Ozone catalyst, preparation method and application thereof

Abstract

The application discloses an ozone catalyst and a preparation method and application thereof, relates to the technical field of ozone catalysts, and comprises the following steps: preparing a three-dimensional net structure continuous fiber group; mixing aluminum alloy powder, catalyst powder and pore-forming agent and adhesive into a paste-shaped ozone catalyst at a weight ratio of 70%-80%, 19%-28% and 1%-2%; spraying the prepared paste-shaped ozone catalyst on the continuous fiber group in a film-hanging mode, removing the excessive ozone catalyst through centrifugation, and obtaining a blank; feeding the dried blank into a sintering furnace for high-temperature calcination, obtaining a sintered blank with defiberization, cooling the obtained sintered blank to normal temperature, and finally obtaining a porous ozone catalytic filler with a connected path in the interior. The application can improve the degradation efficiency of organic matters, improve the flow capacity of sewage in the filler, utilize the carbon source degraded by the ozone catalysis, and improve the economic benefits.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of ozone catalysis, and particularly relates to an ozone catalyst and a preparation method and application thereof. BACKGROUND

[0002] Economic rapid development is accompanied by water pollution, especially urban rivers and lakes, which contain a large amount of organic pollutants and high content of nitrogen elements. Both are elements that cause water eutrophication. At present, the removal of organic matter and nitrogen in wastewater is often carried out separately.

[0003] At present, ozone oxidation technology is widely used in the treatment of organic wastewater, especially in the treatment of refractory organic wastewater. Ozone oxidation technology requires ozone oxidant for the degradation of organic matter. The existing ozone oxidant often adopts a granular pile filling method for wastewater treatment. Since the gap on the surface of the granular is small, the wastewater cannot pass through the inside of the granular for wastewater treatment. The degradation of organic matter only stays on the surface of the granular, thereby affecting the degradation efficiency of the organic matter in the wastewater. In addition, if a better treatment effect is to be achieved, the thickness of the filler needs to be increased. However, increasing the thickness of the filler will hinder the flow and also easily cause the clogging of the filler.

[0004] The ozone oxidation degradation of organic wastewater treatment produces carbon sources, which cannot be effectively utilized if not used, thereby causing waste of energy. Therefore, the application discloses an ozone catalyst and a preparation method and application thereof. SUMMARY

[0005] The ozone catalyst and the preparation method and application thereof are proposed to solve the problems in the prior art, such as low wastewater treatment efficiency of the ozone oxidant adopting the granular pile filling method, easy clogging, and the carbon sources produced in the ozone oxidation degradation of organic wastewater cannot be effectively utilized. The ozone catalyst adopts an integrated block filler, and a porous ozone catalytic filler with a communication path can be formed in the filler, so that the specific surface area of the ozone catalytic filler in contact with the wastewater can be increased. On the one hand, the degradation efficiency of the organic matter in the wastewater is improved. On the other hand, the flow capacity of the wastewater in the filler is improved. In addition, the filler plate designed in a layered and gradually decreasing layer distance can perform layered and deep treatment on the wastewater, and the carbon sources degraded by the ozone catalysis can be utilized. The source of sulfur autotrophic denitrification carbon is increased, the carbon source is reduced, and the carbon source investment cost is saved.

[0006] In order to achieve the above purpose, the application adopts the following technical scheme:

[0007] A preparation method of an ozone catalyst is designed, which comprises the following steps:

[0008] Step 1, preparing a three-dimensional network structure continuous fiber group for standby;

[0009] Step 2, mixing aluminum alloy powder, catalyst powder and pore-forming agent with binder in a weight ratio of 70%-80%, 19%-28% and 1%-2% into a paste-like ozone catalyst;

[0010] Step 3, spraying the paste-like ozone catalyst prepared in step 2 on the continuous fiber body in a film-hanging manner, and removing the excess ozone catalyst by centrifugation to obtain a blank;

[0011] Step 4, sending the dried blank of step 3 into a sintering furnace for high-temperature calcination to obtain a defiberized sintered blank;

[0012] Step 5, cooling the sintered blank obtained in step 4 to room temperature, and finally obtaining a porous ozone catalytic filler with internal connected paths through cutting.

