Ozone oxidation wastewater treatment method and device based on polymerization path

Abstract

The invention discloses an ozone oxidation wastewater treatment method and device based on a polymerization path, and belongs to the technical field of water treatment. The method comprises the following steps: under the action of a micron and / or nano ozone chain initiator, micron and / or nano ozone reacts with pollutants in wastewater to generate free radicals. OH; carrying out coordination reaction on the modified filler and pollutants carrying free radicals. OH to form a complex; and controlling the retention time, polymerizing into a high-density macromolecular organic matter, and separating after cyclone separation. According to the method, under the action of the micron and / or nano ozone chain initiator, the wastewater cooperates with the modified filler to perform substance reaction, the substance reaction path in the wastewater is controlled, high-density macromolecular organic matters are polymerized, and then separation is performed after rotational flow, the method can be applied to treatment of various wastewater, the application range is expanded, and the method is suitable for industrial production. Meanwhile, the reaction rate is increased by adopting the modified filler, and the ozone treatment efficiency is effectively improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of water treatment, and in particular relates to a method and a device for treating wastewater by ozone oxidation based on a polymerization pathway. Background Art

[0002] Ozone is an unstable, light blue gas with a special pungent odor at room temperature and pressure. Ozone has extremely strong oxidizing properties and has an oxidation potential of 2.07V in alkaline solution. Its oxidizing ability is second only to fluorine and higher than chlorine and potassium permanganate. Based on the strong oxidizing property of ozone and its ability to self-decompose in water in a short time without secondary pollution, it is an ideal green oxidizing agent. Therefore, the ozone oxidation method has gradually developed into an advanced oxidation technology. In the field of water treatment, ozone technology has been applied in many aspects. For example, its main functions in water treatment are deodorization, decolorization, sterilization and removal of organic matter.

[0003] At present, the common ozone oxidation process mainly relies on the strong oxidizing property of ozone, which directly or indirectly reacts with pollutants in wastewater to decompose into carbon dioxide and water. This is subject to factors such as the oxidizing capacity of ozone, the type of pollutants, and the concentration of pollutants. Since ozone oxidation is selective and has high production and transportation costs, its application in high-concentration wastewater is restricted.

[0004] In order to solve the above problems, after searching, patent document CN110026242A discloses a preparation method of a Co / Ce bimetallic MOF-based ozone catalyst, its product and application. The Co / Ce bimetallic MOF-based ozone catalyst, which forms a three-dimensional pore structure by self-assembly of two metal centers of cobalt and cerium and organic ligands, can effectively regulate the active sites to promote the catalytic activity of MOFs, increase the decomposition rate of ozone by Co / Ce-based composite materials, generate more active hydroxyl radicals, which is beneficial to catalyze the ozonation of organic pollutants in water and greatly improve 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 activation factor, a metal salt solution and oxygen, etc. The oxygen is formed into the required ozone by an ozone generator, and the carrier, distilled water, an activation factor, a metal salt solution and the ozone form an ozone oxidation catalyst. The ozone oxidation catalyst has a treatment efficiency of 81% higher than that of a certain residence time under certain water quality pH conditions. The patent has the characteristics of high efficiency and universality.

[0006] However, after analyzing the contents disclosed in the above two patents, it was found that ozone needs to be used in combination with a catalyst, which leads to low treatment efficiency in the ozone process, and the effective range of wastewater treated is narrow, which is not conducive to the expansion of the use of technology. Summary of the invention

[0007] 1. Problem to be solved

[0008] In view of the technical problems of low treatment efficiency and narrow application scope in the ozone process in the prior art, the purpose of the present invention is to propose an ozone oxidation wastewater treatment method based on a polymerization pathway, expand the application scope, and at the same time improve 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] In order to solve the above problems, the technical solution adopted by the present invention is as follows:

[0012] The first aspect of the present invention provides an ozone oxidation wastewater treatment method based on a polymerization path, the method comprising the following steps: under the action of micron and / or nano-ozone chain initiators, micron and / or nano-ozone reacts with pollutants in the wastewater to generate free radicals ·OH; modified fillers react with pollutants carrying free radicals ·OH to form complexes; control the residence time to polymerize into high-density macromolecular organic matter, and then separate after cyclone flow.

