CN115301254B - Ozone oxidation catalyst, preparation and application thereof in water treatment - Google Patents
Ozone oxidation catalyst, preparation and application thereof in water treatment Download PDFInfo
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Abstract
The invention belongs to the technical field of advanced materials and environmental protection, relates to a technology for catalytic degradation water treatment, and relates to an ozone oxidation catalyst, preparation and application thereof in water treatment. The ozone oxidation catalyst comprises an inert carrier, wherein the inert carrier is loaded with transition metal oxide and cerium oxide; the transition metal oxide is manganese dioxide or copper oxide; the inert carrier is alpha-Al with the surface covered with metallic silver 2 O 3 (ii) a Metallic silver, alpha-Al 2 O 3 And the mass ratio of the transition metal oxide to the cerium oxide is 5 to 20. The ozone oxidation catalyst provided by the invention is not easy to scale and fall off, and the service life of the ozone oxidation catalyst can be greatly prolonged.
Description
Technical Field
The invention belongs to the technical field of advanced materials and environmental protection, relates to a technology for catalytic degradation water treatment, and relates to an ozone oxidation catalyst, preparation and application thereof in water treatment.
Background
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The advanced oxidation technology adopted in the water treatment industry at present mainly comprises a chlorine system (mainly strong oxidants such as chlorine or chlorine dioxide), an ozone oxidation, an ultraviolet-hydrogen peroxide system, a Fenton reagent oxidation and the like. Compared with other advanced oxidation technologies, ozone oxidation has the advantages of being green, safe and simple to operate, but has the problems of low oxidation efficiency and low ozone utilization rate.
According to the research of the inventor, the current method for improving the ozone oxidation efficiency is mainly gamma-Al 2 O 3 The supported FeMnCe catalyst is used for improving the ozone oxidation efficiency and the utilization rate. Although the catalyst has a certain improvement on the utilization rate of ozone, the improvement capability is still limited, and the catalyst has the defects of short service life and the like.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide an ozone oxidation catalyst, a preparation method and an application thereof in water treatment. Meanwhile, researches show that the fouling of the ozone oxidation catalyst is a main factor for reducing the service life of the ozone oxidation catalyst in the application process of the ozone oxidation catalyst. The ozone oxidation catalyst provided by the invention is not easy to scale and drop, and the service life of the ozone oxidation catalyst can be greatly prolonged.
In order to achieve the purpose, the technical scheme of the invention is as follows:
in one aspect, an ozone oxidation catalyst comprises an inert support supporting a transition metal oxide and cerium oxide; the transition metal oxide is manganese dioxide or copper oxide; the inert carrier is alpha-Al with the surface covered with metallic silver 2 O 3 (ii) a Metallic silver, alpha-Al 2 O 3 And the mass ratio of the transition metal oxide to the cerium oxide is 5 to 20.
In another aspect, a method for preparing the ozone oxidation catalyst comprises the following steps:
alpha-Al is added 2 O 3 Adding the carrier precursor into a silver salt solution, drying to obtain a carrier precursor, and roasting the carrier precursor to obtain an inert carrier;
dissolving transition metal nitrate and cerous nitrate in water to obtain a mixed salt solution;
and adding the inert carrier into the mixed salt solution, drying to obtain a catalyst precursor, and roasting the catalyst precursor to obtain the catalyst.
In a third aspect, use of an ozone oxidation catalyst as described above in water treatment.
The principle of the invention is as follows:
the carrier adopted by the invention is alpha-Al with the surface covered with metallic silver 2 O 3 Wherein alpha-Al 2 O 3 Having an inert surface of its own, the inert surface of the support being in contact with Mg in the water 2+ 、Ga 2+ The ionic interaction is weakened, and Mg is reduced 2+ 、Ga 2+ The deposition of ions on the surface of the catalyst reduces scaling, and simultaneously, the silver can prevent microorganisms from attaching to the carrier, has self-cleaning property, also plays a role in scale inhibition and prolongs the service life of the catalyst. The surface of the inert carrier is covered with metallic silver, the metallic silver also serves as a catalytic active component, and is matched with transition metal oxide and rare earth metal oxide (cerium oxide), so that the compound not only greatly improves the utilization rate of ozone, but also has high-efficiency activation oxidation capacity on ozone oxidation by-product oxygen, and finally greatly improves the total utilization rate of ozone. The high-efficiency catalytic ability of the catalyst is mainly derived from the synergistic effect of metallic silver, transition metal oxide and cerium oxide, wherein the cerium oxide is used as an electron transfer auxiliary agent. The transition metal oxide and the cerium oxide have an adsorption effect on ozone, so that the symmetrical structure of the ozone can be changed to activate the ozone, and the ozone oxidation process can be efficiently catalyzed. On the other hand, the silver can effectively activate oxygen formed in the ozone oxidation process, so that the utilization rate of the oxygen is further improved. This process is a substantial improvement over conventional catalysts (e.g., feMnCe catalyst) in several respects.