[0013] Further, the continuous fiber body is a loofah fiber carrier.

[0014] Further, the catalyst powder is a mixture of one or more of manganese dioxide, titanium dioxide and cerium oxide, the pore-forming agent is a mixture of one or both of cellulose particles and carbon powder particles, and the binder is a polyvinyl alcohol solution.

[0015] To solve the above technical problems, the application further provides a porous ozone catalytic filler prepared by the method.

[0016] To solve the above technical problems, the application further provides an application of an ozone catalyst, and the ozone catalyst is applied in a composite sewage treatment device according to the application, the composite sewage treatment device comprising a filler tower, an ozone catalytic unit being arranged above the inside of the filler tower and a sulfur autotrophic denitrification unit being arranged below the inside of the filler tower; the ozone catalytic unit is composed of a plurality of first filler plates, a plurality of first filler grooves are arranged in an array manner through each of the first filler plates, and a porous ozone catalytic filler is arranged in the first filler grooves.

[0017] Further, the plate spacing of the plurality of first filler plates of the ozone catalytic unit is arranged in a decreasing manner.

[0018] Further, the porous ozone catalytic filler comprises a filler tube, the top of the filler tube is provided with an outwardly protruding protruding ridge, the top of the protruding ridge is in a funnel shape, an ozone catalytic filler is fixedly arranged in the filler tube, and a first bottom support for supporting the ozone catalytic filler is arranged at the bottom of the filler tube.

[0019] Further, the top of the first filler groove is provided with a limiting groove in an annular structure, and the depth of the limiting groove is the same as the thickness of the protruding ridge.

[0020] Further, the filling pipe and the first filling groove are connected by threads, the outer wall of the filling pipe is provided with an outer threaded part, and the first filling groove is internally provided with an inner threaded part matched with the outer threaded part.

[0021] The ozone catalyst, the preparation method and the application have the beneficial effects that:

[0022] (1) The ozone catalyst adopts an integrated block filler, and the porous ozone catalytic filler with a communication path can be formed in the block filler. The sewage can directly pass through the communication path in the porous ozone catalytic filler, flow through the porous ozone catalytic filler, and has a large communication gap in the interior for the flow of the sewage. The specific surface area of the ozone catalytic filler in contact with the sewage can be increased. On the one hand, the degradation efficiency of the organic matter in the sewage is improved. On the other hand, the thickness of the ozone catalytic filler can be reduced, the travel of the sewage in the filler is reduced, the flow capacity is improved, and in addition, the filler plate with the design of the layered and gradually reduced layer distance can be used for layered and deep treatment of the sewage.

[0023] (2) The ozone catalytic unit is arranged above the sulfur autotrophic denitrification unit, so that the sulfur autotrophic denitrification unit can utilize the carbon source generated by the ozone catalytic unit. On the one hand, the carbon source generated by the ozone catalytic unit is utilized, and the utilization of the carbon source is improved. On the other hand, the source of the sulfur autotrophic denitrification unit is increased, the addition of the carbon source is reduced, and the carbon source addition cost is saved.

[0024] (3) The semi-permeable membrane is used to add the carbon source for the sulfur autotrophic denitrification filler, the loss amount of the carbon source after addition is reduced, and the utilization rate of the carbon source is improved. BRIEF DESCRIPTION OF DRAWINGS

[0025] The accompanying drawings are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and serve to explain the principles of the application, and do not limit the application. In the drawings:

[0026] Figure 1 is a structure schematic view of a composite sewage treatment device in the application;

[0027] Figure 2 is a partial sectional structure schematic view of a first filler plate in the application;

[0028] Figure 3 is a structure schematic view of the porous ozone catalytic filler in the application;

[0029] Figure 4 is a split structure schematic view of the porous ozone catalytic filler in the application;

