WO2018068729A1 - 一种空气净化复合催化剂及其制备方法 - Google Patents

一种空气净化复合催化剂及其制备方法 Download PDF

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WO2018068729A1
WO2018068729A1 PCT/CN2017/105713 CN2017105713W WO2018068729A1 WO 2018068729 A1 WO2018068729 A1 WO 2018068729A1 CN 2017105713 W CN2017105713 W CN 2017105713W WO 2018068729 A1 WO2018068729 A1 WO 2018068729A1
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composite catalyst
air
catalyst according
producing
purifying
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PCT/CN2017/105713
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French (fr)
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黄建国
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友好净控科技（浙江）有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • B01D53/8675—Ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8678—Removing components of undefined structure
    • B01D53/8687—Organic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the invention relates to a material for environmental protection, in particular to a composite catalyst material for purifying gas.
  • the harmful gases in the air mainly include formaldehyde, ozone, benzene, toluene, xylene, carbon dioxide, nitrogen oxides, other organic substances and other volatile harmful gases, which are harmful to human health to varying degrees.
  • formaldehyde on the skin and mucous membrane stimulation direct contact with the skin can cause allergic inflammation and even necrosis, high concentrations of formaldehyde can induce bronchial asthma and even cause nasopharyngeal tumors, or a genotoxic substance.
  • Ozone can strongly irritate the human respiratory tract and may even cause neurotoxicity in the human body, causing various diseases.
  • TVOC volatile harmful gases
  • a photocatalyst technology for purifying harmful gases in the air which uses a photocatalyst material as a catalyst material, wherein the photocatalyst catalyst material is mainly a titanium dioxide material, which is generated under the condition of irradiation of light of a certain energy level.
  • the highly oxidizing hydroxyl radicals catalyze the decomposition of toxic and harmful substances in the air to purify the air.
  • transition metal oxides especially manganese oxides
  • have good catalytic activity can achieve spontaneous catalytic reactions in multiple reactions without additional conditions, and are inexpensive, and can meet large-scale applications.
  • the catalytic activity of the catalyst is often affected by its internal lattice structure, particle size, composition, morphology, and surrounding conditions.
  • the manganese oxide material with the same lattice structure has different catalytic activities, and after doping with other metals having complementary and reinforcing effects in the lattice structure, it can play a coordinated catalytic role in the catalytic reaction process, and significantly improve the catalyst.
  • the catalytic activity of the material is often affected by its internal lattice structure, particle size, composition, morphology, and surrounding conditions.
  • the atoms of these different metals are complementary in size and surface structure, so they are usually doped with a variety of materials to prepare a composite catalyst, which plays a synergistic role in the catalytic reaction and improves its catalytic performance; its structure and morphology are different.
  • the catalyst material has different surface area and surface active quantity, and the catalyst material with large specific surface area and more surface active sites can significantly increase the number of effective collisions in the reaction process, so that the material has higher catalytic activity and catalytic decomposition efficiency; In the application process of catalyst materials, the addition of appropriate excipients can effectively improve the catalytic decomposition performance.
  • the excipients with good surface properties and strong adsorption properties are selected and distributed around the catalyst to pre-adsorb the harmful gases in the air and increase
  • concentration of the harmful gas around the active catalyst effectively increases the concentration gradient of the harmful gas distribution around the catalyst and improves the catalytic decomposition efficiency of the catalyst material.
  • CN 104174391 A discloses a nano titanium dioxide photocatalyst material for degrading VOC, and the prepared nano titanium dioxide photocatalyst has strong visible light absorption capacity, low electron hole recombination rate, and can rapidly and completely degrade high concentration.
  • the benzene contaminant can completely degrade the low content of benzene in the small space under the irradiation of visible light within 4 hours with only 0.1 g of mass.
  • the supply and absorption capacity of visible light are the key factors that restrict its catalytic decomposition performance to benzene.
  • An oxidation catalyst and method for destroying CO, VOC and halogenated VOCs is disclosed in CN 102481549 B, which describes a method of depositing on a substrate for destroying CO and volatility in a discharge stream at a temperature of from 250 ° C to 450 ° C.
  • the oxidation catalyst comprises at least two platinum group metals supported on the refractory oxide, one of which is platinum or rhodium, and the refractory oxide is, for example, a solid solution of CeO 2 and ZrO 2 and tin oxide and/or silicon dioxide. .
  • the refractory oxide is, for example, a solid solution of CeO 2 and ZrO 2 and tin oxide and/or silicon dioxide.
  • noble metal is selected as the active catalyst material, and high cost is difficult to realize large-scale application.
  • the catalyst material needs to be subjected to catalytic decomposition reaction under high temperature conditions, high energy consumption, high application cost, and difficult to be applied to ordinary indoor air purification. Provides a field of high temperature environment.
  • CN 103506111 A discloses a preparation method of a catalyst for removing formaldehyde and ozone at room temperature, wherein a precursor is precipitated by a redox reaction in a solution, and a manganese dioxide catalyst material is obtained by a calcination process, and the polluted air is simultaneously at room temperature.
  • the harmful gases formaldehyde and ozone are decomposed into harmless H 2 and CO 2 , which has the advantages of no harmful by-products, high efficiency of de-formaldehyde and ozone.
  • the manganese dioxide catalyst material obtained by the ordinary precipitation method has the problems of low specific surface area and low performance, so that the purification amount is low, and it is difficult to meet the current air purification requirement in an air environment with complicated air pollution and high pollutant content. .
  • Air purification catalyst materials are used to meet a wide range of air purification needs.
  • an object of the present invention is to provide an air purification composite catalyst comprising a manganese oxide composite copper oxide and a cerium oxide, and a method of producing the same.
  • the special reaction conditions in the preparation method enable a large amount of Cu 2+ and Ce 3+ to enter the microscopic lattice structure of the manganese oxide to replace the position of the manganese to obtain a composite catalyst precursor doped at the lattice level, which can Synergistic effect; the addition of excipients with large specific surface area as granulation auxiliary materials, combined with homogeneous mixing molding process, effectively improves the catalytic decomposition activity of air purification catalysts on harmful substances in the air.
  • the present invention is a method for preparing an air purification composite catalyst which is realized by the following technical scheme, and is doped with manganese and copper under high temperature and high pressure reaction conditions.
  • a doped composite catalyst material The oxidant, manganese salt, copper salt and strontium salt are mixed and stirred at room temperature for stirring reaction, and then recrystallization and lattice doping reaction are carried out under high temperature and high pressure to obtain a composite catalyst precursor with high doping amount.
  • the inorganic porous material with large specific surface area is selected as the molding granulation auxiliary material, and the air purification composite catalyst material with uniform mixing and high purification efficiency is obtained by the homogeneous forming process.
  • the air purification composite catalyst material includes manganese oxide composite copper oxide and cerium oxide.
  • the preparation process of the air purification composite catalyst mainly includes preparation of a composite catalyst precursor and a process of coating and granulation.
  • the air-purifying composite catalyst of the present invention is prepared by dissolving an oxidizing agent, a Mn II salt, a Cu II salt, and a Ce III salt in a solvent to obtain a mixed solution, and obtaining a precursor solution after stirring, and a precursor is obtained.
  • the body solution is filtered, washed and dried to obtain a powdery composite catalyst precursor; the powdery composite catalyst precursor is mixed with the auxiliary material and the clay to obtain a composite granulated powder; and the composite granulated powder is obtained.
  • the material is subjected to a molding process to obtain an air purification composite catalyst.
  • the molar ratio of Mn II , Cu II and Ce III in the manganese oxide, copper oxide and cerium oxide is (0.2-2): (0.05-1): (0.05-1), preferably (0.5- 1.5): (0.05-0.5): (0.1-0.5).
  • the air purification composite catalyst further comprises an auxiliary material and a clay, and the auxiliary material is an inorganic porous material.
