CN114669290B - High entropy oxide catalyst for VOCs removal and application - Google Patents

High entropy oxide catalyst for VOCs removal and application Download PDF

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CN114669290B
CN114669290B CN202210359306.0A CN202210359306A CN114669290B CN 114669290 B CN114669290 B CN 114669290B CN 202210359306 A CN202210359306 A CN 202210359306A CN 114669290 B CN114669290 B CN 114669290B
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oxide
catalyst
metal oxide
printing
slurry
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CN114669290A (en
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高立国
王强
刘岩
宋小利
高平强
许云华
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Yulin University
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Yulin University
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Abstract

The invention discloses a high-entropy oxide catalyst for removing VOCs and application thereof, wherein the catalyst is prepared from alkaline earth metal oxide, first transition metal oxide, second transition metal oxide, rare earth metal oxide and carrier oxide by adopting a 3D printing method. The catalyst has developed pore structure, and the specific surface area and pore volume are effectively increased; the catalyst has excellent thermal stability, is not easy to sinter and accumulate carbon, and has good low-temperature catalytic performance; the catalytic oxidation activity at low temperature is good, and the catalytic oxidation performance of VOCs is greatly improved. The catalyst is prepared by a 3D printing method, the shape which is not manufactured by the traditional production technology can be manufactured without machining or any die, the whole production flow can be simplified, the preparation period of the product is greatly shortened, the production efficiency is improved, and the production cost is reduced.

Description

High entropy oxide catalyst for VOCs removal and application
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a high-entropy oxide catalyst for removing VOCs, and a preparation method and application thereof.
Background
Volatile Organic Compounds (VOCs) include primarily hydrocarbons, halogenated hydrocarbons, oxygenated alcohols, ketones, esters, and some nitrogen-and sulfur-containing organic compounds. The processes of chemical production, paint drying, food processing, crude oil extraction, metal degreasing, paper manufacturing, textile industry and the like all discharge a large amount of VOCs.
Most VOCs have unpleasant, characteristic odors, and toxic, irritating, teratogenic and carcinogenic effects, and especially benzene, toluene, formaldehyde, etc., can cause significant harm to human health. Most VOCs are inflammable, explosive and unsafe, and can generate photochemical reaction with nitrogen-oxygen compounds, hydrocarbon and oxidant in the atmosphere under the irradiation of sunlight to generate photochemical smog, harm the health of human bodies and the growth of crops, and destroy ozone layers.
The existing technology for treating VOCs is mainly divided into recovery treatment and destruction treatment, wherein the recovery treatment mainly comprises an adsorption method, an absorption method, a membrane separation method and the like. The destruction treatment mainly comprises a biodegradation method, an incineration method, a photocatalysis method, a plasma method, a catalytic oxidation method and the like. The absorption method is suitable for purifying the tail gas of the VOCs with low concentration only, and the adsorbent needs to be frequently regenerated, so that the further use of the adsorbent is restricted to a certain extent; the membrane separation method is limited by the narrow pollutant concentration range, and is easy to pollute, poor in stability, high in energy consumption and high in operation and maintenance cost; although the photocatalytic method can completely catalyze and oxidize VOCs without being affected by temperature, the photocatalytic method is limited by the wavelength of excitation light, secondary pollutants, time consumption and the like, and cannot be applied to large-scale practical application. Catalytic oxidation of VOCs is a technology with application prospect, however, most of currently used catalysts are noble metal catalysts, and the catalysts have the defects of high price, high reaction temperature, easy sintering at high temperature, easy carbon deposition and the like, so that popularization and application of the catalysts are limited.
Disclosure of Invention
In order to solve the problems of high price, easy sintering at high temperature, easy carbon deposition and the like of the VOCs removal catalyst, the invention provides a high-entropy oxide catalyst which can obviously reduce the cost of the catalyst, is difficult to sinter, is difficult to carbon deposition and has good low-temperature catalytic performance, and provides an application for the catalyst.
In order to achieve the aim, the high-entropy oxide catalyst adopted by the invention comprises alkaline earth metal oxide, first transition metal oxide, second transition metal oxide, rare earth metal oxide and carrier oxide according to the mass ratio of 5-10: 15-20: 20-30: 10 to 15: 25-40.
The alkaline earth metal oxide is any one of magnesium oxide, calcium oxide, strontium oxide and barium oxide.
