosed in stages, passing through a secondary mixing device, and then re-entering the ozone catalytic oxidation tank for a catalytic oxidation reaction under the action of ozone; the pre-treated wastewater flows by gravity into an activated carbon filter tank, where an activated carbon-supported manganese dioxide catalyst is used as the filter media. An ultraviolet or near-infrared irradiation device is also provided to synergistically treat residual ozone with the activated carbon and electromagnetic waves. The combined ozone catalytic oxidation and activated carbon degassing advanced wastewater treatment process employed in the present invention is advanced and mature, with a small footprint, low operating costs, a simple process, a high degree of automation, minimal sludge production, and the ability to achieve comprehensive and efficient removal of pollutants from high-salinity wastewater. This provides valuable technical support and engineering examples for the field of advanced wastewater treatment and zero-emission.

Description

Technical Field

[0001] The present invention relates to the technical field of wastewater advanced treatment, and in particular to a wastewater advanced treatment system and process for ozone catalytic oxidation and degassing. Background Art

[0002] To address water resource shortages caused by my country's rapid industrial development, zero-discharge wastewater processes have become a hot topic in the wastewater treatment sector. The effective removal of refractory organic matter (ODM) is a major challenge in achieving zero-discharge industrial wastewater and upgrading wastewater treatment plants. These refractory organic matter share long molecular chains, high chemical bond energies, and stable chemical structures, making them difficult to directly degrade biochemically. Currently, advanced oxidation processes are the primary method for removing ODM. Commonly used methods include ozone catalytic oxidation, Fenton oxidation, and photocatalytic oxidation. ADM primarily utilizes the potent oxidative action of hydroxyl radicals to remove ODM from wastewater. The redox potential of hydroxyl radicals is E0 = 2.8 eV. At this extremely high potential, most ODMs undergo chain scission reactions, forming short-chain organic compounds or being directly oxidized to CO2 and H2O. Efficient and high-volume OH radical production is a key indicator of the quality of OD technologies. Ozone catalytic oxidation has a good treatment effect on difficult-to-degrade organic matter, and has the advantages of being green and free of secondary pollution. However, the ozone catalytic oxidation method has problems such as low ozone dissolution efficiency in water, low ozone utilization rate, and the impact of ozone residue on subsequent processes. These have limited the further widespread application of the ozone catalytic oxidation method. Summary of the Invention

[0003] The present invention aims to solve one of the technical problems in the related art at least to a certain extent.

[0004] To overcome the practical application challenges of the aforementioned ozone catalytic oxidation technology, a wastewater advanced treatment system and process for ozone catalytic oxidation and degassing is provided. This system can improve ozone utilization and address the impact of residual ozone on subsequent units.

[0005] The purpose of the present invention is to provide an oxygen catalytic oxidation and degassing wastewater deep treatment system, which includes: an ozone catalytic oxidation system and an activated carbon degassing system.

[0006] Furthermore, the ozone catalytic oxidation system is provided with four-stage ozone catalytic oxidation tanks, each of which has the same structure and is connected in sequence to perform multi-stage catalytic oxidation; a multi-element palladium catalyst and its accessories are provided in the tank body; the catalyst is loaded at a height of 1-3m; a special vapor dissolving device, a centrifugal pump and a secondary mixing device for ozone addition are provided in the system;

[0007] Furthermore, the wastewater is transported to the ozone catalytic oxidation tank, and ozone is added in sections in the tank. A centrifugal pump is installed in each section. The pump takes the wastewater from a specific position in the tank and pumps it into a special vapor dissolving device. The special vapor dissolving device forms a negative pressure to suck the ozone. Finally, it passes through a secondary mixing device and enters the ozone catalytic oxidation tank again to undergo catalytic oxidation reaction under the action of ozone.

[0008] Furthermore, the dedicated vapor dissolving device is an ejector, and an electromagnetic coil and an ultrasonic transducer are arranged on the outer wall, and the electromagnetic coil and ultrasonic transducer are arranged at intervals.

[0009] Furthermore, the frequency range of the ultrasonic wave is 50kHz-8.5MHz, preferably 3MHz or 5MHz.