The invention has the following beneficial effects:
1. the ozone oxidation catalyst provided by the invention uses an inert carrier to reduce scaling element Mg in water 2+ 、Ga 2+ The dirt generation amount of the plasma forms a new ozone advanced oxidation process. Compared with the traditional ozone advanced oxidation system, the catalyst has longer service cycle and higher catalytic efficiency.
2. The invention overcomes the defect of low catalytic efficiency of ozone oxidation of the traditional ozone oxidation catalyst (such as Fe-based catalyst such as FeMnCe catalyst) and greatly improves the utilization rate of ozone.
3. The ozone oxidation catalyst provided by the invention is simple in preparation method, wide in source of preparation raw materials, low in price and easy to obtain, and is easy for industrial production.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of the defects of limited improvement of ozone oxidation efficiency, lower service life and the like of the existing ozone oxidation catalyst, the invention provides an ozone oxidation catalyst, preparation and application thereof in water treatment.
In one exemplary embodiment of the present invention, there is provided an ozone oxidation catalyst comprising an inert carrier supporting a transition metal oxide and cerium oxide; the transition metal oxide is manganese dioxide or copper oxide; the inert carrier is covered with a surfacealpha-Al of metallic silver 2 O 3 (ii) a Metallic silver, alpha-Al 2 O 3 And the mass ratio of the transition metal oxide to the cerium oxide is 5 to 20.
The invention firstly adopts alpha-Al 2 O 3 Comparative example of gamma-Al 2 O 3 The catalyst has an inert surface, so that scaling is reduced, and then the surface is covered with metallic silver, so that the attachment of microorganisms on the carrier can be prevented, the scale inhibition effect can be further increased, and the service life of the catalyst is prolonged. At the same time, alpha-Al 2 O 3 The surface is covered with metallic silver, and the metallic silver, the transition metal oxide and the cerium oxide not only greatly improve the utilization rate of ozone, but also have high-efficiency activation oxidation capability on the by-product oxygen of ozone oxidation, and finally greatly improve the total utilization rate of ozone.
In some embodiments, the metal silver, alpha-Al 2 O 3 And the mass ratio of the transition metal oxide to the cerium oxide is 7 to 11, and 20 to 60. The catalyst performance under this condition is higher.
In some embodiments, the metal silver, alpha-Al 2 O 3 The mass ratio of the transition metal oxide to the cerium oxide is 7.85. The performance of the catalyst under this condition is more pronounced.
In some embodiments, α -Al 2 O 3 The material has a particle structure, the diameter of the particles is 2-4mm, and the mechanical strength of each particle is not less than 120N. The strength of the carrier can be ensured, so that the reduction of the service life of the catalyst due to the excessively low strength of the carrier in the using process is avoided.
In another embodiment of the present invention, there is provided a method for preparing the ozone oxidation catalyst, including the steps of:
alpha-Al is reacted with 2 O 3 Adding the silver salt into a silver salt solution, drying to obtain a carrier precursor, and roasting the carrier precursor to obtain an inert carrier;
dissolving transition metal nitrate and cerous nitrate in water to obtain a mixed salt solution;
and adding the inert carrier into the mixed salt solution, drying to obtain a catalyst precursor, and roasting the catalyst precursor to obtain the catalyst.
The invention uses alpha-Al 2 O 3 Adding into silver salt solution for drying, and gradually separating out salt in the solution in the process of drying and removing water, so that salt particles can be compounded in alpha-Al 2 O 3 The inert carrier is obtained by roasting.
The method comprises the steps of adding an inert carrier into a mixed salt solution for drying, gradually separating out salt in the solution in the drying and dewatering process, enabling salt particles to be compounded on the surface of the inert carrier, and obtaining the target catalyst through roasting.
