CN106334565B

CN106334565B - Air purification composite catalyst and preparation method thereof

Info

Publication number: CN106334565B
Application number: CN201610889910.9A
Authority: CN
Inventors: 黄建国
Original assignee: Ucheer Purification Control Technology Zhejiang Co ltd
Current assignee: Ucheer Purification Control Technology Zhejiang Co ltd
Priority date: 2016-10-12
Filing date: 2016-10-12
Publication date: 2020-06-09
Anticipated expiration: 2036-10-12
Also published as: CN106334565A; WO2018068729A1

Abstract

The invention discloses an air purification composite catalyst and a preparation method thereof. The preparation method comprises the steps of mixing an oxidant and Mn^IISalt, Cu^IISalt and Ce^IIIDissolving salt into a solvent, transferring the solution to a high-pressure reaction kettle after stirring reaction, filtering, cleaning and drying the solution after high-temperature high-pressure reaction to obtain a composite catalyst precursor; mixing the composite catalyst precursor, auxiliary materials and clay to obtain composite granulation powder; and granulating the composite granulating powder to obtain the air purification composite catalyst. The composite catalyst prepared by the invention has high surface activity and high catalytic performance.

Description

Air purification composite catalyst and preparation method thereof

Technical Field

The invention relates to a material used in the field of environmental protection, in particular to a composite catalyst material for purifying gas.

Background

At present, two major problems facing human beings are environmental pollution and energy shortage, wherein the environmental pollution problem is particularly prominent. In the last hundred years, a large amount of harmful wastes are generated in the process of the modern industrial development of human beings, so that the environment is seriously polluted, and the content of pollutants in the atmosphere, soil and water far exceeds the tolerable range. Compared with the soil and water environment which can be treated differently, the atmospheric environment, especially the indoor air environment on which people live, directly affects the health of human beings, and the non-porous and non-invasive air pollutants are the first problems to be treated urgently. According to the difference of the forms, the air pollutants are mainly divided into particle pollutants and volatile harmful gas pollutants, wherein the volatile harmful gas pollutants mainly come from waste gas generated in industrial production, tail gas generated in the running of vehicles such as automobiles and ships, and volatile organic compounds emitted from interior decoration materials and furniture.

The harmful gases in the air mainly comprise formaldehyde, ozone, benzene, toluene, xylene, carbon dioxide, nitrogen oxides, other organic matters and other volatile harmful gases which are harmful to human health to different degrees. For example, the stimulation effect of formaldehyde on skin mucosa, the direct contact of skin can easily cause allergic inflammation and even necrosis, and high-concentration formaldehyde can induce bronchial asthma and even cause nasopharyngeal tumor, and is also a genotoxic substance. Ozone can strongly stimulate the respiratory tract of a human body, even cause human nerve poisoning, and cause various diseases. Destroy the immune function of human body, induce the chromosome lesion of lymphocyte, accelerate aging, cause pregnant women to be teratogenic. Most of volatile harmful gases (TVOC) are irritant, cause the immune level of the organism to be disordered, influence the function of the central nervous system, can damage the liver and the hematopoietic system in severe cases, and are classified as carcinogens.

In order to solve the problem of pollution of harmful gases in the air, a great deal of research is carried out by human beings, and various air purification technologies are generated. The earliest air purification products adopt HEPA filter screens to purify air, can only remove particle pollutants in the air, and cannot do any help to harmful gas pollutants. Part of the products use inorganic porous materials such as active carbon and the like to adsorb harmful gas pollutants in the air, so that the aim of reducing the concentration of the gas pollutants can be fulfilled. However, the adsorbing material utilizes the huge specific surface area to adsorb harmful gases in the air purification process. When the surface adsorption amount reaches saturation, not only the adsorption can not be carried out continuously, but also the risk of secondary pollution caused by release exists, and the adsorption material needs to be replaced. The purification material can not achieve the purpose of thorough purification, only one pollutant is transferred, and the adsorption material needs to be replaced regularly in the use process, so that the requirement of purifying harmful substances in air is difficult to meet. At present, a photocatalyst technology for purifying harmful gases in air is also generated, and the technology adopts a photocatalyst material as a catalyst material, wherein the photocatalyst material is mainly a titanium dioxide material, and under the irradiation condition of certain energy level light, the generated hydroxyl radical with extremely strong oxidizing capability is utilized to catalyze and decompose toxic and harmful substances in air, so that the aim of purifying air is achieved. The technology can be realized only under specific illumination conditions, and can not be used in environments which can not provide the conditions, so that the application of the technology is limited; in addition, the catalytic decomposition efficiency is not high, and the wide application is difficult to realize. In addition, the noble metal has good catalytic performance and can effectively catalyze and decompose harmful gases, but large-scale application is difficult to realize due to high application cost.