[0030] Figure 5is a schematic diagram of the internal structure of the porous ozone catalytic filler related to the present application;

[0031] Figure 6 is a schematic diagram of the partial cross-sectional structure of the second filler plate (sulfur autotrophic denitrification filler) related to the present application;

[0032] Figure 7 is a schematic diagram of the partial cross-sectional structure of the second filler plate related to the present application;

[0033] Figure 8 is a schematic diagram of the disassembled structure of the sulfur autotrophic denitrification filler related to the present application;

[0034] Figure 9 is a schematic diagram of the carbon source supply of the sulfur autotrophic denitrification filler related to the present application;

[0035] Figure 10 is a flow chart of the preparation process of the ozone catalyst related to the present application

[0036] In the figure, the marks are: 1, filler tower; 2, first filler plate; 21, first filler groove; 22, limiting groove; 23, internal threaded part; 3, porous ozone catalytic filler; 31, filler pipe; 32, protruding ridge; 33, external threaded part; 34, first bottom support; 4, second filler plate; 41, liquid inlet pipe; 42, liquid outlet pipe; 43, cavity; 44, second filler groove; 45, through hole; 46, second bottom support; 5, sulfur autotrophic denitrification filler; 6, semi-permeable membrane. DETAILED DESCRIPTION

[0037] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application; obviously, the described embodiments are only part of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0038] In the description of the present application, it should be noted that the terms "upper", "lower", "internal", "external", "top / bottom end" and the like indicate the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the present application. In addition, the terms "first", "second" are only for descriptive purposes and cannot be understood as indicating or implying relative importance.

[0039] In the description of the present application, it should be noted that unless otherwise explicitly specified and limited, the terms "mounting", "provided with", "sleeved / connected", "connected" and the like should be understood broadly, for example, "connected" can be fixedly connected, or detachably connected, or integrally connected; can be mechanically connected, or electrically connected; can be directly connected, or indirectly connected through an intermediate medium, or can be connected internally between two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the present application can be understood according to the specific circumstances.

[0040] The structural features of the present application will be described in detail in conjunction with the accompanying drawings.

[0041] Example 1

[0042] Reference Figures 1-9The application relates to an application of an ozone catalyst in a composite sewage treatment device, and the ozone catalysis and sulfur autotrophic denitrification composite sewage treatment device comprises a filler tower 1, the inside of the filler tower 1 is provided with an ozone catalysis unit at the upper portion and is provided with a sulfur autotrophic denitrification unit at the lower portion. The ozone catalysis unit is composed of a plurality of first filler plates 2, a plurality of first filler grooves 21 are arranged in an array mode and are penetrated through each first filler plate 2, porous ozone catalysis fillers 3 are arranged in the first filler grooves 21, the porous ozone catalysis fillers 3 decompose organic matters in flowing sewage into carbon-containing substances and water, the porous ozone catalysis fillers 3 comprise filler pipes 31, the top portions of the filler pipes 31 are provided with outward protruding protrusions 32, the top portions of the first filler grooves 21 are provided with annular limiting grooves 22, the depth of the limiting grooves 22 is the same as the thickness of the protrusions 32, so that the top portions of the filler pipes 31 are flush with the top portions of the first filler plates 2, so that the sewage falling on the first filler plates 2 flows through the porous ozone catalysis fillers 3, the top portions of the protrusions 32 are funnel-shaped, the funnel-shaped structure facilitates the sewage to flow into the porous ozone catalysis fillers 3, ozone catalysis fillers are fixedly arranged in the filler pipes 31, and first bottom supports 34 for supporting the ozone catalysis fillers are arranged at the bottom portions of the filler pipes 31. The sulfur autotrophic denitrification unit is composed of a plurality of second filler plates 4, a plurality of second filler grooves 44 are arranged in an array mode and are penetrated through each second filler plate 4, and sulfur autotrophic denitrification fillers 5 are arranged in the second filler grooves 44. The inside of the second filler plate 4 is a hollow cavity 43, the cavity 43 is used for introducing a carbon source solution and supplying the carbon source for the sulfur autotrophic denitrification fillers 5, liquid inlet pipes 41 and liquid outlet pipes 42 are arranged at the two ends of the second filler plate 4 and are communicated with the cavity 43, and the liquid inlet pipes 41 and the liquid outlet pipes 42 are used for the carbon source solution. A plurality of through holes 45 are arranged on the circumferences of the second filler grooves 44, the through holes 45 are arranged to make the interiors of the second filler grooves 44 communicated with the cavity 43, so that the carbon source solution in the cavity 43 enters the second filler grooves 44, a semi-permeable membrane 6 is arranged between the second filler grooves 44 and the sulfur autotrophic denitrification fillers 5, the semi-permeable membrane 6 allows carbonate ions and metal ions in the carbonate solution (carbon source) to pass through and supply the carbon source for the sulfur autotrophic denitrification fillers 5. In order to make the sewage better pass through the ozone catalysis unit and the sulfur autotrophic denitrification unit, the plate spacing of the plurality of first filler plates 2 of the ozone catalysis unit and the plurality of second filler plates 4 of the sulfur autotrophic denitrification unit is arranged in a decreasing mode, the interval-decreasing arrangement mode can make the filler plates deeply treat the sewage.