The silver salt in the invention refers to a compound which can be dissolved in water and has silver ion as cation, such as silver nitrate.
In some embodiments, the mass concentration of the silver salt in the silver salt solution is 11 to 23%. Can make alpha-Al 2 O 3 The surface of the catalyst is better loaded with silver, thereby improving the performance of the prepared catalyst.
In some embodiments, the carrier precursor is dried at 80 to 90 ℃ for 10 to 12h in the preparation process. The condition is more favorable for silver salt to be loaded on alpha-Al 2 O 3 A surface.
In some embodiments, the temperature for baking the carrier precursor into the inert carrier is 450 to 550 ℃, and the baking time is 1 to 2 hours.
In some embodiments, the mass concentration of the transition metal nitrate in the mixed salt solution is 15 to 33%. Under the condition, the surface of the inert carrier can be better loaded with the transition metal oxide, so that the performance of the prepared catalyst is improved.
In some embodiments, the mass concentration of cerium nitrate in the mixed salt solution is 4 to 18%. Under the condition, the surface of the inert carrier can be better loaded with cerium oxide, so that the performance of the prepared catalyst is improved.
In some examples, the temperature for drying is 80 to 90 ℃ and the drying time is 10 to 12h in the process of drying to obtain the catalyst precursor. The conditions are more favorable for the transition metal nitrate and the cerium nitrate to be loaded on the surface of the inert carrier.
In a third embodiment of the present invention, there is provided a use of the above ozone oxidation catalyst in water treatment.
In some embodiments, the water treatment is catalytic ozonation of organics in the water.
More specifically, the organic matter is methyl orange.
More specifically, the water treatment process comprises: adding an ozone oxidation catalyst into the methyl orange polluted wastewater, and introducing gas containing ozone for oxidative degradation.
In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the technical solution of the present invention will be described in detail below with reference to specific examples and comparative examples.
The raw materials purchased in the following examples are all conventional commercial products. Wherein alpha-Al 2 O 3 The diameter is 3mm, and the mechanical strength is not less than 120N.
Example 1
A preparation method of an ozone oxidation catalyst comprises the following steps: the method comprises the following steps:
(1) Weighing 5.7 g of silver nitrate, weighing 45 mL of deionized water, and preparing a silver nitrate solution; weighing 25 g of alpha-Al 2 O 3 Adding into silver nitrate solution to dip alpha-Al 2 O 3 12 And after h, putting the mixture into a constant-temperature drying oven, setting the temperature to be 85 ℃, and drying for 12h. And then placing the sample into a high-temperature resistance furnace, heating to 510 ℃ for roasting, setting the heating rate to be 5 ℃/min, roasting for 2h, and naturally cooling to room temperature to obtain the silver-covered inert carrier.
(2) 29.6 g of copper nitrate trihydrate and 12.6 g of cerous nitrate hexahydrate are weighed, 100 mL of deionized water is weighed, and a mixed solution of copper nitrate and cerous nitrate is prepared.
(3) Weighing 28.6g of the inert carrier obtained in the step (1), adding the inert carrier into the mixed solution obtained in the step (2), soaking for 12h, drying at 85 ℃ for 12h, then placing the mixture into a high-temperature resistance furnace, roasting at 500 ℃ for 2h at the heating rate of 5 ℃/min, and then naturally cooling to room temperature to obtain the ozone oxidation catalyst A 1 。
Prepared ozone oxidation catalyst A 1 The mass percentage of each component ofComprises the following steps: 8.35% of Ag, alpha-Al 2 O 3 57.65%，CuO 22.49%，CeO 2 11.51%。
Example 2
A preparation method of an ozone oxidation catalyst comprises the following steps: the method comprises the following steps:
(1) Weighing 5.7 g of silver nitrate, weighing 45 mL of deionized water, and preparing a silver nitrate solution; 25 g of alpha-Al are weighed 2 O 3 Adding into silver nitrate solution to dip alpha-Al 2 O 3 12 And after h, putting the mixture into a constant-temperature drying oven, setting the temperature to be 85 ℃, and drying for 12h. And then placing the sample into a high-temperature resistance furnace, heating to 510 ℃ for roasting, setting the heating rate to be 5 ℃/min, roasting for 2h, and then naturally cooling to room temperature to obtain the silver-covered inert carrier.