  • the inorganic porous material comprises one or more of activated carbon, molecular sieve, silica, silica micropowder, titanium dioxide, zeolite, alumina, attapulgite, sepiolite, kaolin, montmorillonite, diatomaceous earth.
  • activated carbon molecular sieve, silica, silica micropowder, titanium dioxide, zeolite, alumina, attapulgite, sepiolite, kaolin, montmorillonite, diatomaceous earth.
  • the oxidizing agent is selected from any one or more of lithium permanganate, sodium permanganate, potassium permanganate, ammonium permanganate, perchloric acid, and Fenton's reagent.
  • the Mn II salt is selected from any one or more of manganese sulfate, manganese nitrate, manganese carbonate, manganese chloride, and manganese acetate.
  • the Cu II salt is selected from any one or more of copper sulfate, copper nitrate, and copper chloride.
  • the Ce III salt is one or more selected from the group consisting of cerium nitrate, cerium sulfate, cerium chloride, and cerium ammonium nitrate.
  • the molar ratio of the oxidizing agent, the Mn II salt, the Cu II salt and the Ce III salt is (0.5-3): (0.2-2): (0.05-1): (0.05-1), of which (1 is preferred) -2.5): (0.5-1.5): (0.05-0.5): (0.1-0.5).
  • the solvent is water.
  • the total solid-liquid ratio mass of the four solids and the solvent of the oxidizing agent, the Mn II salt, the Cu II salt and the Ce III salt in the stirring reaction is 1: (5-30), wherein preferably 1: (8- 18).
  • the stirring reaction temperature is 0-100 ° C, preferably 10-80 ° C.
  • the stirring reaction time is from 10 to 300 min, preferably from 20 to 180 min.
  • the stirring rate in the stirring reaction is from 10 to 1000 r/min, preferably from 100 to 800 r/min.
  • the high temperature and high pressure reaction temperature is from 100 to 200 ° C, preferably from 120 to 190 ° C.
  • the high temperature and high pressure reaction pressure is from 0.3 to 3 MPa, and preferably from 0.4 to 2 MPa.
  • the pressure in the autoclave was 2 MPa under the reaction conditions of 190 ° C, and the pressure in the reactor was 0.3 MPa under the reaction conditions of 100 ° C.
  • the high temperature and high pressure reaction time is from 0.5 to 30 h, preferably from 2 to 24 h.
  • the drying temperature is from 60 to 300 ° C, preferably from 100 to 200 ° C.
  • the drying time is from 3 to 30 h, preferably from 5 to 24 h.
  • the auxiliary material is selected from inorganic porous materials, and may be selected from activated carbon, molecular sieve, silica, silicon micropowder, titanium dioxide, zeolite, alumina material, attapulgite, sepiolite, kaolin, montmorillonite and diatomaceous earth. One or more of them.
  • the clay has a particle size ranging from 200 to 600 mesh.
  • the mixed mass ratio of the composite catalyst precursor, the auxiliary material and the clay is 1: (0.2-2): (0.2-2), preferably 1: (0.5-1.5): (0.4-1.6).
  • the molding process comprises the steps of: adding spherical seed seeds to a granulator, adding the binder and the composite granulated powder at a certain rotation speed, performing granulation and polishing treatment to obtain shaped granules, Finally, a spherical air-purifying composite catalyst is obtained by drying.
  • the spherical particle seed is selected from chemically inert inorganic material particles such as alumina, silica, calcium oxide and zirconia.
  • the spherical particle seed has a particle size ranging from 0.1 to 9 mm, preferably from 0.5 to 9 mm.
  • the granulation speed in the granulation is 10-60 r/min, preferably 10-40 r/min;
  • the polishing granulator has a rotation speed of 20-40 r/min;
  • the polishing is carried out for a period of from 10 to 100 minutes.
  • the molding process comprises the steps of uniformly mixing the composite granulated powder and the binder, and adding it to the material warehouse of the extrusion molding machine for use; and opening the extrusion molding machine for granulation; The obtained granules are dried to obtain a spherical air-purifying composite catalyst.
  • the binder is selected from one or more of water, a non-toxic organic solvent, and glue;
  • the mass ratio of the composite granulated powder to the binder during the granulation process is 1: (0.2-1.2), preferably 1: (0.25-1.0);
  • the shaped particles have a drying temperature of 60-300 ° C, preferably 100-200 ° C;
  • the shaped particles have a drying time of 1-30 h, preferably 3-24 h;
  • the shaped particles have a diameter ranging from 0.2 to 10.2 mm;
  • the air purification composite catalyst is applied to formaldehyde, ozone and TVOC purification in indoors, in the vehicle, in the engine room and in the cabin.
  • the nano-scale composite catalyst material has high surface activity, and realizes spontaneous catalytic decomposition reaction without any additional conditions;
  • the manganese oxide catalyst material with high catalytic activity can effectively purify the harmful gases in the air, and has no loss during the catalytic decomposition reaction, and can be reused;
  • the recrystallization reaction is carried out under high temperature and high pressure conditions, so that the doping reaction is more sufficient;
  • Adding auxiliary materials with large specific surface area which plays the role of adsorbing harmful gases, increases the concentration of harmful substances near the catalyst materials, and accelerates the catalytic decomposition efficiency;
  • inorganic auxiliary materials can effectively improve the surface properties of the catalyst particles, and eliminate the phenomenon of mildew in the long-term use of the particles;
  • the polishing process effectively improves the surface properties of the particles.
  • Figure 1 is an SEM image of a composite catalyst precursor of the present invention.
  • Fig. 3 is a flow chart showing the preparation process of the air purifying composite catalyst of the present invention.
  • the composite catalyst precursor, silica and clay are uniformly mixed at a mass ratio of 1:2:1 to obtain a composite granulated powder to be used.
  • 0.1mm alumina particles were added to the disc granulator at a rotation speed of 60r/min for granulation.
  • Water was used as a binder in the granulation process, and the mass ratio of the composite granulated powder to water was added.
  • the granulation operation was carried out, and when the average particle diameter of the particles reached 0.2 mm, the feeding was stopped and the particles were collected.
  • the collected particulate product was added to a disc granulator rotating at 40 r/min for polishing for 10 minutes to obtain shaped pellets, which were taken out and dried at 200 ° C for 3 hours to obtain air-purified composite catalyst particles.
  • the BET test indicates that the prepared composite catalyst precursor and composite catalyst particles have a large specific surface area.
  • Formaldehyde catalytic decomposition performance test 5.00 g of the air-purified composite catalyst particles prepared above were placed The catalytic decomposition activity evaluation was carried out on a sand core of a glass tube having a diameter of 10 mm. The bottom of the glass tube is connected to the formaldehyde generator and the top is connected to the gas chromatograph online detector. The pump pumps the air into the formaldehyde generator and mixes with formaldehyde to obtain air containing formaldehyde at a concentration of 1000 ppm. The air is added in an amount of 500 mL/min. The air containing formaldehyde enters the glass tube containing the composite catalyst from the bottom and passes through the top of the glass tube.
  • the test results show that the air purification composite catalyst prepared in the present embodiment catalytically decomposes 1000 ppm of formaldehyde at room temperature, and the decomposition efficiency of one pass is 95%.
  • Ozone catalytic decomposition performance test The same evaluation device as the above test was used to evaluate the decomposition performance of the air purification composite catalyst particles on ozone, and the ozone concentration was measured by an ultraviolet spectrophotometer on-line detector.
  • the test method is the same as above, and the test results show that the air purification composite catalyst prepared in the present embodiment catalytically decomposes 120 ppm of ozone at room temperature, and the catalytic decomposition efficiency of the primary pass is shown in Table 2.
  • TVOC gas purification performance test The decomposition performance of the air purification composite catalyst particles for ozone was evaluated by the same evaluation device as the above test, and the concentration of TVOC was measured by a gas chromatograph. The test method is the same as above, and the test results show that the removal efficiency of the air-purifying composite catalyst prepared in the present embodiment to 400 ppm of TVOC at room temperature is shown in Table 2.
