CN107362796B - Noble metal loaded alpha-Al2O3Preparation method of powder catalytic material - Google Patents
Noble metal loaded alpha-Al2O3Preparation method of powder catalytic material Download PDFInfo
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- 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
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0081—Preparation by melting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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Abstract
The invention discloses a noble metal loaded alpha-Al2O3The preparation method of the powder catalytic material obtains the noble metal load type powder catalytic material through the processes of alloy preparation, low-temperature ball milling oxidation, high-temperature oxidation reaction, dealloying corrosion and the like, the noble metal precipitated phase is combined with a matrix, the noble metal precipitated phase is metallurgical combination, the noble metal precipitated phase is not easy to fall off in the use process, the size of noble metal particles is controllable, the noble metal particles cannot grow along with the increase of the temperature in the use process, meanwhile, the preparation of the noble metal particles and the preparation of a carrier are combined into a whole, the process flow is shortened, the preparation method has the characteristics of low cost and short flow of the material preparation technology, and the preparation method can be used in the fields of materials such as photocatalysis, ethylene catalysis to ethylene oxide, propylene catalysis to propylene oxide.
Description
Technical Field
The invention relates to a noble metal loaded alpha-Al2O3A preparation method of a powder catalytic material belongs to the technical field of catalytic materials.
Background
Precious metal materials are known as vitamins in modern industry due to their excellent physicochemical properties as determined by their chemical stability and electronic structure. Ag. The noble metal such as Pt and the alloy thereof have good plasticity and processing performance and good weldability for almost all materials, so that the noble metal can be compounded with most of metal and nonmetal materials to form a material with wide application.
The noble metals such as Pt and Ag have excellent catalytic activity, antibacterial activity, conductivity and heat exchange performance, and can be widely applied to catalytic materials, antibacterial materials, electrode materials, low-temperature heat conduction materials and the like. In order to reduce the consumption of precious metals and save material costs, precious metal particles are usually loaded on a certain carrier or solid surface, for exampleSuch as Al2O3、TiO2Or carbon nanotube surfaces, etc.
The preparation of metal oxide supported noble metal catalyst generally adopts the method of impregnating solution in the existing carrier Al2O3The method is characterized in that the solution is a precursor prepared from one or more active components, namely noble metal salt and an auxiliary agent solution, the carrier is soaked in the solution, and then the carrier is prepared by the steps of chemical reduction or pyrolysis, washing, drying and the like. In the impregnation method, the noble metal precursor is mostly reduced by pyrolysis, i.e. noble metal salt is directly reduced into noble metal nano simple substance by high temperature. The reduction method has simple process and good reduction effect, but the phenomena of concentration, crystallization, noble metal particle migration, recrystallization, agglomeration and the like of noble metal salt inevitably exist in the high-temperature decomposition process, and the dispersion degree of noble metal particles on a carrier and the size of noble metal grains are influenced, so that the performance of the catalyst is influenced.
In order to reduce the thermal decomposition temperature of the precursor, a chemical reducing agent is introduced in the reduction step, a high-temperature process is avoided, the chemical reducing agent is used for reducing the noble metal salt precursor, residual organic matters are removed by washing with water or low-carbon alcohol after heating reduction, and a noble metal ammonium complex formed by the reducing agent such as low-carbon carboxylic acid amide and the like and the noble metal can be decomposed and reduced into a noble metal simple substance below 200 ℃, so that the heat treatment temperature is greatly reduced, and the problems of uncontrollable particle size and the like caused by agglomeration and growth of the noble metal are solved. But the disadvantages brought by the method are the pollution of organic chemical reagents, poor binding strength between the noble metal and the carrier due to low-temperature sintering, easy falling off in the using process and the like.
In the catalytic materials supported by noble metals used at present, on one hand, the size and morphology of the phases need to be controlled in order to improve the activity of the noble metals and prevent agglomeration. On the other hand, the bonding strength between the noble metal and the load body needs to be improved to prevent the noble metal from falling off in use.