(2) 29.6 g of copper nitrate trihydrate and 20.6 g of cerous nitrate hexahydrate are weighed, 100 mL of deionized water is weighed, and a mixed solution of the copper nitrate and the cerous nitrate is prepared.
(3) Weighing 28.6g of the inert carrier obtained in the step (1), adding the inert carrier into the mixed solution obtained in the step (2), soaking for 12 hours, drying at 85 ℃ for 12 hours, then placing the mixture into a high-temperature resistance furnace, roasting at 500 ℃ for 2 hours at the heating rate of 5 ℃/min, and naturally cooling to room temperature to obtain the ozone oxidation catalyst A 2 。
Prepared ozone oxidation catalyst A 2 The weight percentage of each component is as follows: 7.78% of Ag, alpha-Al 2 O 3 53.69%，CuO 20.98%，CeO 2 17.55%。
Example 3
A preparation method of an ozone oxidation catalyst comprises the following steps: the method comprises the following steps:
(1) Weighing 5.7 g of silver nitrate, weighing 45 mL of deionized water, and preparing a silver nitrate solution; weighing 25 g of alpha-Al 2 O 3 Adding into silver nitrate solution to dip alpha-Al 2 O 3 12 And (5) after h, putting the mixture into a constant-temperature drying oven, setting the temperature to be 85 ℃, and drying for 12h. And then placing the sample into a high-temperature resistance furnace, heating to 510 ℃ for roasting, setting the heating rate to be 5 ℃/min, roasting for 2h, and then naturally cooling to room temperature to obtain the silver-covered inert carrier.
(2) 38g of copper nitrate trihydrate and 12.6 g of cerous nitrate hexahydrate are weighed, 100 mL of deionized water is weighed, and a mixed solution of the copper nitrate and the cerous nitrate is prepared.
(3) Weighing 28.6g of the inert carrier obtained in the step (1), adding the inert carrier into the mixed solution obtained in the step (2), soaking for 12h, drying at 85 ℃ for 12h, then placing the mixture into a high-temperature resistance furnace, roasting at 500 ℃ for 2h at the heating rate of 5 ℃/min, and then naturally cooling to room temperature to obtain the ozone oxidation catalyst A 3 。
Prepared ozone oxidation catalyst A 3 The weight percentage of each component is as follows: ag 7.85%, alpha-Al 2 O 3 54.21%，CuO 27.12%，CeO 2 10.82%。
Example 4
A preparation method of an ozone oxidation catalyst comprises the following steps: the method comprises the following steps:
(1) Weighing 7.5 g of silver nitrate, weighing 45 mL of deionized water, and preparing a silver nitrate solution; weighing 25 g of alpha-Al 2 O 3 Adding into silver nitrate solution to dip alpha-Al 2 O 3 12 And (5) after h, putting the mixture into a constant-temperature drying oven, setting the temperature to be 85 ℃, and drying for 12h. And then placing the sample into a high-temperature resistance furnace, heating to 510 ℃ for roasting, setting the heating rate to be 5 ℃/min, roasting for 2h, and then naturally cooling to room temperature to obtain the silver-covered inert carrier.
(2) 29.6 g of copper nitrate trihydrate and 12.6 g of cerous nitrate hexahydrate are weighed, 100 mL of deionized water is weighed, and a mixed solution of copper nitrate and cerous nitrate is prepared.
(3) Weighing 29.77 g of the inert carrier obtained in the step (1), adding the inert carrier into the mixed solution obtained in the step (2), soaking for 12 hours, drying at 85 ℃ for 12 hours, then placing the mixture into a high-temperature resistance furnace, roasting at 500 ℃ for 2 hours at the heating rate of 5 ℃/min, and naturally cooling to room temperature to obtain the ozone oxidation catalyst A 4 。
Prepared ozone oxidation catalyst A 4 The weight percentage of each component is as follows: ag 10.71%, alpha-Al 2 O 3 56.17%，CuO 21.91%，CeO 2 11.21%。
Example 5
A preparation method of an ozone oxidation catalyst comprises the following steps: the method comprises the following steps:
(1) Weighing 7.5 g of silver nitrate, weighing 45 mL of deionized water, and preparing a silver nitrate solution; weighing 25 g of alpha-Al 2 O 3 Adding into silver nitrate solution to dip alpha-Al 2 O 3 12 And after h, putting the mixture into a constant-temperature drying oven, setting the temperature to be 85 ℃, and drying for 12h. And then placing the sample into a high-temperature resistance furnace, heating to 510 ℃ for roasting, setting the heating rate to be 5 ℃/min, roasting for 2h, and naturally cooling to room temperature to obtain the silver-covered inert carrier.