  • Purification performance test of benzene, toluene and xylene The air purification performance evaluation of the multifunctional air purification composite catalyst material was carried out in a test chamber environment with a temperature of 23-27 ° C and a size of 30 m 3 . Three harmful substances, benzene, toluene and xylene, were selected to test the purification effect. After testing, it was found that the 1h purification rate of the multifunctional air purification composite catalyst material prepared in the present example for benzene, toluene and xylene is shown in Table 2.
  • the composite catalyst precursor, the silicon micropowder and the clay are uniformly mixed at a mass ratio of 1:0.5:2 to obtain a composite granulated powder to be used.
  • 0.2mm silica particles were added to the disc granulator at a rotation speed of 45r/min for granulation.
  • Water was used as a binder in the granulation process, and the quality of the composite granulated powder and water was added. The ratio was 1:0.3, and the granulation operation was carried out. When the average particle diameter of the particles reached 2 mm, the feeding was stopped and the particles were collected.
  • the collected granular product was added to a tumble dryer having a rotation speed of 30 r/min for polishing for 50 minutes to obtain shaped pellets, and the air-purified composite catalyst particles were obtained by drying at 150 ° C for 10 hours.
  • the BET test indicates that the prepared composite catalyst precursor and composite catalyst particles have a large specific surface area.
  • the particle performance test method is the same as that in Example 1, and the test results are shown in Table 2.
  • the composite catalyst precursor, diatomaceous earth and clay are uniformly mixed at a mass ratio of 1:0.2:1 to obtain a composite granulated powder to be used.
  • 0.2mm zirconia particles were added to the disc granulator, and the granulation was carried out at a rotation speed of 10r/min.
  • Water was used as a binder in the granulation process, and the mass ratio of the composite granulated powder to water was added.
  • the granulation operation is carried out, and when the average particle diameter of the particles reaches 1 mm, the feeding is stopped. Collect particles.
  • the collected particulate product was added to a tumble dryer having a rotation speed of 20 r/min for polishing for 30 minutes to obtain shaped pellets, which were taken out and dried at 180 ° C for 5 hours to obtain air-purified composite catalyst particles.
  • the BET test indicates that the prepared composite catalyst precursor and composite catalyst particles have a large specific surface area.
  • the particle performance test method is the same as that in Example 1, and the test results are shown in Table 2.
  • the composite catalyst precursor, alumina and clay are uniformly mixed at a mass ratio of 1:0.8:0.2 to obtain a composite granulated powder to be used.
  • 0.4mm alumina particles were added to the disc granulator at a rotation speed of 20r/min for granulation.
  • Water was used as a binder in the granulation process, and the mass ratio of the composite granulated powder to water was added.
  • the granulation operation was carried out, and when the average particle diameter of the particles reached 5 mm, the feeding was stopped and the particles were collected.
  • the collected particulate product was added to a tumble dryer having a rotation speed of 25 r/min for polishing for 80 minutes to obtain shaped pellets, which were taken out and dried at 60 ° C for 30 hours to obtain air-purified composite catalyst particles.
  • the BET test indicates that the prepared composite catalyst precursor and composite catalyst particles have a large specific surface area.
  • the particle performance test method is the same as that in Example 1, and the test results are shown in Table 2.
  • the composite catalyst precursor, the activated carbon and the clay are uniformly mixed at a mass ratio of 1:1:0.5 to obtain a composite granulated powder to be used.
  • 9mm alumina particles were added to the disc granulator, and the granulation was carried out at a rotation speed of 30r/min.
  • Water was used as a binder in the granulation process, and the mass ratio of the composite granulated powder to water was 1:0.35, the granulation operation was carried out, and when the average particle diameter of the particles reached 10 mm, the feeding was stopped and the particles were collected.
  • the collected particulate product was added to a tumble dryer having a rotation speed of 35 r/min for polishing for 100 minutes to obtain shaped pellets, which were taken out and dried at 120 ° C for 15 hours to obtain air-purified composite catalyst particles.
  • the BET test indicates that the prepared composite catalyst precursor and composite catalyst particles have a large specific surface area.
  • the particle performance test method is the same as that in Example 1, and the test results are shown in Table 2.
  • the composite catalyst precursor, silica and clay are uniformly mixed at a mass ratio of 1:2:1 to obtain a composite granulated powder to be used.
  • 0.1mm alumina particles were added to the disc granulator at a rotation speed of 60r/min for granulation.
  • Water was used as a binder in the granulation process, and the mass ratio of the composite granulated powder to water was added.
  • the granulation operation was carried out, and when the average particle diameter of the particles reached 0.2 mm, the feeding was stopped and the particles were collected.
  • the collected particulate product was added to a tumble dryer having a rotational speed of 40 r/min for polishing for 10 minutes to obtain shaped pellets, which were taken out and dried at 200 ° C for 1 hour to obtain air-purified composite catalyst particles.
  • the BET test (see Table 1) showed that the prepared composite catalyst precursor and composite catalyst particles had a small specific surface area.
  • the particle performance test method is the same as that in Example 1, and the test results are shown in Table 2.
  • the composite catalyst precursor, silica and clay are uniformly mixed at a mass ratio of 1:2:1 to obtain a composite granulated powder to be used.
  • 0.1mm alumina particles were added to the disc granulator at a rotation speed of 60r/min for granulation.
  • Water was used as a binder in the granulation process, and the mass ratio of the composite granulated powder to water was added.
  • the granulation operation was carried out, and when the average particle diameter of the particles reached 0.2 mm, the feeding was stopped and the particles were collected.
  • the collected particulate product was added to a tumble dryer having a rotational speed of 40 r/min for polishing for 10 minutes to obtain shaped pellets, which were taken out and dried at 200 ° C for 1 hour to obtain air-purified composite catalyst particles.
  • the BET test indicates that the prepared composite catalyst precursor and composite catalyst particles have a large specific surface area.
  • the particle performance test method is the same as that in Example 1, and the test results are shown in Table 2.
  • the composite catalyst precursor and the clay are uniformly mixed at a mass ratio of 1:1 to obtain a composite granulated powder to be used.
  • 0.1mm alumina particles were added to the disc granulator at a rotation speed of 60r/min for granulation.
  • Water was used as a binder in the granulation process.
  • the mass ratio of the composite catalyst precursor to water was 1:0.2, the granulation operation was carried out, and when the average particle diameter of the particles reached 0.2 mm, the feeding was stopped and the particles were collected.
  • the collected particulate product was added to a disc granulator rotating at 40 r/min for polishing for 10 minutes to obtain shaped pellets, which were taken out and dried at 200 ° C for 3 hours to obtain air-purified composite catalyst particles.
  • the BET test (see Table 1) showed that the prepared composite catalyst precursor and composite catalyst particles had a small specific surface area.
  • the particle performance test method is the same as that in Example 1, and the test results are shown in Table 2.
  • the composite catalyst precursor, the activated carbon and the clay are uniformly mixed at a mass ratio of 1:1:0.5 to obtain a composite granulated powder to be used.
  • 9mm alumina particles were added to the disc granulator, and the granulation was carried out at a rotation speed of 30r/min.
  • Water was used as a binder in the granulation process, and the mass ratio of the composite granulated powder to water was 1:0.35, the granulation operation was carried out, and when the average particle diameter of the particles reached 10 mm, the feeding was stopped and the particles were collected.
  • the collected particulate product was added to a tumble dryer having a rotation speed of 35 r/min for polishing for 100 minutes to obtain shaped pellets, which were taken out and dried at 120 ° C for 15 hours to obtain air-purified composite catalyst particles.
  • the BET test indicates that the prepared composite catalyst precursor and composite catalyst particles have a large specific surface area.
  • the particle performance test method is the same as that in Example 1, and the test results are shown in Table 2.
