CN112871148A - Preparation method of zirconium dioxide carrier for noble metal catalyst - Google Patents
Preparation method of zirconium dioxide carrier for noble metal catalyst Download PDFInfo
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 34
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 title claims abstract description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002244 precipitate Substances 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 19
- 238000010992 reflux Methods 0.000 claims abstract description 17
- 238000009718 spray deposition Methods 0.000 claims abstract description 17
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007921 spray Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 11
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000013049 sediment Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003754 zirconium Chemical class 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
Abstract
The invention discloses a preparation method of a zirconium dioxide carrier for a noble metal catalyst, which comprises the following steps: adding zirconium chloride into glycerol, performing ultrasonic dispersion, and standing in a reaction kettle to obtain a turbid liquid; slowly introducing the ammonia gas mixture into the turbid liquid until the pressure reaches 0.2-0.3MPa, then performing circulating reflux reaction, and slowly releasing pressure to obtain a second turbid liquid; and finally, filtering the second suspension to obtain a white precipitate, washing and filtering the white precipitate for a plurality of times by adopting absolute ethyl alcohol, adding the precipitate into the absolute ethyl alcohol, performing ultrasonic treatment, and performing constant-temperature spray deposition to obtain the nano-grade zirconium dioxide carrier. The method of the invention can form a synergistic promotion effect with noble metal due to the characteristics of the nano material, especially the surface hydroxyl, and increase the reactive sites on the surface.
Description
Technical Field
The invention belongs to the technical field of precious metal catalytic carrier preparation, and particularly relates to a preparation method of a zirconium dioxide carrier for a precious metal catalyst.
Background
Zirconium dioxide is a white odorless and tasteless crystal under the normal condition, is insoluble in water, hydrochloric acid and dilute sulfuric acid, is inactive in chemical property, has the properties of high melting point, high hardness, high strength, high toughness, extremely high wear resistance and chemical corrosion resistance, is a monoclinic system at low temperature, forms a tetragonal crystal form at the temperature of more than 1100 ℃, and forms a cubic crystal form at the temperature of more than 2300 ℃.
CN1195037A discloses zirconium dioxide with at least 80% monoclinic phase, which is prepared by mixing a zirconium salt aqueous solution with ammonia water, then aging and precipitating a product at a certain temperature, and roasting at a lower temperature of 200-600 ℃. However, the zirconium dioxide prepared by this process has a surface area of only 113m2The/g is not favorable for the exposure of active sites and the dispersion of active noble metal components.
CN1267568A discloses a method for preparing large-specific-surface and ultra-fine ZrO by a boiling method2The method comprises the steps of stewing zirconium hydroxide hydrogel for 5-100 hours at the rotating speed of 100-500 rpm and under the conditions of 60-150 ℃ and 0.1-0.5 MPa, drying and roasting to obtain the zirconium dioxide with the specific surface area of 200-450 m2(iii) a particle size of 5.0 to 9.4nm per gram. However, ZrO produced by the process2Only for gas phase catalytic reactions.
CN103379958A discloses a preparation method of sulfate ion-containing zirconium dioxide carrier with high specific surface area, large pores and small particle size by a hydrothermal method, which comprises the steps of contacting a soluble zirconium salt solution with an alkali solution to make the pH value to be 1.2-13.5, generating a zirconium hydrous oxide, carrying out hydrothermal treatment at 50-200 ℃ for 0.5-20 hours, filtering and washing until the pH value of a filtrate is 7 and the filtrate does not contain Cl-Then drying, dipping by using aqueous solution of sulfuric acid or ammonium sulfate with the concentration of 0.1-3.0 mol/L, and then drying to obtain the zirconium dioxide carrier containing sulfate ions, wherein the specific surface area of the zirconium dioxide carrier is 120-250 m2The pore diameter is 4.5-11.0 nm, and the pore volume is more than or equal to 70%.
Disclosure of Invention
The invention aims to provide a preparation method of a zirconium dioxide carrier for a noble metal catalyst, wherein the zirconium dioxide carrier can form a synergistic promotion effect with a noble metal to increase the reactive sites on the surface.
The technical scheme adopted by the invention is that the preparation method of the zirconium dioxide carrier for the noble metal catalyst is implemented according to the following steps:
step 1, adding zirconium chloride into glycerol, performing ultrasonic dispersion, and standing in a reaction kettle to obtain a turbid liquid;
step 2, slowly introducing the ammonia gas mixture into the turbid liquid until the pressure reaches 0.2-0.3MPa, then performing circulating reflux reaction, and slowly releasing pressure to obtain a second turbid liquid;
and 3, filtering the second suspension to obtain a white precipitate, washing and filtering the white precipitate for a plurality of times by adopting absolute ethyl alcohol, adding the precipitate into the absolute ethyl alcohol, performing ultrasonic treatment, and performing constant-temperature spray deposition to obtain the nano-grade zirconium dioxide carrier.