(2) 29.6 g of copper nitrate trihydrate and 20.6 g of cerous nitrate hexahydrate are weighed, 100 mL of deionized water is weighed, and a mixed solution of the copper nitrate and the cerous nitrate is prepared.
(3) Weighing 29.77 g of the inert carrier obtained in the step (1), adding the inert carrier into the mixed solution obtained in the step (2), soaking for 12h, drying at 85 ℃ for 12h, then placing the mixture into a high-temperature resistance furnace, roasting at 500 ℃ for 2h at the heating rate of 5 ℃/min, and then naturally cooling to room temperature to obtain the ozone oxidation catalyst A 5 。
Prepared ozone oxidation catalyst A 5 Comprises the following components in percentage by mass: ag 10.00%, alpha-Al 2 O 3 52.43%，CuO 20.44%，CeO 2 17.13%。
Example 6
A preparation method of an ozone oxidation catalyst comprises the following steps: the method comprises the following steps:
(1) Weighing 7.5 g of silver nitrate, weighing 45 mL of deionized water, and preparing a silver nitrate solution; 25 g of alpha-Al are weighed 2 O 3 Adding into silver nitrate solution to dip alpha-Al 2 O 3 12 And after h, putting the mixture into a constant-temperature drying oven, setting the temperature to be 85 ℃, and drying for 12h. And then placing the sample into a high-temperature resistance furnace, heating to 510 ℃ for roasting, setting the heating rate to be 5 ℃/min, roasting for 2h, and naturally cooling to room temperature to obtain the silver-covered inert carrier.
(2) 38g of copper nitrate trihydrate and 12.6 g of cerous nitrate hexahydrate are weighed, 100 mL of deionized water is weighed, and a mixed solution of copper nitrate and cerous nitrate is prepared.
(3) Weighing 29.77 g of the inert carrier obtained in step (1)Adding the mixture into the mixed solution obtained in the step (2), soaking for 12h, drying at 85 ℃ for 12h, then placing the mixture into a high-temperature resistance furnace, roasting for 2h at 500 ℃ with the heating rate of 5 ℃/min, and naturally cooling to room temperature to obtain the ozone oxidation catalyst A 6 。
Prepared ozone oxidation catalyst A 6 Comprises the following components in percentage by mass: ag 10.09%, alpha-Al 2 O 3 52.89%，CuO 26.46%，CeO 2 10.56%。
Example 7
A preparation method of an ozone oxidation catalyst comprises the following steps: the method comprises the following steps:
(1) Weighing 10 g of silver nitrate, weighing 45 mL of deionized water, and preparing a silver nitrate solution; 25 g of alpha-Al are weighed 2 O 3 Adding into silver nitrate solution to dip alpha-Al 2 O 3 12 And (5) after h, putting the mixture into a constant-temperature drying oven, setting the temperature to be 85 ℃, and drying for 12h. And then placing the sample into a high-temperature resistance furnace, heating to 510 ℃ for roasting, setting the heating rate to be 5 ℃/min, roasting for 2h, and then naturally cooling to room temperature to obtain the silver-covered inert carrier.
(2) Weighing 38g of copper nitrate trihydrate and 12.6 g of cerous nitrate hexahydrate, weighing 100 mL of deionized water, and preparing to obtain a mixed solution of the copper nitrate and the cerous nitrate.
(3) Weighing 31.36 g of the inert carrier obtained in the step (1), adding the inert carrier into the mixed solution obtained in the step (2), soaking for 12h, drying at 85 ℃ for 12h, then placing the mixture into a high-temperature resistance furnace, roasting at 500 ℃ for 2h at the heating rate of 5 ℃/min, and then naturally cooling to room temperature to obtain the ozone oxidation catalyst A 7 。
Prepared ozone oxidation catalyst A 7 The weight percentage of each component is as follows: ag 13.00%, alpha-Al 2 O 3 51.18%，CuO 25.61%，CeO 2 10.21%。
Example 8
A preparation method of an ozone oxidation catalyst comprises the following steps: the method comprises the following steps:
(1) Weighing 5.7 g of silver nitrate, weighing 45 mL of deionized water, and preparing a silver nitrate solution; 25 g of alpha-Al are weighed 2 O 3 Adding to silver nitrateSolution impregnation of alpha-Al 2 O 3 12 And after h, putting the mixture into a constant-temperature drying oven, setting the temperature to be 85 ℃, and drying for 12h. And then placing the sample into a high-temperature resistance furnace, heating to 510 ℃ for roasting, setting the heating rate to be 5 ℃/min, roasting for 2h, and then naturally cooling to room temperature to obtain the silver-covered inert carrier.