[0010] Further, the secondary mixing device is a guide plate or a filter brick;

[0011] The electromagnetic coil uses the magnetochemical effect to perform a high-frequency electromagnetic field instantaneous shearing action on the cluster structure of water molecules, organic molecules, and ion atmospheres in the sewage, breaking the original cluster structure of each microscopic form in the sewage, breaking the hydration and association effects of water molecules, organic molecules and ions, and changing the physical, chemical, molecular mechanical and other properties of the sewage, which are manifested as follows: (1) The clusters of water molecules in the sewage become smaller, the tension becomes greater, the viscosity becomes smaller, the permeability increases, and the fluidity becomes better, which is conducive to the dissolution of gas phase molecules; (2) The molecular clusters of the association molecules of organic matter, ions and water molecules in the sewage become smaller, and the organic molecules are more likely to contact with the oxidant. At the same time, the polar organic molecules are elongated, and the external charge of the organic molecules is redistributed, which is conducive to the next reaction with the oxidant; (3) The adsorption capacity of organic molecules and ions on the surface of the solid-phase catalyst is reduced, and the interfacial reaction efficiency of the solid-phase catalysis is improved.

[0012] Using an ejector for hydrodynamic cavitation, the wastewater, generated by ultrasonic cavitation from the ultrasonic transducer, enters the ejector and further hydrodynamically cavitates the ejector structure. Hydrodynamic cavitation generates cavitation by changing the flow rate of the liquid medium, causing pressure fluctuations, while ultrasonic cavitation uses ultrasound to create cavitation within the liquid. The combination of these two methods can produce a large number of cavitation bubbles, enhancing the oxidation reaction and physical fragmentation, resulting in a greater number and intensity of cavitation bubbles.

[0013] The electromagnetic coil changes the cluster structure of water molecules, organic pollutant molecules and ion atmosphere in the sewage through the action of electromagnetic shear field, and changes the physical, chemical, molecular mechanics and other properties of the treated sewage, thereby achieving the purpose of increasing the ozone solubility, accelerating the reaction time of ozone and organic pollutants, and improving the efficiency of solid-phase catalysis. At the same time, under the action of electromagnetic shear field and multi-element palladium catalyst, ozone-containing sewage is directly stimulated to produce hydroxyl free radicals. Under the strong oxidizing effect of hydroxyl free radicals, the chemical bonds of long-chain organic matter are broken to generate short-chain easily degradable organic matter, which is directly oxidized into end products CO2 and H2O and other chemical forms of end products in this process, thereby achieving the purpose of meeting COD emission standards.

[0014] Activated carbon degassing system, the activated carbon degassing system is equipped with an activated carbon degassing tank and a backwash device; the pre-treated sewage flows into the activated carbon filter tank by gravity, and the activated carbon filter tank is mainly used to degas the effluent from the ozone catalytic oxidation tank to prevent ozone from entering the subsequent process system and causing damage, thereby protecting the safe operation of the subsequent treatment system.

[0015] Furthermore, an irradiation device is provided inside the activated carbon filter tank, which uses ultraviolet rays or near-infrared rays for irradiation;

[0016] Furthermore, the filter material is activated carbon loaded with manganese dioxide, and the specific surface area is preferably 400-800m 2 / g, preferably 600m 2 / g.

[0017] During the degassing process, as the gas-laden liquid passes through the activated carbon adsorption cell, the gas molecules are adsorbed onto the activated carbon surface. Physical adsorption is due to intermolecular forces on the activated carbon surface, while chemical adsorption is the result of a chemical reaction between the functional groups on the activated carbon surface and the gas molecules. Through these two adsorption methods, the gas molecules are fixed within the pores of the activated carbon, achieving the purpose of degassing.

[0018] Furthermore, the activated carbon is loaded with manganese dioxide, which acts as a catalyst to decompose ozone into oxygen, thereby accelerating the removal of residual ozone.

[0019] Furthermore, an irradiation device is provided inside the activated carbon filter, which uses ultraviolet or near-infrared radiation in combination with manganese dioxide to accelerate the decomposition rate of ozone.

