CN108339546B - A kind of ozone decomposition catalyst and its preparation method and application - Google Patents

A kind of ozone decomposition catalyst and its preparation method and application Download PDF

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CN108339546B
CN108339546B CN201810147109.6A CN201810147109A CN108339546B CN 108339546 B CN108339546 B CN 108339546B CN 201810147109 A CN201810147109 A CN 201810147109A CN 108339546 B CN108339546 B CN 108339546B
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manganese
catalyst
manganese source
carrier
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CN108339546A (en
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贺泓
邓华
马金珠
李要彬
单文坡
康顺宇
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Lingti Beijing Environmental Technology Co ltd
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Ningbo Urban Environment Observation And Research Station-Nueors Chinese Academy Of Sciences
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32Manganese, technetium or rhenium
    • B01J23/34Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8671Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • B01D53/8675Ozone
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract

本发明涉及一种臭氧分解催化剂及其制备方法和应用,所述方法为:将成型载体与锰源溶液混合,充分浸润后进行干燥,然后与添加剂混合,恒温进行反应,反应完成后得到锰前驱物包覆的规则载体,焙烧后得到成型催化剂产品;其中当锰源中的锰为+7价时,所述添加剂为还原剂;当锰源中的锰为+2价时,所述添加剂为氧化剂。本发明将催化剂制备过程与成型过程相融合,依托成型载体,在其外表面原位生长高效的锰基臭氧催化剂,催化剂和载体结合稳固,催化剂表面稳定不易脱粉且颗粒粒径尺寸大小可调,既有成型的外观,又有高效的臭氧分解能力,方便填装到各种空气净化器或新风系统模块之中,可加速制作空气净化模块的生产,具有良好的应用前景。

Figure 201810147109

The invention relates to an ozonolysis catalyst and a preparation method and application thereof. The method comprises the following steps: mixing a shaped carrier with a manganese source solution, fully infiltrating it, drying it, then mixing it with an additive, and reacting at a constant temperature, and obtaining a manganese precursor after the reaction is completed. When the manganese in the manganese source has a valence of +7, the additive is a reducing agent; when the manganese in the manganese source has a valence of +2, the additive is a oxidant. The invention integrates the catalyst preparation process and the molding process, relies on the molding carrier to grow a high-efficiency manganese-based ozone catalyst on its outer surface in situ, the catalyst and the carrier are firmly combined, the catalyst surface is stable and difficult to remove powder, and the particle size can be adjusted. , It has both a molded appearance and efficient ozone decomposition ability, which is convenient for filling into various air purifiers or fresh air system modules, which can speed up the production of air purification modules and has a good application prospect.

Figure 201810147109

Description

Ozone decomposition catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalyst preparation and air pollution purification, in particular to an ozone decomposition catalyst and a preparation method and application thereof.
Background
Ozone (O)3) With oxygen (O)2) Is an allotrope of oxygen element, and has double-edged sword function for human living environment. In the atmosphere homothermal layer,ozone is beneficial to our living environment, and can resist harmful ultraviolet rays; however, near the surface, ozone is an invisible killer, which can affect the skin and nervous system of human body to different degrees and also damage the immune function of human body, so that the lymphocyte can generate chromosome lesion, thus accelerating the aging of human body and increasing the birth rate of malformed infants. The world health organization stipulates that the concentration of ozone in an environment of 8 hours of continuous operation cannot exceed 0.1 ppm. At present, the ozone pollution problem exists in indoor houses, office places, large-scale entertainment places and the like, and the ozone removing equipment with excellent development and practical effects has better market prospect.
The current methods for treating ozone mainly comprise: heat treatment method, active carbon adsorption method, electromagnetic wave radiation decomposition method, liquid medicine absorption method and catalytic method, wherein the catalytic decomposition method is one of the most ideal methods for eliminating ozone at present. Catalyst development is one of the research hotspots for ozone pollution removal. The existing ozone decomposition catalysts are various and are mostly loaded on a carrier for application.