The first transition metal oxide is any one of vanadium pentoxide, chromium trioxide, manganese dioxide, niobium pentoxide, molybdenum trioxide, tantalum oxide, tungsten dioxide, rhenium heptaoxide and osmium tetroxide.
The second transition metal oxide is any one of ferric oxide, cobaltosic oxide, nickel oxide, copper oxide and zinc oxide.
The rare earth metal oxide is any one of lanthanum oxide, cerium oxide, scandium oxide and yttrium oxide.
The carrier oxide is any one of aluminum oxide, silicon dioxide, titanium dioxide and zirconium dioxide.
The preparation method of the high-entropy oxide catalyst comprises the following steps:
(1) Mixing alkaline earth metal oxide, first transition metal oxide and solvent A, and putting into a ball mill for ball milling for 0.5-4 h to obtain first slurry; the mass ratio of the total mass of the alkaline earth metal oxide and the first transition metal oxide to the solvent a is 1:0.3 to 0.5;
(2) Mixing the second transition metal oxide with the solvent B, and putting the mixture into a ball mill for ball milling for 0.5 to 4 hours to obtain second slurry; the mass ratio of the second transition metal oxide to the solvent B is 1:0.5 to 0.8;
(3) Mixing rare earth metal oxide, carrier oxide and solvent C, and putting into a ball mill for ball milling for 0.5-4 h to obtain third slurry; the mass ratio of the total weight of the alkaline earth metal oxide to the first transition metal oxide and the solvent C is 1:0.8 to 1.0;
(4) Putting the first slurry, the second slurry and the third slurry into a kneader, adding dispersing agents accounting for 0.2-2.0% of the total mass of the three slurries, and fully kneading for 0.5-2 h to obtain a 3D printing material;
(5) Loading 3D printing materials into a charging barrel of a 3D gel printer, leading the shape of a product to be printed into a computer control system for printing, wherein the diameter of a nozzle selected for printing is 0.1-1.0 mm, the viscosity of slurry passing through the nozzle is 14-32 Pa.s, the height of a printing layer is 0.08-0.80 mm, and the extrusion rate is 50-200 mm 3 Every min, the printing speed is 5-10 mm/s, and when one layer of printing is finished, a spraying device sprays a layer of mist initiator and curing agent on the printing surface to realize printing and curing simultaneously; and (3) vacuum drying the printed blank for 8-24 h at 30-50 ℃, degreasing the dried blank for 2-10 h at 150-400 ℃ in nitrogen atmosphere, sintering at 150-400 ℃ in air atmosphere for 1-6 h, and cooling to obtain the high-entropy oxide catalyst.
The solvent A is any one of benzene, toluene and xylene.
The solvent B is any one of ethanol, propanol, isopropanol, butanol and ethylene glycol.
The solvent C is any one of nitric acid aqueous solution and acetic acid aqueous solution, and the mass concentration of nitric acid or acetic acid in the solvent C is 0.5% -5.0%.
The dispersing agent is any one of oleic acid, lauric acid, citric acid, malic acid and gallic acid.
The particle sizes of the first slurry, the second slurry and the third slurry are all smaller than 300 mu m.
The initiator is any one of benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyvalerate, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.
The curing agent is any one of vinyl triamine, diaminocyclohexane, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, diethylaminopropylamine, trimethylhexamethylenediamine, dihexyltriamine, hexamethylenediamine, trimethylhexamethylenediamine and diethylamine.
The specific surface area of the high entropy oxide catalyst is 100-400 m 2 Per gram, pore volume of 0.3-0.8 m 3 And/g, the pore diameter is 3-20 nm.
The high entropy oxide catalyst of the invention can be used for removing VOCs.