[0020] Furthermore, the activated carbon degassing tank is divided into 4 compartments, each series can be operated independently, and the activated carbon backwash adopts air flushing, air-water backwashing and water flushing; the filter media thickness is 2.0m, and the filtration rate is 8.7m / h;

[0021] The purpose of the present invention is to provide a wastewater advanced treatment process of oxygen catalytic oxidation and degassing: the wastewater is transported to an ozone catalytic oxidation tank, ozone is added in sections in the tank, a centrifugal pump is installed in each section, the pump draws wastewater from a specific position in the tank and pumps it into a special vapor dissolving device, a negative pressure is formed in the special vapor dissolving device to suck the ozone, and finally passes through a secondary mixing device and enters the ozone catalytic oxidation tank again, where a catalytic oxidation reaction is carried out under the action of ozone;

[0022] Then, ozone catalytic oxidation is carried out, and the mixed sewage is put into the ozone catalytic oxidation tank, and catalytic oxidation reaction is carried out under the action of ozone and multi-element palladium catalyst;

[0023] The pre-treated sewage flows by gravity into the activated carbon filter. The main function of the activated carbon filter is to degas the effluent from the ozone catalytic oxidation tank to prevent ozone from entering the subsequent process system and causing damage, thereby protecting the safe operation of the subsequent treatment system.

[0024] Furthermore, the ozone dosage ratio of the four-stage ozone catalytic oxidation tank is 4:3:1:1;

[0025] Furthermore, the catalyst loading height is 1-3m; the ratio of ozone (O3) dosage to CODcr removal amount is preferably 1.2-3.0; the reaction time of the catalytic oxidation reaction is 0.5-2h;

[0026] Furthermore, the inlet suspended solids concentration (SS) of the ozone catalytic oxidation system is less than 10 mg / L; the inlet pH of the ozone catalytic oxidation system is 6-9;

[0027] Furthermore, an irradiation device is provided inside the activated carbon filter tank, which uses ultraviolet rays or near-infrared rays for irradiation;

[0028] Furthermore, the wavelength of the near infrared ray is in the range of 1000-1500 nm, preferably 1200-1300 nm;

[0029] Furthermore, the irradiation device is arranged at the bottom or middle of the activated carbon filter;

[0030] Furthermore, the thickness of the filter material inside the activated carbon filter is 2.0m, and activated carbon loaded with manganese dioxide is used as the filter material, and the specific surface area is preferably 400-800m 2 / g, preferably 600m 2 / g, the loading amount of manganese dioxide on the activated carbon is 5-20%, preferably 13%;

[0031] Furthermore, a filter brick is provided at the bottom of the activated carbon filter as a supporting structure. The filter brick is an S-shaped filter brick, and an infrared irradiation device is provided inside the primary water distribution cavity.

[0032] Furthermore, the reaction temperature of the activated carbon filter is 4°C-80°C, preferably 20-60°C, and more preferably 40°C, 48°C, and 50°C;

[0033] Furthermore, the hydraulic retention time of the activated carbon filter is 0.2-3 hours, preferably 0.5 hours.

[0034] Activated carbon degassing technology offers advantages such as high efficiency, environmental friendliness, and cost-effectiveness. By rationally designing the degassing tank structure and selecting the appropriate activated carbon type, efficient gas adsorption and degassing can be achieved. Activated carbon-supported manganese dioxide catalysts are used as the filter media within the activated carbon filter, along with ultraviolet or near-infrared irradiation devices. These devices, along with the activated carbon and electromagnetic waves, synergize to treat residual ozone. By introducing oxygen vacancies, the catalyst's ozone decomposition activity can be enhanced, improving the catalyst's regeneration performance and service life. Electromagnetic wave radiation can be combined with the catalyst to photoexcite the catalyst, enhancing its catalytic activity and leading to more effective ozone decomposition. The synergistic effect of manganese dioxide, activated carbon, and electromagnetic waves can significantly improve the treatment efficiency of residual ozone and enhance the catalyst's stability and water resistance, which is of great significance for enhancing the practical application value of ozone treatment technology.