[0013] According to any embodiment of the first aspect of the present invention, the chain initiator is H 2 O 2 , H 2 SO 4 、HMnO 4 One or more of the .

[0014] According to any embodiment of the first aspect of the present invention, 0.1-3% by mass of chain initiator 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 H 2 O 2 , H 2 SO 4 、HMnO 4 Prepared in a ratio of 3:1:3 (mass ratio). Through the synergistic effect of the three, 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 TiCl 4 -Al(C 2 H 5 )3 , one or more of dicyclohexyl peroxydicarbonate, di-tert-butyl peroxide, sodium persulfate, azobisisobutyronitrile, dimethyl azobisisobutyrate, N,N-dimethylaniline, and benzoyl peroxide.

[0017] It should be emphasized that through a large number of experimental analyses, it is known that the modified filler can lose electrons to ozone, thereby forming active sites, and then obtain electrons from water to form hydroxyl radicals. Hydroxyl radicals can initiate chain polymerization and can treat the remaining COD in the water after the polymerization is completed, thereby reducing the COD content in 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, and the reaction polymerization time is fully considered to ensure the polymerization effect.

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

[0021] The device body has a conical shape, is provided with a water inlet and a water outlet, and is provided with a receiving cavity inside the device body, the bottom of the receiving cavity extends into the conical portion of the device body;

[0022] An ozone reactor connected to the conical bottom of the device body and capable of producing micron and / or nano ozone, wherein the micron and / or nano ozone reacts with pollutants in the wastewater to produce free radicals·OH;

[0023] The modified filler placed in the containing cavity can undergo coordination reaction with the pollutant carrying free radical ·OH to form a complex.

[0024] According to any embodiment of the second aspect of the present invention, the accommodating chamber includes a straight cylindrical portion and a flared portion, the flared portion extends into the tapered portion of the device body, and the modified filler is arranged in sections along the inner side of the accommodating chamber.

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

[0026] 3. Beneficial effects

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] (1) The ozone oxidation wastewater treatment method based on the polymerization path of the present invention, the wastewater is subjected to the action of micron and / or nanometer ozone chain initiators, and the modified filler is coordinated to react with substances, the reaction path of substances in the wastewater is controlled, and polymerized into high-density macromolecular organic matter, and then separated after cyclone flow. This method can be applied to the treatment of various wastewaters, expanding the scope of application. At the same time, the modified filler is used to increase 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. The dosage accounts for 0.1-3% of the mass fraction relative to the removal of pollutants, which effectively saves the use cost;

[0030] (3) The ozone oxidation wastewater treatment method based on the polymerization pathway of the present invention, wherein the chain initiator (H 2 O 2 , H 2 SO 4 、HMnO 4 ) are 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 path of the present invention, wherein the modified filler adopts (TiCl 4 -Al(C 2 H 5 ) 3 ), this substance can control the concentration increase of the molecular active center, increase the reaction rate, increase the polymerization effect and the size of the polymerization molecular weight, thereby improving the treatment effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] The technical solution of the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments, but it should be understood that these drawings are designed only for explanation purposes and are not intended to limit the scope of the present invention. In addition, unless otherwise specified, these drawings are intended only to conceptually illustrate the structural configurations described herein and are not necessarily drawn to scale.

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

[0035] Description of reference numerals:

[0036] 1. Device body; 11. Water inlet; 12. Water outlet; 13. Accommodating chamber; 131. Straight tube portion; 132. Expanded portion; 14. Conical portion;

[0037] 2. Ozone reactor;

[0038] 3. Modified filler. DETAILED DESCRIPTION

[0039] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Generally, the components of the embodiments of the present invention described and shown in the drawings here can be arranged and designed in various different configurations.

[0040] Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0041] It should be noted that similar reference numerals and letters denote similar items in the following drawings, and therefore, once an item is defined in one drawing, further definition and explanation thereof is not required in subsequent drawings.