In the high-entropy oxide catalyst, the alkaline earth metal oxide can improve the electron cloud density of the catalyst, provide more active sites for catalytic reaction and participate in catalytic oxidation reaction, so that the catalytic oxidation capacity of the system is improved; the first transition metal oxide has a good adsorption effect on acid gas, so that the catalytic activity of the catalyst can be improved to a certain extent, the specific surface area of the catalyst can be improved, active oxide components can be effectively dispersed, and particle aggregation of the active oxide components can be reduced; the second transition metal oxide is a potential catalyst capable of replacing noble metal to realize low-temperature catalytic oxidation of VOCs, and the transition metal in the second transition metal oxide has more valence-changing metals capable of forming an oxidation-reduction system, so that the adsorption capacity of the transition metal oxide to the VOCs can be greatly enhanced; the rare earth metal oxide has better oxygen affinity, so that the capturing effect of the catalyst on oxygen can be increased in the catalytic process, the migration and conversion of active oxygen in the catalyst can be effectively promoted, the capability of the catalyst for catalyzing and oxidizing VOCs can be improved, and the catalyst plays a role of a promoter; conventional support oxides can increase the dispersibility of other metal oxides in the catalyst and enhance its adsorption capacity for VOCs.
Compared with the prior art, the invention has the following beneficial effects:
1. the catalyst has developed pore structure, and the specific surface area and pore volume of the high-entropy oxide are effectively increased; the catalyst has excellent thermal stability, is not easy to sinter and accumulate carbon, and has good low-temperature catalytic performance; the catalytic oxidation activity at low temperature is good, and the catalytic oxidation performance of VOCs is greatly improved.
2. The high-entropy oxide catalyst is prepared by a 3D printing method, the 3D printing method can manufacture the shape which is not manufactured by the traditional production technology without mechanical processing or any mould, so that the catalyst space structure is improved, the catalyst has a developed pore structure, the specific surface area and the pore volume of the high-entropy oxide can be effectively increased, and the catalyst has better catalytic oxidation activity. Meanwhile, the whole production process can be simplified, the preparation period of the product is greatly shortened, the production efficiency is improved, and the production cost is reduced.
Detailed Description
The technical scheme of the invention is further described by the following specific examples. It will be apparent to those skilled in the art that the specific embodiments described herein are for illustrative purposes only and are not limiting, as various changes and modifications can be made without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions are also within the scope of the present invention, which is defined by the claims.
Example 1
The high-entropy oxide catalyst of the embodiment comprises magnesium oxide, vanadium pentoxide, cobaltosic oxide, cerium dioxide and zirconium dioxide according to the mass ratio of 5:18.5:20.5:9.5:25, the specific preparation steps are as follows:
(1) Mixing 5.0g of magnesium oxide, 18.5g of vanadium pentoxide and toluene, and putting into a ball mill for ball milling for 1.5h to obtain first slurry with the granularity smaller than 300 mu m; wherein the mass ratio of the total mass of magnesium oxide to vanadium pentoxide to toluene is 1:0.3;
(2) Mixing 20.5g of cobaltosic oxide with propanol, and putting the mixture into a ball mill for ball milling for 2 hours to obtain second slurry with the granularity smaller than 300 mu m; wherein, the mass ratio of the cobaltosic oxide to the propanol is 1:0.8;
(3) Mixing 9.5g of cerium oxide, 25.0g of zirconium oxide and 2% of nitric acid aqueous solution by mass concentration, and putting the mixture into a ball mill for ball milling for 0.5h to obtain third slurry with the granularity smaller than 300 mu m; wherein, the mass ratio of the cerium oxide to the zirconium oxide in the nitric acid aqueous solution with the total mass and the mass concentration of 2 percent is 1:0.8;
(4) Putting the first slurry, the second slurry and the third slurry into a kneader, adding citric acid with the total mass of 0.2% of the three slurries, and fully kneading for 1h to obtain a 3D printing material;
(5) Filling 3D printing materials into a charging barrel of a 3D gel printer, and shaping a product to be printed(hollow sphere, outer diameter 5mm, inner diameter 3 mm) is introduced into a computer control system for printing, the diameter of a nozzle used for printing is 0.1mm, the viscosity of slurry passing through the nozzle is 14 Pa.s, the height of a printing layer is 0.08mm, and the extrusion rate is 50mm 3 Every min, the printing speed is 5mm/s, and when one layer of printing is finished, the spraying device sprays one layer of mist benzoyl peroxide and ethylenediamine on the printing surface to realize the simultaneous printing and curing; and (3) drying the printed blank for 24 hours at 30 ℃ in vacuum, degreasing the dried blank for 10 hours at 150 ℃ in nitrogen atmosphere, sintering at 150 ℃ in air atmosphere for 6 hours, and cooling to obtain the high-entropy oxide catalyst. The specific surface area of the catalyst was 345m 2 Per g, pore volume of 0.71m 3 The pore diameter is 6.2nm.