For example, CN1259398A discloses an ozonolysis catalyst prepared by an impregnation-deposition method using activated carbon as a carrier and containing metal oxides of nickel, copper, cobalt, or the like in addition to manganese dioxide, and a preparation method thereof. CN101402047A discloses an ozone decomposition catalyst and a preparation method thereof, the catalyst uses activated carbon particles or activated carbon fibers as a carrier, uses manganese, nickel, silver and cerium as active components of the catalyst, and loads the active components on the activated carbon particles or activated carbon fibers by an impregnation method. CN101757933A discloses an ozone decomposition catalyst, comprising: metallic nickel foam as a catalyst support and catalyst co-active component; manganese or iron oxide which is taken as a main active component and is coated on the surface of the foamed nickel in an impregnation mode. CN107649145A discloses a catalyst for decomposing ozone and a preparation method thereof, wherein the catalyst comprises: diatomite and Fe-doped manganese oxide loaded on the diatomite; wherein the Mn element in the manganese oxide accounts for 2-10% of the total mass of the catalyst.
In the prior art, an ozone decomposition catalyst is directly loaded on a carrier by an impregnation method, but the product loaded by the impregnation method is easy to have the problems of insufficient binding force between the catalyst and the carrier and easy falling of the catalyst. Therefore, it is very significant to develop a new technology for supporting an ozonolysis catalyst.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide an ozone decomposition catalyst, a preparation method and an application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing an ozonolysis catalyst, the method comprising: mixing the formed carrier with a manganese source solution, drying after fully soaking, then mixing with an additive, reacting at constant temperature to obtain a regular carrier coated by a manganese precursor after the reaction is finished, and roasting to obtain a manganese-based catalyst;
when the manganese in the manganese source is +7, the additive is a reducing agent; when the manganese in the manganese source is +2 valent, the additive is an oxidizing agent.
The invention relies on various shaped carriers, cryptomelane type manganese dioxide which can catalyze ozonolysis grows in situ on the outer surface of the carrier, and the preparation process of the catalyst is fused with the load shaping process, so that the cryptomelane type manganese dioxide can firmly grow on the outer surface of regular particles, the thickness is micron grade, abundant ozonolysis active sites are provided, and the ozone is efficiently degraded. Because the carrier has regular size and shape, the carrier can be conveniently filled into various module components, and an ozone degradation module and an application interface are added for the field of air purification.
According to the invention, the formed carrier is any one of alumina pellets, molecular sieve pellets, silica pellets or activated carbon particles. The shaped carriers have various specifications and sizes and are commercially available.
Before mixing the formed carrier with the manganese source solution, the formed carrier is cleaned by using ionized water to assist ultrasonic waves, and the cleaned small balls are put into an oven for drying.
According to the invention, the size of the alumina pellets is in the range of 1-5mm, for example 1mm, 2mm, 3mm, 4mm or 5mm, and the specific values therebetween are limited by space and for the sake of brevity and are not exhaustive.
According to the invention, the size of the molecular sieve beads is in the range of 2-5mm, for example 2mm, 3mm, 4mm or 5mm, and the specific values between the above values, which are limited by space and for the sake of brevity, are not exhaustive.
Preferably, the silica spheres have a particle size in the range of 1-8mm, such as 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm or 8mm, and the specific values therebetween are not exhaustive for the sake of brevity and simplicity.
Preferably, the particle size of the activated carbon particles is in the range of 1-6mm, for example, 1mm, 2mm, 3mm, 4mm, 5mm or 6mm, and the specific values therebetween are limited by space and for brevity, and are not exhaustive.
According to the invention, the manganese source is a source of manganese with a valence of +7 or + 2; the + 7-valent manganese source is potassium permanganate; the + 2-valent manganese source is any one or a combination of at least two of manganese nitrate, manganese sulfate, manganese acetate or manganese chloride, and may be, for example, any one of manganese nitrate, manganese sulfate, manganese acetate or manganese chloride, and typical but non-limiting combinations are manganese nitrate and manganese sulfate, manganese acetate and manganese chloride, manganese nitrate, manganese sulfate and manganese acetate, and the like, and the disclosure is not intended to be exhaustive for the sake of brevity and clarity.
