CN110975610A - Ozone room temperature decomposition honeycomb module and preparation method thereof - Google Patents
Ozone room temperature decomposition honeycomb module and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an ozone room temperature decomposition honeycomb module and a preparation method thereof. The ozone room temperature decomposition honeycomb module has the characteristics of light weight, corrosion resistance, low wind resistance, high decomposition efficiency, long service life and the like, and the preparation process of the module is simple, convenient and environment-friendlyAnd no gaseous pollutants such as nitrogen oxides, sulfur oxides and the like and sewage discharge. The prepared honeycomb module can be applied to catalytic decomposition treatment of ozone in air, and the ozone concentration is 1-20mg/m under the conditions of-10-40 ℃ and 30-98 RH%3All can be effectively degraded to 0.02mg/m3The ozone degradation rate is more than 98 percent, and the long time can be realized>3500h) The purification requirement of effectively removing ozone.
Description
Technical Field
The invention relates to the technical field of normal-temperature catalysis and air pollution treatment, in particular to an ozone room-temperature decomposition honeycomb module and a preparation method thereof.
Background
Research shows that the long-term harm of ozone-based photochemical oxidant to human body mainly includes damage to body membrane (including various organ tissues and cell membranes), decline of cardiac function, oxidation of elastic fiber in tissue, premature senility and shortened life. The world health organization therefore sets safety standards for ozone: the maximum concentration allowed in an 8-hour working environment should be less than 0.10 ppm. In daily life, if no treatment measures are taken, the escaped ozone poses great threat to the health of people, such as electrostatic copiers, printers, laser printers, fax machines, electrostatic dust collectors, ozone sterilization disinfection cabinets, vacuum ultraviolet sterilization equipment and the like. Along with the popularization of fresh air buildings in recent years, the ozone escape accompanied by common high-voltage electrostatic dust removal modules and ultraviolet sterilization modules is also in urgent need of excellent ozone decomposition materials for treatment.
Currently, the researches for eliminating ozone mainly include an activated carbon method, a thermal decomposition method, an electromagnetic wave radiation decomposition method, a liquid medicine absorption method and a catalytic decomposition ozone method. Wherein the activated carbon method for removing ozone has short service life and high replacement cost; the thermal decomposition method and the electromagnetic wave radiation decomposition method have high energy consumption; the liquid medicine absorption method can generate waste water, which is commonly seen in the treatment of industrial ozone-containing tail gas; the catalytic decomposition method is operated at normal temperature mostly and only generates oxygen, has the advantages of high decomposition rate, low energy consumption, safety and the like, and is an ideal ozonolysis method. The technical core of the catalytic decomposition method is a high-efficiency ozonolysis material, namely an ozonolysis catalyst.
The catalysts used in the catalytic decomposition process are mainly of the following types: 1) manganese-containing catalysts comprising MnO of large specific surface area2Ozonolysis catalyst, manganese oxide ozonolysis catalyst using polymer material as carrier, silver-containing copper-manganese oxidation mixture ozonolysis catalyst, and MnO2And MnCO3A mixed ozone decomposition catalyst. CN90106857 uses manganese oxide and copper oxide as active components to decompose ozone; CN103272612A, CN102240567A and CN102240568A use oxides of manganese, copper, nickel and iron supported on molecular sieves and honeycomb ceramics as catalysts. But the moisture resistance and the low-temperature activity of the manganese oxide are to be improved; 2) an ozonolysis catalyst containing transition metal oxide, which is a cheap material with good continuous catalytic performance and is used for deodorizing, decoloring, sterilizing and decomposing organic mattersThe decomposition of ozone is particularly effective. The transition metal mainly comprises iron, nickel and cobalt, and the carrier has a specific surface area of 5-50 m2Carbon particles, zeolite and hydrated aluminum per gram. However, the catalyst has the defects that a certain water vapor environment is required to exist during use; 3) loaded with noble metals (e.g. gold, silver, platinum) and TiO2The photocatalytic ozone elimination catalyst, however, the material can only work under the irradiation of ultraviolet light, and in addition, the cost of the catalyst is high due to the high price of noble metals, the catalyst is not beneficial to large-scale commercialization, and the preparation and treatment processes are complicated.
The non-noble metal active component precursors adopted in the reported ozone decomposition catalyst patent documents are nitrate, sulfate and other inorganic salts of Mn, Fe, Ni, Co, Cu and the like or EDTA type N-containing chelate salts, so that a large amount of NO can be generated in the preparation processx、SO2Gaseous pollutants, or a large amount of waste water and the like, and the pollution is great in the preparation process. The prepared catalyst is usually in a powder form (coprecipitation method, sol-gel method and the like) or a particle form (commonly found in supported catalysts such as modified activated carbon, modified alumina and the like). The powder can not be directly used in the existing air purification equipment, and the purification filter element can be prepared by fixedly carrying the powder above a carrier prepared in a certain shape; the particle-loaded catalyst can be directly used, but the catalyst needs to be packaged to form a catalytic filter element module, the packaging is troublesome, the wind resistance of the packaged catalyst is large, and the particle-loaded catalyst is not suitable for being used on equipment with large wind volume, particularly fresh air systems and the like.