A large number of researches report that the transition metal oxide, particularly the manganese oxide, has good catalytic activity, can realize the effect of spontaneous catalytic reaction in a plurality of reactions without additional conditions, has low price and can meet the large-scale application. However, during the course of a particular catalytic reaction, the catalytic activity of the catalyst is often affected by its internal lattice structure, particle size, composition, morphology, and surrounding conditions. The manganese oxide materials with different lattice structures have different catalytic activities, and after other metals with complementary and enhancing effects are doped in the lattice structures, the manganese oxide materials can play a role in coordinated catalysis in the catalytic reaction process, so that the catalytic activity of the catalyst materials is obviously improved. The atoms of different metals have complementarity on the size and the surface structure, so that a plurality of materials are usually selected and doped to prepare the composite catalyst, and the composite catalyst plays a synergistic effect in catalytic reaction and improves the catalytic performance of the composite catalyst; the catalyst materials with different structures and appearances have different surface areas and surface activity numbers, and the catalyst materials with large specific surface areas and more surface active sites can obviously increase the effective collision times in the reaction process, so that the materials have higher catalytic activity and catalytic decomposition efficiency; in the application process of the catalyst material, proper auxiliary materials are added to effectively improve the catalytic decomposition performance of the catalyst material, the auxiliary materials with good surface performance and strong adsorption performance are selected and distributed around the catalyst, so that the effects of adsorbing harmful gases in the air in advance and increasing the concentration of the harmful gases around the active catalyst are achieved, the concentration gradient of the harmful gases around the catalyst is effectively increased, and the catalytic decomposition efficiency of the catalyst material is improved.

CN 104174391A discloses a nanometer titanium dioxide photocatalyst material for degrading VOC, the prepared nanometer titanium dioxide photocatalyst has stronger visible light absorption capacity and lower electron hole recombination rate, can rapidly and completely degrade high-concentration benzene pollutants, and can completely degrade low-content benzene in a small space within 4 hours by only using 0.1g of the weight. In which the supply amount and absorption capacity of visible light are restrictedThe key factors of the catalytic decomposition performance of the catalyst can be presumed to be that under the condition of weak light or no light, the catalytic decomposition performance of the catalyst can be greatly reduced or even invalid, and the requirement of air purification in a plurality of areas or time periods cannot be comprehensively met. An oxidation catalyst and process for destruction of CO, VOCs and halogenated VOCs is disclosed in CN 102481549B, describing an oxidation catalyst deposited on a substrate for destruction of CO and volatile organic compounds, in particular halogenated organic compounds, in an effluent stream at a temperature of 250 ℃ to 450 ℃. The oxidation catalyst comprises at least two platinum group metals, one of which is platinum or ruthenium, supported on a refractory oxide, such as CeO₂And ZrO₂And tin oxide and/or silicon dioxide. Wherein, noble metal is selected as an active catalyst material, so that the cost is high and the large-scale application is difficult to realize; in addition, the catalyst material needs to be subjected to catalytic decomposition reaction at high temperature, has high energy consumption and high application cost, and is difficult to be applied to the fields of common indoor air purification and the like which cannot provide high-temperature environment. CN 103506111A discloses a method for preparing a catalyst for removing formaldehyde and ozone at room temperature, which comprises the steps of precipitating a precursor by adopting an oxidation-reduction reaction in a solution, combining a calcination process to obtain a manganese dioxide catalyst material, and decomposing harmful gases formaldehyde and ozone in polluted air into harmless H at room temperature₂And CO₂Has the advantages of no harmful by-products, high formaldehyde and ozone removing efficiency. However, the manganese dioxide catalyst material obtained by using the common precipitation method has the problems of low specific surface area and low apparent activity, so that the purification amount is low, and the requirement of air purification in the current air environment with complex air pollution and high pollutant content is difficult to meet.

In order to purify the air environment with serious pollution and complex pollutant components at present and solve the global air pollution problem, an air purification catalyst material which has high degradation efficiency, good performance, capability of degrading various harmful gases simultaneously, reusability and low cost is urgently needed for meeting the air purification requirement in a large range.

Disclosure of Invention

In view of the above-mentioned problems, it is an object of the present invention to provide an air-purifying composite catalyst material including manganese oxide composite copper oxide and cerium oxide, and a method of preparing the same. The special reaction conditions in the preparation method enable a large amount of Cu²⁺And Ce³⁺The precursor enters the micro lattice structure of the manganese oxide to replace the position of manganese to obtain the composite catalyst precursor doped at the lattice level, and the synergistic effect can be achieved; the auxiliary material with large specific surface area is added as a granulation auxiliary material, and the catalytic decomposition activity of the air purification catalyst on harmful substances in the air is effectively improved by combining a homogeneous phase mixing forming process.