Example 2
The high-entropy oxide catalyst of the embodiment comprises calcium oxide, chromium oxide, ferric oxide, lanthanum oxide and aluminum oxide according to the mass ratio of 6:19:22:11:27.5, the specific preparation steps are as follows:
(1) Mixing 6.0g of calcium oxide, 19.0g of chromium oxide and benzene, and putting the mixture into a ball mill for ball milling for 0.5h to obtain first slurry with the granularity smaller than 300 mu m; wherein the mass ratio of the total mass of the calcium oxide to the chromium oxide to the mass of the benzene is 1:0.32;
(2) Mixing 22.0g of ferric oxide with ethanol, and putting the mixture into a ball mill for ball milling for 4 hours to obtain second slurry with the granularity smaller than 300 mu m; wherein, the mass ratio of ferric oxide to ethanol is 1:0.75;
(3) Mixing 11.0g of lanthanum oxide, 27.5g of aluminum oxide and an acetic acid aqueous solution with the mass concentration of 5%, and putting the mixture into a ball mill for ball milling for 3.5 hours to obtain third slurry with the granularity of less than 300 mu m; wherein, the mass ratio of the lanthanum oxide to the aluminum oxide is 1:0.82;
(4) Putting the first slurry, the second slurry and the third slurry into a kneader, adding malic acid accounting for 0.5% of the total mass of the three slurries, and fully kneading for 1h to obtain a 3D printing material;
(5) Filling 3D printing materials into a charging barrel of a 3D gel printer, andthe shape of the product to be printed (hollow cylinder, outer diameter 5mm, inner diameter 2mm, outer height 6mm, inner height 3 mm) is introduced into a computer control system for printing, the diameter of the nozzle selected for printing is 0.2mm, the viscosity of slurry passing through the nozzle is 17 Pa.s, the height of the printing layer is 0.12mm, and the extrusion rate is 66mm 3 Every min, the printing speed is 5.8mm/s, and when one layer of printing is finished, the spraying device sprays one layer of mist lauroyl peroxide and diethylenetriamine to the printing surface to realize the simultaneous printing and curing; and (3) drying the printed blank for 20 hours at 35 ℃ in vacuum, degreasing the dried blank for 8 hours at 200 ℃ in nitrogen atmosphere, sintering at 200 ℃ in air atmosphere for 5 hours, and cooling to obtain the high-entropy oxide catalyst. The specific surface area of the catalyst is 397m 2 Per gram, pore volume of 0.8m 3 The pore diameter is 3.2nm.
Example 3
The high-entropy oxide catalyst of the embodiment comprises strontium oxide, manganese dioxide, copper oxide, scandium oxide and silicon dioxide according to the mass ratio of 7:18:24:12:30, the specific preparation steps are as follows:
(1) Mixing 7.0g of strontium oxide, 18.0g of manganese dioxide and xylene, and putting the mixture into a ball mill for ball milling for 4 hours to obtain first slurry with the granularity smaller than 300 mu m; wherein the mass ratio of the total mass of strontium oxide and manganese dioxide to the mass of xylene is 1:0.35;
(2) Mixing 24.0g of copper oxide with butanol, and putting the mixture into a ball mill for ball milling for 2.5 hours to obtain second slurry with the granularity smaller than 300 mu m; wherein, the mass ratio of the copper oxide to the butanol is 1:0.7;
(3) Mixing 12.0g of scandium oxide and 30.0g of silicon dioxide with a nitric acid aqueous solution with the mass concentration of 1%, and putting the mixture into a ball mill for ball milling for 1.5 hours to obtain third slurry with the granularity of less than 300 mu m; wherein the mass ratio of the scandia to the nitric acid aqueous solution with the total mass and the mass concentration of the silicon dioxide of 1 percent is 1:0.85;
(4) Putting the first slurry, the second slurry and the third slurry into a kneader, adding gallic acid accounting for 1% of the total mass of the three slurries, and fully kneading for 1h to obtain a 3D printing material;
(5) 3D printing material is filledIntroducing the shape of the product to be printed (hollow chamfered octahedron, outer edge length 4mm, inner edge length 2 mm) into a cylinder of a 3D gel printer, printing with a nozzle diameter of 0.3mm, a slurry viscosity of 20Pa.s when passing through the nozzle, a printing layer height of 0.22mm, and an extrusion rate of 80mm 3 Every min, the printing speed is 7.0mm/s, and when one layer of printing is finished, the spraying device sprays one layer of mist di-tert-butyl peroxide and triethylene tetramine on the printing surface to realize the simultaneous printing and curing; and (3) drying the printed blank for 16 hours at 40 ℃ in vacuum, degreasing the dried blank for 8 hours at 250 ℃ in nitrogen atmosphere, then sintering at 235 ℃ in air atmosphere for 4.5 hours, and cooling to obtain the high-entropy oxide catalyst. The specific surface area of the catalyst is 301m 2 Per g, pore volume of 0.55m 3 The pore diameter was 9.3nm.