(2) 39.45 g of manganese nitrate tetrahydrate and 12.6 g of cerous nitrate hexahydrate are weighed, 100 mL of deionized water is weighed, and a mixed solution of the manganese nitrate and the cerous nitrate is prepared.
(3) Weighing 28.6g of the inert carrier obtained in the step (1), adding the inert carrier into the mixed solution obtained in the step (2), soaking for 12h, drying at 85 ℃ for 12h, then placing the mixture into a high-temperature resistance furnace, roasting at 500 ℃ for 2h at the heating rate of 5 ℃/min, and then naturally cooling to room temperature to obtain the ozone oxidation catalyst A 8 。
Prepared ozone oxidation catalyst A 8 The weight percentage of each component is as follows: 7.66% of Ag, alpha-Al 2 O 3 52.89%，MnO 2 28.90%，CeO 2 10.55%。
Example 9
A preparation method of an ozone oxidation catalyst comprises the following steps: the method comprises the following steps:
(1) Weighing 5.7 g of silver nitrate, 38g of copper nitrate trihydrate and 12.6 g of cerium nitrate hexahydrate, measuring 100 mL of deionized water, and preparing to obtain a mixed solution of the silver nitrate, the copper nitrate and the cerium nitrate.
(2) 25 g of alpha-Al are weighed 2 O 3 Adding the mixture into the mixed solution obtained in the step (1), soaking for 12h, putting into a constant-temperature drying oven, setting the temperature to be 85 ℃, and drying for 12h. Then placing the sample into a high-temperature resistance furnace, heating to 510 ℃ for roasting, setting the heating rate to 5 ℃/min, roasting for 2h, and then naturally cooling to room temperature to obtain the catalyst A 9 。
Prepared ozone oxidation catalyst A 9 Comprises the following components in percentage by mass: 7.85% of Ag, alpha-Al 2 O 3 54.21%，CuO 27.12%，CeO 2 10.82%。
Comparative example 1
Adopts a traditional FeMnCe system as a catalyst, is bought from the bobble of Guangzhou cityThe catalyst of SAO3-II from environmental science and technology, inc., namely D 1 . The catalyst comprises the components of gamma-Al in percentage by mass 2 O 3 51.5%，Fe 2 O 3 25.8%，MnO 15.4%，CeO 2 7.3%。
Comparative example 2
A preparation method of an ozone oxidation catalyst comprises the following steps: the method comprises the following steps:
(1) 38g of copper nitrate trihydrate and 12.6 g of cerous nitrate hexahydrate are weighed, 100 mL of deionized water is weighed, and a mixed solution of copper nitrate and cerous nitrate is prepared.
(2) Weighing 25 g of alpha-Al 2 O 3 Adding the mixed solution into the step (1) to dip alpha-Al 2 O 3 12 And (5) after h, putting the mixture into a constant-temperature drying oven, setting the temperature to be 85 ℃, and drying for 12h. Then putting the sample into a high-temperature resistance furnace, heating to 510 ℃ for roasting, setting the heating rate to 5 ℃/min, roasting for 2h, and naturally cooling to room temperature to obtain the ozone oxidation catalyst D 2 。
Prepared ozone oxidation catalyst D 2 The weight percentage of each component is as follows: alpha-Al 2 O 3 58.84%，CuO 29.42%，CeO 2 11.74%。
Comparative example 3
A preparation method of an ozone oxidation catalyst comprises the following steps: the method comprises the following steps:
(1) Weighing 5.7 g of silver nitrate, weighing 45 mL of deionized water, and preparing a silver nitrate solution; weighing 25 g of gamma-Al 2 O 3 Adding into silver nitrate solution to dip gamma-Al 2 O 3 12 And (5) after h, putting the mixture into a constant-temperature drying oven, setting the temperature to be 85 ℃, and drying for 12h. And then placing the sample into a high-temperature resistance furnace, heating to 510 ℃ for roasting, setting the heating rate to be 5 ℃/min, roasting for 2h, and then naturally cooling to room temperature to obtain the silver-covered inert carrier.