[0043] The application of the ozone catalyst in the composite sewage treatment device can utilize the carbon source degraded by the ozone catalysis, increases the carbon source of the sulfur autotrophic denitrification, reduces the carbon source discharge, saves the carbon source discharge cost, increases the carbon source for the sulfur autotrophic denitrification fillers through the semi-permeable membrane, reduces the loss of the carbon source after addition, and improves the utilization rate of the carbon source.

[0044] Specifically, in use, sewage is sprayed from the top of the filler tower 1 into the ozone catalytic unit, and the organic matter is removed through the multi-layer first filler plate 2, and the organic matter is decomposed into carbon source and water, and enters the sulfur autotrophic denitrification unit with the solution, part of the carbon source source of the sulfur autotrophic denitrification unit, in the sulfur autotrophic denitrification unit, a high-concentration carbon source solution is introduced into the second filler plate 4 through the liquid inlet pipe 41, and the sodium carbonate solution is used as the carbon source here, when the sewage flows through the sulfur autotrophic denitrification filler 5, the sulfur autotrophic denitrification filler 5 carries out sulfur autotrophic denitrification, and consumes the carbon source, at this time, the concentration of sodium carbonate solution in the sulfur autotrophic denitrification filler 5 is lower than that in the cavity 43, at this time, the sodium carbonate solution in the cavity 43 is continuously supplied to the sulfur autotrophic denitrification filler 5 through the inner semi-permeable membrane 6, thereby ensuring the supply of carbon source in the sulfur autotrophic denitrification filler 5, reducing the loss of carbon source, and improving the utilization of carbon source.

[0045] Example 2

[0046] Referring to Figures 2-3 , as another preferred embodiment of the present application, the difference from example 1 is that the threaded connection is adopted between the filler pipe 31 and the first filler groove 21, the outer wall of the filler pipe 31 is provided with an outer threaded part 33, and the first filler groove 21 is provided with an inner threaded part 23 matched with the outer threaded part 33, and the threaded connection is adopted, on the one hand, the installation and disassembly of the porous ozone catalytic filler 3 are facilitated, and on the other hand, the porous ozone catalytic filler 3 is prevented from being separated from the first filler groove 21.

[0047] Example 3

[0048] Referring to Figures 4-5 and Figure 10 , in order to further illustrate the present application, an ozone catalyst and a preparation method thereof are further provided.

[0049] The ozone catalyst is a porous ozone catalytic filler 3, and the method for preparing the porous ozone catalytic filler 3 comprises the following steps:

[0050] Step 1, preparing a three-dimensional network structure continuous fiber group for standby, wherein the continuous fiber group is a loofah fiber carrier.