[0042] In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inside", "outside", etc. indicate positions or positional relationships based on the positions or positional relationships shown in the accompanying drawings, or the positions or positional relationships in which the product of the invention is usually placed when in use. They are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific position, be constructed and operated in a specific position, and therefore cannot be understood as limiting the present invention. In addition, the terms "first", "second", "third", etc. are only used to distinguish the description, and cannot be understood as indicating or implying relative importance.

[0043] In addition, the terms "horizontal", "vertical" and the like do not mean that the components are required to be absolutely horizontal or suspended, but can be slightly tilted. For example, "horizontal" only 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 the present invention, it is also necessary to explain that, unless otherwise clearly specified and limited, the terms "set", "install", "connect", and "connect" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0045] The ozone oxidation wastewater treatment method based on the polymerization path of the present invention comprises the following steps: adding a chain initiator with a mass fraction of 0.1-3% to the wastewater, and reacting the micron and / or nano ozone with the pollutants in the wastewater under the action of the micron and / or nano ozone chain initiator to generate free radicals OH, wherein the chain initiator is H 2 O 2 , H 2 SO 4 、HMnO 4 One or more of the following; the modified filler reacts with the pollutant carrying the free radical OH to form a complex, wherein the modified filler is TiCl 4 -Al(C 2 H 5 ) 3 , dicyclohexyl peroxydicarbonate, di-tert-butyl peroxide, sodium persulfate, azobisisobutyronitrile, dimethyl azobisisobutyrate, N,N-dimethylaniline, benzoyl peroxide, one or more of the following, the amount of the above modified filler added is 0.01-0.2%; the residence time is controlled to be 0.1-2h, polymerized into high-density macromolecular organic matter, and then separated after cyclone flow.

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

[0047] The amount of the modified filler added cannot be less than 0.01%. As mentioned above, it is not conducive to controlling the increase in the concentration of the molecular active center and improving the reaction rate; the amount added cannot be higher than 0.2%. When the amount added exceeds this value, it is not conducive to accurately controlling the stereoregularity of the polymer in the wastewater, resulting in unsatisfactory treatment efficiency.

[0048] Preferably, the chain initiator is H 2 O 2 , H 2 SO 4 、HMnO 4Prepared in a ratio of 3:1:3. Through the synergistic effect of the three, the initiation effect is maximized and the amount of chain initiator used is reduced.

[0049] Preferably, the modified filler is TiCl 4 -Al(C 2 H 5 ) 3 This substance can control the increase in the concentration of molecular active centers, increase the reaction rate, increase the polymerization effect, and increase the size of the polymerization molecular weight, thereby improving the treatment effect.

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

[0051] The device body 1 has a conical shape, and is provided with a water inlet 11 and a water 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 portion 14 of the device body 1;

[0052] An ozone reactor 2 is connected to the conical bottom of the device body 1 and can produce micron and / or nano ozone. The micron and / or nano ozone reacts with pollutants in the wastewater to produce free radicals OH. The ozone reactor 2 can adopt an ozone reactor in the prior art, so it is not described here.

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

[0054] exist Figure 1 Specifically, the accommodating chamber 13 includes a straight tube portion 131 and a flared portion 132, the flared portion 132 extends into the conical portion 14 of the device body 1, and the modified filler 3 is arranged in sections along the inner side of the accommodating chamber 13. The modified filler 3 is TiCl 4 -Al(C 2 H 5 ) 3 , one or more of dicyclohexyl peroxydicarbonate, di-tert-butyl peroxide, sodium persulfate, azobisisobutyronitrile, dimethyl azobisisobutyrate, N,N-dimethylaniline, and benzoyl peroxide.