(2) 38g of copper nitrate trihydrate and 12.6 g of cerous nitrate hexahydrate are weighed, 100 mL of deionized water is weighed, and a mixed solution of copper nitrate and cerous nitrate is prepared.
(3) Weighing 28.6g of the inert carrier obtained in the step (1), adding the inert carrier into the mixed solution obtained in the step (2), soaking for 12 hours,drying at 85 deg.C for 12h, calcining at 500 deg.C for 2h in a high temperature resistance furnace at a heating rate of 5 deg.C/min, and naturally cooling to room temperature to obtain ozone oxidation catalyst D 3 。
Prepared ozone oxidation catalyst D 3 The weight percentage of each component is as follows: 7.85% of Ag and gamma-Al 2 O 3 54.21%，CuO 27.12%，CeO 2 10.82%。
Application example 1:
the catalysts prepared in the examples 1 to 9 and the comparative examples 1 to 3 are used for treating methyl orange simulated polluted water sources (COD =120 mg/L) and comprise the following steps:
1 g of a ground catalyst (20 to 40 meshes) sample is put into a three-neck flask with the volume of 500mL, 200mL of reaction liquid (consisting of water and methyl orange and having the COD of 120 mg/L) is added, and ozone and the COD are introduced into the three-neck flask at the normal temperature and the normal pressure according to the ratio of 2.
And measuring the COD value of the solution after the reaction to evaluate the quality of the catalyst, and reflecting the utilization rate of ozone from the side:
the results of evaluating the reactivity of the catalyst samples prepared in examples 1 to 9 and comparative examples 1 to 3 are shown in Table 1, and the activity data are data obtained by performing a reaction for 30 minutes.
TABLE 1 catalytic Activity (COD removal Rate) of different catalysts
As can be seen from Table 1, the catalyst of the present invention has significantly increased reactivity for treating methyl orange organic pollutants compared with FeMnCe system. The catalyst system of the invention is more effective for catalyzing ozone catalytic oxidation.
Meanwhile, the catalytic efficiency of the catalyst is obviously higher than that of the traditional gamma-Al catalyst by adopting an inert carrier with the surface covered with metallic silver 2 O 3 Catalytic ozonationThe efficiency of the method is obviously improved.
Application example 2:
30g of the catalysts prepared in the examples 1 to 9 and the comparative examples 1 to 3 are put into a flask, and the rotating speed of a magnetic stirrer is set to be 50 rpm; harsh precipitation conditions were used: configuration of Mg 2+ 、Ga 2+ The ion concentration is 350 mg/L solution, and the method is used for simulating the scaling condition of the catalyst under the action of water flow scouring and comprises the following steps:
crushing the catalyst into 60 to 80 meshes, and weighing M 0 (30g) The sample was poured into a 500mL flask, and 200mL of the above Mg was added 2+ 、Ga 2+ Putting the beaker on a magnetic stirrer, adjusting the rotation speed to 50 rpm, treating for 48 h, taking out the sample, drying, and weighing the sample to obtain a mass M 1 。
The fouling rate (ω) of the catalyst was calculated according to the following formula:
wherein, M 0 And M 1 The mass before and after fouling, respectively.
The catalyst samples prepared in examples 1 to 9 and comparative examples 1 to 3 were subjected to fouling treatment, and the evaluation results are shown in table 2.
TABLE 2 comparison of fouling rates of different catalysts
From D of Table 2 1 Compared with the fouling rate of the catalyst prepared by other examples, the catalyst of the invention has larger anti-fouling capability compared with the FeMnCe system. From D 2 Compared with the fouling rates of the catalysts prepared in other examples, the fouling rate of the catalyst covered by the metallic silver is lower, and the anti-fouling capability is stronger. From D 3 As can be seen from the comparison of the fouling rates of the catalysts prepared in the other examples, the use of alpha-Al 2 O 3 The catalyst has lower scaling rate and stronger anti-scaling capability.