According to the invention, the concentration of the manganese source solution is 0.01-1mol/L, for example, 0.01mol/L, 0.02mol/L, 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L or 1mol/L, and the specific values between the above values are limited to space and are not exhaustive for the sake of brevity.
According to the invention, the oxidant is ammonium persulfate.
According to the invention, the reducing agent is absolute ethanol and/or urea.
The present invention generally adds an excess (5 to 20 times the molar amount of Mn) of the additive (reducing agent or oxidizing agent) to fully react the manganese source.
According to the invention, when the manganese in the manganese source is +7 valent, the reaction is carried out under acidic conditions; in this case, an acid solution is added to make the solution acidic, and the acid solution may be sulfuric acid, nitric acid, glacial acetic acid, etc., but is not limited thereto, and other types of acid solutions are also suitable for the present invention, which is not exhaustive for the sake of brevity and simplicity.
The invention optionally adds an auxiliary agent at the same time of mixing the forming carrier and the additive, the addition of the auxiliary agent is beneficial to the reaction of bivalent manganese to form tetravalent manganese oxide and plays the role of a structure template agent, the auxiliary agent can be any one or the combination of at least two of potassium nitrate, ammonium sulfate, pseudo-boehmite, alumina sol or silica sol, for example, any one of potassium nitrate, ammonium sulfate, pseudo-boehmite, alumina sol or silica sol, the typical but non-limiting combination is potassium nitrate and ammonium sulfate, alumina sol or silica sol, potassium nitrate and boehmite, potassium nitrate, alumina sol, silica sol and the like, and the invention is not exhaustive for the sake of space and simplicity.
The addition amount of the auxiliary agent is not specially limited, and the addition amount of the auxiliary agent is properly adjusted according to actual requirements in the operation process.
According to the invention, the isothermal reaction temperature is between 40 ℃ and 90 ℃, for example 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃, and the specific values between the above values are not exhaustive for reasons of space and simplicity.
According to the invention, the isothermal reaction time is between 0.5 and 12h, and may be, for example, 0.5h, 1h, 3h, 5h, 7h, 10h or 12h, and the specific values therebetween, are limited to space and for the sake of brevity, and are not exhaustive.
According to the present invention, the temperature of the calcination is 300-600 ℃, for example, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃, and the specific values therebetween are limited to space and for brevity, and the present invention is not exhaustive.
According to the invention, the calcination time is 1-5h, for example 1h, 2h, 3h, 4h or 5h, and the specific values between the above values, which are limited by space and for the sake of brevity, are not exhaustive.
As a preferred technical solution, the method for preparing the ozonolysis catalyst of the present invention comprises the steps of:
(1) mixing the formed carrier with a manganese source solution with the concentration of 0.01-1mol/L, and drying after the manganese source solution fully infiltrates the formed carrier; the forming carrier is any one of alumina pellets, molecular sieve pellets, silicon oxide pellets or activated carbon particles, the manganese source is a + 7-valent manganese source or a + 2-valent manganese source, the + 7-valent manganese source is potassium permanganate, and the + 2-valent manganese source is any one or the combination of at least two of manganese nitrate, manganese sulfate, manganese acetate or manganese chloride;
(2) mixing the dried carrier in the step (1) with an additive, optionally adding an auxiliary agent, reacting at a constant temperature of 40-90 ℃ for 0.5-12h to obtain a regular carrier coated by a manganese precursor after the reaction is finished; when the manganese in the manganese source is +7, the additive is absolute ethyl alcohol and/or urea, and acid liquor is added to carry out the reaction under an acidic condition; when the manganese in the manganese source is +2, the additive is ammonium persulfate; the auxiliary agent is any one or the combination of at least two of potassium nitrate, ammonium sulfate, pseudo-boehmite, aluminum sol or silica sol;
(3) and (3) roasting the regular carrier coated with the manganese precursor obtained in the step (2) at the temperature of 300-600 ℃ for 1-5h to obtain a catalyst product formed by in-situ growth of the manganese-based catalyst on the surface of the molded carrier.
In a second aspect, the present invention provides a catalyst prepared by the method of the first aspect, wherein the catalyst is obtained by in-situ growth of a manganese-based catalyst on the surface of a shaped carrier, and is stable and not easy to fall off.