  • the composite catalyst precursor, the activated carbon and the clay are uniformly mixed at a mass ratio of 1:1:0.5 to obtain a composite granulated powder to be used.
  • 9mm alumina particles were added to the disc granulator at a rotation speed of 30r/min for granulation.
  • Water was used as a binder in the granulation process, in which the composite granulated powder and water were used.
  • the addition mass ratio was 1:0.35, and the granulation operation was carried out.
  • the average particle diameter of the particles reached 10 mm, the feeding was stopped and the particles were collected.
  • the collected particulate product was added to a tumble dryer having a rotation speed of 35 r/min for polishing for 100 minutes to obtain shaped pellets, which were taken out and dried at 120 ° C for 15 hours to obtain air-purified composite catalyst particles.
  • the BET test indicates that the prepared composite catalyst precursor and composite catalyst particles have a large specific surface area.
  • the particle performance test method is the same as that in Example 1, and the test results are shown in Table 2.
  • Table 1 Specific surface area tables of composite catalyst precursors and composite catalyst particles

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Abstract

一种空气净化复合催化剂及其制备方法，空气净化复合催化剂包括锰氧化物复合铜氧化物和铈氧化物。制备方法是将氧化剂、Mn II盐、Cu II盐和Ce III盐溶解到溶剂中，搅拌反应后转移到高压反应釜，经过高温高压反应后再过滤清洗干燥，得到复合催化剂前驱体；将复合催化剂前驱体与辅料及黏土混合得到复合造粒粉料；将复合造粒粉料进行造粒得到空气净化复合催化剂。制备得到的复合催化剂表面活性高，催化性能高。

Description

一种空气净化复合催化剂及其制备方法 技术领域
本发明涉及一种环保领域用材料，尤其涉及一种用于净化气体的复合催化剂材料。
背景技术
目前，人类面临两大问题是环境污染与能源短缺，其中环境污染问题特别突出。由于近百年来，人类现代化工业发展的过程中产生了大量的有害废弃物，对环境造成了严重的污染，使得大气、土壤和水体中污染物的含量远远超过了其所能承受的范围。相较于可以区别处理的土壤和水环境，大气环境特别是人们赖以生存的室内空气环境直接影响着人类的健康，无孔不入的空气污染物已经成为急需处理的首要问题。根据其形态的区别，空气污染物主要分为颗粒污染物和挥发性有害气体污染物，其中挥发性有害气体污染物主要来自于工业生产所产生的废气、汽车和轮船等交通工具运行中产生的尾气和室内装修材料及家具中所散发出的挥发性有机物。
空气中的有害气体主要有甲醛、臭氧、苯、甲苯、二甲苯、二氧化碳、氮氧化物、其他有机物等多种挥发性有害气体，这些有害气体都在不同程度上危害着人类的健康。如甲醛对皮肤粘膜的刺激作用，皮肤直接接触易引起过敏性炎症甚至坏死，高浓度甲醛可诱发支气管哮喘甚至引起鼻咽肿瘤，还是一种基因毒性物质。臭氧会强烈刺激人的呼吸道，甚至会引起人体神经中毒，引发多种疾病。破坏人体的免疫机能，诱发淋巴细胞染色体病变，加速衰老，致使孕妇生畸形儿。 挥发性有害气体(TVOC)大多有刺激性，引起机体免疫水平失调，影响中枢神经系统功能，严重时可损伤肝脏和造血系统，部分物质已被列为致癌物。
人类为了解决空气中有害气体的污染问题，进行了大量的研究，产生了多种空气净化技术。最早的空气净化产品采用HEPA过滤网进行空气净化，仅能去除空气中的颗粒污染物，对于有害气体污染物则无能为力。部分产品中应用了活性炭等无机多孔材料吸附空气中的有害气体污染物，可以达到降低气体污染物浓度的目的。然而吸附材料在进行空气净化的过程中，是利用其巨大的比表面积吸附有害气体。当其表面吸附量达到饱和之后，不但无法继续进行吸附，而且存在着释放造成二次污染的风险，需要更换吸附材料。这种净化材料无法达到彻底净化的目的，只是一个污染物的转移，且使用过程中需要定期更换吸附材料，难以满足净化空气中有害物质的需求。目前，还产生了一种用于净化空气中有害气体的光触媒技术，该技术采用光触媒材料作为催化剂材料，其中光触媒催化剂材料主要为二氧化钛材料，在一定能级光的照射的条件下，利用产生的氧化能力极强的氢氧自由基，催化分解空气中的有毒有害物质，达到净化空气的目的。这种技术需要特定的光照条件下才能实现，对于无法提供这些条件的环境内无法使用，使得其应用受到了局限；此外，其催化分解效率不高，难以实现广泛的应用。此外，贵金属具有良好的催化性能，可以有效催化分解有害气体，然而由于其应用成本高，难以实现大规模的应用。