Further, from catalyst A 9 Compared with other examples, the metal silver covering mode has certain influence on the anti-scaling capability, and the metal silver is adopted to cover alpha-Al 2 O 3 Catalyst ratio alpha-Al of supported transition metal oxide and cerium oxide 2 O 3 Meanwhile, the anti-scaling capability of the catalyst loaded with the metal silver, the transition metal oxide and the cerium oxide is stronger.
Application example 3:
the catalysts prepared in examples 1 to 9 and comparative examples 1 to 3 were used for treating salicylic acid simulated polluted water sources (COD =210 mg/L) according to the following steps:
1 g of a ground catalyst (20 to 40 meshes) sample is put into a three-neck flask with the volume of 500mL, 200mL of reaction liquid (consisting of water and salicylic acid and having the COD of 210 mg/L) is added, and ozone and the COD are introduced into the three-neck flask at the normal temperature and the normal pressure according to the ratio of 2.
And measuring the COD value of the solution after the reaction to evaluate the quality of the catalyst, and reflecting the utilization rate of ozone from the side:
COD (removal rate) = [ COD (total) -COD (residual) ]/COD (total)
The results of evaluating the reactivity of the catalyst samples prepared in examples 1 to 9 and comparative examples 1 to 3 are shown in Table 3, and the activity data are data obtained by performing the reaction for 30 minutes.
TABLE 3 catalytic activity (COD removal rate) of the different catalysts
As can be seen from Table 3, the catalyst of the invention is also suitable for other organic pollutants, has a wide application range, and has stronger catalytic efficiency of ozone catalytic oxidation compared with the traditional FeMnCe catalyst.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of an ozone oxidation catalyst for catalyzing organic matters in ozone oxidation water is characterized by comprising the following steps:
alpha-Al is added 2 O 3 Adding the precursor into silver salt solution for drying to obtain a carrier precursor, and roasting the carrier precursor to obtain alpha-Al with the surface covered with metallic silver 2 O 3 (ii) a The baking temperature is 450 to 550 ℃, and the baking time is 1 to 2h;
dissolving transition metal nitrate and cerous nitrate in water to obtain a mixed salt solution;
alpha-Al with surface covered with metallic silver 2 O 3 Adding the catalyst precursor into the mixed salt solution, drying to obtain a catalyst precursor, and roasting the catalyst precursor to obtain the ozone oxidation catalyst;
the ozone oxidation catalyst comprises alpha-Al with the surface covered with metallic silver 2 O 3 The surface is covered with alpha-Al of metallic silver 2 O 3 Supporting a transition metal oxide and cerium oxide; the transition metal oxide is manganese dioxide or copper oxide; metallic silver, alpha-Al 2 O 3 And the mass ratio of the transition metal oxide to the cerium oxide is 5 to 20.
2. The method for producing an ozone oxidation catalyst according to claim 1, wherein the silver salt solution has a mass concentration of from 11 to 23%.
3. The method for producing an ozonation catalyst according to claim 1, wherein the carrier precursor is dried at a temperature of 80 to 90 ℃ for a time of 10 to 12h.
4. The method for preparing an ozone oxidation catalyst according to claim 1, wherein the mass concentration of the transition metal nitrate in the mixed salt solution is 15 to 33%; the mass concentration of the cerium nitrate in the mixed salt solution is 4-18%; and in the process of drying to obtain the catalyst precursor, the drying temperature is 80 to 90 ℃, and the drying time is 10 to 12h.
5. The method for preparing an ozonation catalyst according to claim 1, wherein the metallic silver is metallic silver, and the α -Al is metallic silver 2 O 3 And the mass ratio of the transition metal oxide to the cerium oxide is 7 to 11, and 20 to 60.
6. The method for producing an ozone oxidation catalyst according to claim 5, wherein the alpha-Al is 2 O 3 The material has a particle structure, the diameter of the particles is 2-4mm, and the mechanical strength of each particle is not less than 120N.
7. An ozone oxidation catalyst produced by the production method according to any one of claims 1 to 6.
8. Use of the ozonation catalyst of claim 7 in water treatment.
9. Use according to claim 8, wherein the water treatment is catalytic ozonation of organic matter in water.
10. Use according to claim 8, characterized in that the water treatment process is: adding an ozone oxidation catalyst into the methyl orange polluted wastewater, and introducing gas containing ozone for oxidative degradation.
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