阅读说明：本技术 臭氧分解催化剂及其制备方法与应用 (Ozone decomposition catalyst and preparation method and application thereof ) 是由 张彭义 李连欣 于 2019-11-27 设计创作，主要内容包括：本发明涉及一种臭氧分解催化剂的制备方法,其包括：将高锰酸盐与金属盐的混合水溶液与还原剂充分反应后固液分离,将固体组分干燥；其中所述金属盐主要为铈的三价可溶性盐和/或铁的二价可溶性盐；所述还原剂主要为多巴胺或其可溶性盐；所述反应在10℃～30℃下搅拌进行,搅拌的时间为1至12小时。该方法制备方法能够有效降低制备成本,且所得到的产品在室温与较高湿度条件下,可高效稳定地分解空气中的臭氧污染物。(The invention relates to a preparation method of an ozone decomposition catalyst, which comprises the following steps: fully reacting the mixed aqueous solution of permanganate and metal salt with a reducing agent, then carrying out solid-liquid separation, and drying solid components; wherein the metal salt is mainly trivalent soluble salt of cerium and/or divalent soluble salt of iron; the reducing agent is mainly dopamine or soluble salt thereof; the reaction is carried out under stirring at 10-30 ℃ for 1-12 hours. The preparation method can effectively reduce the preparation cost, and the obtained product can efficiently and stably decompose ozone pollutants in the air at room temperature and higher humidity.)

1. A method for preparing an ozonolysis catalyst, comprising:

fully reacting the mixed aqueous solution of permanganate and metal salt with a reducing agent, then carrying out solid-liquid separation, and drying solid components;

wherein the metal salt is mainly trivalent soluble salt of cerium and/or divalent soluble salt of iron;

the reducing agent is mainly dopamine or soluble salt thereof;

the reaction is carried out under stirring at 10-30 ℃ for 1-12 hours.

2. The method of producing an ozonolysis catalyst according to claim 1, wherein the atomic ratio of the metal atom to the manganese atom in the metal salt in the mixed aqueous solution is 0.005 to 0.3.

3. The method for preparing an ozonolysis catalyst according to claim 2, wherein the mixed aqueous solution is obtained by mixing a permanganate solution with a metal salt solution, the concentration of the permanganate being 1g/L to 50g/L, and the concentration of the metal salt being 0.5g/L to 20 g/L.

4. The method of producing an ozonolysis catalyst according to claim 1, characterized in that the reducing agent is brought into contact with the mixed aqueous solution in the form of a previously prepared aqueous solution to effect the reaction;

optionally, the concentration of the reducing agent in the aqueous solution of the reducing agent is 10 g/L-100 g/L;

optionally, the contacting is performed by adding the mixed aqueous solution dropwise to the aqueous solution of the reducing agent.

5. The method for preparing an ozonolysis catalyst according to claim 1, wherein the drying is oven-drying at a temperature of 80 to 300 ℃.

6. The method of producing an ozonolysis catalyst according to any one of claims 1 to 5, wherein the permanganate is selected from a salt of lithium, sodium, potassium, ammonium, calcium, barium, zinc, magnesium, mercury, cadmium, rubidium, or a mixture of any two or more thereof;

and/or;

the trivalent soluble salt of cerium is at least one of cerium (III) nitrate, cerium (III) chloride or cerium (III) sulfate;

and/or;

the divalent soluble salt of the iron is at least one of ferrous nitrate, ferrous chloride or ferrous sulfate;

and/or;

the reducing agent is mainly dopamine hydrochloride.

7. The ozonolysis catalyst prepared as described above.

8. A catalyst composition comprising the ozone decomposition catalyst of claim 7 and a binder.

9. An atmosphere contacting surface coated with the catalyst composition of claim 8.

10. An apparatus having the atmosphere contacting surface of claim 9.

Technical Field

The invention relates to a chemical catalytic decomposition technology, belongs to the technical field of pollutant decomposition in ambient air, and particularly relates to an ozone decomposition catalyst and a preparation method and application thereof.