大量研究报道表面，过渡金属氧化物特别是锰氧化物具有良好的催化活性，在无外加条件下可以实现在多个反应中起到自发催化反应的作用，且价格低廉，可以满足大规模的应用。然而，在具体催化反应的进行过程中，催化剂的催化活性往往会受到其内部晶格结构、粒径、组成成分、形貌、及周边条件的影响。不 同晶格结构的锰氧化物材料具有不同的催化活性，在其晶格结构中掺杂了具有互补和增强作用的其他金属之后，在催化反应过程中可以起到协调催化的作用，显著提高催化剂材料的催化活性。这些不同金属的原子在尺寸和表面结构上存在着互补性，故通常会选用多种材料掺杂制备成复合催化剂，在催化反应中起到协同作用，提高其催化性能；自身结构和形貌不同的催化剂材料具有不同的表面面积和表面活性数量，比表面积大、表面活性位点多的催化剂材料可以显著增加反应过程中的有效碰撞次数，使得材料具备更高的催化活性和催化分解效率；在催化剂材料的应用过程中，添加适当的辅料可以有效提高其催化分解性能，选用表面性能好的、吸附性能强的辅料，分布在在催化剂的周边，可以起到预先吸附空气中的有害气体，增加活性催化剂周边有害气体的浓度的作用，有效增大催化剂周边有害气体分布的浓度梯度，提高催化剂材料的催化分解效率。
CN 104174391 A中公开了一种用于降解VOC的纳米二氧化钛光催化剂材料，制备的纳米二氧化钛光催化剂具有较强的可见光吸收能力，较低的电子空穴复合速率，能够快速完全的降解高浓度的苯污染物，仅用0.1g质量能在4小时内在可见光照射下完全降解小空间内低含量的苯。其中可见光的供给量和吸收能力是制约着其对苯催化分解性能的关键因素，可以推测在弱光或无光照条件下，其催化分解性能会大大降低甚至失效，无法全面满足多个区域或时间段内空气净化的需求。CN 102481549 B中公开了用于破坏CO、VOC和卤化VOC的氧化催化剂和方法，描述了一种沉积在基底上的用于在250℃至450℃的温度下破坏排放物流中的CO和挥发性有机化合物，特别是卤化有机化合物的氧化催化剂。氧化催化剂包括负载在耐高温氧化物上的至少两种铂族金属，其中一种为铂或钌，所述耐高温氧化物例如为CeO2和ZrO2的固溶体以及氧化锡和/或二氧化硅。其中选用贵金属作为活性催化剂材料，成本高难以实现大规模的应用；另外，该催化剂材料 需要再高温条件下进行催化分解反应，能耗高，应用成本高，难以应用于普通的室内空气净化等无法提供高温环境的领域。CN 103506111 A中公开了一种室温下除甲醛和臭氧的催化剂的制备方法，采用溶液中的氧化还原反应沉淀出前驱体，结合煅烧工艺得到二氧化锰催化剂材料，在室温条件下同时将污染空气中的有害气体甲醛和臭氧分解成无害的H2和CO2，具有无任何有害副产物、去甲醛和臭氧效率高的优点。然而其利用普通沉淀法得到的二氧化锰催化剂材料存在比表面积低、表现活性低的问题，使得其净化量较低，难以满足当前空气污染复杂、污染物含量高的空气环境内空气净化的需求。
为了净化当前污染严重且污染物成分复杂的空气环境，解决这一全球性的空气污染问题，急需一种兼具降解效率高、性能好、可同时降解多种有害气体、可重复使用且成本低廉的空气净化催化剂材料，用于满足大范围内的空气净化需求。
发明内容
针对上述所涉及的问题，本发明的目的是提供一种空气净化复合催化剂及其制备方法，所述空气净化复合催化剂材料包括锰氧化物复合铜氧化物和铈氧化物。所述制备方法中特殊的反应条件使得大量的Cu2+和Ce3+进入到锰氧化物的微观晶格结构当中取代锰的位置得到在晶格水平掺杂的复合催化剂前驱体，可以起到协同作用；添加具有大比表面积的辅料作为造粒辅料，结合均相混合成型工艺，都有效提高了空气净化催化剂对空气中有害物质的催化分解活性。
为了实现上述目的，本发明是采用如下技术方案实现的一种空气净化复合催化剂的制备方法，在高温高压的反应条件下，采用铜和铈对锰氧化物进行掺杂处 理，得到掺杂型复合催化剂材料。选取氧化剂、锰盐、铜盐、和铈盐在常温下混合进行搅拌反应，再在高温高压的条件下进行重结晶和晶格掺杂反应，得到具有高掺杂量的复合催化剂前驱体。选取大比表面积的无机多孔材料作为成型造粒辅料，通过均相成型工艺得到混合均匀、净化效率高的空气净化复合催化剂材料。
该空气净化复合催化剂材料包括锰氧化物复合铜氧化物和铈氧化物。
该空气净化复合催化剂的制备工艺主要包括复合催化剂前驱体的制备和包覆造粒的过程。具体如下：本发明所述的空气净化复合催化剂通过如下方法制备：将氧化剂、MnⅡ盐、CuⅡ盐和CeⅢ盐溶解到溶剂中得到混合液，进行搅拌反应之后得到前驱体溶液，将前驱体溶液经过高温高压反应之后再过滤、清洗、干燥，得到粉末状复合催化剂前驱体；将上述粉末状复合催化剂前驱体与辅料及黏土混合均匀得到复合造粒粉料；将所述复合造粒粉料经过成型处理后得到空气净化复合催化剂。
作为优选，锰氧化物、铜氧化物和铈氧化物中MnⅡ、CuⅡ和CeⅢ的摩尔比为(0.2-2)：(0.05-1):(0.05-1)，优选为(0.5-1.5)：(0.05-0.5)：(0.1-0.5)。
作为优选，所述空气净化复合催化剂还包括辅料和黏土，所述辅料选用无机多孔材料。
作为优选，所述无机多孔材料包括活性炭、分子筛、二氧化硅、硅微粉、二氧化钛、沸石、氧化铝、凹凸棒土、海泡石、高岭土、蒙脱石、硅藻土中的一种或多种。
作为优选，所述的氧化剂选用高锰酸锂、高锰酸钠、高锰酸钾、高锰酸铵、高氯酸，芬顿试剂中的任意一种或多种。
作为优选，所述的MnⅡ盐选用硫酸锰、硝酸锰、碳酸锰、氯化锰、乙酸锰中 的任意一种或多种。
作为优选，所述的CuⅡ盐选用硫酸铜、硝酸铜、氯化铜中的任意一种或多种。
作为优选，所述的CeⅢ盐选用硝酸铈、硫酸铈、氯化铈、硝酸铈铵中一种或多种。
作为优选，氧化剂、MnⅡ盐、CuⅡ盐和CeⅢ盐的投料摩尔比为(0.5-3)：(0.2-2)：(0.05-1):(0.05-1)，其中优选为(1-2.5)：(0.5-1.5)：(0.05-0.5)：(0.1-0.5)。
作为优选，所述的溶剂选用水。
作为优选，所述的搅拌反应中氧化剂、MnⅡ盐、CuⅡ盐和CeⅢ盐四种固体与溶剂的总固液比质量为1：(5-30)，其中优选为1：(8-18)。
作为优选，所述的搅拌反应温度为0-100℃，其中优选为10-80℃。
作为优选，所述的搅拌反应时间为10-300min，优选为20-180min。
作为优选，所述的搅拌反应中搅拌速率为10-1000r/min，优选为100-800r/min。
作为优选，所述的高温高压反应温度为100-200℃，优选为120-190℃。
作为优选，所述的高温高压反应压力为0.3-3兆帕，其中优选为0.4-2兆帕。在上述高温高压反应过程中，溶液温度越高，其会发出的蒸汽量越多，反应釜内产生的压力也就越大，反应釜内溶液在不同的温度下会产生相对于的高压。如在190℃的反应条件下，反应釜内的压力为2兆帕，在100℃的反应条件下，反应釜内的压力为0.3兆帕。
作为优选，所述的高温高压反应时间为0.5-30h，其中优选为2-24h。
作为优选，所述的干燥温度为60-300℃，优选为100-200℃。
作为优选，所述的干燥时间为3-30h，优选为5-24h。
作为优选，所述的辅料选用无机多孔材料，可以选用活性炭、分子筛、二氧化硅、硅微粉、二氧化钛、沸石、氧化铝材料、凹凸棒土、海泡石、高岭土、蒙脱石、硅藻土中的一种或多种。
作为优选，所述的黏土的粒度范围为200-600目。
作为优选，所述的复合催化剂前驱体、辅料和黏土的混合质量比为1:(0.2-2):(0.2-2)，优选为1:(0.5-1.5):(0.4-1.6).
