A method and apparatus for ozone oxidation wastewater treatment based on polymerization pathway

Abstract

This invention discloses a method and apparatus for ozone oxidation wastewater treatment based on a polymerization pathway, belonging to the field of water treatment technology. The method includes the following steps: under the action of micron and / or nano-sized ozone chain initiators, micron and / or nano-sized ozone reacts with pollutants in the wastewater to generate free radicals (·OH); modified filler undergoes a coordination reaction with the pollutants carrying free radicals (·OH) to form complexes; the residence time is controlled to polymerize into high-density macromolecular organic matter, which is then separated after cyclone separation. In this invention, wastewater undergoes a reaction with micron and / or nano-sized ozone chain initiators and, in conjunction with modified filler, controls the reaction pathway in the wastewater, polymerizes into high-density macromolecular organic matter, and is then separated after cyclone separation. This method can be applied to the treatment of various wastewater types, expanding its application range. Simultaneously, the use of modified filler enhances the reaction rate, effectively improving the ozone treatment efficiency.

Description

Technical Field

[0001] This invention belongs to the field of water treatment technology, specifically relating to a method and apparatus for treating ozone oxidation wastewater based on a polymerization pathway. Background Technology

[0002] Ozone is an unstable, pale blue gas with a distinctive, pungent odor at room temperature and pressure. It possesses extremely strong oxidizing properties, exhibiting an oxidation potential of 2.07V in alkaline solutions. Its oxidizing power is second only to fluorine, and higher than chlorine and potassium permanganate. Due to its strong oxidizing properties and its ability to decompose spontaneously in water without secondary pollution, ozone is an ideal green oxidant. Therefore, ozone oxidation has gradually developed into an advanced oxidation technology, and it has been applied in many aspects of water treatment, primarily for deodorization, decolorization, sterilization, and removal of organic matter.

[0003] Currently, common ozone oxidation processes mainly rely on the strong oxidizing properties of ozone to react directly or indirectly with pollutants in wastewater, decomposing them into carbon dioxide and water. This is limited by factors such as the oxidizing capacity of ozone, the type of pollutant, and the concentration of the pollutant. Furthermore, the selective nature of ozone oxidation and its high production and transportation costs restrict its application in high-concentration wastewater.

[0004] To address the aforementioned issues, a search revealed that patent document CN110026242A discloses a method for preparing a Co / Ce bimetallic MOF-based ozone catalyst, along with its products and applications. This Co / Ce bimetallic MOF-based ozone catalyst utilizes cobalt and cerium metal centers and organic ligands to self-assemble into a three-dimensional porous structure. This effectively modulates active sites, thereby promoting the catalytic activity of MOFs, increasing the ozone decomposition rate of the Co / Ce-based composite material, generating more active hydroxyl radicals, which is beneficial for the catalytic ozonation of organic pollutants in water, and significantly improving the mineralization rate of organic matter.

[0005] Furthermore, patent document CN110052269A discloses a method for preparing an ozone catalytic oxidation catalyst for deep water treatment, which mainly includes a carrier, distilled water, an activating factor, a metal salt solution, and oxygen. The oxygen is used to generate the desired ozone through an ozone generator. The carrier, distilled water, activating factor, metal salt solution, and ozone form an ozone oxidation catalyst. Under certain water quality pH conditions, the ozone oxidation catalyst has a treatment efficiency of up to 81% within a certain residence time. This patent has the characteristics of high efficiency and universality.

[0006] However, analysis of the contents disclosed in the two patents revealed that ozone requires the use of a catalyst, resulting in low treatment efficiency in the ozone process, limited effective treatment range for wastewater, and narrow application scope, which is not conducive to the expansion of the technology's use. Summary of the Invention

[0007] 1. The problem to be solved

[0008] To address the technical problems of low treatment efficiency and narrow application range in existing ozone processes, the present invention aims to propose an ozone oxidation wastewater treatment method based on the polymerization pathway, thereby expanding the application range and improving the reaction rate and ozone treatment efficiency.