The present invention is also characterized in that,
in the step 1, the mass concentration of zirconium chloride in glycerol is 70-100 g/L; the ultrasonic dispersion time is 20-50min, the ultrasonic dispersion frequency is 80-100kHz, and the ultrasonic dispersion temperature is 20-50 ℃; standing for 2-5 h.
In the step 1, the reaction kettle is filled with mixed gas of water vapor and nitrogen, the volume of the water vapor accounts for 10-30%, the standing pressure is 0.1-0.2MPa, and the temperature is 30-60 ℃.
In the step 2, the ammonia gas mixture is a mixed gas of ammonia gas and nitrogen gas, wherein the volume of the ammonia gas accounts for 10-20%, and the feeding speed of the ammonia gas mixture is 8-12 mL/min.
In the step 2, the circulation speed of the circulation reflux reaction is 5-10mL/min, the reaction time is 20-30min, the reaction temperature is 20-30 ℃, the temperature for slow pressure relief is 60-70 ℃, and the pressure relief speed is 0.01-0.02 MPa/min;
in the step 3, the concentration of the white precipitate in the washing process in the absolute ethyl alcohol is 10-20g/L, and the washing temperature is 40-50 ℃.
In the step 3, the concentration of the sediment in the absolute ethyl alcohol in the ultrasonic treatment is 80-150g/L, the ultrasonic temperature is 50-60 ℃, and the ultrasonic frequency is 50-100 kHz; the ultrasonic treatment time is 10-20 min.
In the step 3, the temperature of constant-temperature spray deposition is 200-2。
The invention has the beneficial effects that: the invention utilizes the in-situ hydrolysis method to form stable positioning hydrolysis effect, achieves the dispersibility, even achieves the nanocrystallization and increases the reactive sites on the surface.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments.
The invention relates to a preparation method of a zirconium dioxide carrier for a noble metal catalyst, which is implemented according to the following steps:
step 1, adding zirconium chloride into glycerol, performing ultrasonic dispersion, and standing in a reaction kettle to obtain a turbid liquid;
the mass concentration of zirconium chloride in glycerol is 70-100 g/L;
the ultrasonic dispersion time is 20-50min, the ultrasonic dispersion frequency is 80-100kHz, and the ultrasonic dispersion temperature is 20-50 ℃; standing for 2-5 h;
the reaction kettle is filled with mixed gas of water vapor and nitrogen, the volume of the water vapor accounts for 10-30%, the pressure of standing is 0.1-0.2MPa, and the temperature is 30-60 ℃;
step 2, slowly introducing the ammonia gas mixture into the turbid liquid until the pressure reaches 0.2-0.3MPa, then performing circulating reflux reaction, and slowly releasing pressure to obtain a second turbid liquid;
the ammonia gas mixture is a mixed gas of ammonia gas and nitrogen gas, wherein the volume of the ammonia gas accounts for 10-20%, and the introduction speed of the ammonia gas mixture is 8-12 mL/min; the circulation speed of the circulation reflux reaction is 5-10mL/min, the reaction time is 20-30min, the reaction temperature is 20-30 ℃, the temperature for slow pressure relief is 60-70 ℃, and the pressure relief speed is 0.01-0.02 MPa/min;
step 3, filtering the second suspension to obtain a white precipitate, washing and filtering the white precipitate for a plurality of times by adopting absolute ethyl alcohol, then adding the precipitate into the absolute ethyl alcohol, carrying out ultrasonic treatment for 10-20min, and carrying out constant-temperature spray deposition to obtain a nano-grade zirconium dioxide carrier;
the concentration of the white precipitate in the washing process in absolute ethyl alcohol is 10-20g/L, and the washing temperature is 40-50 ℃;
the concentration of the sediment in the absolute ethyl alcohol in the ultrasonic treatment is 80-150g/L, the ultrasonic temperature is 50-60 ℃, and the ultrasonic frequency is 50-100 kHz;
the temperature of constant-temperature spray deposition is 200-250 ℃, the spray amount is 10-20mL/min, and the spray area is 20-40cm2。
Example 1
The invention relates to a preparation method of a zirconium dioxide carrier for a noble metal catalyst, which is implemented according to the following steps:
step 1, adding zirconium chloride into glycerol, performing ultrasonic dispersion, and standing in a reaction kettle to obtain a turbid liquid;
the mass concentration of zirconium chloride in glycerol is 70 g/L;
the ultrasonic dispersion time is 20min, the ultrasonic dispersion frequency is 80kHz, and the ultrasonic dispersion temperature is 20 ℃; standing for 2 h;