For example, CN106179396B provides a method for preparing a composite catalyst for decomposing ozone, which comprises dissolving permanganate, divalent Mn salt and divalent Cu salt respectively to obtain three salt solutions; rapidly mixing the three salt solutions, stirring the three salt solutions for oxidation-reduction reaction, and then filtering and cleaning the mixture to obtain filter residues of the composite oxide; and adding water into the filter residue for mixing to form a suspension of the filter residue and the water, carrying out superfine grinding on the suspension, fully grinding the suspension, and then carrying out a freeze drying process to obtain the composite catalyst for decomposing ozone. The preparation process of the catalyst is complex, a large amount of washing wastewater can be formed, and the prepared powder catalyst can be used only by secondary molding.
For example, CN101757933B provides an ozonolysis catalyst comprising: metallic nickel foam as a catalyst support and catalyst co-active component; manganese or iron oxide which is taken as a main active component and is coated on the surface of the foamed nickel in an impregnation mode. The preparation method comprises the following steps: A. preparing an active component solution consisting of manganese nitrate or ferromanganese nitrate; B. impregnating the active component solution with foamed nickel as a carrier; C. and drying the impregnated carrier and baking at a certain temperature. The manganese nitrate and ferric nitrate adopted in the patent can generate a large amount of NO when being roastedxWaste gas, and when the equipment loaded with the foamed nickel and having small pore size is used, the wind resistance is large and the energy consumption is high.
For example, CN106824218B provides a high-efficiency moisture-resistant ozonolysis catalyst and a preparation method thereof, the high-efficiency moisture-resistant ozonolysis catalyst of the invention uses oxides of manganese, copper, nickel and cobalt as active components, the method is a sol-gel method, the preparation process comprises the steps of dissolving manganese nitrate tetrahydrate, copper nitrate trihydrate, nickel nitrate hexahydrate and cobalt nitrate hexahydrate in deionized water to obtain a nitrate solution, slowly adding the nitrate solution into a mixed solution of citric acid and a cationic surfactant, adjusting the pH value of the mixed solution through ammonia water, stirring at constant temperature to obtain gel, drying the gel, and calcining to obtain the ozonolysis catalyst. The active component precursors adopted by the method are all nitrates, a large amount of NOx can be released when the obtained gel is roasted, the gel is a powder material which is difficult to be directly used in air purification equipment, and the filter element can be prepared for use after secondary forming or loading on a molded base material.
Therefore, the ozone decomposing material which is green and environment-friendly in the preparation process, high in degradation efficiency, long in service life and capable of being directly and simply used is very important for treating ozone in air, and can promote the real green environmental protection concept that the material production and the rear-end treatment are all-chain pollution-free and emission are promoted, rather than the pseudo environmental protection that the pollution is eliminated at the rear end and the pollution is produced and manufactured at the front end.
Disclosure of Invention
The invention aims to provide an ozone room temperature decomposition honeycomb module which has the characteristics of light weight, corrosion resistance, low wind resistance, high decomposition efficiency, long service life and the like, is simple, convenient and environment-friendly in module preparation process, and does not discharge nitrogen oxide, sulfur oxide and other gaseous pollutants and sewage, and a preparation method thereof aiming at the defects and the defects of the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that: the utility model provides an ozone room temperature decomposition honeycomb module which innovation point lies in: the catalyst slurry is sprayed on the aluminum honeycomb, and then the finished product is prepared by blowing, drying and roasting.