Example 4
The high-entropy oxide catalyst of the embodiment comprises barium oxide, niobium pentoxide, zinc oxide, yttrium oxide and titanium dioxide according to the mass ratio of 8:17.5:26:12.5:32.5, the specific preparation steps are as follows:
(1) Mixing 8.0g of barium oxide, 17.5g of niobium pentoxide and benzene, and putting into a ball mill for ball milling for 2.5 hours to obtain first slurry with the granularity smaller than 300 mu m; wherein the mass ratio of the total mass of the barium oxide to the niobium pentoxide to the benzene is 1:0.40;
(2) Mixing 26.0g of zinc oxide with ethylene glycol, and putting the mixture into a ball mill for ball milling for 0.5h to obtain second slurry with the granularity smaller than 300 mu m; wherein, the mass ratio of zinc oxide to ethylene glycol is 1:0.7;
(3) Mixing 12.5g of yttrium oxide, 32.5g of titanium dioxide and an acetic acid aqueous solution with the mass concentration of 4%, and putting the mixture into a ball mill for ball milling for 0.5h to obtain a third slurry with the granularity of less than 300 mu m; wherein, the mass ratio of the yttrium oxide to the titanium dioxide is 1:0.88;
(4) Putting the first slurry, the second slurry and the third slurry into a kneader, adding salicylic acid accounting for 1.2% of the total mass of the three slurries, and fully kneading for 1h to obtain a 3D printing material;
(5) 3D printing materials are filled into a charging barrel of a 3D gel printer, the shape of a product to be printed (a hollow cube, an outer edge length of 3mm and an inner edge length of 1.5 mm) is led into a computer control system to be printed, the diameter of a nozzle selected for printing is 0.3mm, the viscosity of slurry passing through the nozzle is 20 Pa.s, the height of a printing layer is 0.22mm, and the extrusion rate is 80mm 3 Every min, the printing speed is 7.0mm/s, and when one layer of printing is finished, the spraying device sprays one layer of mist dicumyl peroxide and tetraethylenepentamine on the printing surface to realize the simultaneous printing and curing; and (3) drying the printed blank for 17 hours at 40 ℃ in vacuum, degreasing the dried blank for 6 hours at 260 ℃ in nitrogen atmosphere, then sintering at 250 ℃ in air atmosphere for 3.5 hours, and cooling to obtain the high-entropy oxide catalyst. The specific surface area of the catalyst is 245m 2 Per g, pore volume of 0.45m 3 The pore diameter is 12.4nm.