the reaction kettle is filled with mixed gas of water vapor and nitrogen, the volume of the water vapor accounts for 10 percent, the standing pressure is 0.1MPa, and the temperature is 30 ℃;
step 2, slowly introducing the ammonia gas mixture into the turbid liquid until the pressure reaches 0.2MPa, then performing circulating reflux reaction, and slowly releasing pressure to obtain a second turbid liquid;
the ammonia gas mixture is a mixture of ammonia gas and nitrogen gas, wherein the volume of the ammonia gas accounts for 10%, and the introduction speed of the ammonia gas mixture is 8 mL/min; the circulation speed of the circulation reflux reaction is 5mL/min, the reaction time is 20min, the reaction temperature is 20 ℃, the temperature for slow pressure relief is 60 ℃, and the pressure relief speed is 0.01 MPa/min;
step 3, filtering the second suspension to obtain a white precipitate, washing and filtering the white precipitate for a plurality of times by adopting absolute ethyl alcohol, then adding the precipitate into the absolute ethyl alcohol, carrying out ultrasonic treatment for 10min, and carrying out constant-temperature spray deposition to obtain a nano-grade zirconium dioxide carrier;
the concentration of the white precipitate in the washing process in absolute ethyl alcohol is 10g/L, and the washing temperature is 40 ℃;
the concentration of the sediment in the absolute ethyl alcohol in the ultrasonic treatment is 80g/L, the ultrasonic temperature is 50 ℃, and the ultrasonic frequency is 50 kHz;
the constant temperature spray deposition temperature is 200 deg.C, spray amount is 10mL/min, and spray area is 20cm2。
Example 2
The invention relates to a preparation method of a zirconium dioxide carrier for a noble metal catalyst, which is implemented according to the following steps:
step 1, adding zirconium chloride into glycerol, performing ultrasonic dispersion, and standing in a reaction kettle to obtain a turbid liquid;
the mass concentration of zirconium chloride in glycerol is 80 g/L;
the ultrasonic dispersion time is 30min, the ultrasonic dispersion frequency is 85kHz, and the ultrasonic dispersion temperature is 25 ℃; standing for 2.5 h;
the reaction kettle is filled with mixed gas of water vapor and nitrogen, the volume occupancy of the water vapor is 15%, the standing pressure is 0.1MPa, and the temperature is 40 ℃;
step 2, slowly introducing the ammonia gas mixture into the turbid liquid until the pressure reaches 0.25MPa, then performing circulating reflux reaction, and slowly releasing pressure to obtain a second turbid liquid;
the ammonia gas mixture is a mixture of ammonia gas and nitrogen gas, wherein the volume of the ammonia gas accounts for 12%, and the introduction speed of the ammonia gas mixture is 9 mL/min; the circulation speed of the circulation reflux reaction is 6mL/min, the reaction time is 25min, the reaction temperature is 20 ℃, the temperature for slow pressure relief is 70 ℃, and the pressure relief speed is 0.01 MPa/min;
step 3, filtering the second suspension to obtain a white precipitate, washing and filtering the white precipitate for a plurality of times by adopting absolute ethyl alcohol, adding the precipitate into the absolute ethyl alcohol, carrying out ultrasonic treatment for 15min, and carrying out constant-temperature spray deposition to obtain a nano-grade zirconium dioxide carrier;
the concentration of the white precipitate in the washing process in absolute ethyl alcohol is 15g/L, and the washing temperature is 45 ℃;
the concentration of the sediment in the absolute ethyl alcohol in the ultrasonic treatment is 90g/L, the ultrasonic temperature is 55 ℃, and the ultrasonic frequency is 60 kHz;
the constant temperature spray deposition temperature is 210 deg.C, spray amount is 15mL/min, and spray area is 25cm2。
Example 3
The invention relates to a preparation method of a zirconium dioxide carrier for a noble metal catalyst, which is implemented according to the following steps:
step 1, adding zirconium chloride into glycerol, performing ultrasonic dispersion, and standing in a reaction kettle to obtain a turbid liquid;
the mass concentration of zirconium chloride in glycerol is 90 g/L;
the ultrasonic dispersion time is 40min, the ultrasonic dispersion frequency is 95kHz, and the ultrasonic dispersion temperature is 35 ℃; standing for 4 h;
the reaction kettle is filled with mixed gas of water vapor and nitrogen, the volume of the water vapor accounts for 20%, the standing pressure is 0.2MPa, and the temperature is 50 ℃;
step 2, slowly introducing the ammonia gas mixture into the turbid liquid until the pressure reaches 0.2MPa, then performing circulating reflux reaction, and slowly releasing pressure to obtain a second turbid liquid;