Background

Ozone is a common pollutant in the atmosphere stratosphere, and long-term exposure to low-concentration ozone will cause respiratory tract and cardiopulmonary related diseasesSymptoms and diseases. It is reported that about one million deaths worldwide in 2010 due to respiratory diseases are caused by long-term exposure in ozone-contaminated environments (Environmental Health Perspectives,2017,125 (8)). At present, the environmental air quality standard (GB3095-2012) of China stipulates: the first-level limit and the second-level limit of the ozone concentration of 8 hours in the day are respectively 100 mu g/m³And 160. mu.g/m³. In addition, in the Special requirements of air purifiers with antibacterial, sterilizing and purifying functions for household and similar appliances (GB21551.3-2010), the limit of 5cm ozone at the air outlet of the air purifier is 100 mug/m³. According to the national urban air quality report issued by the China environmental monitoring Master station in 2018, 7-9 months, the number of days with ozone as the primary pollutant in the pollutant exceeding days in the period is the largest, and the 90 th percentile concentration of the maximum eight-hour mean value of the ozone day in three months is 148 mug/m³、153μg/m³And 139. mu.g/m³The first level limit in the standard is exceeded. Therefore, the ozone pollution is widely existed in China, so that the effective control of the indoor ozone pollution is particularly important.

The ozone removal methods reported so far include an activated carbon adsorption method, a solution absorption method, a thermal decomposition method, and the like, but these methods are high in energy consumption and may cause secondary pollution. The ozone pollution control technology widely studied at present is a normal temperature catalytic decomposition method, and reported catalytic materials comprise noble metal materials, transition metal oxides, composite materials of the noble metal materials and the transition metal oxides, and the like. Among the above materials, the manganese oxide catalysts with excellent catalytic performance and low cost have the most potential for wide application. Although many manganese oxide catalysts have been reported to be capable of efficiently removing ozone under dry gas conditions, their performance is usually significantly reduced due to moisture-induced deactivation, which limits the practical application of the materials. In recent years, manganese oxide materials with excellent ozone catalytic performance under certain humidity are reported, but the preparation method is often hydrothermal synthesis at high temperature and is difficult to realize in production application (Applied Catalysis B: Environmental,2017,201, 503-.

On the other hand, the composite catalytic material of the noble metal and the transition metal oxide has high and stable performance, and the transition metal oxide loaded on a large specific surface area also has better catalytic performance. However, these types of catalysts have long been patented, for example, the Engelhard Pt/transition metal composite catalyst (WO2000/013790a1) and the Johnson Matthey particulate supported amorphous manganese oxide catalyst (WO2012/167280a1) and the like. Although the research and report about the ozone decomposition catalyst in China, the catalytic material which can be widely applied is rare, and related commodities on the market are still few. Therefore, it is necessary to develop a manganese oxide catalytic material with high efficiency, stability and proprietary intellectual property rights.

In general, in order to eliminate the harm to human health caused by the widely existing ozone pollution, the manganese oxide catalyst which is simple in preparation process, good in moisture resistance and high-efficiency and stable in ozone catalytic decomposition performance has important practical value.

Disclosure of Invention

Aiming at ozone pollution, the invention aims to solve the problem of preparing the catalyst for efficiently and stably removing the ozone pollutant at room temperature and certain humidity. The manganese oxide catalyst synthesized by the method has simple and convenient preparation method, and the prepared catalyst can efficiently and stably decompose ozone pollutants into oxygen under the conditions of certain humidity and room temperature without introducing other pollutants.

The invention relates to a preparation method of an ozone decomposition catalyst, which comprises the following steps:

fully reacting the mixed aqueous solution of permanganate and metal salt with a reducing agent, then carrying out solid-liquid separation, and drying solid components;

wherein the metal salt is mainly trivalent soluble salt of cerium and/or divalent soluble salt of iron;

the reducing agent is mainly dopamine or soluble salt thereof;

the reaction is carried out under stirring at 10-30 ℃ for 1-12 hours.