[0009] Another object of the present invention is to provide an ozone oxidation wastewater treatment device based on a polymerization pathway.

[0010] 2. Technical Solution

[0011] To solve the above problems, the technical solution adopted by the present invention is as follows:

[0012] The first aspect of this invention provides a method for treating ozone oxidation wastewater based on a polymerization pathway. The method includes the following steps: under the action of micron and / or nano-sized ozone chain initiators, micron and / or nano-sized ozone reacts with pollutants in the wastewater to generate free radicals ·OH; modified fillers undergo coordination reactions with pollutants carrying free radicals ·OH to form complexes; the residence time is controlled to polymerize into high-density macromolecular organic matter, which is then separated after cyclone separation.

[0013] According to any embodiment of the first aspect of the present invention, the chain initiator is one or more of H2O2, H2SO4, and HMnO4.

[0014] According to any embodiment of the first aspect of the present invention, a chain initiator with a mass fraction of 0.1-3% is added to the wastewater. It should be noted that the amount of chain initiator added is calculated based on the total mass of COD in the wastewater.

[0015] According to any embodiment of the first aspect of the present invention, the chain initiator is prepared by mixing H2O2, H2SO4, and HMnO4 in a ratio of 3:1:3 (mass ratio). Through the synergistic effect of the three components, the initiation effect is maximized, and the amount of chain initiator used is reduced.

[0016] According to any embodiment of the first aspect of the present invention, the modified filler is one or more of TiCl4-Al(C2H5)3, dicyclohexyl peroxide, di-tert-butyl peroxide, sodium persulfate, azobisisobutyronitrile, dimethyl azobisisobutyrate, N,N-dimethylaniline, and benzoyl peroxide.

[0017] It is important to emphasize that, through extensive experimental analysis, it has been found that modified fillers can lose electrons to ozone, thereby forming active sites, and then gain electrons from the water to form hydroxyl radicals. Hydroxyl radicals can initiate chain polymerization, which can treat the remaining COD in the water after polymerization and reduce the COD content of the effluent.

[0018] According to any embodiment of the first aspect of the present invention, the amount of the modified filler added is 0.01-0.2% (mass fraction). It should be noted that the amount of the modified filler added is calculated based on the total mass of COD in the wastewater.

[0019] According to any embodiment of the first aspect of the present invention, the residence time is controlled to be 0.1-2 hours. The reaction time for polymerization is fully considered to ensure the effectiveness of the polymerization.

[0020] A second aspect of the present invention provides an ozone oxidation transfer device based on a polymerization pathway, comprising:

[0021] The device body has a conical shape and is provided with an inlet and an outlet. Inside the device body is a receiving cavity, the bottom of which extends into the conical part of the device body.

[0022] An ozone reactor connected to the conical bottom of the device body is capable of generating micron and / or nano ozone. The micron and / or nano ozone reacts with pollutants in wastewater to generate free radicals ·OH.

[0023] The modified filler placed in the cavity can coordinate with pollutants carrying free radicals ·OH to form complexes.

[0024] According to any embodiment of the second aspect of the present invention, the receiving cavity includes a straight cylindrical portion and a flared portion, the flared portion extending into the conical portion of the device body, and modified filler is provided in segments along the inner side of the receiving cavity.

[0025] According to any embodiment of the second aspect of the present invention, the cross-section of the straight section is circular, and the modified filler is divided into two sections distributed in the receiving cavity.

[0026] 3. Beneficial effects

[0027] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0028] (1) The ozone oxidation wastewater treatment method based on polymerization path of the present invention involves wastewater undergoing a material reaction under the action of micron and / or nano ozone chain initiator and synergistic modified filler, controlling the material reaction path in the wastewater, polymerizing into high-density macromolecular organic matter, and then separating it after cyclone separation. This method can be applied to the treatment of various wastewaters, expanding the application range. At the same time, the modified filler is used to improve the reaction rate, effectively improving the ozone treatment efficiency.