[0035] This deep treatment process has the following characteristics: 1. It adopts advanced and mature technology, occupies a small area, has low operating costs, is simple in process, has a high degree of automation, has a simple flow, and produces very little sludge. 2. Ozone catalytic oxidation has three proprietary technologies that greatly improve the efficiency of sewage treatment compared to traditional ozone contact oxidation: (1) Jet injection system: greatly increases the solubility of ozone in water, improves the utilization rate of ozone, dissolves gas at low pressure, reduces the water pump head, saves electricity, and thus reduces operating costs. (2) Electromagnetic generator: changes the structure of water molecule clusters, increases the solubility of ozone in water, and makes it easier for difficult-to-degrade organic matter to be oxidized and removed. After the above technical improvements, the ozone utilization rate of electromagnetic advanced catalytic oxidation can reach 99%. (3) Activated carbon degassing technology uses the synergistic effect of manganese dioxide, activated carbon, and electromagnetic waves to significantly improve the treatment efficiency of residual ozone and enhance the stability and water resistance of the catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 The present invention provides a schematic flow diagram of a wastewater deep treatment system for oxygen catalytic oxidation and degassing.

[0037] Figure 2 The present invention provides a schematic diagram of an activated carbon filter brick structure of a wastewater deep treatment system for oxygen catalytic oxidation and degassing.

[0038] The following items are included: 1. Centrifugal pump; 2. Special vapor dissolving device; 3. Secondary mixing device; 4. Anti-backflow device; 5. Tail gas destroyer; 6. Respirator; 7. Multi-element palladium catalyst; 8. Activated carbon; 9. S-type filter brick; 10. Primary water distribution chamber; 11. Irradiation device; DETAILED DESCRIPTION

[0039] The following describes embodiments of the present invention in detail, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, and are not to be construed as limiting the present invention.

[0040] The technical solution of the present application will be described in detail below with reference to the accompanying drawings and in combination with the implementation methods.

[0041] like Figure 1 As shown, a wastewater deep treatment system for oxygen catalytic oxidation and degassing includes: ozone is generated in an ozone preparation room and connected to a dedicated vapor dissolving device 2 via a pipeline, and the pipeline is equipped with a backflow prevention device 4. The ozone catalytic oxidation system is equipped with four ozone catalytic oxidation tanks, each of which has the same structure and is connected in sequence to perform multi-stage catalytic oxidation; the tanks are equipped with a multi-element palladium catalyst 7 and its accessories; wastewater is transported to the ozone catalytic oxidation tanks, and ozone is added in sections. Each section is equipped with a centrifugal pump 1, which draws wastewater from a specific location in the tank and pumps it into the dedicated vapor dissolving device 2. The dedicated vapor dissolving device creates a negative pressure to draw in ozone, and finally passes through a secondary mixing device 3 and re-enters the ozone catalytic oxidation tank to undergo a catalytic oxidation reaction under the action of ozone; the dedicated vapor dissolving device 2 is an ejector, and the outer wall is equipped with an electromagnetic coil and an ultrasonic transducer, which are arranged at intervals. The secondary mixing device 3 is a guide plate or filter brick. The ozone catalytic oxidation tank is equipped with a respirator 6 to ensure gas exchange and pressure balance, enhancing system safety. The activated carbon degassing tank is connected to an exhaust gas destroyer 5 to decompose ozone in the exhaust gas, thereby reducing the potential threat posed by ozone to the environment. The activated carbon degassing tank uses activated carbon 8 loaded with manganese dioxide as the filter media. The bottom of the activated carbon degassing tank is equipped with an S-shaped filter brick 9. The primary water distribution chamber 10 inside the S-shaped filter brick 9 is equipped with an irradiation device.

[0042] The wastewater deep treatment process of ozone catalytic oxidation will be further explained below with reference to the accompanying drawings.