In order to achieve the purpose, the invention discloses a preparation method of an air purification composite catalyst, which adopts the following technical scheme that under the reaction conditions of high temperature and high pressure, manganese oxide is doped by copper and cerium to obtain a doped composite catalyst material. And mixing an oxidant, a manganese salt, a copper salt and a cerium salt at normal temperature, stirring for reaction, and performing recrystallization and lattice doping reaction under the conditions of high temperature and high pressure to obtain the composite catalyst precursor with high doping amount. An inorganic porous material with large specific surface area is selected as a forming granulation auxiliary material, and the air purification composite catalyst material with uniform mixing and high purification efficiency is obtained through a homogeneous forming process.

The air purification composite catalyst material comprises manganese oxide composite copper oxide and cerium oxide.

The preparation process of the air purification composite catalyst mainly comprises the processes of preparation of a composite catalyst precursor and coating granulation. The method comprises the following specific steps: the air purification composite catalyst is prepared by the following method: oxidizing agent and Mn^IISalt, Cu^IISalt and Ce^IIIDissolving salt into a solvent to obtain a mixed solution, carrying out stirring reaction to obtain a precursor solution, carrying out high-temperature and high-pressure reaction on the precursor solution, and then filtering, cleaning and drying to obtain a powdery composite catalyst precursor; uniformly mixing the powdery composite catalyst precursor, auxiliary materials and clay to obtain composite granulation powder; compounding the mixtureAnd forming the granulated powder to obtain the air purification composite catalyst.

Preferably, Mn is contained in manganese oxide, copper oxide and cerium oxide^II、Cu^IIAnd Ce^IIIThe molar ratio of (1) to (0.05-1), preferably (0.5-1.5) to (0.05-0.5) to (0.1-0.5).

Preferably, the air purification composite catalyst further comprises an auxiliary material and clay, wherein the auxiliary material is an inorganic porous material.

Preferably, the inorganic porous material comprises one or more of activated carbon, molecular sieve, silica micropowder, titanium dioxide, zeolite, alumina, attapulgite, sepiolite, kaolin, montmorillonite and diatomite.

Preferably, the oxidant is any one or more of lithium permanganate, sodium permanganate, potassium permanganate, ammonium permanganate, perchloric acid and fenton reagent.

Preferably, the Mn is^IIThe salt is selected from one or more of manganese sulfate, manganese nitrate, manganese carbonate, manganese chloride and manganese acetate.

Preferably, the Cu is^IIThe salt is selected from one or more of copper sulfate, copper nitrate and copper chloride.

Preferably, the Ce is^IIIThe salt is one or more of cerous nitrate, cerous sulfate, cerous chloride and ceric ammonium nitrate.

Preferably, the oxidizing agent, Mn^IISalt, Cu^IISalt and Ce^IIIThe feeding molar ratio of the salt is (0.5-3): (0.2-2): (0.05-1), wherein the preferred ratio is (1-2.5): (0.5-1.5): (0.05-0.5): (0.1-0.5).

Preferably, the solvent is water.

Preferably, the oxidizing agent and Mn are added in the stirring reaction^IISalt, Cu^IISalt and Ce^IIIThe total solid-liquid ratio of the four salt solids to the solvent is 1 to (5-30), wherein the total solid-liquid ratio is preferably 1 to (8-18).

Preferably, the stirring reaction temperature is 0 to 100 ℃, and preferably 10 to 80 ℃.

Preferably, the stirring reaction time is 10-300min, preferably 20-180 min.

Preferably, the stirring speed in the stirring reaction is 10-1000r/min, and preferably 100-800 r/min.

Preferably, the high-temperature high-pressure reaction temperature is 100-200 ℃, and preferably is 120-190 ℃.

Preferably, the high-temperature high-pressure reaction pressure is 0.3 to 3 MPa, and preferably 0.4 to 2 MPa. In the high-temperature high-pressure reaction process, the higher the temperature of the solution is, the more steam is emitted, the higher the pressure generated in the reaction kettle is, and the solution in the reaction kettle can generate relative high pressure at different temperatures. For example, the pressure in the reaction kettle is 2 MPa under the reaction condition of 190 ℃ and the pressure in the reaction kettle is 0.3 MPa under the reaction condition of 100 ℃.

Preferably, the reaction time at high temperature and high pressure is 0.5-30h, and preferably 2-24 h.

Preferably, the drying temperature is 60-300 ℃, preferably 100-200 ℃.