[0029] (2) The ozone oxidation wastewater treatment method based on the polymerization pathway of the present invention uses ozone as a chain initiator for the reaction of organic pollutants. Compared with the removal of pollutants, its dosage accounts for 0.1-3% by mass, which effectively saves the cost of use.

[0030] (3) The ozone oxidation wastewater treatment method based on the polymerization pathway of the present invention, wherein the chain initiator (H2O2, H2SO4, HMnO4) is used in a ratio of 3:1:3 to maximize the initiation effect and reduce the amount of chain initiator used;

[0031] (4) The ozone oxidation wastewater treatment method based on the polymerization pathway of the present invention uses (TiCl4-Al(C2H5)3) as the modified filler. This substance can control the increase of the concentration of molecular active centers, improve the reaction rate, increase the polymerization effect and the size of the polymer molecular weight, thereby improving the treatment effect. Attached Figure Description

[0032] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. However, it should be understood that these drawings are designed for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, unless specifically indicated, these drawings are intended only to conceptually illustrate the structural construction described herein and are not necessarily drawn to scale.

[0033] Figure 1 This is a schematic diagram of the main structure of the ozone oxidation wastewater treatment device based on the polymerization path of the present invention;

[0034] Figure 2 This is a top view schematic diagram of the ozone oxidation wastewater treatment device based on the polymerization path of the present invention;

[0035] Explanation of reference numerals in the attached figures:

[0036] 1. Device body; 11. Inlet; 12. Outlet; 13. Receiving cavity; 131. Straight section; 132. Flared section; 14. Conical section;

[0037] 2. Ozone reactor;

[0038] 3. Modified fillers. Detailed Implementation

[0039] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The components of the embodiments of the present invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0040] Therefore, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without inventive effort are within the scope of protection of the invention.

[0041] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

[0042] In the description of this invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship commonly used when the product of this invention is in use. They are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this invention. In addition, the terms "first," "second," "third," etc., are only used to distinguish descriptions and should not be construed as indicating or implying relative importance.

[0043] Furthermore, terms such as "horizontal" and "vertical" do not imply that components must be absolutely horizontal or suspended, but rather that they can be slightly tilted. For example, "horizontal" simply means that its direction is more horizontal than "vertical," and does not mean that the structure must be completely horizontal, but can be slightly tilted.

[0044] In the description of this invention, it should also be noted that, unless otherwise explicitly specified and limited, the terms "set," "install," "connect," and "link" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art will understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0045] The ozone oxidation wastewater treatment method based on the polymerization pathway of the present invention includes the following steps: adding a chain initiator with a mass fraction of 0.1-3% to the wastewater; under the action of micron and / or nano-sized ozone chain initiators, micron and / or nano-sized ozone reacts with pollutants in the wastewater to generate free radicals ·OH; the chain initiator is one or more of H2O2, H2SO4, and HMnO4; a modified filler undergoes a coordination reaction with the pollutants carrying free radicals ·OH to form a complex; the modified filler is one or more of TiCl4-Al(C2H5)3, dicyclohexyl peroxide, di-tert-butyl peroxide, sodium persulfate, azobisisobutyronitrile, dimethyl azobisisobutyrate, N,N-dimethylaniline, and benzoyl peroxide; the amount of the modified filler added is 0.01-0.2%; controlling the residence time to 0.1-2 h, polymerizing into high-density macromolecular organic matter, and then separating it after cyclone separation.

[0046] It should be noted that the amount of chain initiator added should not be less than 0.1%, and the generation of ozone free radicals ·OH should be fully considered; at the same time, the amount of chain initiator added should not be more than 3%, and when the amount added exceeds this value, it may affect the effect of the modified filler.