In a third aspect, the present invention provides the use of a catalyst prepared according to the method of the first aspect, wherein the catalyst is used for catalyzing ozonolysis.
The product obtained by the invention has regular shape, is convenient to fill and manufacture various module components, can be widely used in an air purifier, a fresh air system, an air conditioner filtering component or other ozone removing modules, adds technical means and actual functional modules for ozone removal, and can increase the function of air purification and ozone removal by placing the filled module into an air purification air channel.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the invention relies on the shaping carrier, grows the high-efficient manganese-based ozone catalyst on its external surface home position, catalyst and carrier combine firm difficult to drop, have already shaped appearance, have high-efficient ozone decomposition ability, can accelerate the production making air cleaning module.
(2) Compared with the conventional preparation method of the manganese-based ozone catalyst (the temperature is over 100 ℃, the hydrothermal reaction time is over 24 hours), the method has the advantages of lower treatment temperature and shorter time, and can effectively reduce the energy consumption of production, thereby reducing the production cost.
(3) The method provided by the invention has simple process, the obtained product has regular appearance size and adjustable size, the surface of the catalyst is stable and is not easy to remove powder, the method can be widely applied to various purification ports to add ozone purification modules and functions, various ozone pollution problems are effectively treated, and the method has good application prospect.
Drawings
FIG. 1 is a graph showing the catalytic efficiency of ozone of an ozonolysis catalyst obtained in example 1 of the present invention;
FIG. 2 is a graph showing the catalytic efficiency of ozone in an ozone decomposing catalyst obtained in example 2 of the present invention;
FIG. 3 is a graph showing the ozone catalytic efficiency of the alumina spheres of the blank in comparative example 1 of the present invention;
FIG. 4 is a graph showing the catalytic efficiency of ozone of the ozonolysis catalyst according to the invention obtained in comparative example 2.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
the catalysts prepared in the examples and comparative examples were evaluated for ozone purification according to the following methods: taking 0.5g of catalyst, and loading the catalyst into a fixed bed reactor, wherein the reaction conditions are as follows: ozone concentration 15ppm, O2: 20%, relative humidity 45%, nitrogen balance. The reaction temperature was controlled to 20 ℃ by a constant temperature bath.
Example 1
Weighing 3.16g of potassium permanganate, dissolving in 50mL of deionized water, mixing 150g of aluminum oxide pellets with the particle size of 2-3mm with the obtained solution, completely wetting the aluminum oxide pellets by the potassium permanganate solution, and drying at 120 ℃; dissolving 25mL of ethanol and 5mL of glacial acetic acid in 30mL of deionized water, mixing with the dried carrier to enable the carrier to be fully soaked by liquid, stirring, placing the carrier into an oven to perform constant-temperature reaction for 1h at 50 ℃, and removing excessive water to obtain a regular carrier coated by a manganese precursor; and placing the obtained carrier in a muffle furnace, heating to 500 ℃ at the speed of 5 ℃/min, calcining for 3h, and naturally cooling to obtain a catalyst product.
In this example, potassium permanganate is reduced by ethanol on the surface of the alumina pellet to obtain a manganese dioxide catalyst, the color of the outer surface of the catalyst is uniform and brownish black, and the formed catalyst has no powder removal phenomenon. The ozone purification evaluation is carried out on the catalyst, and the result is shown in figure 1, and the catalyst prepared by the embodiment has the ozone removal efficiency of about 90 percent and has better application value.
Example 2
Weighing 3.16g of potassium permanganate, dissolving in 50mL of deionized water, mixing 150g of activated carbon particles with the particle size of 2-3mm with the obtained solution, completely wetting the activated carbon particles by the potassium permanganate solution, and drying at 120 ℃; dissolving 25mL of ethanol and 5mL of glacial acetic acid in 30mL of deionized water, mixing with the dried carrier, fully soaking the carrier in liquid, stirring, mixing the solution with the activated carbon particles, fully soaking the carrier in the liquid, stirring, placing the mixture into an oven, reacting for 2 hours at a constant temperature of 60 ℃, and removing excessive water to obtain a regular carrier coated with a manganese precursor; and placing the obtained carrier in a muffle furnace, heating to 550 ℃ at the speed of 5 ℃/min, calcining for 2.5h, and naturally cooling to obtain a catalyst product.