[0043] In one embodiment of the present invention, wastewater is transported to an ozone catalytic oxidation tank, and ozone is added to the tank in sections. A centrifugal pump 1 is installed in each section. The pump takes sewage from a specific position in the tank and pumps it into a special vapor dissolving device 2. The special vapor dissolving device 2 is preferably an ejector. The outer wall of the ejector is provided with an electromagnetic coil and an ultrasonic transducer, and the electromagnetic coil and ultrasonic transducer are arranged at intervals. Negative pressure is formed in the special vapor dissolving device 2 to suck ozone, and finally passes through a secondary mixing device 3 and enters the ozone catalytic oxidation tank again, where a catalytic oxidation reaction is carried out under the action of ozone; ozone catalytic oxidation is then carried out, and the mixed sewage is put into the ozone catalytic oxidation tank, where a catalytic oxidation reaction is carried out under the action of ozone and a multi-element palladium catalyst 7; the pre-treated sewage flows by gravity into the activated carbon filter, which mainly serves to degas the effluent from the ozone catalytic oxidation tank to prevent ozone from entering the subsequent process system and causing damage, thereby protecting the safe operation of the subsequent treatment system. The activated carbon filter is equipped with an S-shaped filter brick 9 at the bottom. Wastewater flows through the primary water distribution chamber 10 within the S-shaped filter brick 9 and upwards into the activated carbon filter. An irradiation device is installed within the primary water distribution chamber 10 to promote the conversion of ozone in the wastewater into oxygen. Manganese dioxide-loaded activated carbon is used as the filter media. The introduction of oxygen vacancies enhances the catalyst's ozone decomposition activity, improving the catalyst's regeneration performance and service life. It can quickly and efficiently decompose low- and medium-concentration ozone into oxygen at room temperature. The irradiation device uses ultraviolet light or near-infrared light of 1200-1300nm to irradiate ozone. Under light excitation, ozone is first converted to singlet O₂ and then to ground state O₂. Electromagnetic radiation synergizes with the catalyst, enhancing its catalytic activity through light excitation, leading to more efficient ozone decomposition. The synergistic effect of manganese dioxide, activated carbon, and electromagnetic waves significantly improves the efficiency of residual ozone treatment and enhances the catalyst's stability and water resistance.

[0044] Example 1:

[0045] The first phase of a sewage treatment plant in an industrial park in Sichuan Province treats the wastewater discharged by a certain company, including production process wastewater, acid and alkali waste gas scrubber drainage, and R&D laboratory wastewater. The plant uses the oxygen catalytic oxidation and degassing wastewater deep treatment process of the present invention. The design scale of this process section is Q d =10000m 3 / d, coefficient of variation K Z =1.1, Q=458.3m 3 / h;

[0046] (1) Ozone catalytic oxidation pool and activated carbon pool

[0047] A combined ozone catalytic oxidation tank and activated carbon tank were constructed, with a total floor plan of 38.3m x 13.8m. The ozone catalytic oxidation tank was dosed at 100.0mg / L and was divided into two series, each capable of independent operation. Ozone was dosed in four sections with a catalyst thickness of 0.5m and a total residence time of 175min. The activated carbon degassing tank was divided into four compartments, each capable of independent operation. Activated carbon backwashing consisted of air flushing, air-water backwashing, and water flushing. The filter media was 2.0m thick and the filtration rate was 8.7m / h.

[0048] (2) Ozone generator room

[0049] The total plan size of the ozone generator room is 17.0m×12.0m; it uses three 25kg / h ozone generators (two in use and one in reserve), with a rated ozone concentration of 150mg / L (10.2wt%), and is equipped with an exhaust destructor, heat exchange system, ozone concentration meter, flow meter, ozone leakage meter, etc.

[0050] (3) Liquid oxygen station

[0051] The liquid oxygen station covers an area of ​​10.0m×6.0m; the liquid oxygen tank V=80m 3 , supporting vaporizer and pressure stabilizing device, totaling 1 set.

[0052] Construction on the project concluded in June 2021, and process commissioning began. The project has been in normal operation since then. The ozone catalytic oxidation unit and degassing unit are operating stably, achieving excellent treatment results, and the effluent quality meets design standards. The original design inlet and outlet water indicators and operational results for the project are shown in Tables 1 and 2.