Further, the catalyst slurry is prepared from the following components in parts by weight:
the preparation method of the ozone room temperature decomposition honeycomb module is characterized by comprising the following steps:
1) mixing and homogenizing catalyst slurry: weighing 100 parts by weight of deionized water, 20-40 parts by weight of alumina powder, 2-10 parts by weight of organic manganese salt, 2-10 parts by weight of organic nickel salt, 2-5 parts by weight of pseudo-boehmite and 2-10 parts by weight of film-forming agent, pouring into a mixing barrel, starting a lifting stirring machine head to mix for 20-30min at 700rpm, and homogenizing the mixture for 30-60min at 8000rpm of 5000-plus high-speed shearing emulsifying machine to obtain catalyst slurry;
2) spraying catalyst slurry: inserting an inlet pipe of a slurry pump into a catalyst slurry barrel, connecting an outlet pipe with a spray gun material pipe, connecting a spray gun gas source with a compressed air tank, hanging a spray gun nozzle on a fixed frame above a conveying mesh belt, laying and placing an aluminum honeycomb on the conveying mesh belt, wherein the spraying direction of the spray gun and the cross section of the aluminum honeycomb form an angle of 45 degrees, the distance from the cross section is 5-10cm, the atomizing coverage diameter of a single nozzle is 5-15cm, and the number of the spray nozzles can be adjusted according to the size of the sprayed aluminum honeycomb; when spraying, starting the conveying mesh belt and starting the slurry pump and the spray gun, spraying the aluminum honeycomb, controlling the spraying air pressure to be 0.3-0.5MPa, and adjusting the feeding speed of the slurry pump and the traveling speed of the conveying belt to ensure that the spraying amount reaches 5-35% of the volume of the aluminum honeycomb; the process can realize zero waste of slurry and has no sewage discharge problem of a conventional dipping method;
3) purging the honeycomb module: after the aluminum honeycomb sprayed with the catalyst slurry is conveyed out of the spraying area, purging ports are arranged above and below the conveying mesh belt, a purging gas source is connected with an air pressure tank, the purging wind pressure is set to be 0.1-0.3MPa, the wind speed is 0.5-1m/s, a purging wind port is flat, the gap is 0.5-1mm, the width is 15cm, the number of the blowing ports is adjusted according to the size of a honeycomb module, and the uneven distribution of a film layer and liquid dropping are prevented; the blown slurry can be recycled for use in the slurry spraying section;
4) drying the honeycomb module: the swept honeycomb module enters a blast drying area through a conveying mesh belt and is dried for 30min at 80 ℃; drying at 130 deg.C for 30 min; the two-stage drying procedure ensures that the sprayed layer is smooth and does not bubble, and reduces the risk of later-stage peeling;
5) roasting the honeycomb module: the dried honeycomb module enters a roasting area through a conveying mesh belt, roasting is carried out for 60min at the temperature of 350-450 ℃, and the roasted honeycomb module enters a normal-temperature cooling area to be cooled to the room temperature, so that the ozone room-temperature decomposition honeycomb module is obtained; the roasting process mainly comprises the steps of roasting and decomposing organic manganese salt and organic nickel salt into active oxides, and further improving the binding force between the spray coating and the aluminum honeycomb substrate.
Furthermore, the aluminum honeycomb material is aluminum or aluminum alloy which can endure heating at 400 ℃ for more than 3h without deformation and collapse and has no dust, grease or impurities on the surface. The active component on the surface of the filter element is favorably attached and thermally processed at the later stage, the aperture of the aluminum honeycomb is adjustable, the size of the aluminum honeycomb is adjustable, the aluminum honeycomb can be purchased in batches in the market, the aluminum honeycomb is cheap and easy to obtain, the aluminum honeycomb is light and convenient to resist ozone corrosion, and the module carrying the active component can be manufactured into the ozone purification filter element with low wind resistance only by simply cutting and assembling.
Furthermore, the crystal form of the alumina powder is gamma-type, and the granularity is 800-1000 meshes. The granularity and the crystal form can realize high dispersion of Mn-Ni roasting components and promote the activity of the catalyst to be improved.
Further, the organic manganese salt is any one of acetate, oxalate and citrate of manganese. Can ensure that the roasting decomposed gaseous products only contain CO2And H2O, reduced to the corresponding MnO2The weight of the alumina powder accounts for 2-6 wt%, and MnOx generated after roasting is one of main active components for ozone decomposition.
Further, the organic nickel salt is any one of acetate, oxalate and citrate of nickel. Can ensure that the roasting decomposed gaseous products only contain CO2And H2O, which is 2-6 wt% of corresponding NiO, and NiOx generated after roasting is one of the main active components for ozone decomposition.
Further, the film forming agent is mainly prepared by mixing polyvinyl alcohol, phosphoric acid, aluminum sol and acrylic resin emulsion according to the mass ratio of 1:2:7: 10. The polyvinyl alcohol and acrylic resin emulsion is an organic bonding component for enhancing the low-temperature flatness and the bonding property of the spray coating, and the phosphoric acid and the aluminum sol are inorganic bonding components for enhancing the high-temperature bonding force of the spray coating and the base material.
Furthermore, the pseudo-boehmite used in the catalyst slurry can form better bonding with alumina and an aluminum plate due to high-temperature dehydration, so that the high-temperature bonding degree of the alumina powder and the honeycomb aluminum substrate can be enhanced.