[0051] Step 2, mixing aluminum alloy powder, catalyst powder and pore-forming agent and adhesive into paste-shaped ozone catalyst according to a weight ratio of 70%, 28% and 2%.

[0052] Step 3, spraying the paste-shaped ozone catalyst prepared in step 2 on the loofah in a membrane-hanging manner, and removing the excess ozone catalyst by centrifugation to obtain a blank.

[0053] Step 4, after the blank completed in step 3 is placed at room temperature and air dried, it is sent to a sintering furnace for high temperature baking, the baking temperature is controlled at 500-600 degrees Celsius, finally the porous ozone catalytic filler 3 with internal connected path is obtained.

[0054] Wherein, the catalyst powder is a mixture of one or more of manganese dioxide, titanium dioxide and cerium oxide, the pore-forming agent is a mixture of one or both of cellulose particles or carbon powder particles, and the binder is a polyvinyl alcohol solution.

[0055] Example 4

[0056] Reference Figures 4-5 and Figure 10 In order to further illustrate, the present application also proposes an ozone catalyst and a preparation method thereof.

[0057] The ozone catalyst is a porous ozone catalytic filler 3, and the method for preparing the porous ozone catalytic filler 3 comprises the following steps:

[0058] Step 1, prepare a continuous fiber group with a three-dimensional reticular structure, for standby, wherein the continuous fiber group is a loofah fiber carrier.

[0059] Step 2, mix aluminum alloy powder, catalyst powder and pore-forming agent and binder in a weight ratio of 80%, 19% and 1% into a paste-shaped ozone catalyst.

[0060] Step 3, the paste-shaped ozone catalyst prepared in step 2 is sprayed on the loofah in a membrane-hanging manner, and the excess ozone catalyst is removed by centrifugation to obtain a blank.

[0061] Step 4, after the blank completed in step 3 is placed at room temperature and air dried, it is sent to a sintering furnace for high temperature baking, the baking temperature is controlled at 500-600 degrees Celsius, finally the porous ozone catalytic filler 3 with internal connected path is obtained.

[0062] Wherein, the catalyst powder is a mixture of one or more of manganese dioxide, titanium dioxide and cerium oxide, the pore-forming agent is a mixture of one or both of cellulose particles or carbon powder particles, and the binder is a polyvinyl alcohol solution.

[0063] In the examples 3 and 4, the porous ozone catalytic filler 3 after calcination, the internal continuous fiber groups are carbonized under the action of high temperature, so that a three-dimensional network structure continuous channel is formed in the internal of the porous ozone catalytic filler 3, and due to the pore-forming agent contained in the channel wall, a through hole is formed on the channel wall of the three-dimensional network structure continuous channel under high temperature, so that a more permeable network channel is formed in the internal of the whole porous ozone catalytic filler 3, so that the sewage can flow through the internal of the porous ozone catalytic filler 3, the ozone catalyst adopts an integrated block filler, the porous ozone catalytic filler 3 with the internal connected path, the sewage can directly pass through the internal connected path of the porous ozone catalytic filler 3, and the sewage can flow through the internal of the porous ozone catalytic filler 3, and the internal has a larger connected gap for the sewage to flow, so that the specific surface area of the ozone catalytic filler in contact with the sewage can be increased, on the one hand, the degradation efficiency of the organic matter in the sewage is improved, and on the other hand, the thickness of the ozone catalytic filler can be reduced, the travel of the sewage in the filler is reduced, and the flow capacity of the sewage treatment is improved.

[0064] Example 5

[0065] As another preferred embodiment of the present application, the difference from example 1 is that the sulfur autotrophic denitrification filler 5 takes loofah as the carrier, and the sulfur autotrophic denitrification filler is obtained by film hanging, drying and the like with the sulfur autotrophic denitrification filler agent.

[0066] The preparation method of the sulfur autotrophic denitrification filler includes the following steps:

[0067] Step 1, select dry loofah and cut it into a cylindrical structure with a desired size.

[0068] Step 2, soak the cut loofah in a solution inoculated with sulfur autotrophic denitrifying bacteria, and take it out to dry.