Disclosure of Invention
The invention enables the formation of noble metal particles to be controllable through the structural design of the carrier metal oxide, and the noble metal particles and the matrix Al are in contact with each other2O3Metallurgy ofIn combination, the catalyst does not fall off and grow in the using process, and simultaneously the preparation of the noble metal particles and the preparation of the carrier are combined into a whole, so that the process flow is shortened, and the development trend of low-cost short flow and environment-friendly material preparation technology is reflected.
The invention aims to provide a noble metal loaded alpha-Al2O3The preparation method of the powder catalytic material can prepare the catalytic material with the noble metal particles loaded by the metal oxide with uniform surface distribution, firm combination and controllable noble metal particles.
The technological scheme of the present invention is that Al and noble metal are mixed in certain proportion, the mixture is smelted, atomized and sprayed, the sprayed powder is sieved and ball milled at low temperature, and through oxidation reaction at certain temperature, noble metal is separated from alloy and Al is changed into alpha-Al2O3And removing the surface oxide film through acid corrosion to obtain the metal oxide loaded noble metal powder composite material.
Noble metal loaded alpha-Al2O3The preparation method of the powder catalytic material comprises the following specific preparation steps:
(1) mixing Al and noble metal in proportion, putting the mixture into a vacuum smelting furnace of a high-pressure atomization powder making device, preserving the heat of the Al and the noble metal at 600-800 ℃ for 0.5-1 h, and then atomizing and spraying powder by argon gas, wherein the granularity of the obtained powder is less than or equal to 50 um;
(2) performing ball milling on the atomized powder obtained in the step (1) for two times, wherein the particle size of the powder after ball milling is less than or equal to 10 um;
(3) performing high-temperature oxidation reaction on the powder subjected to ball milling in the step (2), precipitating noble metal from the interior of the alloy, and oxidizing metal Al to generate alpha-Al2O3Then cooling along with the furnace;
(4) performing acid corrosion on the product obtained in the step (3), performing an alloying post-treatment process to remove a surface oxidation film and internal unoxidized alloy, namely placing the product in hydrochloric acid with the concentration of 0.1-0.6 mol/L for 5-30 min, washing with water, and drying at 100-200 ℃ for 1-2 h to obtain the noble metal loaded alpha-Al2O3A powder catalytic material.
The noble metal in the step (1) is Ag or Pt, and the purity of the noble metal and Al is more than 99.9%.
After the noble metal in the step (1) is mixed with Al, the noble metal accounts for 5-20% of the mixture by mass percent.
The specific process of the two ball milling in the step (2) is a first ball milling: ball milling at-10 to-50 ℃ under the protection of argon gas for 1h, wherein the ratio of large balls to small balls is 1: 5, the diameter of the large balls is 5mm, the diameter of the small balls is 2mm, and the rotation speed is 200 r/min; ball milling for the second time: ball milling is carried out at the temperature of-10 ℃ to-50 ℃ in an air atmosphere, the ratio of large balls to small balls in the ball milling tank is 2: 1, the diameter of the large balls is 5mm, the diameter of the small balls is 2mm, the ratio of ball materials is 5-20: 1, the rotating speed is 400-600 r/min, ball milling is carried out for 5-10 h, and the ball milling tank is opened every other hour during ball milling to allow air to enter.
And (3) adopting a liquid nitrogen cooling ball mill as a ball mill for ball milling, adopting a ball milling tank with a WC (wolfram carbide) lining and an agate milling ball, opening the ball milling tank in a vacuum glove box, and opening the ball milling tank when the pressure in the glove box is less than the external atmospheric pressure, wherein the ball mills adopted for the two ball milling processes are the same.
And (3) carrying out the high-temperature oxidation reaction in an oxygen atmosphere, wherein the oxygen flow is 100-500 mL/min, the temperature is increased to 300-500 ℃ at the temperature increase rate of 5 ℃/min, and the temperature is kept for 0.5-2 h.
The high pressure atomization powder making apparatus is commercially available.
Compared with the prior art, the invention has the following advantages;
(1) the process flow is simple, and the repeatable operability is high.
(2) The noble metal particles are metallurgically bonded to the carrier and can be effectively fixed to the carrier.
(3) The specific surface area can be regulated and controlled through acid corrosion and temperature control, and the performance of the catalytic material is further improved.