The invention has the beneficial effects that:
the process design of the invention is scientific and reasonable, the substrate aluminum honeycomb selected by the honeycomb module is light and easy to process, the prepared decomposed honeycomb module can be directly cut and assembled to prepare the filter element, the wind resistance is extremely low when the filter element is used, and the assembly cost is low; the catalyst slurry selected by the honeycomb module takes organic manganese and organic nickel as main active component precursors, and no waste gas such as NOx, SOx and the like is discharged during preparation, so that the honeycomb module is green and environment-friendly; the preparation method adopts a slurry spraying method, is based on a section-by-section heating type mesh belt kiln process, is simple and controllable in preparation process, and has no waste liquid; the ozone room temperature decomposition honeycomb module has the advantages of excellent performance, quick and effective ozone removal, long operation time, and low temperature and high humidity resistance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The specification of the raw materials used in the examples: alumina powder, gamma-Al2O3Purity of 99 percent and 1000 meshes; manganese acetate is tetrahydrate salt Mn (CH)3COO)2·4H2O, purity 99.5%; manganese oxalate as dihydrate salt MnC2O4·2H2O, purity 99.5%; the manganese citrate is anhydrous Mn3(C6H5O7)2The purity is 99.5 percent; the nickel acetate is tetrahydrate salt Ni (CH)3COO)2·4H2O, purity 99.5%; nickel oxalate is NiC as anhydrous salt2O4Purity 99.5%, 1000 mesh; the nickel citrate is anhydrous Ni3(C6H5O7)2The purity is 98 percent; pseudo-boehmite with a specific surface area of 250m2Per gram, 1000 meshes; the polyvinyl alcohol is PVA1788, 160 mesh powder; 85% of phosphoric acid, wherein the preparation amounts listed in the invention are calculated by the amount of the solution; the aluminum sol has the solid content of 20 percent, the pH value of 3-5 and the disposable particles of 10-20nm, and the preparation amount is calculated by the solution amount; the acrylic resin emulsion has the solid content of 36 percent, and the preparation amounts listed in the invention with the viscosity of 500-1200mPa & s are all calculated by the amount of the emulsion; the carrier aluminum honeycomb listed in the examples has hexagonal holes, the length of the hole edge is 3mm, the thickness of aluminum foil is 0.06mm, the length of the honeycomb plate is 1600mm, the width is 1200mm, and the thickness is 10 mm.
The invention is further illustrated by the following examples:
example 1
A preparation method of an ozone room temperature decomposition honeycomb module comprises the following steps:
1) 1000g of deionized water and 300g of gamma-Al are weighed2O3、16.9g Mn(CH3COO)2·4H2O、20.0g Ni(CH3COO)2·4H2O, 20g of pseudo-boehmite, 30g of film forming agent (1.5g of polyvinyl alcohol, 3.0g of phosphoric acid, 10.5g of alumina sol and 15g of acrylic resin emulsion) are poured into a mixing barrel, and a lifting stirring head is started to mix at 600rpmMixing for 30min, and homogenizing the mixture for 60min at 8000rpm of a lifting high-speed shearing emulsifying machine to obtain catalyst slurry;
2) spraying catalyst slurry: inserting an inlet pipe of a slurry pump into a catalyst slurry barrel, connecting an outlet pipe with a spray gun material pipe, connecting a spray gun gas source with a compressed air tank, hanging a spray gun nozzle on a fixed frame above a conveying mesh belt, laying and placing an aluminum honeycomb on the conveying mesh belt, wherein the spraying direction of the spray gun and the cross section of the aluminum honeycomb form an angle of 45 degrees, the distance from the cross section is 5-10cm, and the atomizing coverage diameter of a single nozzle is 5-15cm, and 8 nozzles are arranged; when spraying, starting the conveying mesh belt (5m/h) and starting a slurry pump and a spray gun to spray the aluminum honeycomb, wherein the spraying air pressure is controlled to be 0.3-0.5MPa, the spraying liquid feeding amount of a single honeycomb plate is 960g, namely the liquid feeding speed is 3000 g/h;
3) purging the honeycomb module: after the aluminum honeycomb coated with the catalyst slurry is conveyed out of the spraying area (conveying speed is 5m/h), blowing ports are arranged above and below the conveying mesh belt, a blowing gas source is connected with an air pressure tank, blowing wind pressure is set to be 0.1-0.3MPa, wind speed is 0.5-1m/s, a blowing air port is flat, a gap is 0.5-1mm, the width is 15cm, and 9 blowing ports are arranged at the upper part and the lower part respectively to prevent uneven distribution of a film layer and dropping liquid;
4) drying the honeycomb module: the swept honeycomb module enters a blowing drying area (the conveying speed is 5m/h) by a conveying mesh belt, and is dried for 30min at the temperature of 80 ℃; drying at 130 deg.C for 30 min;
5) roasting the honeycomb module: and (3) the dried honeycomb module enters a roasting region by a conveying mesh belt (conveying speed is 5m/h), roasting is carried out at 380-400 ℃ for 60min, and the roasted honeycomb module enters a normal-temperature cooling region and is cooled to room temperature, so that the ozone room-temperature decomposition honeycomb module is obtained.