the ammonia gas mixture is a mixture of ammonia gas and nitrogen gas, wherein the volume of the ammonia gas accounts for 18%, and the introduction speed of the ammonia gas mixture is 11 mL/min; the circulation speed of the circulation reflux reaction is 8mL/min, the reaction time is 28min, the reaction temperature is 30 ℃, the temperature for slow pressure relief is 70 ℃, and the pressure relief speed is 0.02 MPa/min;
step 3, filtering the second suspension to obtain a white precipitate, washing and filtering the white precipitate for a plurality of times by adopting absolute ethyl alcohol, then adding the precipitate into the absolute ethyl alcohol, carrying out ultrasonic treatment for 20min, and carrying out constant-temperature spray deposition to obtain a nano-grade zirconium dioxide carrier;
the concentration of the white precipitate in the washing process in absolute ethyl alcohol is 18g/L, and the washing temperature is 45 ℃;
the concentration of the sediment in the absolute ethyl alcohol in the ultrasonic treatment is 100g/L, the ultrasonic temperature is 55 ℃, and the ultrasonic frequency is 80 kHz;
the constant temperature spray deposition temperature is 220 deg.C, spray amount is 15mL/min, and spray area is 30cm2。
Example 4
The invention relates to a preparation method of a zirconium dioxide carrier for a noble metal catalyst, which is implemented according to the following steps:
step 1, adding zirconium chloride into glycerol, performing ultrasonic dispersion, and standing in a reaction kettle to obtain a turbid liquid;
the mass concentration of zirconium chloride in glycerol is 90 g/L;
the ultrasonic dispersion time is 40min, the ultrasonic dispersion frequency is 80kHz, and the ultrasonic dispersion temperature is 45 ℃; standing for 4 h;
the reaction kettle is filled with mixed gas of water vapor and nitrogen, the volume occupancy of the water vapor is 30%, the standing pressure is 0.2MPa, and the temperature is 55 ℃;
step 2, slowly introducing the ammonia gas mixture into the turbid liquid until the pressure reaches 0.2MPa, then performing circulating reflux reaction, and slowly releasing pressure to obtain a second turbid liquid;
the ammonia gas mixture is a mixture of ammonia gas and nitrogen gas, wherein the volume of the ammonia gas accounts for 10%, and the introduction speed of the ammonia gas mixture is 12 mL/min; the circulation speed of the circulation reflux reaction is 10mL/min, the reaction time is 25min, the reaction temperature is 20 ℃, the temperature for slow pressure relief is 70 ℃, and the pressure relief speed is 0.02 MPa/min;
step 3, filtering the second suspension to obtain a white precipitate, washing and filtering the white precipitate for a plurality of times by adopting absolute ethyl alcohol, then adding the precipitate into the absolute ethyl alcohol, carrying out ultrasonic treatment for 10min, and carrying out constant-temperature spray deposition to obtain a nano-grade zirconium dioxide carrier;
the concentration of the white precipitate in the washing process in absolute ethyl alcohol is 18g/L, and the washing temperature is 48 ℃;
the concentration of the sediment in the absolute ethyl alcohol in the ultrasonic treatment is 130g/L, the ultrasonic temperature is 60 ℃, and the ultrasonic frequency is 95 kHz;
the constant temperature spray deposition temperature is 230 deg.C, spray amount is 20mL/min, and spray area is 48cm2。
Example 5
The invention relates to a preparation method of a zirconium dioxide carrier for a noble metal catalyst, which is implemented according to the following steps:
step 1, adding zirconium chloride into glycerol, performing ultrasonic dispersion, and standing in a reaction kettle to obtain a turbid liquid;
the mass concentration of zirconium chloride in glycerol is 100 g/L;
the ultrasonic dispersion time is 50min, the ultrasonic dispersion frequency is 100kHz, and the ultrasonic dispersion temperature is 50 ℃; standing for 5 h;
the reaction kettle is filled with mixed gas of water vapor and nitrogen, the volume occupancy of the water vapor is 30%, the standing pressure is 0.2MPa, and the temperature is 60 ℃;
step 2, slowly introducing the ammonia gas mixture into the turbid liquid until the pressure reaches 0.3MPa, then performing circulating reflux reaction, and slowly releasing pressure to obtain a second turbid liquid;