This example reduced potassium permanganate with ethanol on the surface of activated carbon particles to produce manganese dioxide catalyst, and the formed catalyst did not suffer from dusting. The ozone purification evaluation is carried out on the catalyst, and the result is shown in figure 2, and the catalyst prepared in the embodiment has the ozone removal efficiency of about 70 percent and has better application value.
Example 3
Weighing 6.76g of manganese sulfate, dissolving in 50mL of deionized water, mixing 150g of alumina pellets with the particle size of 2-3mm with the obtained solution, completely wetting the alumina pellets by using the manganese sulfate solution, and drying at 120 ℃; dissolving 9.12g of ammonium persulfate, 5.28g of ammonium sulfate and 10g of potassium nitrate in 50mL of deionized water, mixing with the dried carrier to enable the carrier to be fully soaked by liquid, stirring, placing the carrier into an oven to perform constant-temperature reaction for 1h at 50 ℃, and removing excessive water to obtain a regular carrier coated by a manganese precursor; and placing the obtained carrier in a muffle furnace, heating to 500 ℃ at the speed of 5 ℃/min, calcining for 3h, and naturally cooling to obtain a catalyst product.
In the embodiment, manganese sulfate is oxidized on the surface of the alumina pellet by ammonium persulfate to prepare the manganese dioxide catalyst, the color of the outer surface of the catalyst is uniform and black, and the formed catalyst has no powder removal phenomenon. When the catalyst is subjected to ozone purification evaluation, the ozone removal efficiency of the catalyst prepared by the embodiment is about 85%, and the catalyst has a good application value.
Example 4
Weighing 9.80g of manganese acetate, dissolving in 50mL of deionized water, mixing 150g of molecular sieve pellets with the particle size of 2-5mm with the obtained solution, completely wetting the molecular sieve pellets by using manganese acetate solution, and drying at 120 ℃; dissolving 9.12g of ammonium persulfate, 5.28g of ammonium sulfate and 10g of potassium nitrate in 50mL of deionized water, mixing with the dried carrier to enable the carrier to be fully soaked by liquid, stirring, placing the carrier into an oven to perform constant-temperature reaction for 1h at 50 ℃, and removing excessive water to obtain a regular carrier coated by a manganese precursor; and placing the obtained carrier in a muffle furnace, heating to 500 ℃ at the speed of 5 ℃/min, calcining for 3h, and naturally cooling to obtain a catalyst product.
In the embodiment, manganese acetate is oxidized on the surface of the alumina pellet by utilizing ammonium persulfate to prepare the manganese dioxide catalyst, the color of the outer surface of the catalyst is uniform, and the formed catalyst has no powder removal phenomenon. When the catalyst is subjected to ozone purification evaluation, the ozone removal efficiency of the catalyst prepared by the embodiment is about 88%, and the catalyst has a good application value.
Comparative example 1
The same alumina pellets as used in example 1 were selected and dried at 120 ℃.
The ozone purification evaluation was performed on the dried pellets, and the results are shown in FIG. 3, where the blank alumina pellets had little capacity to purify ozone contamination and quickly penetrated through the bed.
Comparative example 2
Pouring 5g of cryptomelane type manganese dioxide (commercial catalyst) into 50mL of deionized water, adding 2g of pseudo-boehmite and 2g of alumina sol, adding nitric acid to adjust the pH value to 3, and strongly stirring to obtain slurry; adding 100g of small alumina balls with the particle size of 2-3mm into the obtained slurry, stirring and adhering, heating to 50 ℃ by using a constant-temperature water bath to remove excessive water, and drying the obtained sample at 120 ℃ to obtain a sample in which the manganese-based catalyst is impregnated on the formed carrier.
In the comparative example, the manganese-based catalyst is impregnated on the surface of the alumina pellet, and as shown in fig. 4, the obtained molded sample has good ozone removal capacity, and the ozone purification efficiency is about 80%; however, the sample has serious powder falling, the catalyst powder on the outer surface of the catalyst is unstable, and the powder falls once being rubbed, so that the sample has no practical application value.