Preferably, the drying time is 3 to 30 hours, preferably 5 to 24 hours.

Preferably, the auxiliary material is an inorganic porous material, and can be one or more of activated carbon, molecular sieve, silica micropowder, titanium dioxide, zeolite, alumina material, attapulgite, sepiolite, kaolin, montmorillonite and diatomite.

Preferably, the particle size range of the clay is 200-600 meshes.

Preferably, the mixing mass ratio of the composite catalyst precursor to the auxiliary material to the clay is 1 to (0.2-2), and preferably 1 to (0.5-1.5) to (0.4-1.6).

Preferably, the molding process comprises the steps of: adding spherical particle seeds into a granulator, adding the binder and the composite granulation powder at a certain rotating speed, granulating and polishing to obtain molded particles, and finally drying to obtain the spherical air purification composite catalyst.

Preferably, the spherical particle seeds are selected from chemically inert inorganic material particles, such as alumina, silica, calcia and zirconia.

Preferably, the spherical particle seeds have a particle size in the range of 0.1 to 9mm, preferably 0.5 to 9 mm.

Preferably, the rotating speed of a granulator in the granulation is 10-60r/min, preferably 10-40 r/min;

preferably, the rotation speed of the pelletizer in the polishing is 20-40 r/min;

preferably, the polishing time is 10-100 min.

Preferably, the molding process comprises the steps of: uniformly mixing the composite granulation powder and the binder, and adding the mixture into a material bin of an extrusion molding machine for later use; starting an extrusion molding machine for granulation; and drying the obtained particles to obtain the spherical air purification composite catalyst.

Preferably, the binder is selected from one or more of water, nontoxic organic solvent and glue;

preferably, the mass ratio of the composite granulating powder to the binder in the granulating process is 1: 0.2-1.2, preferably 1: 0.25-1.0;

preferably, the drying temperature of the formed particles is 60-300 ℃, preferably 100-200 ℃;

preferably, the drying time of the formed particles is 1 to 30 hours, preferably 3 to 24 hours;

preferably, the diameter of the formed particle is in the range of 0.2-10.2 mm;

the air purification composite catalyst is applied to the purification of formaldehyde, ozone and TVOC in rooms, vehicles, engine rooms and ship cabins.

Compared with the prior art, the method has the following advantages:

1. the nano-scale composite catalyst material has high surface activity, and realizes spontaneous catalytic decomposition reaction without any additional condition;

2. the manganese oxide catalyst material with high catalytic activity is adopted, so that harmful gases in the air can be effectively purified, and the catalyst is lossless in the catalytic decomposition reaction process and can be repeatedly used;

3. the doping components with coordinated catalysis are selected, so that the catalytic performance of the catalyst material is obviously improved;

4. carrying out recrystallization reaction under the conditions of high temperature and high pressure, so that the doping reaction is more sufficient;

5. the auxiliary material with large specific surface area is added to play a role in adsorbing harmful gas, so that the concentration of harmful substances near the catalyst material is improved, and the catalytic decomposition efficiency is accelerated;

6. inorganic auxiliary materials are used, so that the surface performance of the catalyst particles is effectively improved, and the phenomenon that the particles are mildewed in the long-term use process is avoided;

7. the polishing process effectively improves the surface properties of the particles.

Drawings

Fig. 1 is an SEM image of the composite catalyst precursor of the present invention.

Fig. 2 is yet another SEM image of the composite catalyst precursor of the present invention.

Fig. 3 is a flow chart of a process for preparing the air purification composite catalyst of the present invention.

Detailed Description

The present invention now will be described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments of the invention are shown.

Example 1

1708g of pure water is added with 39.5g of potassium permanganate, 19.8g of manganese chloride tetrahydrate, 12.5g of copper sulfate pentahydrate and 13.6g of cerous nitrate hexahydrate in sequence, stirred until the mixture is fully dispersed and dissolved, the rotating speed of a stirrer is 10r/min, and the mixture reacts for 300min at 0 ℃. And transferring the mixed solution into a high-pressure reaction kettle, reacting at 150 ℃ for 16h, taking out, cleaning, filtering, and drying at 60 ℃ for 30h to obtain the precursor of the air purification composite catalyst.

Uniformly mixing the composite catalyst precursor, silicon dioxide and clay according to the mass ratio of 1: 2: 1 to obtain composite granulation powder for later use. And adding 0.1mm of alumina particles into a disc granulator, granulating at the rotating speed of 60r/min, adopting water as a binder in the granulating process, wherein the adding mass ratio of the composite granulating powder to the water is 1: 0.2, granulating, stopping feeding when the average particle size of the particles reaches 0.2mm, and collecting the particles. And adding the collected particle products into a disc granulator with the rotating speed of 40r/min, polishing for 10min to obtain formed particles, taking out, and drying at 200 ℃ for 3h to obtain the air purification composite catalyst particles.