Drawings
FIG. 1 shows that the noble metal of the present invention supports alpha-Al2O3The flow diagram of the preparation method of the powder catalytic material is shown;
FIG. 2 shows a noble metal-supported α -Al alloy prepared in example 1 of the present invention2O3Powder catalystChanging a material XRD spectrum;
FIG. 3 shows a noble metal-supported α -Al alloy prepared in example 1 of the present invention2O3SEM picture a of powder catalytic material;
FIG. 4 shows a noble metal-supported α -Al prepared in example 1 of the present invention2O3SEM picture b of the powder catalytic material;
FIG. 5 shows a noble metal-supported α -Al prepared in example 2 of the present invention2O3O of powder catalytic material2-a TPD spectrum;
FIG. 6 shows a noble metal-supported α -Al prepared in example 2 of the present invention2O3The ethylene epoxidation performance effect diagram of the powder catalytic material is (a) the outlet concentration of ethylene oxide, (b) the selectivity, and (c) the conversion rate.
Detailed Description
The invention is further illustrated with reference to the following figures and specific examples, which should not be construed as limiting the scope of the invention.
Example 1
The noble Metal of this example supported alpha-Al2O3The preparation method of the powder catalytic material is shown in figure 1 and comprises the following specific preparation steps:
(1) mixing Ag with the purity of more than 99.9% and metal Al with the purity of more than 99.9%, wherein the mass percent of Ag in the mixture is 20wt%, the mass percent of aluminum in the mixture is 80wt%, putting the mixture into a vacuum smelting furnace of a high-pressure atomization powder preparation device, smelting at 600 ℃ for 0.5h to fully melt the noble metal Ag and Al, spraying powder by adopting an argon gas atomization mode, wherein the atomization pressure is 3.5MPa, and the powder granularity of the obtained product after screening is less than or equal to 50 um;
(2) ball-milling the atomized powder obtained in the step (1) in a low-temperature argon protective atmosphere, wherein the ball-milling temperature is-40 ℃, the proportion of large balls to small balls is 1: 5, the diameter of the large balls is 5mm, the diameter of the small balls is 2mm, and the size of a ball-milling tank is as follows: 250mL, ball milling rotation speed of 200 r/min, ball milling for 1 h; then carrying out secondary ball milling at-30 ℃ in an air atmosphere, wherein the ratio of large balls to small balls in the tank is 2: 1, the diameter of the large balls is 5mm, the diameter of the small balls is 2mm, the ball-material ratio is 5: 1, the rotating speed is 400 rpm, the ball milling time is 5h, opening the ball milling tank every other hour to allow air to enter, sieving the powder after ball milling to ensure that the particle size of the powder is less than or equal to 10um, and adopting a liquid nitrogen cooled ball mill as a ball mill for the secondary ball milling, wherein the ball milling tank is a WC (wolfram carbide) lining with controllable atmosphere and agate milling balls;
(3) carrying out high-temperature oxidation reaction on the powder subjected to ball milling in the step (2), putting the product into a conventional heat treatment furnace, introducing industrial pure oxygen at a heating rate of 5 ℃/min, heating to 300 ℃, keeping the temperature for 2h, cooling along with the furnace, separating out the noble metal Ag from the interior of the alloy, and oxidizing the metal Al to generate alpha-Al2O3；
(4) Performing acid corrosion on the product obtained in the step (3), performing an alloying treatment process to remove a surface oxide film and internal unoxidized alloy, namely placing the product obtained in the step (3) in hydrochloric acid with the concentration of 0.5mol/L for 20min, pouring out corrosive liquid, cleaning a sample by using distilled water, and drying at 120 ℃ for 1h to obtain the Ag-loaded alpha-Al2O3A powder catalytic material.
The Ag prepared in this example supported alpha-Al2O3The specific surface area of the powder catalytic material is 1.95m2/g。
FIG. 2 shows that the noble metal-supported alpha-Al prepared in this example2O3The XRD pattern of the powder catalytic material shows that the phases in the powder are Ag and alpha-Al2O3(ii) a FIGS. 3 and 4 show that the alpha-Al prepared in this example2O3The SEM picture of the noble metal-supported catalytic material shows that the Ag particles are uniformly distributed throughout the material as shown in fig. 3, and that the Ag particles have a particle size of less than 300nm as shown in fig. 4.