Example 5
The high-entropy oxide catalyst of the embodiment comprises magnesium oxide, molybdenum trioxide, nickel oxide, cerium oxide and aluminum oxide according to the mass ratio of 6:17:27:13:35, the specific preparation steps are as follows:
(1) Mixing 6.0g of magnesium oxide, 17.0g of molybdenum trioxide and toluene, and putting the mixture into a ball mill for ball milling for 1.5 hours to obtain first slurry with the granularity smaller than 300 mu m; wherein the mass ratio of the total mass of magnesium oxide and molybdenum trioxide to toluene is 1:0.42;
(2) Mixing 27.0g of nickel oxide with isopropanol, and putting the mixture into a ball mill for ball milling for 1 hour to obtain second slurry with the granularity smaller than 300 mu m; wherein, the mass ratio of nickel oxide to isopropanol is 1:0.5;
(3) Mixing 13.0g of cerium oxide, 35.0g of aluminum oxide and a nitric acid aqueous solution with the mass concentration of 0.6%, and putting the mixture into a ball mill for ball milling for 1.5 hours to obtain third slurry with the granularity of less than 300 mu m; the mass ratio of the total weight of the cerium oxide and the aluminum oxide to the nitric acid aqueous solution with the mass concentration of 0.6 percent is 1:0.9;
(4) Placing the first slurry, the second slurry and the third slurry into a kneader, adding oleic acid accounting for 1.5% of the total mass of the three slurries, and fully kneading for 1h to obtain a 3D printing material;
(5) Loading 3D printing materials into a charging barrel of a 3D gel printer, introducing the shape of a product to be printed (hollow clover, single cylinder with outer diameter of 1mm, inner diameter of 0.5mm and length of 4 mm) into a computer control system for printing, wherein the diameter of a nozzle selected for printing is 0.4mm, the viscosity of slurry passing through the nozzle is 23 Pa.s, the height of a printing layer is 0.42mm, and the extrusion rate is 120mm 3 Every min, the printing speed is 7.5mm/s, and when one layer of printing is finished, the spraying device sprays one layer of atomized tertiary butyl peroxybenzoate and diacrylamine on the printing surface to realize the simultaneous printing and curing; and (3) drying the printed blank body in vacuum at 45 ℃ for 12 hours, degreasing the dried blank body at 280 ℃ for 5 hours in nitrogen atmosphere, then sintering at 300 ℃ in air atmosphere for 2.5 hours, and cooling to obtain the high-entropy oxide catalyst. The specific surface area of the catalyst is 198m 2 Per gram, pore volume of 0.30m 3 The pore diameter is 15.1nm.
Example 6
The high-entropy oxide catalyst of the embodiment comprises strontium oxide, tungsten dioxide, cobaltosic oxide, lanthanum oxide and silicon dioxide according to the mass ratio of 10:16:28:14:40, the specific preparation steps are as follows:
(1) Mixing 10.0g of strontium oxide, 16.0g of tungsten dioxide and xylene, and putting into a ball mill for ball milling for 1h to obtain first slurry with the granularity smaller than 300 mu m; wherein the mass ratio of the total mass of strontium oxide to tungsten dioxide to the mass of xylene is 1:0.45;
(2) Mixing 28.0g of cobaltosic oxide with propanol, and putting the mixture into a ball mill for ball milling for 3 hours to obtain second slurry with the granularity smaller than 300 mu m; wherein, the mass ratio of the cobaltosic oxide to the propanol is 1:0.55;
(3) Mixing 14.0g of lanthanum oxide, 40.0g of silicon dioxide and an acetic acid aqueous solution with the mass concentration of 4%, and putting the mixture into a ball mill for ball milling for 2.5 hours to obtain third slurry with the granularity of less than 300 mu m; wherein, the mass ratio of the lanthanum oxide to the silicon dioxide is 1:0.95;
(4) Putting the first slurry, the second slurry and the third slurry into a kneader, adding citric acid accounting for 1.8% of the total mass of the three slurries, and fully kneading for 1h to obtain a 3D printing material;
(5) 3D printing materials are filled into a charging barrel of a 3D gel printer, the shape of a product (hollow cuboid, length 5mm, cross section is square, side length 1.2mm, hollow length 3mm in the interior, cross section is square, side length 0.5 mm) to be printed is led into a computer control system to be printed, the diameter of a nozzle selected for printing is 0.72mm, the viscosity of slurry when passing through the nozzle is 25Pa s, the height of a printing layer is 0.50mm, and the extrusion rate is 150mm 3 Every min, the printing speed is 7.8mm/s, and once one layer of printing is finished, a spraying device sprays one layer of atomized tertiary butyl peroxytert-valerate and diethylaminopropylamine to the printing surface to realize printing and curing simultaneously; and (3) drying the printed blank body in vacuum at 45 ℃ for 10 hours, degreasing the dried blank body at 300 ℃ for 4 hours in a nitrogen atmosphere, then sintering at 350 ℃ in an air atmosphere for 2 hours, and cooling to obtain the high-entropy oxide catalyst. The specific surface area of the catalyst is 155m 2 Per gram, pore volume of 0.39m 3 The pore diameter is 14.5nm.