[0053] Table 1 Designed inlet and outlet water quality of this project (unit: mg / L)

[0054]

[0055] Table 2 Actual inlet and outlet water quality of this project (unit: mg / L)

[0056]

[0057] Example 2:

[0058] In order to meet the reclaimed water effluent index, an industrial wastewater treatment plant in Inner Mongolia adopted the wastewater advanced treatment process of oxygen catalytic oxidation and degassing of the present invention. The design scale of the process section is: Q = 11040m 3 / d, design hourly flow Q = 460.0m 3 / h. An experimental study was conducted at the pilot site. The specific implementation process is as follows: (1) The sewage first enters the regulating water tank, where the water volume and water quality are balanced, and then it is lifted to the ozone catalytic oxidation tank by the lifting pump. (2) The outlet water of the front unit enters the ozone catalytic oxidation tank, and ozone is added in sections in a zigzag mode at each stage. (3) A centrifugal pump is set up in each section, and the pump takes water from a specific position in the pool and pumps it into a special vapor dissolving device, which forms a negative pressure to suck ozone. The sewage and ozone are efficiently mixed and fully contacted with the catalyst, and are stimulated to produce hydroxyl free radicals under the action of the active components of the catalyst. Under the strong oxidizing action of hydroxyl free radicals, most of the difficult-to-degrade organic matter undergoes chain breaking reactions to form short-chain organic matter or is directly oxidized to CO2 and H2O. (4) The outlet water of the ozone catalytic oxidation tank flows into the activated carbon degassing unit for degassing treatment to prevent the safe operation of the subsequent treatment system of ozone protection.

[0059] The pilot test for this project employed a water flow rate of 500 L / h, an ozone dosage of 170.0 mg / L, an OC ratio of 2.6, and a total residence time of 120 minutes. The pilot test data demonstrates that the present oxygen catalytic oxidation and degassing process significantly removes COD from this type of wastewater. The ozone catalytic oxidation and activated carbon degassing units operate stably, achieving excellent treatment results, and the effluent quality meets design standards. The original design inlet and effluent water quality indicators for this project, as well as the operational results, are shown in Tables 3 and 4.

[0060] Table 3 Designed inlet and outlet water quality of this project (unit: mg / L)

[0061]

[0062] Table 4 Actual inlet and outlet water quality of the pilot test of this project (unit: mg / L)

[0063]

[0064] In summary, due to the adoption of the above-mentioned technical solution, according to an embodiment of the present invention, a wastewater deep treatment system and process using a combined technology of ozone catalytic oxidation and activated carbon degassing solves the problems of low ozone dissolution efficiency in water, unstable number of free radicals, low ozone utilization rate, and the impact of residual ozone on subsequent units in the existing ozone catalytic oxidation process. The process is advanced and mature, with a small footprint, low operating costs, a simple process, a high degree of automation, a simple flow, and very little sludge production. By combining the hydrodynamic cavitation of the ejector with ultrasonic cavitation technology and the magnetochemical effect, the dissolution efficiency of ozone in water is greatly increased, the utilization rate of ozone is improved, low-pressure gas is dissolved, the water pump head is reduced, power consumption is saved, and operating costs are reduced. By utilizing this magnetochemical effect, the structure of water molecule clusters is changed, the solubility of ozone in water is increased, and at the same time, difficult-to-degrade organic matter is more easily oxidized and removed. After the above technical improvements, the ozone utilization rate of electromagnetic advanced catalytic oxidation can reach 99%. The technology disclosed in the present invention adopts a residual ozone treatment process and uses an activated carbon-supported manganese dioxide catalyst as a filter material. At the same time, an ultraviolet or near-infrared irradiation device is provided in the activated carbon degassing system to synergistically treat residual ozone with the activated carbon and electromagnetic waves. The synergistic effect of manganese dioxide, activated carbon and electromagnetic waves can significantly improve the treatment efficiency of residual ozone and enhance the stability and water resistance of the catalyst, which is of great significance for improving the practical application value of ozone treatment technology.

[0065] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of the technical features being referred to. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "plurality" means at least two, such as two, three, etc., unless otherwise specifically defined.

[0066] In the description of this specification, the reference terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction.

[0067] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention.