Example 2
The noble Metal of this example supported alpha-Al2O3The preparation method of the powder catalytic material comprises the following specific preparation steps:
(1) mixing Ag with the purity of more than 99.9% and metal Al with the purity of more than 99.9%, wherein the mass percent of Ag in the mixture is 10wt%, the mass percent of aluminum in the mixture is 90wt%, putting the mixture into a vacuum smelting furnace of a high-pressure atomization powder preparation device, smelting at 700 ℃ for 0.6h to fully melt Ag and Al, spraying powder by adopting an argon gas atomization mode, wherein the atomization pressure is 3.5MPa, and the powder granularity of the obtained product after screening is less than or equal to 50 um;
(2) ball-milling the atomized powder obtained in the step (1) in a low-temperature argon protective atmosphere, wherein the ball-milling temperature is-50 ℃, the proportion of large balls to small balls is 1: 5, the diameter of the large balls is 5mm, the diameter of the small balls is 2mm, and the size of a ball-milling tank is as follows: 250mL, ball milling rotation speed of 200 r/min, ball milling for 1 h; then adjusting the temperature to-10 ℃ and carrying out ball milling in the air atmosphere, wherein the ratio of large balls to small balls in the tank is 2: 1, the diameter of the large balls is 5mm, the diameter of the small balls is 2mm, the ratio of ball to material is 5: 1, the rotating speed is 500 rpm, the ball milling time is 10h, the ball milling tank is opened every other hour to allow air to enter, the powder after ball milling is sieved, the particle size of the powder is less than or equal to 10um, the ball milling machine adopted in the two ball milling processes is a liquid nitrogen cooling ball milling machine, the ball milling tank is a WC (wolfram carbide) lining with controllable atmosphere, and aga;
(3) carrying out high-temperature oxidation reaction on the powder subjected to ball milling in the step (2), putting the product into a conventional heat treatment furnace, introducing industrial pure oxygen at a heating rate of 5 ℃/min, heating to 400 ℃, keeping the temperature for 1h, cooling along with the furnace, separating out the noble metal Ag from the interior of the alloy, and oxidizing the metal Al to generate alpha-Al2O3；
(4) Performing acid corrosion on the product obtained in the step (3), performing an alloying treatment process to remove a surface oxide film and internal unoxidized alloy, namely placing the product obtained in the step (3) in hydrochloric acid with the concentration of 0.1mol/L for 30min, pouring out corrosive liquid, cleaning a sample by using distilled water, and drying at 150 ℃ for 1.5h to obtain the Ag-loaded alpha-Al2O3A powder catalytic material.
The Ag obtained in this example supported alpha-Al2O3The Ag size in the noble metal of the powder catalytic material is 20-100nm, and the specific surface area of the catalytic material is 2.25m2/g。
FIG. 5 shows α -Al prepared in this example2O3Loaded Ag catalytic material O2TPD spectrum, EO (ethylene oxide) preparation by catalytic ethylene epoxidation over a supported catalyst, O and AgThe surface interaction was initially studied as a focus, and one of the most important studies was O2Temperature programmed desorption (O)2-TPD）(O2temperatureprogrammed desorption O2TPD), experiments are commonly used for researching the adsorption and desorption performance of the catalyst on oxygen, the experiments have practical significance for knowing the oxygen species adsorbed on the surface of the catalyst, the strength between Ag and O bonds is an important factor for measuring the selectivity of the catalyst and is a key for the catalyst to exert the catalytic effect, the stronger the valence between the Ag and O bonds is, the weaker the catalytic selectivity is, and on the contrary, the stronger the selectivity is, and the oxygen species corresponding to the oxygen peaks desorbed at 220 ℃ and 315 ℃ are related to the epoxidation of ethylene.