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

[0056] Example 1

[0057] The ozone oxidation wastewater treatment method based on the polymerization pathway of this embodiment comprises the following steps: adding a chain initiator with a mass fraction of 0.1% to high-concentration wastewater, wherein the COD content in the wastewater is 5000, and reacting the micron and / or nano ozone with the pollutants in the wastewater under the action of the micron and / or nano ozone chain initiator to generate free radicals ·OH, wherein the chain initiator is H 2 O 2 +H 2 SO 4 +HMnO 4 ; Mass ratio 1:3:1; Benzoyl peroxide reacts with pollutants carrying free radicals ·OH to form a complex, and the amount of benzoyl peroxide added is 0.01%; the residence time is controlled to be 2h, polymerized into high-density macromolecular organic matter, and then separated after cyclone flow. 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 based on the polymerization path of this embodiment are shown in Table 1, and the results of the wastewater treatment are shown in Table 2.

[0060] Example 3

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

[0062] Example 4

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

[0064] Comparative Example 1

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

[0066] Comparative Example 2

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

[0068] Comparative Example 3

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

[0070] Table 1 Materials and parameters of the examples and comparative examples

[0071]

[0072]

[0073] Table 2 Comparison of wastewater quality of the embodiment and the comparative example

[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 Table 1 and Table 2, the present invention changes the size of the introduced micro-nano ozone particles, the concentration and ratio of the chain initiator, and the residence time in the device in real time according to the change of the water quality of the influent, thereby achieving an increase in the molecular weight of the polymer and efficiently separating pollutants. In addition, the addition of modified fillers (especially TiCl 4 -Al(C 2 H 5 ) 3 ) has no effect on OH yield and may even promote it. The minimum requirement is that it has basically no effect.

[0076] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, some improvements and modifications can be made without departing from the technical principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for treating wastewater by ozone oxidation based on a polymerization pathway, characterized in that: The method comprises the following steps: under the action of micron and / or nanometer ozone chain initiators, micron and / or nanometer ozone reacts with pollutants in wastewater to generate free radicals·OH; modified fillers react with pollutants carrying free radicals·OH to form complexes; control the residence time to polymerize into high-density macromolecular organic matter, and then separate after cyclone flow.

2. The method for treating wastewater by ozone oxidation based on a polymerization pathway according to claim 1, characterized in that: The chain initiator is one or more of H2O2, H2SO4, and HMnO4.

3. The method for treating wastewater by ozone oxidation based on a polymerization pathway according to claim 1, characterized in that: 0.1%-3% chain initiator is added to the wastewater.

4. The method for treating wastewater by ozone oxidation based on a polymerization pathway according to claim 2, characterized in that: The chain initiator is H2O2, H2SO4, and HMnO4 prepared in a ratio of 3:1:

3.

5. The method for treating wastewater by ozone oxidation based on a polymerization pathway according to claim 1, characterized in that: The modified filler is one or more of TiCl4-Al(C2H5)3, dicyclohexyl peroxydicarbonate, di-tert-butyl peroxide, sodium persulfate, azobisisobutyronitrile, dimethyl azobisisobutyrate, N,N-dimethylaniline, and benzoyl peroxide.

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

7. The method for treating wastewater by ozone oxidation based on a polymerization pathway according to claim 1, characterized in that: The control residence time is 0.1-2h.

8. An ozone oxidation wastewater treatment device based on a polymerization pathway, characterized in that: include: The device body (1) has a conical outer contour and is provided with a water inlet (11) and a water 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 portion (14) of the device body (1); An ozone reactor (2) connected to the conical bottom of the device body (1) and capable of producing micron and / or nano ozone, wherein the micron and / or nano ozone reacts with pollutants in the wastewater to produce free radicals·OH; The modified filler (3) placed in the containing cavity (13) can undergo coordination reaction with the pollutant carrying the free radical ·OH to form a complex.

9. The ozone oxidation wastewater treatment device based on polymerization path according to claim 8 is characterized in that: The accommodating chamber (13) comprises a straight cylindrical portion (131) and a flared portion (132), wherein the flared portion (132) extends into the conical portion (14) of the device body (1), and the modified filler (3) is arranged in sections along the inner side of the accommodating chamber (13).

10. The ozone oxidation wastewater treatment device based on polymerization path according to claim 8, characterized in that: The cross section of the straight cylindrical portion (131) is circular, and the modified filler (3) is divided into two sections and distributed in the accommodating cavity (13).

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