[0047] The amount of the modified filler added should not be less than 0.01%, as mentioned above, which is not conducive to controlling the increase in the concentration of molecular active centers and improving the reaction rate; the amount added should not be more than 0.2%, as when the amount added exceeds this value, it is not conducive to accurately controlling the stereoregularity of polymers in wastewater, resulting in unsatisfactory treatment efficiency.

[0048] Preferably, the chain initiator is prepared by mixing H2O2, H2SO4, and HMnO4 in a ratio of 3:1:3. The synergistic effect of these three components maximizes the initiation effect and reduces the amount of chain initiator used.

[0049] Preferably, the modified filler is TiCl4-Al(C2H5)3, which can control the increase of the concentration of molecular active centers, improve the reaction rate, increase the polymerization effect, increase the molecular weight of the polymer, and thus improve the treatment effect.

[0050] Combination Figure 1 and Figure 2 As shown, the ozone oxidation transfer device based on the polymerization pathway of the present invention includes:

[0051] The device body 1 has a conical shape and is provided with an inlet 11 and an outlet 12. A receiving cavity 13 is provided inside the device body 1, and the bottom of the receiving cavity 13 extends into the conical part 14 of the device body 1.

[0052] An ozone reactor 2, connected to the conical bottom of the device body 1, is capable of generating micron and / or nano-sized ozone. The micron and / or nano-sized ozone reacts with pollutants in the wastewater to generate free radicals ·OH. The ozone reactor 2 can be an existing ozone reactor, so it will not be described in detail here.

[0053] The modified filler 3 placed in the receiving cavity 13 can undergo a coordination reaction with pollutants carrying free radicals ·OH to form a complex.

[0054] exist Figure 1 Specifically, the receiving cavity 13 includes a straight cylindrical portion 131 and a flared portion 132. The flared portion 132 extends into the conical portion 14 of the device body 1, and modified filler 3 is arranged in segments along the inner side of the receiving cavity 13. The modified filler 3 is one or more of TiCl4-Al(C2H5)3, dicyclohexyl peroxide, di-tert-butyl peroxide, sodium persulfate, azobisisobutyronitrile, dimethyl azobisisobutyrate, N,N-dimethylaniline, and benzoyl peroxide.

[0055] Furthermore, the cross-section of the straight cylindrical portion 131 is circular, and the modified filler 3 is divided into two sections distributed in the receiving cavity 13.

[0056] Example 1

[0057] The ozone oxidation wastewater treatment method based on the polymerization pathway in this embodiment includes the following steps: adding a chain initiator with a mass fraction of 0.1% to high-concentration wastewater with a COD content of 5000; under the action of micron and / or nano-sized ozone chain initiators, micron and / or nano-sized ozone reacts with pollutants in the wastewater to generate free radicals ·OH; the chain initiator is H2O2 + H2SO4 + HMnO4 in a mass ratio of 1:3:1; benzoyl peroxide undergoes a coordination reaction with pollutants carrying free radicals ·OH to form a complex; the amount of benzoyl peroxide added is 0.01%; controlling the residence time to 2 hours, polymerizing into high-density macromolecular organic matter, and then separating it after cyclone separation; the COD content after treatment is 100, and the treatment efficiency is 98%.

[0058] Example 2

[0059] The specific parameters of the ozone oxidation wastewater treatment method in this embodiment are shown in Table 1, and the wastewater treatment results are shown in Table 2.

[0060] Example 3

[0061] The specific parameters of the ozone oxidation wastewater treatment method in this embodiment are shown in Table 1, and the wastewater treatment results are shown in Table 2.

[0062] Example 4

[0063] The specific parameters of the ozone oxidation wastewater treatment method in this embodiment are shown in Table 1, and the wastewater treatment results are shown in Table 2.

[0064] Comparative Example 1

[0065] The specific parameters of the ozone oxidation wastewater treatment method for the polymerization pathway in this comparative example are shown in Table 1, and the wastewater treatment results are shown in Table 2.