FIG. 6 shows the Ag-supported alpha-Al prepared in this example2O3An ethylene epoxidation performance test of the powder catalytic material is carried out in a fixed bed microreactor under the reaction conditions (the volume ratio of ethylene to oxygen to carbon dioxide to nitrogen is 15:7:5: 73), wherein (a) is shown as EO outlet concentration, (b) is selectivity, and (c) is conversion rate, the material has a catalytic effect on EO on the whole, in a high-temperature reaction stage (290-330 ℃), the EO outlet concentration of a sample is increased along with the temperature rise, which shows that the activity is gradually increased along with the increase of the reaction temperature, 330 ℃ reaches the highest value, and the EO selectivity is reduced, as shown in (b) of FIG. 6, because the temperature rise, CO is adopted2The result is generated. The temperature increased and the ethylene conversion increased, as shown in figure 6 (c), and the conversion was close to 17% at a selectivity of 75% at 240 c in this experiment.
Example 3
The noble Metal of this example supported alpha-Al2O3The preparation method of the powder catalytic material comprises the following specific preparation steps:
(1) mixing Pt with the purity of more than 99.9 percent and metal Al with the purity of more than 99.9 percent, wherein the mass percent of Pt in the mixture is 10wt percent, the mass percent of aluminum in the mixture is 90wt percent, putting the mixture into a vacuum smelting furnace of a high-pressure atomization powder preparation device, smelting at the temperature of 800 ℃ for 1h to fully melt the noble metal Pt and Al, spraying powder by adopting an argon gas atomization mode, wherein the atomization pressure is 3.5MPa, and the granularity of the powder after sieving the obtained product is less than or equal to 50 um;
(2) ball-milling the atomized powder obtained in the step (1) in a low-temperature argon protective atmosphere, wherein the ball-milling temperature is-20 ℃, the proportion of large balls to small balls is 1: 5, the diameter of the large balls is 5mm, the diameter of the small balls is 2mm, and the size of a ball-milling tank is as follows: 250mL, ball milling rotation speed of 200 r/min, ball milling for 1 h; cooling to-50 ℃ and carrying out ball milling in air atmosphere, wherein the ratio of large balls to small balls in the tank is 2: 1, the diameter of large balls is 5mm, the diameter of small balls is 2mm, the ball-material ratio is 10: 1, the rotating speed is 500 rpm, the ball milling time is 8h, opening the ball milling tank every other hour to allow air to enter, screening the powder after ball milling to ensure that the particle size of the powder is less than or equal to 10um, and adopting a liquid nitrogen cooled ball mill as a ball mill for two ball milling, wherein the ball milling tank is a WC (wolfram carbide) lining with controllable atmosphere and agate milling balls;
(3) carrying out high-temperature oxidation reaction on the powder subjected to ball milling in the step (2), putting the product into a conventional heat treatment furnace, introducing industrial pure oxygen at a heating rate of 5 ℃/min, heating to 400 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 1.5h, cooling along with the furnace, separating out the noble metal Pt from the interior of the alloy, and oxidizing the metal Al to generate alpha-Al2O3；
(4) Performing acid corrosion on the product obtained in the step (3), performing an alloying treatment process to remove a surface oxide film and internal unoxidized alloy, namely placing the product obtained in the step (3) in hydrochloric acid with the concentration of 0.5mol/L for 20min, pouring out corrosive liquid, cleaning a sample by using distilled water, and drying at 100 ℃ for 2h to obtain Pt-loaded alpha-Al2O3A powder catalytic material.