According to one aspect of the invention, the invention also relates to the ozonolysis catalyst prepared by the method and the application thereof.

Compared with the prior art, the invention has the beneficial effects that:

(1) the preparation process is simple: one-step synthesis does not involve high-temperature and high-pressure conditions, the reaction time is short, and noble metals can not be added into the catalyst to be used as active components.

(2) In the preparation process of the method, the acid environment required by the reaction can be obtained through the primary reaction of the potassium permanganate and the cerium salt or the ferric salt, and no additional pH regulator is needed. The primary reaction of potassium permanganate with cerium salt or iron salt forms an acidic environment, and the organic reducing agent reacts with H in the acidic environment⁺The synergistic effect regulates and controls the appearance of the material.

(3) The material has good moisture resistance and good ozone decomposition performance: under the conditions of room temperature and higher humidity, the ozone pollutant in the air can be efficiently and stably decomposed.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 is a scanning electron micrograph (a) (c) and a transmission electron micrograph (b) (d) of a catalyst sample prepared according to some embodiments of the present invention;

FIG. 2 is a diagram of an X-ray diffraction crystal structure of a catalyst sample in accordance with one embodiment of the present invention;

FIG. 3 is a comparison of the ozone removal performance of the catalyst prepared in one example of the present invention with a commercial ozonolysis material at equivalent mass;

FIG. 4 is a long term catalytic performance test of a catalyst sample prepared in accordance with some embodiments of the present invention;

FIG. 5 is a graph of ozone removal rates at different humidities for catalyst samples prepared according to some embodiments of the present invention;

FIG. 6 is a photograph of samples of catalysts prepared in accordance with some examples of the present invention with varying amounts of cerium doped;

FIG. 7 is a comparison of pore size distribution and bulk density for different cerium-doped catalyst samples prepared in accordance with certain examples of the present invention;

FIG. 8 is a graph showing the comparison of the ozone removal performance of the catalyst prepared in one example of the present invention with that of a commercial ozonolysis material at the same quality;

FIG. 9 is a photograph of samples of catalysts prepared with different iron loadings according to some examples of the invention.

Detailed Description

Reference will now be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment.

It is therefore intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are disclosed in or are apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.

The invention relates to a preparation method of an ozone decomposition catalyst, which comprises the following steps:

fully reacting the mixed aqueous solution of permanganate and metal salt with a reducing agent, then carrying out solid-liquid separation, and drying solid components;

wherein the metal salt is mainly trivalent soluble salt of cerium and/or divalent soluble salt of iron;

the reducing agent is mainly dopamine or soluble salt thereof;

the reaction is carried out under stirring at 10-30 ℃ for 1-12 hours.

The reaction is usually carried out under normal pressure.

In some embodiments, the metal salt in the mixed aqueous solution has an atomic ratio of metal atoms to manganese atoms of 0.005 to 0.3; and may also be 0.007, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, or 0.29.

In some embodiments, when the metal atoms in the metal salt are predominantly trivalent cerium, the atomic ratio of metal atoms to manganese atoms is from 0.008 to 0.25.

In some embodiments, when the metal atoms in the metal salt are predominantly ferrous iron, the atomic ratio of metal atoms to manganese atoms is from 0.08 to 0.25.

In some embodiments, the concentration of the permanganate in the mixed aqueous solution is 1g/L to 50g/L (alternatively, 2g/L, 3g/L, 4g/L, 5g/L, 10g/L, 15g/L, 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, and 45g/L), and the concentration of the metal salt is 0.5g/L to 20g/L (alternatively, 1g/L, 2g/L, 3g/L, 4g/L, 5g/L, 10g/L, and 15 g/L).

In some embodiments, the reducing agent is contacted with the mixed aqueous solution in the form of a pre-formulated aqueous solution to effect the reaction.