The BET test (see Table 1) shows that the prepared composite catalyst precursor and composite catalyst particles have larger specific surface area.

And (3) testing the catalytic decomposition performance of formaldehyde: 5.00g of the air-purifying composite catalyst particles prepared above were placed on a sand core in a glass tube having a diameter of 10mm to evaluate the catalytic decomposition activity. The bottom of the glass tube is connected with a formaldehyde generator, and the top of the glass tube is connected with an online detector of a gas chromatograph. The air is pumped into a formaldehyde generator by a pump and mixed with formaldehyde to obtain air with the formaldehyde concentration of 1000ppm, the adding amount of the air is 500mL/min, the air containing the formaldehyde enters a glass tube filled with a composite catalyst from the bottom, and then enters a gas chromatograph for online detection of the formaldehyde content through the top of the glass tube. The detection result shows that the air purification composite catalyst prepared in the embodiment can be used for catalytically decomposing 1000ppm of formaldehyde at room temperature, and the decomposition efficiency of one-time passing is 95%.

Ozone catalytic decomposition performance test: the same evaluation device as the above test is used to evaluate the decomposition performance of the air purification composite catalyst particles on ozone, and an ultraviolet spectrophotometer on-line detector is used to measure the concentration of ozone. The test method is the same as the above, and the detection result shows that the air purification composite catalyst prepared in this example catalytically decomposes 120ppm of ozone at room temperature, and the catalytic decomposition efficiency in one pass is shown in table 2.

TVOC gas purification performance test: the same evaluation apparatus as the above test was used to evaluate the decomposition performance of the air-purifying composite catalyst particles for ozone, and the concentration of TVOC was measured by a gas chromatograph. The test method is the same as the above, and the detection result shows that the removal efficiency of the air purification composite catalyst prepared in this example for one pass of TVOC of 400ppm at room temperature is shown in table 2.

Benzene, toluene and xylene purification performance test: selecting the material with the temperature of 23-27 deg.C and the size of 30m³The air purification performance of the multifunctional air purification composite catalyst material is evaluated in the test cabin environment. Three harmful substances, namely benzene, toluene and xylene, are selected as purification effects to carry out a test project. Through detection, the 1h purification rate of benzene, toluene and xylene of the multifunctional air purification composite catalyst material prepared in the embodiment is shown in table 2.

Example 2

28g of potassium permanganate, 28.7g of manganese nitrate hexahydrate, 8.5g of copper chloride dihydrate and 17.7g of cerium chloride hexahydrate are sequentially added into 786g of pure water, stirred until the mixture is fully dispersed and dissolved, the rotating speed of a stirrer is 1000r/min, and the mixture reacts for 10min at 100 ℃. And transferring the mixed solution into a high-pressure reaction kettle, reacting at 100 ℃ for 30h, taking out, cleaning, filtering, and drying at 200 ℃ for 2h to obtain the precursor of the air purification composite catalyst.

Uniformly mixing the composite catalyst precursor, the silicon micropowder and the clay according to the mass ratio of 1: 0.5: 2 to obtain composite granulation powder for later use. And (2) adding silica particles with the particle size of 0.2mm into a disc granulator, granulating at the rotating speed of 45r/min, adopting water as a binder in the granulating process, wherein the adding mass ratio of the composite granulating powder to the water is 1: 0.3, granulating, stopping feeding when the average particle size of the particles reaches 2mm, and collecting the particles. And adding the collected particle products into a roller dryer with the rotating speed of 30r/min, polishing for 50min to obtain formed particles, taking out, and drying at 150 ℃ for 10h to obtain the air purification composite catalyst particles.

The particle performance test method is the same as that of example 1, and the test results are shown in Table 2.

Example 3

31.6g of potassium permanganate, 17.8g of manganese sulfate tetrahydrate, 1.2g of copper nitrate trihydrate and 6.4g of cerium sulfate tetrahydrate are sequentially added into 285g of pure water, stirred until the mixture is fully dispersed and dissolved, the rotating speed of a stirrer is 150r/min, and the mixture reacts for 180min at 20 ℃. And transferring the mixed solution into a high-pressure reaction kettle, reacting at 180 ℃ for 2h, taking out, cleaning, filtering, and drying at 100 ℃ for 20h to obtain the precursor of the air purification composite catalyst.