And (3) detecting the binding force performance: 50g of the catalyst samples obtained in examples 1 to 4 and comparative example 2 were put in an ultrasonic cleaning tank and subjected to ultrasonic treatment for 2 hours at room temperature in a beaker at a frequency of 40 Hz. The product was subjected to mechanical shock screening, sieved through 20-40 mesh sieve, and then the pellets were weighed and their weight loss (i.e. the weight of the desorbed powder) was calculated, with the results shown in table 1:
TABLE 1
Example 1 Example 2 Example 3 Example 4 Comparative example 2
Weight loss (%) 0.13 0.21 0.15 0.11 2.5
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (17)

1.一种臭氧分解催化剂的制备方法,其特征在于,所述方法为:将成型载体与锰源溶液混合,充分浸润后进行干燥,然后与添加剂混合,恒温进行反应,反应完成后得到锰前驱物包覆的规则载体,焙烧后得到成型催化剂产品;1. a preparation method of an ozonolysis catalyst, is characterized in that, described method is: shape carrier is mixed with manganese source solution, dry after fully soaking, then mix with additive, react at constant temperature, obtain manganese precursor after reaction is completed The regular carrier coated with the material is calcined to obtain a shaped catalyst product; 当锰源中的锰为+7价时,所述添加剂为还原剂;当锰源中的锰为+2价时,所述添加剂为氧化剂;When the manganese in the manganese source is +7, the additive is a reducing agent; when the manganese in the manganese source is +2, the additive is an oxidizing agent; 所述氧化剂为过硫酸铵;Described oxidizing agent is ammonium persulfate; 所述还原剂为无水乙醇和/或尿素;The reducing agent is absolute ethanol and/or urea; 所述成型载体为氧化铝小球、分子筛小球、氧化硅小球或活性炭颗粒中的任意一种;The shaped carrier is any one of alumina pellets, molecular sieve pellets, silica pellets or activated carbon particles; 与添加剂混合的同时加入助剂,所述助剂为硝酸钾、硫酸铵、拟薄水铝石、铝溶胶或硅溶胶中的任意一种或至少两种的组合。When mixing with the additive, an auxiliary agent is added, and the auxiliary agent is any one or a combination of at least two of potassium nitrate, ammonium sulfate, pseudo-boehmite, alumina sol or silica sol. 2.如权利要求1所述的方法,其特征在于,所述氧化铝小球的粒径范围为1-5mm。2 . The method of claim 1 , wherein the particle size of the alumina pellets ranges from 1 to 5 mm. 3 . 3.如权利要求1所述的方法,其特征在于,所述分子筛小球的粒径范围为2-5mm。3. The method of claim 1, wherein the molecular sieve pellets have a particle size range of 2-5 mm. 4.如权利要求1所述的方法,其特征在于,所述氧化硅小球的粒径范围为1-8mm。4. The method of claim 1, wherein the particle size of the silica pellets ranges from 1 to 8 mm. 5.如权利要求1所述的方法,其特征在于,所述活性炭颗粒的粒径范围为1-6mm。5. The method of claim 1, wherein the particle size of the activated carbon particles ranges from 1 to 6 mm. 6.如权利要求1或2所述的方法,其特征在于,所述锰源为+7价锰源或+2价锰源。6. The method of claim 1 or 2, wherein the manganese source is a +7-valent manganese source or a +2-valent manganese source. 7.如权利要求6所述的方法,其特征在于,所述+7价锰源为高锰酸钾。7. The method of claim 6, wherein the +7 manganese source is potassium permanganate. 8.如权利要求6所述的方法,其特征在于,所述+2价锰源为硝酸锰、硫酸锰、乙酸锰或氯化锰中的任意一种或至少两种的组合。8. The method of claim 6, wherein the +2 manganese source is any one or a combination of at least two of manganese nitrate, manganese sulfate, manganese acetate or manganese chloride. 9.如权利要求1或2所述的方法,其特征在于,所述锰源溶液的浓度为0.01-1mol/L。9. The method of claim 1 or 2, wherein the concentration of the manganese source solution is 0.01-1 mol/L. 10.