Claims

1. A wastewater deep treatment system with ozone catalytic oxidation and degassing, characterized in that: include: Ozone catalytic oxidation system, activated carbon degassing system; the ozone catalytic oxidation system is provided with four-stage ozone catalytic oxidation tanks, each of which has the same structure and is connected in sequence for multi-stage catalytic oxidation; a multi-element palladium catalyst and its accessories are provided in the tank body; the catalyst is loaded at a height of 1-3m; a special vapor dissolving device, a centrifugal pump and a secondary mixing device for ozone addition are provided in the system; wastewater is transported to the ozone catalytic oxidation tank, ozone is added in sections in the tank, a centrifugal pump is provided in each section, the pump draws sewage from the tank into the special vapor dissolving device, a negative pressure is formed in the special vapor dissolving device to suck ozone, and finally passes through the secondary mixing device and re-enters the ozone catalytic oxidation tank to carry out catalytic oxidation reaction under the action of ozone; the special vapor dissolving device is an ejector, and an electromagnetic coil and an ultrasonic transducer are provided on the outer wall, and the above-mentioned electromagnetic coil and ultrasonic transducer are arranged at intervals; An activated carbon degassing system is provided with an activated carbon degassing tank and a backwash device. The pre-treated sewage flows by gravity into the activated carbon filter tank, which uses activated carbon loaded with manganese dioxide as the filter material. The filter material has a specific surface area of ​​600m² / g and a manganese dioxide loading on the activated carbon of 13%. An irradiation device is provided inside the activated carbon filter tank, which uses ultraviolet rays or near-infrared rays for irradiation. The bottom of the activated carbon filter tank is provided with filter bricks as a supporting structure. The filter bricks are S-shaped filter bricks, and an irradiation device is provided inside the primary water distribution cavity.

2. The wastewater deep treatment system for ozone catalytic oxidation and degassing according to claim 1 is characterized in that: The ultrasonic frequency range of the ultrasonic transducer is 50kHz-8.5MHz, and the secondary mixing device is a guide plate or a filter brick.

3. The wastewater deep treatment system for ozone catalytic oxidation and degassing according to claim 1 is characterized in that: The activated carbon degassing tank is divided into 4 sections, each series can be operated independently, and the activated carbon backwashing adopts air flushing, air-water backwashing or water flushing; the filter material thickness is 2.0m, and the filtration rate is 8.7m / h.

4. The wastewater deep treatment system for ozone catalytic oxidation and degassing according to claim 1, characterized in that: The irradiation device is arranged at the bottom or the middle of the activated carbon filter.

5. A wastewater deep treatment process with ozone catalytic oxidation and degassing, characterized in that: A wastewater deep treatment system comprising the combined ozone catalytic oxidation and activated carbon degassing technology according to any one of claims 1 to 4, further comprising the following process: transporting the wastewater to an ozone catalytic oxidation tank, adding ozone in sections into the tank, providing a centrifugal pump in each section, pumping wastewater from the tank into a dedicated vapor dissolving device, forming a negative pressure in the dedicated vapor dissolving device to draw ozone, and finally passing through a secondary mixing device before re-entering the ozone catalytic oxidation tank; Then, ozone catalytic oxidation is carried out, and the mixed sewage is put into the ozone catalytic oxidation tank, and catalytic oxidation reaction is carried out under the action of ozone and multi-element palladium catalyst; The pre-treated sewage flows into the activated carbon filter by gravity. The main function of the activated carbon filter is to degas the effluent from the ozone catalytic oxidation tank.

6. The wastewater advanced treatment process of ozone catalytic oxidation and degassing according to claim 5, characterized in that: The ozone dosage ratio of the four-stage ozone catalytic oxidation tank is 4:3:1:1, and the catalyst filling height is 1-3m; the ratio of ozone dosage to CODcr removal amount is preferably 1.2-3.0; and the reaction time of the catalytic oxidation reaction is 0.5-2h.

7. The wastewater advanced treatment process of ozone catalytic oxidation and degassing according to claim 5, characterized in that: An irradiation device is provided inside the activated carbon filter tank, which uses ultraviolet rays or near-infrared rays for irradiation, and the wavelength range of the near-infrared rays used is 1000-1500nm.

8. The wastewater advanced treatment process of ozone catalytic oxidation and degassing according to claim 5, characterized in that: The thickness of the filter material inside the activated carbon filter is 2.0m, and the reaction temperature of the activated carbon filter is 4℃-80℃.

9. The wastewater advanced treatment process of ozone catalytic oxidation and degassing according to claim 5, characterized in that: The bottom of the activated carbon filter tank is provided with filter bricks as a supporting structure. The filter bricks are S-shaped filter bricks, and an infrared irradiation device is provided inside the primary water distribution cavity.

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