Uniformly mixing the composite catalyst precursor, diatomite and clay according to the mass ratio of 1: 0.2: 1 to obtain composite granulation powder for later use. And adding 0.2mm of zirconium oxide particles into a disc granulator, granulating at the rotating speed of 10r/min, adopting water as a binder in the granulating process, wherein the adding mass ratio of the composite granulating powder to the water is 1: 0.45, granulating, stopping feeding when the average particle size of the particles reaches 1mm, and collecting the particles. And adding the collected particle products into a roller dryer with the rotating speed of 20r/min, polishing for 30min to obtain formed particles, taking out, and drying at 180 ℃ for 5h to obtain the air purification composite catalyst particles.

Example 4

223.7g of potassium permanganate, 17.2g of manganese nitrate hexahydrate, 7.3g of copper nitrate trihydrate and 10.6g of cerium chloride hexahydrate are sequentially added into 1470g of pure water, the mixture is stirred until the mixture is fully dispersed and dissolved, the rotating speed of a stirrer is 800r/min, and the mixture reacts for 50min at 80 ℃. And transferring the mixed solution into a high-pressure reaction kettle, reacting at 200 ℃ for 0.5h, taking out, cleaning, filtering, and drying at 120 ℃ for 15h to obtain the precursor of the air purification composite catalyst.

Uniformly mixing the composite catalyst precursor, alumina and clay according to the mass ratio of 1: 0.8: 0.2 to obtain composite granulation powder for later use. And adding 0.4mm of alumina particles into a disc granulator, granulating at the rotation speed of 20r/min, adopting water as a binder in the granulating process, wherein the adding mass ratio of the composite granulating powder to the water is 1: 0.4, granulating, stopping feeding when the average particle size of the particles reaches 5mm, and collecting the particles. And adding the collected particle products into a roller dryer with the rotating speed of 25r/min, polishing for 80min to obtain formed particles, taking out, and drying at 60 ℃ for 30h to obtain the air purification composite catalyst particles.

Example 5

28.4g of potassium permanganate, 20.1g of manganese nitrate hexahydrate, 10.2g of copper chloride dihydrate and 12.8g of cerium sulfate tetrahydrate are sequentially added into 2145g of pure water, stirred until the mixture is fully dispersed and dissolved, the rotating speed of a stirrer is 300r/min, and the mixture reacts for 100min at 60 ℃. And transferring the mixed solution into a high-pressure reaction kettle, reacting at 120 ℃ for 15h, taking out, cleaning, filtering, and drying at 150 ℃ for 10h to obtain the precursor of the air purification composite catalyst.

Uniformly mixing the composite catalyst precursor, the activated carbon and the clay according to the mass ratio of 1: 0.5 to obtain composite granulation powder for later use. And adding 9mm of alumina particles into a disc granulator, granulating at the rotation speed of 30r/min, using water as a binder in the granulation process, wherein the adding mass ratio of the composite granulation powder to the water is 1: 0.35, performing granulation operation, stopping feeding when the average particle size of the particles reaches 10mm, and collecting the particles. And adding the collected particle products into a roller dryer with the rotating speed of 35r/min, polishing for 100min to obtain formed particles, taking out, and drying at 120 ℃ for 15h to obtain the air purification composite catalyst particles.

Comparative example 1 (No high temperature high pressure reaction Process)

Adding 39.5g of potassium permanganate, 19.8g of manganese chloride tetrahydrate, 12.5g of copper sulfate pentahydrate and 13.6g of cerous nitrate hexahydrate into 1708g of pure water in sequence, stirring until the potassium permanganate, the manganese chloride tetrahydrate, the copper sulfate pentahydrate and the cerous nitrate hexahydrate are fully dispersed and dissolved, reacting at 0 ℃ for 300min at the rotating speed of a stirrer, cleaning, filtering, and drying at 60 ℃ for 30h to obtain the precursor of the air purification composite catalyst.

Uniformly mixing the composite catalyst precursor, silicon dioxide and clay according to the mass ratio of 1: 2: 1 to obtain composite granulation powder for later use. And adding 0.1mm of alumina particles into a disc granulator, granulating at the rotating speed of 60r/min, adopting water as a binder in the granulating process, wherein the adding mass ratio of the composite granulating powder to the water is 1: 0.2, granulating, stopping feeding when the average particle size of the particles reaches 0.2mm, and collecting the particles. And adding the collected particle products into a roller dryer with the rotating speed of 40r/min, polishing for 10min to obtain formed particles, taking out, and drying at 200 ℃ for 1h to obtain the air purification composite catalyst particles.

The BET test (see Table 1) shows that the specific surface areas of the prepared composite catalyst precursor and the composite catalyst particles are smaller.