作为优选，所述成型处理包括如下步骤：将球形颗粒种子加入造粒机中，在一定转速下加入所述粘结剂和所述复合造粒粉料，进行造粒和抛光处理得到成型颗粒，最后烘干得到球形的空气净化复合催化剂。
作为优选，所述的球形颗粒种子选用化学惰性的无机材料颗粒，如氧化铝、氧化硅、氧化钙和氧化锆。
作为优选，所述的球形颗粒种子的粒径范围为0.1-9mm，优选为0.5-9mm。
作为优选，所述的造粒中造粒机转速为10-60r/min，优选为10-40r/min；
作为优选，所述的抛光中造粒机的转速为20-40r/min；
作为优选，所述的抛光的时间为10-100min。
作为优选，所述成型处理包括如下步骤：将所述复合造粒粉料和粘结剂混合均匀，并将其加入至挤压成型机物料仓内待用；开启挤压成型机进行造粒；将所得到的颗粒烘干即得到球形的空气净化复合催化剂。
作为优选，所述的粘结剂选用水、无毒有机溶剂、胶水中的一种或多种；
作为优选，所述的造粒过程中复合造粒粉料和粘结剂的质量比为 1:(0.2-1.2)，优选为1:(0.25-1.0)；
作为优选，所述的成型颗粒烘干温度为60-300℃，优选为100-200℃；
作为优选，所述的成型颗粒烘干时间为1-30h，优选为3-24h；
作为优选，所述的成型颗粒直径范围为0.2-10.2mm；
所述空气净化复合催化剂应用在室内、车内、机舱、船舱中甲醛、臭氧和TVOC净化上。
与现有技术相比，具有如下优点：
1、该纳米级复合催化剂材料表面活性高，实现了在无任何外加条件的情况下自发进行催化分解反应；
2、采用高催化活性的锰氧化物催化剂材料，可以有效净化空气中的有害气体，且在催化分解反应过程中无损耗，可以重复使用；
3、选用具有协调催化作用的掺杂成分，显著提高催化剂材料的催化性能；
4、在高温高压条件下进行重结晶反应，使得掺杂反应更加充分；
5、添加大比表面积的辅料，起到吸附有害气体的作用，提高了催化剂材料附近有害物质的浓度，加快了催化分解效率；
6、使用无机辅料，在有效改善催化剂颗粒表面性能的同时，杜绝了颗粒在长期使用过程中发生霉变的现象；
7、抛光过程有效提高了颗粒的表面性能。
附图说明
图1是本发明的复合催化剂前驱体的一个SEM图。
图2是本发明的复合催化剂前驱体的又一SEM图。
图3是本发明的空气净化复合催化剂的制备工艺流程图。
具体实施方式
下面参照附图对本发明进行更全面的描述，其中说明本发明的示例性实施例。
实施例1
在1708g纯水中依次加入39.5g高锰酸钾、19.8g四水氯化锰、12.5g五水硫酸铜和13.6g六水硝酸铈，搅拌至充分分散和溶解后，搅拌机转速为10r/min，在0℃下反应300min。将上述混合溶液转移至高压反应釜中，设置在150℃条件下反应16h后取出，清洗、过滤后于60℃条件下烘干30h，即得到空气净化复合催化剂前驱体。
将上述复合催化剂前驱体、二氧化硅和黏土按照质量比1:2:1混合均匀得到复合造粒粉料待用。选取0.1mm的氧化铝颗粒加入到圆盘造粒机中，转动速度为60r/min进行造粒，在造粒过程中采用水作为粘结剂，其中复合造粒粉料和水的添加质量比为1:0.2，进行造粒操作，待颗粒平均粒径达到0.2mm时，停止加料，收集颗粒。将上述收集到的颗粒产品加入转速为40r/min的圆盘造粒机中进行抛光10min后得到成型颗粒，取出在200℃下干燥3h即得到空气净化复合催化剂颗粒。
经BET测试(见表1)，表明所制备的复合催化剂前驱体和复合催化剂颗粒比表面积较大。
甲醛催化分解性能测试：取5.00g上述制备的空气净化复合催化剂颗粒置于 直径为10mm的玻璃管内砂芯上进行催化分解活性评估。玻璃管的底部和甲醛发生器相连，顶部与气相色谱仪在线检测仪相连。泵将空气打入甲醛发生器中和甲醛混合得到含甲醛浓度为1000ppm的空气，空气添加量为500mL/min，含甲醛的空气从底部进入装有复合催化剂的玻璃管中，再经玻璃管顶部进入到气相色谱仪在线检测甲醛的含量。检测结果表明，本实施例中制备的空气净化复合催化剂在室温条件下对1000ppm的甲醛进行催化分解，一次通过的分解效率为95％。
臭氧催化分解性能测试：采用和上述测试相同的评估装置评估空气净化复合催化剂颗粒对臭氧的分解性能，采用紫外分光光度计在线检测仪测量臭氧的浓度。测试方法同上，检测结果表明，本实施例中制备的空气净化复合催化剂在室温条件下对120ppm的臭氧进行催化分解，其一次通过的催化分解效率见表2。
TVOC气体净化性能测试：采用和上述测试相同的评估装置评估空气净化复合催化剂颗粒对臭氧的分解性能，采用气相色谱仪测量TVOC的浓度。测试方法同上，检测结果表明，本实施例中制备的空气净化复合催化剂在室温条件下对400ppm的TVOC一次通过的去除效率见表2。
苯、甲苯和二甲苯净化性能测试：选取温度为23-27℃、尺寸为30m3的测试舱环境内进行该多功能空气净化复合催化剂材料的空气净化性能评价。选取苯、甲苯和二甲苯这三种有害物质为净化效果进行测试项目。经过检测发现，本实施例中所制备的多功能空气净化复合催化剂材料对苯、甲苯和二甲苯的1h净化率见表2。
实施例2
在786g纯水中依次加入28g高锰酸钾、28.7g六水硝酸锰、8.5g二水氯化铜和17.7g六水氯化铈，搅拌至充分分散和溶解后，搅拌机转速为1000r/min， 在100℃下反应10min。将上述混合溶液转移至高压反应釜中，设置在100℃条件下反应30h后取出，清洗、过滤后于200℃条件下烘干2h，即得到空气净化复合催化剂前驱体。
将上述复合催化剂前驱体、硅微粉和黏土按照质量比1:0.5:2混合均匀得到复合造粒粉料待用。选取0.2mm的二氧化硅颗粒加入到圆盘造粒机中，转动速度为45r/min进行造粒，在造粒过程中采用水作为粘结剂，其中复合造粒粉料和水的添加质量比为1:0.3，进行造粒操作，待颗粒平均粒径达到2mm时，停止加料，收集颗粒。将上述收集到的颗粒产品加入转速为30r/min的滚筒干燥机中进行抛光50min后得到成型颗粒，取出在150℃下干燥10h即得到空气净化复合催化剂颗粒。
经BET测试(见表1)，表明所制备的复合催化剂前驱体和复合催化剂颗粒比表面积较大。
颗粒性能测试方法同实施例1，其检测结果见表2。
实施例3
在285g纯水中依次加入31.6g高锰酸钾、17.8g四水硫酸锰、1.2g三水硝酸铜和6.4g四水硫酸铈，搅拌至充分分散和溶解后，搅拌机转速为150r/min，在20℃下反应180min。将上述混合溶液转移至高压反应釜中，设置在180℃条件下反应2h后取出，清洗、过滤后于100℃条件下烘干20h，即得到空气净化复合催化剂前驱体。
将上述复合催化剂前驱体、硅藻土和黏土按照质量比1:0.2:1混合均匀得到复合造粒粉料待用。选取0.2mm的氧化锆颗粒加入到圆盘造粒机中，转动速度为10r/min进行造粒，在造粒过程中采用水作为粘结剂，其中复合造粒粉料和水的添加质量比为1:0.45，进行造粒操作，待颗粒平均粒径达到1mm时，停止加料， 收集颗粒。将上述收集到的颗粒产品加入转速为20r/min的滚筒干燥机中进行抛光30min后得到成型颗粒，取出在180℃下干燥5h即得到空气净化复合催化剂颗粒。
经BET测试(见表1)，表明所制备的复合催化剂前驱体和复合催化剂颗粒比表面积较大。
颗粒性能测试方法同实施例1，其检测结果见表2。
实施例4
在1470g纯水中依次加入223.7g高锰酸钾、17.2g六水硝酸锰、7.3g三水硝酸铜和10.6g六水氯化铈，搅拌至充分分散和溶解后，搅拌机转速为800r/min，在80℃下反应50min。将上述混合溶液转移至高压反应釜中，设置在200℃条件下反应0.5h后取出，清洗、过滤后于120℃条件下烘干15h，即得到空气净化复合催化剂前驱体。