如权利要求1或2所述的方法,其特征在于,当锰源中的锰为+7价时,所述反应在酸性条件下进行。10. The method of claim 1 or 2, wherein when the manganese in the manganese source has a valence of +7, the reaction is carried out under acidic conditions. 11.如权利要求要求1或2所述的方法,其特征在于,所述恒温反应的温度为40-90℃。11. The method of claim 1 or 2, wherein the temperature of the isothermal reaction is 40-90°C. 12.如权利要求要求1或2所述的方法,其特征在于,所述恒温反应的时间为0.5-12h。12. The method according to claim 1 or 2, wherein the time of the constant temperature reaction is 0.5-12h. 13.如权利要求要求1或2所述的方法,其特征在于,所述焙烧的温度为300-600℃。13. The method of claim 1 or 2, wherein the calcination temperature is 300-600°C. 14.如权利要求要求1或2所述的方法,其特征在于,所述焙烧的时间为1-5h。14. The method of claim 1 or 2, wherein the roasting time is 1-5h. 15.如权利要求1所述的方法,其特征在于,所述方法包括以下步骤:15. The method of claim 1, wherein the method comprises the steps of: (1)将成型载体与浓度为0.01-1mol/L锰源溶液混合,锰源溶液充分浸润成型载体后进行干燥;所述成型载体为氧化铝小球、分子筛小球、氧化硅小球或活性炭颗粒中的任意一种,所述锰源为+7价锰源或+2价锰源,所述+7价锰源为高锰酸钾,所述+2价锰源为硝酸锰、硫酸锰、乙酸锰或氯化锰中的任意一种或至少两种的组合;(1) Mix the shaped carrier with a manganese source solution with a concentration of 0.01-1mol/L, and dry the manganese source solution after fully infiltrating the shaped carrier; the shaped carrier is alumina pellets, molecular sieve pellets, silica pellets or activated carbon In any one of the particles, the manganese source is a +7-valent manganese source or a +2-valent manganese source, the +7-valent manganese source is potassium permanganate, and the +2-valent manganese source is manganese nitrate, manganese sulfate , any one or a combination of at least two in manganese acetate or manganese chloride; (2)将步骤(1)干燥后的载体与添加剂混合,同时加入助剂,在40-90℃下恒温反应0.5-12h,反应完成后得到锰前驱物包覆的规则载体;当锰源中的锰为+7价时,所述添加剂为无水乙醇和/或尿素,同时加入酸液使反应在酸性条件下进行;当锰源中的锰为+2价时,所述添加剂为过硫酸铵;所述助剂为硝酸钾、硫酸铵、拟薄水铝石、铝溶胶或硅溶胶中的任意一种或至少两种的组合;(2) Mixing the dried carrier and additives in step (1), adding additives at the same time, and reacting at a constant temperature of 40-90 ° C for 0.5-12 h, after the reaction is completed, a regular carrier coated with manganese precursor is obtained; when the manganese source is in the When the manganese is +7 valence, the additive is absolute ethanol and/or urea, and acid solution is added simultaneously to make the reaction proceed under acidic conditions; when the manganese in the manganese source is +2 valence, the additive is persulfuric acid Ammonium; the auxiliary agent is any one or a combination of at least two in potassium nitrate, ammonium sulfate, pseudoboehmite, alumina sol or silica sol; (3)将步骤(2)得到的锰前驱物包覆的规则载体在300-600℃下焙烧1-5h,得到锰基催化剂在成型载体表面原位长成的催化剂产品。(3) calcining the regular carrier coated with the manganese precursor obtained in step (2) at 300-600° C. for 1-5 h to obtain a catalyst product in which the manganese-based catalyst is grown in situ on the surface of the shaped carrier. 16.如权利要求1-15任一项所述的方法制备得到的催化剂。16. The catalyst prepared by the method of any one of claims 1-15. 17.如权利要求1-15任一项所述的方法制备得到的催化剂的应用,其特征在于,所述催化剂应用于催化臭氧分解。17. Use of the catalyst prepared by the method according to any one of claims 1-15, wherein the catalyst is used for catalyzing ozonolysis.
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