COMPARATIVE EXAMPLE 2 (undoped component)

And adding 39.5g of potassium permanganate and 19.8g of manganese chloride tetrahydrate into 1708g of pure water in sequence, stirring until the potassium permanganate and the manganese chloride are fully dispersed and dissolved, and reacting for 300min at 0 ℃ at the rotating speed of a stirrer of 10 r/min. And transferring the mixed solution into a high-pressure reaction kettle, reacting at 150 ℃ for 16h, taking out, cleaning, filtering, and drying at 60 ℃ for 30h to obtain the precursor of the air purification composite catalyst.

Uniformly mixing the composite catalyst precursor, silicon dioxide and clay according to the mass ratio of 1: 2: 1 to obtain composite granulation powder for later use. And adding 0.1mm of alumina particles into a disc granulator, granulating at the rotating speed of 60r/min, adopting water as a binder in the granulating process, wherein the adding mass ratio of the composite granulating powder to the water is 1: 0.2, granulating, stopping feeding when the average particle size of the particles reaches 0.2mm, and collecting the particles. And adding the collected particle products into a roller dryer with the rotating speed of 40r/min, polishing for 10min to obtain formed particles, taking out, and drying lh at the temperature of 200 ℃ to obtain the air purification composite catalyst particles.

Comparative example 3 (granulation process without addition of adjuvants)

And uniformly mixing the composite catalyst precursor and clay according to the mass ratio of 1: 1 to obtain composite granulation powder for later use. And adding 0.1mm of alumina particles into a disc granulator, granulating at the rotating speed of 60r/min, adopting water as a binder in the granulating process, wherein the adding mass ratio of the composite catalyst precursor to the water is 1: 0.2, granulating, stopping feeding when the average particle size of the particles reaches 0.2mm, and collecting the particles. And adding the collected particle products into a disc granulator with the rotating speed of 40r/min, polishing for 10min to obtain formed particles, taking out, and drying at 200 ℃ for 3h to obtain the air purification composite catalyst particles.

The BET test (see Table 1) shows that the specific surface areas of the prepared composite catalyst precursor and the composite catalyst particles are not large.

COMPARATIVE EXAMPLE 4 (COMPARATIVE EXAMPLE OF MATERIALS MIXING)

1.58g of potassium permanganate, 20.1g of manganese nitrate hexahydrate, 10.2g of copper chloride dihydrate and 12.8g of cerium sulfate tetrahydrate are sequentially added into 2145g of pure water, the solid-to-liquid ratio of the reaction materials is 1: 36, the mixture is stirred until the reaction materials are fully dispersed and dissolved, the rotating speed of a stirrer is 300r/min, and the reaction is carried out for 100min at the temperature of 60 ℃. And transferring the mixed solution into a high-pressure reaction kettle, reacting at 120 ℃ for 15h, taking out, cleaning, filtering, and drying at 150 ℃ for 10h to obtain the precursor of the air purification composite catalyst.

COMPARATIVE EXAMPLE 5 (COMPARATIVE EXAMPLE OF MATERIALS MIXING)

28.4g of potassium permanganate, 20.1g of manganese nitrate hexahydrate, 0.17g of copper chloride dihydrate and 12.8g of cerium sulfate tetrahydrate are sequentially added into 2145g of pure water, the solid-to-liquid ratio of the reaction materials is 1: 36, the mixture is stirred until the mixture is fully dispersed and dissolved, the rotating speed of a stirrer is 300r/min, and the reaction is carried out for 100min at the temperature of 60 ℃. And transferring the mixed solution into a high-pressure reaction kettle, reacting at 120 ℃ for 15h, taking out, cleaning, filtering, and drying at 150 ℃ for 10h to obtain the precursor of the air purification composite catalyst.

Table 1: specific surface area tables of composite catalyst precursor and composite catalyst particles

Table 2: composite catalyst particle air purification performance test result table

Sample (I)

Formaldehyde (I)

Ozone generator

TVOC

Benzene and its derivatives

Toluene

Xylene

Example 1

95％

98％

99％

Example 2

93％

91％

98％

99％

98％

99％

Example 3

91％

88％

99％

98％

99％

97％

Example 4

88％

92％

99％

96％

98％

99％

Example 5

90％

86％

97％

99％

96％

99％

Comparative example 1

24％

17％

21％

26％

27％

22％

Comparative example 2

40％

23％

20％

28％

29％

30％

Comparative example 3

46％

52％

47％

57％

53％

61％

Comparative example 4

16％

9％

23％

19％

16％

21％

Comparative example 5

62％

59％

67％

56％

51％

68％

The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.