Cutting the obtained honeycomb module into pieces of 363X275X10mm, and placing in an air purifier with air flow of 300m3H, air inlet speed of 1.5m/s, at 30m3The initial ozone concentration is 1.28mg/m by testing in a national standard purification bin3The temperature is 22 ℃, the humidity is 60 percent RH, and the indoor concentration is reduced to 0.02mg/m within 20min3Rate of degradation>98.4％。
Example 2
A preparation method of an ozone room temperature decomposition honeycomb module comprises the following steps:
1) 1000g of deionized water and 250g of gamma-Al are weighed2O3、15.4g MnC2O4·2H2O、25.0gNi(CH3COO)2·4H2Pouring O, 25g of pseudo-boehmite and 30g of film forming agent (1.5g of polyvinyl alcohol, 3.0g of phosphoric acid, 10.5g of alumina sol and 15g of acrylic resin emulsion) into a mixing barrel, starting a lifting stirrer head to mix for 30min at 500rpm, and homogenizing the mixture for 60min at 7000rpm of a lifting high-speed shearing emulsifier to obtain catalyst slurry;
2) spraying catalyst slurry: inserting an inlet pipe of a slurry pump into a catalyst slurry barrel, connecting an outlet pipe with a spray gun material pipe, connecting a spray gun gas source with a compressed air tank, hanging a spray gun nozzle on a fixed frame above a conveying mesh belt, laying and placing an aluminum honeycomb on the conveying mesh belt, wherein the spraying direction of the spray gun and the cross section of the aluminum honeycomb form an angle of 45 degrees, the distance from the cross section is 5-10cm, and the atomizing coverage diameter of a single nozzle is 5-15cm, and 8 nozzles are arranged; when spraying, starting the conveying mesh belt (5m/h) and starting a slurry pump and a spray gun to spray the aluminum honeycomb, wherein the spraying air pressure is controlled to be 0.3-0.5MPa, the spraying liquid feeding amount of a single honeycomb plate is 1152g, namely the liquid feeding speed is 3600 g/h;
3) purging the honeycomb module: after the aluminum honeycomb coated with the catalyst slurry is conveyed out of the spraying area (conveying speed is 5m/h), blowing ports are arranged above and below the conveying mesh belt, a blowing gas source is connected with an air pressure tank, blowing wind pressure is set to be 0.1-0.3MPa, wind speed is 0.5-1m/s, a blowing air port is flat, a gap is 0.5-1mm, the width is 15cm, and 9 blowing ports are arranged at the upper part and the lower part respectively to prevent uneven distribution of a film layer and dropping liquid;
4) drying the honeycomb module: the swept honeycomb module enters a blowing drying area (the conveying speed is 5m/h) by a conveying mesh belt, and is dried for 30min at the temperature of 80 ℃; drying at 130 deg.C for 30 min;
5) roasting the honeycomb module: and (3) the dried honeycomb module enters a roasting region by a conveying mesh belt (conveying speed is 5m/h), roasting is carried out for 60min at the temperature of 400-420 ℃, and after roasting, the honeycomb module enters a normal-temperature cooling region and is cooled to room temperature, thus obtaining the ozone room-temperature decomposition honeycomb module.