将上述复合催化剂前驱体、氧化铝和黏土按照质量比1:0.8:0.2混合均匀得到复合造粒粉料待用。选取0.4mm的氧化铝颗粒加入到圆盘造粒机中，转动速度为20r/min进行造粒，在造粒过程中采用水作为粘结剂，其中复合造粒粉料和水的添加质量比为1:0.4，进行造粒操作，待颗粒平均粒径达到5mm时，停止加料，收集颗粒。将上述收集到的颗粒产品加入转速为25r/min的滚筒干燥机中进行抛光80min后得到成型颗粒，取出在60℃下干燥30h即得到空气净化复合催化剂颗粒。
经BET测试(见表1)，表明所制备的复合催化剂前驱体和复合催化剂颗粒比表面积较大。
颗粒性能测试方法同实施例1，其检测结果见表2。
实施例5
在2145g纯水中依次加入28.4g高锰酸钾、20.1g六水硝酸锰、10.2g二水氯化铜和12.8g四水硫酸铈，搅拌至充分分散和溶解后，搅拌机转速为300r/min，在60℃下反应100min。将上述混合溶液转移至高压反应釜中，设置在120℃条件下反应15h后取出，清洗、过滤后于150℃条件下烘干10h，即得到空气净化复合催化剂前驱体。
将上述复合催化剂前驱体、活性炭和黏土按照质量比1:1:0.5混合均匀得到复合造粒粉料待用。选取9mm的氧化铝颗粒加入到圆盘造粒机中，转动速度为30r/min进行造粒，在造粒过程中采用水作为粘结剂，其中复合造粒粉料和水的添加质量比为1:0.35，进行造粒操作，待颗粒平均粒径达到10mm时，停止加料，收集颗粒。将上述收集到的颗粒产品加入转速为35r/min的滚筒干燥机中进行抛光100min后得到成型颗粒，取出在120℃下干燥15h即得到空气净化复合催化剂颗粒。
经BET测试(见表1)，表明所制备的复合催化剂前驱体和复合催化剂颗粒比表面积较大。
颗粒性能测试方法同实施例1，其检测结果见表2。
对比例1(无高温高压反应过程)
在1708g纯水中依次加入39.5g高锰酸钾、19.8g四水氯化锰、12.5g五水硫酸铜和13.6g六水硝酸铈，搅拌至充分分散和溶解后，搅拌机转速为10r/min，在0℃下反应300min后，清洗、过滤后于60℃条件下烘干30h，即得到空气净化复合催化剂前驱体。
将上述复合催化剂前驱体、二氧化硅和黏土按照质量比1:2:1混合均匀得到复合造粒粉料待用。选取0.1mm的氧化铝颗粒加入到圆盘造粒机中，转动速度为60r/min进行造粒，在造粒过程中采用水作为粘结剂，其中复合造粒粉料和水的添加质量比为1:0.2，进行造粒操作，待颗粒平均粒径达到0.2mm时，停止加料，收集颗粒。将上述收集到的颗粒产品加入转速为40r/min的滚筒干燥机中进行抛光10min后得到成型颗粒，取出在200℃下干燥1h即得到空气净化复合催化剂颗粒。
经BET测试(见表1)，表明所制备的复合催化剂前驱体和复合催化剂颗粒比表面积较小。
颗粒性能测试方法同实施例1，其检测结果见表2。
对比例2(无掺杂成分)
在1708g纯水中依次加入39.5g高锰酸钾和19.8g四水氯化锰，搅拌至充分分散和溶解后，搅拌机转速为10r/min，在0℃下反应300min。将上述混合溶液转移至高压反应釜中，设置在150℃条件下反应16h后取出，清洗、过滤后于60℃条件下烘干30h，即得到空气净化复合催化剂前驱体。
将上述复合催化剂前驱体、二氧化硅和黏土按照质量比1:2:1混合均匀得到复合造粒粉料待用。选取0.1mm的氧化铝颗粒加入到圆盘造粒机中，转动速度为60r/min进行造粒，在造粒过程中采用水作为粘结剂，其中复合造粒粉料和水的添加质量比为1:0.2，进行造粒操作，待颗粒平均粒径达到0.2mm时，停止加料，收集颗粒。将上述收集到的颗粒产品加入转速为40r/min的滚筒干燥机中进行抛光10min后得到成型颗粒，取出在200℃下干燥1h即得到空气净化复合催化剂颗粒。
经BET测试(见表1)，表明所制备的复合催化剂前驱体和复合催化剂颗粒比表面积较大。
颗粒性能测试方法同实施例1，其检测结果见表2。
对比例3(造粒过程无辅料添加)
在1708g纯水中依次加入39.5g高锰酸钾、19.8g四水氯化锰、12.5g五水硫酸铜和13.6g六水硝酸铈，搅拌至充分分散和溶解后，搅拌机转速为10r/min，在0℃下反应300min。将上述混合溶液转移至高压反应釜中，设置在150℃条件下反应16h后取出，清洗、过滤后于60℃条件下烘干30h，即得到空气净化复合催化剂前驱体。
将上述复合催化剂前驱体和黏土按照质量比1:1混合均匀得到复合造粒粉料待用。选取0.1mm的氧化铝颗粒加入到圆盘造粒机中，转动速度为60r/min进行造粒，在造粒过程中采用水作为粘结剂，其中复合催化剂前驱体和水的添加质量比为1:0.2，进行造粒操作，待颗粒平均粒径达到0.2mm时，停止加料，收集颗粒。将上述收集到的颗粒产品加入转速为40r/min的圆盘造粒机中进行抛光10min后得到成型颗粒，取出在200℃下干燥3h即得到空气净化复合催化剂颗粒。
经BET测试(见表1)，表明所制备的复合催化剂前驱体和复合催化剂颗粒比表面积不大。
颗粒性能测试方法同实施例1，其检测结果见表2。
对比例4(物料配比对比例)
在2145g纯水中依次加入1.58g高锰酸钾、20.1g六水硝酸锰、10.2g二水氯化铜和12.8g四水硫酸铈，其反应物料的固液比为1:36，搅拌至充分分散和 溶解后，搅拌机转速为300r/min，在60℃下反应100min。将上述混合溶液转移至高压反应釜中，设置在120℃条件下反应15h后取出，清洗、过滤后于150℃条件下烘干10h，即得到空气净化复合催化剂前驱体。
将上述复合催化剂前驱体、活性炭和黏土按照质量比1:1:0.5混合均匀得到复合造粒粉料待用。选取9mm的氧化铝颗粒加入到圆盘造粒机中，转动速度为30r/min进行造粒，在造粒过程中采用水作为粘结剂，其中复合造粒粉料和水的添加质量比为1:0.35，进行造粒操作，待颗粒平均粒径达到10mm时，停止加料，收集颗粒。将上述收集到的颗粒产品加入转速为35r/min的滚筒干燥机中进行抛光100min后得到成型颗粒，取出在120℃下干燥15h即得到空气净化复合催化剂颗粒。
经BET测试(见表1)，表明所制备的复合催化剂前驱体和复合催化剂颗粒比表面积较大。
颗粒性能测试方法同实施例1，其检测结果见表2。
对比例5(物料配比对比例)
在2145g纯水中依次加入28.4g高锰酸钾、20.1g六水硝酸锰、0.17g二水氯化铜和12.8g四水硫酸铈，其反应物料的固液比为1:36，搅拌至充分分散和溶解后，搅拌机转速为300r/min，在60℃下反应100min。将上述混合溶液转移至高压反应釜中，设置在120℃条件下反应15h后取出，清洗、过滤后于150℃条件下烘干10h，即得到空气净化复合催化剂前驱体。
将上述复合催化剂前驱体、活性炭和黏土按照质量比1:1:0.5混合均匀得到复合造粒粉料待用。选取9mm的氧化铝颗粒加入到圆盘造粒机中，转动速度为30r/min进行造粒，在造粒过程中采用水作为粘结剂，其中复合造粒粉料和水的 添加质量比为1:0.35，进行造粒操作，待颗粒平均粒径达到10mm时，停止加料，收集颗粒。将上述收集到的颗粒产品加入转速为35r/min的滚筒干燥机中进行抛光100min后得到成型颗粒，取出在120℃下干燥15h即得到空气净化复合催化剂颗粒。
经BET测试(见表1)，表明所制备的复合催化剂前驱体和复合催化剂颗粒比表面积较大。
颗粒性能测试方法同实施例1，其检测结果见表2。
表1：复合催化剂前驱体和复合催化剂颗粒的比表面积表
Figure PCTCN2017105713-appb-000001