Claims

1. The application of the air purification composite catalyst material in purifying formaldehyde, ozone and TVOC in rooms, cars, cabins and cabins at room temperature comprises manganese oxide composite copper oxide and cerium oxide, and Mn in the manganese oxide, the copper oxide and the cerium oxide^II、Cu^IIAnd Ce^IIIThe molar ratio of (0.5-1.5) to (0.05-0.5) to (0.1-0.5), the air purification composite catalyst also comprises auxiliary materials and clay, and the auxiliary materials are inorganic porous materials;

the preparation method of the air purification composite catalyst comprises the following steps:

oxidizing agent and Mn^IISalt, Cu^IISalt and Ce^IIIDissolving salt into a solvent to obtain a mixed solution, carrying out stirring reaction to obtain a precursor solution, carrying out high-temperature and high-pressure reaction on the precursor solution, and then filtering, cleaning and drying to obtain a powdery composite catalyst precursor;

uniformly mixing the powdery composite catalyst precursor, auxiliary materials and clay to obtain composite granulation powder;

molding the composite granulated powder to obtain the air purification composite catalyst;

wherein, the Cu^IIThe salt is one or more of copper sulfate, copper nitrate and copper chloride; the inorganic porous material comprises activated carbon and inorganic particlesOne or more of a sub-sieve, silicon dioxide, titanium dioxide, zeolite, alumina, attapulgite, sepiolite, kaolin, montmorillonite and diatomite;

the Mn is^IIThe salt is selected from one or more of manganese sulfate, manganese nitrate, manganese carbonate, manganese chloride and manganese acetate;

the Ce^IIIThe salt is one or more of cerous nitrate, cerous sulfate, cerous chloride and ceric ammonium nitrate;

the oxidant is any one or more of lithium permanganate, sodium permanganate, potassium permanganate, ammonium permanganate, perchloric acid and Fenton reagent;

the molding treatment comprises the following steps: adding spherical particle seeds into a granulator, adding the composite granulation powder and the binder at a certain rotating speed, granulating and polishing to obtain formed particles, and finally drying to obtain the spherical air purification composite catalyst.

2. Use according to claim 1, wherein the oxidant, Mn^IISalt, Cu^IISalt and Ce^IIIThe feeding molar ratio of the salt is (1-2.5) to (0.5-1.5) to (0.05-0.5) to (0.1-0.5).

3. Use according to claim 2, wherein the solvent is selected from water.

4. Use according to claim 2, wherein the stirring reaction is carried out with an oxidant, Mn^IISalt, Cu^IISalt and Ce^IIIThe total solid-liquid ratio of the four salt solids to the solvent is 1: 8-18.

5. The use according to claim 2, wherein the stirred reaction temperature is 10-80 ℃.

6. The use according to claim 2, wherein the stirring reaction time is 20-180 min.

7. The use of claim 2, wherein the stirring rate in the stirring reaction is 100-800 r/min.

8. The use as claimed in claim 2, wherein the reaction temperature is 120-190 ℃.

9. The use according to claim 2, wherein the elevated temperature and pressure reaction pressure is from 0.4 to 2 mpa.

10. The use according to claim 2, wherein the reaction time at elevated temperature and pressure is 2-24 h.

11. The use as claimed in claim 2, wherein the drying temperature is 100-200 ℃.

12. Use according to claim 2, wherein the drying time is 5-24 h.

13. The use of claim 2, wherein the clay has a particle size of 200-600 mesh.

14. The application of the composite catalyst as claimed in claim 2, wherein the mixing mass ratio of the composite catalyst precursor, the auxiliary material and the clay is 1: 0.5-1.5: 0.4-1.6.

15. The use according to claim 2, wherein the spherical seeds are selected from the group consisting of chemically inert particles of inorganic materials.

16. Use according to claim 2, wherein the spherical particle seeds have a particle size in the range of 0.5-9 mm.

17. Use according to claim 2, wherein the granulator is operated at 10-40r/min during the granulation.

18. Use according to claim 2, wherein the polishing time is 10-100 min.

19. Use according to claim 2, wherein the forming process comprises the steps of: uniformly mixing the composite granulation powder and the binder, and adding the mixture into a material bin of an extrusion molding machine for later use; starting an extrusion molding machine for granulation; and drying the obtained particles to obtain the spherical air purification composite catalyst.

20. The use according to claim 19, wherein the binder is selected from one or more of water, non-toxic organic solvents, and glue.

21. The use of claim 19, wherein the mass ratio of the composite granulated powder to the binder in the granulation process is 1: 0.25-1.0.

22. The use of claim 19, wherein the shaped particle drying temperature is 100-200 ℃.

23. Use according to claim 19, wherein the shaped particle is dried for a period of 3 to 24 hours.

24. Use according to claim 19, wherein the shaped particles have a diameter in the range of 0.2-10.2 mm.