Cutting the obtained honeycomb module into pieces of 363X275X10mm, and placing in an air purifier with air flow of 300m3H, the air inlet speed is 1.5m/s, in30m3The initial ozone concentration is 10.81mg/m by testing in a national standard purification bin3At 25 deg.C and 90% RH humidity, the concentration in 50min room is reduced to 0.02mg/m3Rate of degradation>99.8％。
Example 3
A preparation method of an ozone room temperature decomposition honeycomb module comprises the following steps:
1) 1000g of deionized water and 350g of gamma-Al are weighed2O3、28.8g MnC2O4·2H2O、17.3g Ni3(C6H5O7)2Pouring 30g of pseudo-boehmite and 35g of film forming agent (1.8g of polyvinyl alcohol, 3.5g of phosphoric acid, 12.2g of alumina sol and 17.5g of acrylic resin emulsion) into a mixing barrel, starting a lifting stirring machine head to mix at 700rpm for 30min, and homogenizing the mixture at 8000rpm of a lifting high-speed shearing emulsifying machine for 60min to obtain catalyst slurry;
2) spraying catalyst slurry: inserting an inlet pipe of a slurry pump into a catalyst slurry barrel, connecting an outlet pipe with a spray gun material pipe, connecting a spray gun gas source with a compressed air tank, hanging a spray gun nozzle on a fixed frame above a conveying mesh belt, laying and placing an aluminum honeycomb on the conveying mesh belt, wherein the spraying direction of the spray gun and the cross section of the aluminum honeycomb form an angle of 45 degrees and is 5-10cm away from the cross section, and the atomizing coverage diameter of a single nozzle is 5-15cm, and 8 nozzles are arranged; when spraying, starting the conveying mesh belt (5m/h) and starting a slurry pump and a spray gun to spray the aluminum honeycomb, wherein the spraying air pressure is controlled to be 0.3-0.5MPa, the spraying liquid feeding amount of a single honeycomb plate is 1344g, namely the liquid feeding speed is 4200 g/h;
3) purging the honeycomb module: after the aluminum honeycomb coated with the catalyst slurry is conveyed out of the spraying area (conveying speed is 5m/h), blowing ports are arranged above and below the conveying mesh belt, a blowing gas source is connected with an air pressure tank, blowing wind pressure is set to be 0.1-0.3MPa, wind speed is 0.5-1m/s, a blowing air port is flat, a gap is 0.5-1mm, the width is 15cm, and 9 blowing ports are arranged at the upper part and the lower part respectively to prevent uneven distribution of a film layer and dropping liquid;
4) drying the honeycomb module: the swept honeycomb module enters a blowing drying area (the conveying speed is 5m/h) by a conveying mesh belt, and is dried for 30min at the temperature of 80 ℃; drying at 130 deg.C for 30 min;
5) roasting the honeycomb module: and (3) the dried honeycomb module enters a roasting region by a conveying mesh belt (conveying speed is 5m/h), roasting is carried out at the temperature of 410-430 ℃ for 60min, and after roasting, the honeycomb module enters a normal-temperature cooling region and is cooled to room temperature, thus obtaining the ozone room-temperature decomposition honeycomb module.
Cutting the obtained honeycomb module into pieces of 363X275X10mm, and placing in an air purifier with air flow of 300m3H, air inlet speed of 1.5m/s, at 30m3The initial ozone concentration is 2.73mg/m by testing in a national standard purification bin3At 25 deg.C and 95% RH humidity, the concentration in the room is reduced to 0.02mg/m within 30min3Rate of degradation>99.2％。
Example 4
A preparation method of an ozone room temperature decomposition honeycomb module comprises the following steps:
1) 1000g of deionized water, 350g of gamma-Al 2O3, and 29.1g of Mn were weighed3(C6H5O7)2、13.7g NiC2O4Pouring 35g of pseudo-boehmite and 50g of film forming agent (2.5g of polyvinyl alcohol, 5g of phosphoric acid, 17.5g of alumina sol and 25.0g of acrylic resin emulsion) into a mixing barrel, starting a lifting stirring machine head to mix for 30min at 700rpm, and then homogenizing the mixture for 60min at 8000rpm of a lifting high-speed shearing emulsifying machine to obtain catalyst slurry;
2) spraying catalyst slurry: inserting an inlet pipe of a slurry pump into a catalyst slurry barrel, connecting an outlet pipe with a spray gun material pipe, connecting a spray gun gas source with a compressed air tank, hanging a spray gun nozzle on a fixed frame above a conveying mesh belt, laying and placing an aluminum honeycomb on the conveying mesh belt, wherein the spraying direction of the spray gun and the cross section of the aluminum honeycomb form an angle of 45 degrees, the distance from the cross section is 5-10cm, and the atomizing coverage diameter of a single nozzle is 5-15cm, and 8 nozzles are arranged; when spraying, starting the conveying mesh belt (5m/h) and starting a slurry pump and a spray gun to spray the aluminum honeycomb, wherein the spraying air pressure is controlled to be 0.3-0.5MPa, the spraying liquid feeding amount of a single honeycomb plate is 1344g, namely the liquid feeding speed is 4200 g/h;
3) purging the honeycomb module: after the aluminum honeycomb coated with the catalyst slurry is conveyed out of the spraying area (conveying speed is 5m/h), blowing ports are arranged above and below the conveying mesh belt, a blowing gas source is connected with an air pressure tank, blowing wind pressure is set to be 0.1-0.3MPa, wind speed is 0.5-1m/s, a blowing air port is flat, a gap is 0.5-1mm, the width is 15cm, and 9 blowing ports are arranged at the upper part and the lower part respectively to prevent uneven distribution of a film layer and dropping liquid;
4) drying the honeycomb module: the swept honeycomb module enters a blowing drying area (the conveying speed is 5m/h) by a conveying mesh belt, and is dried for 30min at the temperature of 80 ℃; drying at 130 deg.C for 30 min;
5) roasting the honeycomb module: and (3) the dried honeycomb module enters a roasting region by a conveying mesh belt (conveying speed is 5m/h), roasting is carried out for 60min at the temperature of 430-450 ℃, and enters a normal-temperature cooling region after roasting, and then the honeycomb module is cooled to the room temperature, thus obtaining the ozone room-temperature decomposition honeycomb module.