表2：复合催化剂颗粒空气净化性能检测结果表
Figure PCTCN2017105713-appb-000002
以上内容仅为本发明的较佳实施例，对于本领域的普通技术人员，依据本发明的思想，在具体实施方式及应用范围上均会有改变之处，本说明书内容不应理解为对本发明的限制。

Claims (36)

  1. 一种空气净化复合催化剂，其特征在于，所述空气净化复合催化剂材料包括锰氧化物复合铜氧化物和铈氧化物。
  2. 根据权利要求1所述的空气净化复合催化剂，其中，锰氧化物、铜氧化物和铈氧化物中MnⅡ、CuⅡ和CeⅢ的摩尔比为(0.2-2)：(0.05-1):(0.05-1)，优选为(0.5-1.5)：(0.05-0.5)：(0.1-0.5)。
  3. 根据权利要求1或2所述的空气净化复合催化剂，其中，所述空气净化复合催化剂还包括辅料和黏土，所述辅料选用无机多孔材料。
  4. 根据权利要求3所述的空气净化复合催化剂，其中，所述无机多孔材料包括活性炭、分子筛、二氧化硅、二氧化钛、沸石、氧化铝、凹凸棒土、海泡石、高岭土、蒙脱石、硅藻土中的一种或多种。
  5. 一种权利要求1-4任一项所述的空气净化复合催化的制备方法，包括如下步骤：
    将氧化剂、MnⅡ盐、CuⅡ盐和CeⅢ盐溶解到溶剂中得到混合液，进行搅拌反应之后得到前驱体溶液，将所述前驱体溶液经过高温高压反应之后再过滤、清洗、干燥，得到粉末状复合催化剂前驱体；
    将所述粉末状复合催化剂前驱体与辅料及黏土混合均匀得到复合造粒粉料；
    将所述复合造粒原料经过成型处理后得到所述空气净化复合催化剂。
  6. 根据权利要求5所述的空气净化复合催化剂的制备方法，其中，所述的氧化剂选用高锰酸锂、高锰酸钠、高锰酸钾、高锰酸铵、高氯酸，芬顿试剂中的任意一种或多种。
  7. 根据权利要求5或6所述的空气净化复合催化剂的制备方法，其中，所述MnⅡ盐选用硫酸锰、硝酸锰、碳酸锰、氯化锰、乙酸锰中的任意一种或多种。
  8. 根据权利要求5-7任一项所述的空气净化复合催化剂的制备方法，其中， 所述的CuⅡ盐选用硫酸铜、硝酸铜、氯化铜中的任意一种或多种。
  9. 根据权利要求5-8任一项所述的空气净化复合催化剂的制备方法，其中，所述CeⅢ盐选用硝酸铈、硫酸铈、氯化铈、硝酸铈铵中一种或多种。
  10. 根据权利要求5-9任一项所述的空气净化复合催化剂的制备方法，其中，氧化剂、MnⅡ盐、CuⅡ盐和CeⅢ盐的投料摩尔比为(0.5-3)：(0.2-2)：(0.05-1):(0.05-1)，其中优选为(1-2.5)：(0.5-1.5)：(0.05-0.5)：(0.1-0.5)。
  11. 根据权利要求5-10任一项所述的空气净化复合催化剂的制备方法，其中，所述的溶剂选用水。
  12. 根据权利要求5-11任一项所述的空气净化复合催化剂的制备方法，其中，所述的搅拌反应中氧化剂、MnⅡ盐、CuⅡ盐和CeⅢ盐四种固体与溶剂的总固液比质量为1：(5-30)，其中优选为1：(8-18)。
  13. 根据权利要求5-12所述的空气净化复合催化剂的制备方法，其中，所述的搅拌反应温度为0-100℃，其中优选为10-80℃。
  14. 根据权利要求5-13任一项所述的空气净化复合催化剂的制备方法，其中，所述的搅拌反应时间为10-300min，优选为20-180min。
  15. 根据权利要求5-14任一项所述的空气净化复合催化剂的制备方法，其中，所述的搅拌反应中搅拌速率为10-1000r/min，优选为100-800r/min。
  16. 根据权利要求5-15任一项所述的空气净化复合催化剂的制备方法，其中，所述的高温高压反应温度为100-200℃，优选为120-190℃。
  17. 根据权利要求5-16任一项所述的空气净化复合催化剂的制备方法，其中，所述的高温高压反应压力为0.3-3兆帕，其中优选为0.4-2兆帕。
  18. 根据权利要求5-17任一项所述的空气净化复合催化剂的制备方法，其中，所述的高温高压反应时间为0.5-30h，其中优选为2-24h。
  19. 根据权利要求5-18任一项所述的空气净化复合催化剂的制备方法，其中，所述的干燥温度为60-300℃，优选为100-200℃。
  20. 根据权利要求5-19任一项所述的空气净化复合催化剂的制备方法，其中，所述的干燥时间为3-30h，优选为5-24h。
  21. 根据权利要求5-20任一项所述的空气净化复合催化剂的制备方法，其中，所述的辅料选用无机多孔材料，可以选用活性炭、分子筛、二氧化硅、硅微粉、二氧化钛、沸石、氧化铝、凹凸棒土、海泡石、高岭土、蒙脱石、硅藻土中的一种或多种。
  22. 根据权利要求5-21任一项所述的空气净化复合催化剂的制备方法，其中，所述的黏土的粒度范围为200-600目。
  23. 根据权利要求5-22任一项所述的空气净化复合催化剂的制备方法，其中，所述的复合催化剂前驱体、辅料和黏土的混合质量比为1:(0.2-2):(0.2-2)，优选为1:(0.5-1.5):(0.4-1.6)。
  24. 根据权利要求5-23任一项所述的空气净化复合催化剂的制备方法，其中，所述成型处理包括如下步骤：将球形颗粒种子加入造粒机中，在一定转速下加入所述复合造粒粉料和粘结剂，进行造粒和抛光处理得到成型颗粒，最后烘干得到球形的空气净化复合催化剂。
  25. 根据权利要求5-24任一项所述的空气净化复合催化剂的制备方法，其中，所述的球形颗粒种子选用化学惰性的无机材料颗粒，优选氧化铝、氧化硅、氧化钙和氧化锆。
  26. 根据权利要求5-25任一项所述的空气净化复合催化剂的制备方法，其中，所述的球形颗粒种子的粒径范围为0.1-9mm，优选为0.5-8mm。
  27. 根据权利要求5-26任一项所述的空气净化复合催化剂的制备方法，其 中，所述的造粒中造粒机转速为10-60r/min，优选为10-40r/min。
  28. 根据权利要求5-27任一项所述的空气净化复合催化剂的制备方法，其中，所述的抛光中造粒机的转速为20-40r/min。
  29. 根据权利要求5-28任一项所述的空气净化复合催化剂的制备方法，其中，所述的抛光的时间为10-100min。
  30. 根据权利要求5-23任一项所述的空气净化复合催化剂的制备方法，其中，所述成型处理包括如下步骤：将所述复合造粒粉料和粘结剂混合均匀，并将其加入至挤压成型机物料仓内待用；开启挤压成型机进行造粒；将所得到的颗粒烘干即得到球形的空气净化复合催化剂。
  31. 根据权利要求5-30任一项所述的空气净化复合催化剂的制备方法，其中，所述的粘结剂选用水、无毒有机溶剂、胶水中的一种或多种。
  32. 根据权利要求5-31任一项所述的空气净化复合催化剂的制备方法，其中，所述的造粒过程中复合造粒粉料和粘结剂的质量比为1:(0.2-1.2)，优选为1:(0.25-1.0)。
  33. 根据权利要求5-32任一项所述的空气净化复合催化剂的制备方法，其中，所述的成型颗粒烘干温度为60-300℃，优选为100-200℃。
  34. 根据权利要求5-33任一项所述的空气净化复合催化剂的制备方法，其中，所述的成型颗粒烘干时间为1-30h，优选为3-24h。
  35. 根据权利要求5-34任一项所述的空气净化复合催化剂的制备方法，其中，所述的成型颗粒直径范围为0.2-10.2mm。
  36. 一种根据权利要求1-4任一项所述空气净化复合催化剂在室内、车内、机舱、船舱中甲醛、臭氧和TVOC净化的应用。
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