In some embodiments, the concentration of the reducing agent in the aqueous solution of the reducing agent is 10g/L to 100g/L, and can also be selected from 20g/L, 30g/L, 40g/L, 50g/L, 60g/L, 70g/L, 80g/L or 90 g/L.

In some embodiments, the contacting is by dropwise addition of the mixed aqueous solution to an aqueous solution of the reducing agent.

In some embodiments, the drying is oven drying, the drying temperature is 80-300 deg.C, and can also be selected from 100 deg.C, 120 deg.C, 140 deg.C, 160 deg.C, 180 deg.C, 200 deg.C, 220 deg.C, 240 deg.C, 260 deg.C, 280 deg.C.

In some embodiments, the permanganate salt is selected from a salt of lithium, sodium, potassium, ammonium, calcium, barium, zinc, magnesium, mercury, cadmium, rubidium or a mixture of any two or more thereof.

In some embodiments, the trivalent soluble salt of cerium is at least one of cerium (III) nitrate, cerium (III) chloride, or cerium (III) sulfate.

In some embodiments, the divalent soluble salt of iron is at least one of ferrous nitrate, ferrous chloride, or ferrous sulfate.

In some embodiments, the reducing agent is predominantly dopamine hydrochloride.

In some embodiments, the metal salt does not contain a noble metal.

In some embodiments, the noble metal is selected from the group consisting of platinum group metals, silver, and gold.

In some embodiments, the platinum group metal is selected from platinum, palladium, and rhodium.

In some embodiments, no additional pH modifier is added to the system of the reaction.

According to one aspect of the invention, the invention also relates to an ozonolysis catalyst prepared according to the method described above.

According to one aspect of the invention, the invention also relates to a catalyst composition comprising an ozone decomposition catalyst as described above and a binder.

In some embodiments, the binder is an inorganic binder, preferably a silicate-based, alumina-based or ammonium zirconium carbonate-based inorganic binder.

In some embodiments, the binder is polyethylene, polypropylene, polyolefin copolymers, polyisoprene, polybutadiene copolymers, chlorinated rubber, nitrile rubber, polychloroprene, ethylene propylene diene monomer rubber, polystyrene, polyacrylates, polymethacrylates, polyacrylonitrile, polyvinyl esters, polyvinyl halides, polyamides, acrylic polymers, vinyl acrylic polymers, ethylene vinyl acetate copolymers, styrene-acrylic polymers, polyvinyl alcohol, thermoplastic polyesters, thermosetting polyesters, polyphenylene oxide, polyphenylene sulfide, fluorinated polymers, polytetrafluoroethylene, polyvinylidene 1, 1-difluoroethylene, polyvinyl fluoride, chloro/fluoro copolymers, ethylene, chlorotrifluoroethylene copolymers, polyamides, phenolic resins, epoxy resins, polyurethanes, silicone polymers, or mixtures of any two or more thereof.

According to one aspect of the invention, the invention also relates to an atmosphere contacting surface coated with a catalyst composition as described above.

In some embodiments, the atmosphere contacting surface comprises a heat exchanger, a fan blade, a fan grill, or a conduit for transporting a fluid.

In some embodiments, the heat exchanger comprises a radiator, an intake air cooler, an air conditioning condenser, an oil cooler, a power steering oil cooler, or a transmission oil cooler.

According to one aspect of the invention, the invention also relates to a device having an atmosphere contacting surface as described above.

In some embodiments, the device is a vehicle device, such as a building air conditioning system or a mobile billboard.

In some embodiments, the device is a power tool, such as a lawn mower, cutter, lawnmower, circular saw, chain saw, or leaf blower/harvester.

In some embodiments, the device is a ventilation device (e.g., an air conditioner), an air humidification device, or an air purification device.

In some embodiments, the device is a uv disinfection device.

Embodiments of the present invention will be described in detail with reference to examples.