Example 7
The high-entropy oxide catalyst of the embodiment comprises barium oxide, rhenium heptaoxide, copper oxide, yttrium oxide and zirconium oxide according to the mass ratio of 9:15:27.5:13.5:37.5, the specific preparation steps are as follows:
(1) Mixing 9.0g of barium oxide, 15.0g of rhenium heptaoxide and toluene, and putting the mixture into a ball mill for ball milling for 1h to obtain first slurry with the granularity smaller than 300 mu m; wherein the mass ratio of the total mass of the barium oxide to the rhenium heptaoxide to the mass of the toluene is 1:0.50;
(2) Mixing 27.5g of copper oxide with isopropanol, and putting the mixture into a ball mill for ball milling for 3 hours to obtain second slurry with the granularity smaller than 300 mu m; wherein, the mass ratio of the copper oxide to the isopropanol is 1:0.5;
(3) Mixing 13.5g of yttrium oxide, 37.5g of zirconium dioxide and 2% of nitric acid aqueous solution by mass concentration, and putting the mixture into a ball mill for ball milling for 1.5 hours to obtain third slurry with the granularity smaller than 300 mu m; wherein, the mass ratio of the yttrium oxide to the zirconium dioxide in the nitric acid aqueous solution with the total mass and the mass concentration of 2 percent is 1:1, a step of;
(4) Putting the first slurry, the second slurry and the third slurry into a kneader, adding lauric acid accounting for 2% of the total mass of the three slurries, and fully kneading for 1h to obtain a 3D printing material;
(5) 3D printing materials are filled into a charging barrel of a 3D gel printer, the shape of a product (hollow ellipsoid, maximum external diameter of 6mm, maximum internal diameter of 3.5mm, maximum internal diameter of 4.5mm and maximum internal diameter of 2.0 mm) to be printed is led into a computer control system to be printed, the diameter of a nozzle selected for printing is 1.0mm, the viscosity of slurry when passing through the nozzle is 32 Pa.s, the height of a printing layer is 0.80mm, and the extrusion rate is 200mm 3 Every min, the printing speed is 10.0mm/s, and when one layer of printing is finished, the spraying device sprays one layer of vaporous diisopropyl peroxydicarbonate and tetramethyl ethylenediamine on the printing surface to realize printing and curing simultaneously; and (3) drying the printed blank for 8 hours at 50 ℃ in vacuum, degreasing the dried blank for 2 hours at 400 ℃ in nitrogen atmosphere, then sintering at 400 ℃ in air atmosphere for 1 hour, and cooling to obtain the high-entropy oxide catalyst. The specific surface area of the catalyst was 118m 2 Per gram, pore volume of 0.51m 3 The pore diameter was 19.2nm.
The catalysts prepared in examples 1 to 7 were used for removing VOCs, and the catalyst activity was evaluated by the specific evaluation method: the high-entropy oxide catalyst powder is placed in a fixed bed quartz tube reactor which continuously flows, the catalyst is not required to be reduced, raw material gas is directly introduced into the reactor under normal pressure, the chlorobenzene concentration in the raw material gas is 600ppm, the toluene concentration is 500ppm, the dichloromethane concentration is 700ppm, the trichloroethylene concentration is 600ppm, the oxygen content is 4%, and the balance is inert nitrogen, so that the flow rate of the raw material gas is 1L/min. The results of the catalyst activity evaluation are shown in Table 1.
TABLE 1 evaluation results of initial Activity of catalysts
Note that: the comparative example in the table is a commercial honeycomb VOCs catalytic combustion catalyst, and the main components of the catalyst are Pt, cu, si, al and the like according to the detection result, and the specific performance test conditions are the same. The 97% removal temperature in the table refers to the minimum temperature required for 97% and above of these VOCs in the feed gas.
From the data in table 1, it can be seen that: the catalyst has the remarkable advantages of high VOCs removal rate and low reaction temperature, and the catalyst does not need to be reduced before the reaction. This is because the developed pore structure of the catalyst increases the specific surface area and pore volume of the high entropy oxide, and improves the low temperature catalytic oxidation activity.