[0066] Comparative Example 2

[0067] The specific parameters of the ozone oxidation wastewater treatment method for the polymerization pathway in this comparative example are shown in Table 1, and the wastewater treatment results are shown in Table 2.

[0068] Comparative Example 3

[0069] The specific parameters of the ozone oxidation wastewater treatment method for the polymerization pathway in this comparative example are shown in Table 1, and the wastewater treatment results are shown in Table 2.

[0070] Table 1. Substances and parameters of the examples and comparative examples.

[0071]

[0072]

[0073] Table 2. Comparison of wastewater quality between the examples and comparative examples.

[0074] COD content before treatment COD content after treatment Processing efficiency Example 1 5000 100 0.98 Example 2 10000 96 0.9904 Example 3 20000 88 0.9956 Example 4 30000 102 0.9966 Comparative Example 1 10000 4200 0.58 Comparative Example 2 10000 201 0.977 Comparative Example 3 10000 163 0.979

[0075] As shown in Tables 1 and 2, this invention adjusts the particle size of the introduced micro-nano ozone, the concentration and ratio of the chain initiator, and the residence time within the device in real time according to changes in the influent water quality, thereby increasing the polymer molecular weight and achieving efficient pollutant separation. Furthermore, the addition of modified filler (especially TiCl4-Al(C2H5)3) has no effect on the OH yield and may even promote it; the minimum requirement is that it has virtually no impact.

[0076] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. An ozone oxidation wastewater treatment device based on a polymerization pathway, characterized in that, include: The device body (1) has a conical shape and is provided with an inlet (11) and an outlet (12). Inside the device body (1) is a receiving cavity (13), the bottom of which extends into the conical part (14) of the device body (1). An ozone reactor (2) connected to the conical bottom of the device body (1) is capable of generating micron and / or nano ozone. The micron and / or nano ozone reacts with pollutants in the wastewater to generate free radicals ·OH. The modified filler (3) placed in the cavity (13) can coordinate with pollutants carrying free radicals ·OH to form complexes; The receiving cavity (13) includes a straight cylindrical part (131) and a flared part (132). The flared part (132) extends into the conical part (14) of the device body (1), and the modified filler (3) is arranged in segments along the inner side of the receiving cavity (13). The cross-section of the straight section (131) is circular, and the modified filler (3) is divided into two sections distributed in the receiving cavity (13).

2. A treatment method using the ozone oxidation wastewater treatment device based on the polymerization pathway as described in claim 1, characterized in that, The method includes the following steps: under the action of micron and / or nano ozone chain initiators, micron and / or nano ozone react with pollutants in wastewater to generate free radicals ·OH; modified filler reacts with pollutants carrying free radicals ·OH to form complexes; the residence time is controlled to polymerize into high-density macromolecular organic matter, which is then separated after cyclone separation.

3. The treatment method of the ozone oxidation wastewater treatment device based on the polymerization pathway according to claim 2, characterized in that, Add 0.1%-3% chain initiator to the wastewater.

4. The treatment method of the ozone oxidation wastewater treatment device based on the polymerization pathway according to claim 3, characterized in that, The chain initiator is prepared by mixing H2O2, H2SO4, and HMnO4 in a ratio of 3:1:

3.

5. The treatment method of the ozone oxidation wastewater treatment device based on the polymerization pathway according to claim 4, characterized in that, The modified filler is one or more of TiCl4-Al(C2H5)3, dicyclohexyl peroxide, di-tert-butyl peroxide, sodium persulfate, azobisisobutyronitrile, dimethyl azobisisobutyrate, N,N-dimethylaniline, and benzoyl peroxide.

6. The treatment method of the ozone oxidation wastewater treatment device based on the polymerization pathway according to claim 5, characterized in that, The amount of the modified filler added is 0.01-0.2%.

7. The treatment method of the ozone oxidation wastewater treatment device based on the polymerization pathway according to claim 6, characterized in that, The stay time should be controlled to be 0.1-2 hours.

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