Cutting the obtained honeycomb module into pieces of 363X275X10mm, and placing in an air purifier with air flow of 300m3H, air inlet speed of 1.5m/s, at 30m3The initial ozone concentration is 1.11mg/m by testing in a national standard purification bin3At 21 deg.C and 98% RH humidity, the concentration in 20min room is reduced to 0.01mg/m3Rate of degradation>99％。
Comparative example 1
Cutting an uncoated blank 1600X1200X10mm honeycomb plate into pieces 363X275X10mm, and placing the honeycomb plates in an air purifier with an air volume of 300m3H, air inlet speed of 1.5m/s, at 30m3The initial ozone concentration is 1.43mg/m by testing in a national standard purification bin3At 25 deg.C and 56% RH humidity, the concentration in the room is reduced to 0.54mg/m in 60min3The 60min degradation rate is only 62.2%.
Comparative example 2
Filling commercial ozone-removing granular carbon (300g) into 363X275X10mm filter element, and placing in air purifier with air flow of 300m3H, air inlet speed of 1.5m/s, at 30m3The initial ozone concentration is 1.25mg/m by testing in a national standard purification bin3At 23 deg.C and 80% RH humidity, the concentration in 60min room is reduced to 0.07mg/m3And the 60min degradation rate is 95%.
The degradation rates of the honeycomb modules and commercial ozone-removing granular carbon used in the examples and comparative examples are shown in the table.
Watch 1
In conclusion, the honeycomb module prepared by the invention can be applied to the catalytic decomposition treatment of ozone in air, and the ozone concentration is 1-20mg/m under the conditions that the temperature is-10-40 ℃ and the humidity is 30-98 RH%3All can be effectively degraded to 0.02mg/m3The ozone degradation rate is more than 98 percent, and the long time can be realized>3500h) The purification requirement of effectively removing ozone.
The above description is only for the purpose of illustrating the technical solutions of the present invention and not for the purpose of limiting the same, and other modifications or equivalent substitutions made by those skilled in the art to the technical solutions of the present invention should be covered within the scope of the claims of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. An ozone room temperature decomposition honeycomb module, its characterized in that: the catalyst slurry is sprayed on the aluminum honeycomb, and then the finished product is prepared by blowing, drying and roasting.
2. The ozone room temperature decomposition honeycomb module of claim 1, wherein: the catalyst slurry is prepared from the following components in parts by weight:
3. a method for preparing the ozone room temperature decomposition honeycomb module according to claim 1 or 2, comprising the steps of:
1) mixing and homogenizing catalyst slurry: weighing 100 parts by weight of deionized water, 20-40 parts by weight of alumina powder, 2-10 parts by weight of organic manganese salt, 2-10 parts by weight of organic nickel salt, 2-5 parts by weight of pseudo-boehmite and 2-10 parts by weight of film-forming agent, pouring into a mixing barrel, starting a lifting stirring machine head to mix for 20-30min at 700rpm, and homogenizing the mixture for 30-60min at 8000rpm of 5000-plus high-speed shearing emulsifying machine to obtain catalyst slurry;
2) spraying catalyst slurry: inserting an inlet pipe of a slurry pump into a catalyst slurry barrel, connecting an outlet pipe with a spray gun material pipe, connecting a spray gun gas source with a compressed air tank, hanging a spray gun nozzle on a fixed frame above a conveying mesh belt, laying and placing an aluminum honeycomb on the conveying mesh belt, wherein the spraying direction of the spray gun and the cross section of the aluminum honeycomb form an angle of 45 degrees, the distance from the cross section is 5-10cm, the atomizing coverage diameter of a single nozzle is 5-15cm, and the number of the spray nozzles can be adjusted according to the size of the sprayed aluminum honeycomb; when spraying, starting the conveying mesh belt and starting the slurry pump and the spray gun, spraying the aluminum honeycomb, controlling the spraying air pressure to be 0.3-0.5MPa, and adjusting the feeding speed of the slurry pump and the traveling speed of the conveying belt to ensure that the spraying amount reaches 5-35% of the volume of the aluminum honeycomb;
3) purging the honeycomb module: after the aluminum honeycomb sprayed with the catalyst slurry is conveyed out of the spraying area, purging ports are arranged above and below the conveying mesh belt, a purging gas source is connected with an air pressure tank, the purging wind pressure is set to be 0.1-0.3MPa, the wind speed is 0.5-1m/s, a purging wind port is flat, the gap is 0.5-1mm, the width is 15cm, the number of the blowing ports is adjusted according to the size of a honeycomb module, and the uneven distribution of a film layer and liquid dropping are prevented;
4) drying the honeycomb module: the swept honeycomb module enters a blast drying area through a conveying mesh belt and is dried for 30min at 80 ℃; drying at 130 deg.C for 30 min;
5) roasting the honeycomb module: and the dried honeycomb module enters a roasting area through a conveying mesh belt, roasting is carried out for 60min at the temperature of 350-450 ℃, and enters a normal-temperature cooling area after roasting, and the cooled honeycomb module is cooled to the room temperature, so that the ozone room-temperature decomposition honeycomb module is obtained.