Claims (7)

1. A high entropy oxide catalyst for VOCs removal, characterized by: the catalyst is prepared from alkaline earth metal oxide, first transition metal oxide, second transition metal oxide, rare earth metal oxide and carrier oxide according to the mass ratio of 5-10: 15-20: 20-30: 10 to 15: 25-40 parts of a material;
the alkaline earth metal oxide is any one of magnesium oxide, calcium oxide, strontium oxide and barium oxide;
the first transition metal oxide is any one of vanadium pentoxide, chromium trioxide, manganese dioxide, niobium pentoxide, molybdenum trioxide, tantalum oxide, tungsten dioxide, rhenium heptaoxide and osmium tetroxide;
the second transition metal oxide is any one of ferric oxide, cobaltosic oxide, nickel oxide, copper oxide and zinc oxide;
the rare earth metal oxide is any one of lanthanum oxide, cerium oxide, scandium oxide and yttrium oxide;
the carrier oxide is any one of aluminum oxide, silicon dioxide, titanium dioxide and zirconium dioxide;
the preparation steps of the catalyst are as follows:
(1) Mixing alkaline earth metal oxide, first transition metal oxide and solvent A, and putting into a ball mill for ball milling for 0.5-4. 4h to obtain first slurry; the mass ratio of the total mass of the alkaline earth metal oxide and the first transition metal oxide to the solvent a is 1:0.3 to 0.5; the solvent A is any one of benzene, toluene and xylene;
(2) Mixing the second transition metal oxide with the solvent B, and putting the mixture into a ball mill for ball milling for 0.5-4. 4h to obtain second slurry; the mass ratio of the second transition metal oxide to the solvent B is 1:0.5 to 0.8; the solvent B is any one of ethanol, propanol, isopropanol, butanol and ethylene glycol;
(3) Mixing rare earth metal oxide, carrier oxide and solvent C, and putting into a ball mill for ball milling for 0.5-4. 4h to obtain third slurry; the mass ratio of the total weight of the rare earth metal oxide to the carrier oxide to the solvent C is 1:0.8 to 1.0; the solvent C is any one of nitric acid aqueous solution and acetic acid aqueous solution, and the mass concentration of nitric acid or acetic acid in the solvent C is 0.5% -5.0%;
(4) The first sizing agent, the second sizing agent and the third sizing agent are put into a kneader, dispersing agents accounting for 0.2 to 2.0 percent of the total mass of the three sizing agents are added, and the materials are fully kneaded for 0.5 to 2h, so as to obtain a 3D printing material;
(5) 3D printing materials are put into a charging barrel of a 3D gel printer, the shape of a product to be printed is led into a computer control system for printing, the diameter of a nozzle selected for printing is 0.1-1.0 mm, the viscosity of slurry passing through the nozzle is 14-32 Pa s, the printing layer height is 0.08-0.80 mm, and the extrusion rate is 50-200 mm 3 Every min, the printing speed is 5-10 mm/s, and when one layer of printing is finished, a spraying device sprays a layer of mist initiator and curing agent on the printing surface to realize printing and curing simultaneously; and (3) drying the printed blank in vacuum at 30-50 ℃ for 8-24 h, degreasing the dried blank at 150-400 ℃ for 2-10 h in nitrogen atmosphere, sintering at 150-400 ℃ in air atmosphere for 1-6 h, and cooling to obtain the high-entropy oxide catalyst.
2. The high entropy oxide catalyst for VOCs removal according to claim 1, characterized in that: the dispersing agent is any one of oleic acid, lauric acid, citric acid, malic acid and gallic acid.
3. The high entropy oxide catalyst for VOCs removal according to claim 1, characterized in that: the particle sizes of the first slurry, the second slurry and the third slurry are all smaller than 300 mu m.
4. The high entropy oxide catalyst for VOCs removal according to claim 1, characterized in that: the initiator is any one of benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyvalerate, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.
5. The high entropy oxide catalyst for VOCs removal according to claim 1, characterized in that: the curing agent is any one of vinyl triamine, diaminocyclohexane, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, diethylaminopropylamine, trimethylhexamethylenediamine, dihexyltriamine, hexamethylenediamine, trimethylhexamethylenediamine and diethylamine.
6. The high entropy oxide catalyst for VOCs removal according to claim 1, characterized in that: the specific surface area of the catalyst is 100-400 m 2 Per gram, pore volume of 0.3-0.8 m 3 And/g, the pore diameter is 3-20 nm.
7. Use of the high entropy oxide catalyst according to any one of claims 1 to 6 for the removal of VOCs.
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CN101204654A (en) * 2006-12-20 2008-06-25 中国科学院生态环境研究中心 Supported noble metal catalyst for low-temperature catalytic oxidation benzene series and preparation method thereof
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