the ammonia gas mixture is a mixture of ammonia gas and nitrogen gas, wherein the volume of the ammonia gas accounts for 20%, and the introduction speed of the ammonia gas mixture is 12 mL/min; the circulation speed of the circulation reflux reaction is 10mL/min, the reaction time is 30min, the reaction temperature is 30 ℃, the temperature for slow pressure relief is 70 ℃, and the pressure relief speed is 0.02 MPa/min;
step 3, filtering the second suspension to obtain a white precipitate, washing and filtering the white precipitate for a plurality of times by adopting absolute ethyl alcohol, then adding the precipitate into the absolute ethyl alcohol, carrying out ultrasonic treatment for 20min, and carrying out constant-temperature spray deposition to obtain a nano-grade zirconium dioxide carrier;
the concentration of the white precipitate in the washing process in absolute ethyl alcohol is 20g/L, and the washing temperature is 50 ℃;
the concentration of the sediment in the absolute ethyl alcohol in the ultrasonic treatment is 150g/L, the ultrasonic temperature is 60 ℃, and the ultrasonic frequency is 100 kHz;
the constant temperature spray deposition temperature is 250 deg.C, spray amount is 10mL/min, and spray area is 40cm2。
According to the method, due to the characteristics of the nano material, particularly the surface hydroxyl, a synergistic promotion effect can be formed with the noble metal, and the reactive sites on the surface are increased; the photocatalysis of the noble metal is matched with the reflection characteristic of the zirconium dioxide to form an internal and external illumination system so as to form a stable inner layer photocatalysis system (the noble metal is coated on the surface of the zirconium dioxide); thermal conductivity, under the condition that reaction temperature constantly promotes, electric conductivity promotes along with the temperature rise to reach the effect that promotes the circulation of surface electron, further promote catalytic effect.
Claims (8)
1. A preparation method of a zirconium dioxide carrier for a noble metal catalyst is characterized by comprising the following steps:
step 1, adding zirconium chloride into glycerol, performing ultrasonic dispersion, and standing in a reaction kettle to obtain a turbid liquid;
step 2, slowly introducing the ammonia gas mixture into the turbid liquid until the pressure reaches 0.2-0.3MPa, then performing circulating reflux reaction, and slowly releasing pressure to obtain a second turbid liquid;
and 3, filtering the second suspension to obtain a white precipitate, washing and filtering the white precipitate for a plurality of times by adopting absolute ethyl alcohol, adding the precipitate into the absolute ethyl alcohol, performing ultrasonic treatment, and performing constant-temperature spray deposition to obtain the nano-grade zirconium dioxide carrier.
2. The method according to claim 1, wherein in step 1, the zirconium chloride is present in glycerol at a concentration of 70-100 g/L; the ultrasonic dispersion time is 20-50min, the ultrasonic dispersion frequency is 80-100kHz, and the ultrasonic dispersion temperature is 20-50 ℃; standing for 2-5 h.
3. The method of claim 1, wherein in the step 1, the reaction vessel is filled with a mixed gas of water vapor and nitrogen, the water vapor is 10 to 30% by volume, the reaction vessel is allowed to stand at a pressure of 0.1 to 0.2MPa and a temperature of 30 to 60 ℃.
4. The method according to claim 1, wherein in the step 2, the ammonia gas mixture is a mixture of ammonia gas and nitrogen gas, wherein the volume of the ammonia gas mixture is 10-20%, and the ammonia gas mixture is introduced at a rate of 8-12 mL/min.
5. The method of claim 1, wherein in the step 2, the circulation rate of the circulation reflux reaction is 5-10mL/min, the reaction time is 20-30min, the reaction temperature is 20-30 ℃, the temperature for slow pressure release is 60-70 ℃, and the pressure release rate is 0.01-0.02 MPa/min.
6. The method of claim 1, wherein the concentration of the white precipitate in the washing step in the absolute ethanol in the step 3 is 10-20g/L, and the washing temperature is 40-50 ℃.
7. The method for preparing a zirconia carrier for noble metal catalysts according to claim 1, wherein in the step 3, the concentration of the precipitates in the absolute ethanol in the ultrasonic treatment is 80 to 150g/L, the ultrasonic temperature is 50 to 60 ℃, and the ultrasonic frequency is 50 to 100 kHz; the ultrasonic treatment time is 10-20 min.
8. The method as claimed in claim 1, wherein the temperature of the isothermal spray deposition in step 3 is 200 ℃ to 250 ℃, the spray amount is 10-20mL/min, and the spray area is 20-40cm2。
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