4. The method of claim 3, wherein the ozone room temperature decomposition honeycomb module is prepared by: the aluminum honeycomb material is aluminum or aluminum alloy which can endure heating at 400 ℃ for more than 3 hours without deformation and collapse and has no dust, grease or impurities on the surface.
5. The method of claim 3, wherein the ozone room temperature decomposition honeycomb module is prepared by: the crystal form of the alumina powder is gamma-type, and the granularity is 800-1000 meshes.
6. The method of claim 3, wherein the ozone room temperature decomposition honeycomb module is prepared by: the organic manganese salt is any one of acetate, oxalate and citrate of manganese.
7. The method of claim 3, wherein the ozone room temperature decomposition honeycomb module is prepared by: the organic nickel salt is any one of acetate, oxalate and citrate of nickel.
8. The method of claim 3, wherein the ozone room temperature decomposition honeycomb module is prepared by: the film forming agent is mainly prepared by mixing polyvinyl alcohol, phosphoric acid, alumina sol and acrylic resin emulsion according to the mass ratio of 1:2:7: 10.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112742378A (en) * | 2021-01-22 | 2021-05-04 | 上海大学 | Melanese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module, preparation method thereof and application of catalyst module in catalytic decomposition of hydrogen peroxide |
| CN116815552A (en) * | 2023-08-30 | 2023-09-29 | 德州广源环保科技有限公司 | Novel honeycomb zeolite module molding process for rotating wheel |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02187148A (en) * | 1988-10-31 | 1990-07-23 | Sakai Chem Ind Co Ltd | Catalyst for decomposing ozone |
| CN1785507A (en) * | 2005-11-22 | 2006-06-14 | 天津化工研究设计院 | Ozone decomposition catalyst and its preparation method |
| CN102755912A (en) * | 2012-07-17 | 2012-10-31 | 无锡威孚环保催化剂有限公司 | Ceramic honeycombed catalyst capable of purifying organic waste gas and preparation method thereof |
| CN103990490A (en) * | 2014-05-16 | 2014-08-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Integral type ozone catalyst applicable to printing and dyeing wastewater and preparation method of catalyst |
| CN105312061A (en) * | 2014-06-24 | 2016-02-10 | 江苏瑞丰科技实业有限公司 | Normal-temperature ozone-removal catalytic material |
-
2019
- 2019-12-27 CN CN201911375209.5A patent/CN110975610B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02187148A (en) * | 1988-10-31 | 1990-07-23 | Sakai Chem Ind Co Ltd | Catalyst for decomposing ozone |
| CN1785507A (en) * | 2005-11-22 | 2006-06-14 | 天津化工研究设计院 | Ozone decomposition catalyst and its preparation method |
| CN102755912A (en) * | 2012-07-17 | 2012-10-31 | 无锡威孚环保催化剂有限公司 | Ceramic honeycombed catalyst capable of purifying organic waste gas and preparation method thereof |
| CN103990490A (en) * | 2014-05-16 | 2014-08-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Integral type ozone catalyst applicable to printing and dyeing wastewater and preparation method of catalyst |
| CN105312061A (en) * | 2014-06-24 | 2016-02-10 | 江苏瑞丰科技实业有限公司 | Normal-temperature ozone-removal catalytic material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112742378A (en) * | 2021-01-22 | 2021-05-04 | 上海大学 | Melanese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module, preparation method thereof and application of catalyst module in catalytic decomposition of hydrogen peroxide |
| CN116815552A (en) * | 2023-08-30 | 2023-09-29 | 德州广源环保科技有限公司 | Novel honeycomb zeolite module molding process for rotating wheel |
| CN116815552B (en) * | 2023-08-30 | 2023-10-31 | 德州广源环保科技有限公司 | Forming process of honeycomb zeolite module for rotating wheel |
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