[0069] Step 3, mix pyrite powder and sulfur powder with the binder in a proportion of 1:1 by weight to form a paste-like sulfur autotrophic denitrification filler agent.

[0070] Step 4, pour the paste-like sulfur autotrophic denitrification filler agent prepared in step 3 on the loofah in a film-hanging manner, and remove the excess sulfur autotrophic denitrification filler agent by centrifugation to obtain a blank.

[0071] Step 4, place the blank completed in step 3 at room temperature for air drying, polish the side part to expose the loofah, and finally obtain a porous sulfur autotrophic denitrification filler with internal connected fibers. The reason for polishing the side part of the sulfur autotrophic denitrification filler is to expose the loofah on the side part of the sulfur autotrophic denitrification filler and contact with the semi-permeable membrane 6, so that the carbon source in the internal of the semi-permeable membrane 6 can better enter the internal of the sulfur autotrophic denitrification filler.

[0072] The above merely describes the preferred embodiments of the present application and is not used to limit the present application, and although the present application is described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions recorded in the foregoing embodiments, or equivalently replace some technical features thereof. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for producing a porous ozone catalytic filler, characterized by, It comprises the following steps: S1, preparing a continuous fiber group of three-dimensional reticular structure, standby; S2, mixing aluminum alloy powder, catalyst powder and pore-forming agent with adhesive in a weight ratio of 70%-80%, 19%-28% and 1%-2% into a paste-like ozone catalyst; S3, spraying the paste-like ozone catalyst prepared in S2 on the continuous fiber group in a membrane-hanging manner, and removing the excess ozone catalyst by centrifugation to obtain a blank; S4, sending the dried blank in S3 into a sintering furnace for high-temperature calcination to obtain a defiberized sintered blank; S5, cooling the sintered blank obtained in S4 to room temperature, and finally obtaining a porous ozone catalytic filler (3) with a connected path inside after cutting; The continuous fiber group is a loofah fiber carrier; The catalyst powder is a mixture of one or more of manganese dioxide, titanium dioxide and cerium oxide, the pore-forming agent is a mixture of one or both of cellulose particles and carbon powder particles, and the adhesive is a polyvinyl alcohol solution.

2. A porous ozone catalytic packing, characterized by, The porous ozone catalytic filler (3) prepared by the method of claim 1.

3. Use of a porous ozone catalyst packing, characterized in that, The application of the porous ozone catalytic filler according to claim 2 in a composite sewage treatment device, wherein the composite sewage treatment device comprises a filler tower (1), and an ozone catalytic unit is arranged above the inside of the filler tower (1), and a sulfur autotrophic denitrification unit is arranged below the inside of the filler tower (1); The ozone catalytic unit is composed of a plurality of first filler plates (2), and a plurality of first filler grooves (21) are arranged in an array on each first filler plate (2), and the first filler grooves (21) are provided with the porous ozone catalytic filler (3).

4. Use according to claim 3, characterized in that, The plate spacing of the plurality of first filler plates (2) of the ozone catalytic unit is arranged in a decreasing manner.

5. Use according to claim 3, characterized in that, The porous ozone catalytic filler (3) comprises a filler tube (31), the top of the filler tube (31) is provided with a protruding ridge (32) outwardly protruding, the top of the protruding ridge (32) is funnel-shaped, the ozone catalytic filler is fixedly arranged in the filler tube (31), and the bottom of the filler tube (31) is provided with a first bottom support (34) for supporting the ozone catalytic filler.

6. Use according to claim 5, characterized in that, The top of the first filler groove (21) is provided with a limiting groove (22) of an annular structure, and the depth of the limiting groove (22) is the same as the thickness of the protruding ridge (32).

7. Use according to claim 5, characterized in that, The filler tube (31) and the first filler groove (21) are connected by threads, the outer wall of the filler tube (31) is provided with an outer threaded portion (33), and the first filler groove (21) is provided with an inner threaded portion (23) matched with the outer threaded portion (33).

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