Pt-loaded alpha-Al obtained in this example2O3The size of the noble metal Pt in the powder catalytic material is 50-150nm, and the specific surface area of the catalytic material is 2.14m2/g。
Example 4
The noble Metal of this example supported alpha-Al2O3The preparation method of the powder catalytic material comprises the following specific preparation steps:
(1) mixing Pt with the purity of more than 99.9 percent and metal Al with the purity of more than 99.9 percent, wherein the mass percent of Pt in the mixture is 5wt percent, the mass percent of Al in the mixture is 95wt percent, putting the mixture into a vacuum smelting furnace of a high-pressure atomization powder preparation device, smelting at the temperature of 700 ℃ for 1h to fully melt the noble metal Pt and Al, spraying powder by adopting an argon gas atomization mode, wherein the atomization pressure is 3.5MPa, and the granularity of the powder after sieving the obtained product is less than or equal to 50 um;
(2) ball-milling the atomized powder obtained in the step (1) in a low-temperature argon protective atmosphere, wherein the ball-milling temperature is-10 ℃, the proportion of large balls to small balls is 1: 5, the diameter of the large balls is 5mm, the diameter of the small balls is 2mm, and the size of a ball-milling tank is as follows: 250mL, ball milling rotation speed of 200 r/min, ball milling for 1 h; cooling to-40 ℃ and carrying out ball milling in air atmosphere, wherein the ratio of large balls to small balls in the tank is 2: 1, the diameter of large balls is 5mm, the diameter of small balls is 2mm, the ball-material ratio is 20: 1, the rotating speed is 600 rpm, the ball milling time is 8h, opening the ball milling tank every other hour to allow air to enter, sieving the powder after ball milling to ensure that the particle size of the powder is less than or equal to 10um, and adopting a liquid nitrogen cooled ball mill as a ball mill for two ball milling, wherein the ball milling tank is a WC (wolfram carbide) lining with controllable atmosphere and agate milling balls;
(3) performing high-temperature oxidation reaction on the powder subjected to ball milling in the step (2), putting the product into a conventional heat treatment furnace, introducing industrial pure oxygen at a rate of 500mL/min, heating to 500 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 0.5h, cooling along with the furnace, separating out the noble metal Pt from the interior of the alloy, and oxidizing the metal Al to generate alpha-Al2O3；
(4) Performing acid corrosion on the product obtained in the step (3), performing an alloying treatment process to remove a surface oxide film and internal unoxidized alloy, namely placing the product obtained in the step (3) in hydrochloric acid with the concentration of 0.6mol/L for 5min, pouring out corrosive liquid, cleaning a sample by using distilled water, and drying at 200 ℃ for 1h to obtain Pt-loaded alpha-Al2O3A powder catalytic material.
Pt-loaded alpha-Al obtained in this example2O3The size of the noble metal Pt in the powder catalytic material is 50-100nm, and the specific surface area of the catalytic material is 1.88m2/g。
Claims (3)
1. Noble metal loaded alpha-Al2O3Preparation method of powder catalytic materialThe method is characterized by comprising the following specific steps:
(1) mixing Al and noble metal in proportion, preserving heat for 0.5-1 h at 600-800 ℃, then atomizing and spraying argon gas to obtain powder with the particle size of less than or equal to 50 mu m; the noble metal is Ag or Pt, and the purity of the noble metal and Al is more than 99.9%;
(2) performing ball milling on the atomized powder obtained in the step (1) for two times, wherein the particle size of the powder after ball milling is less than or equal to 10 microns; the specific process of the two ball milling processes is as follows: ball milling at-10 to-50 ℃ under the protection of argon gas for 1h, wherein the ratio of large balls to small balls is 1: 5, the diameter of the large balls is 5mm, the diameter of the small balls is 2mm, and the rotation speed is 200 r/min; ball milling for the second time: ball milling is carried out at the temperature of-10 ℃ to-50 ℃ in the air atmosphere, the ratio of large balls to small balls in the ball milling tank is 2: 1, the diameter of the large balls is 5mm, the diameter of the small balls is 2mm, the ratio of ball materials is 5-20: 1, the rotating speed is 400-600 r/min, the ball milling is carried out for 5-10 h, and the ball milling tank is opened every other hour during ball milling to allow air to enter;
(3) carrying out high-temperature oxidation reaction on the powder subjected to ball milling in the step (2), wherein the high-temperature oxidation reaction is carried out in an oxygen atmosphere, the oxygen flow is 100-500 mL/min, the temperature is increased to 300-500 ℃ at the temperature increase rate of 5 ℃/min, the temperature is kept for 0.5-2 h, and then the powder is cooled along with a furnace;
(4) performing acid corrosion on the product obtained in the step (3), namely placing the product in hydrochloric acid with the concentration of 0.1-0.6 mol/L for corrosion for 5-30 min, washing with water, and drying at 100-200 ℃ for 1-2 h to obtain the noble metal loaded alpha-Al2O3A powder catalytic material.
2. The noble metal-supported alpha-Al of claim 12O3The preparation method of the powder catalytic material is characterized in that after the noble metal in the step (1) is mixed with Al, the noble metal accounts for 5-20% of the mixture by mass percent.
3. The noble metal-supported alpha-Al of claim 12O3The preparation method of the powder catalytic material is characterized in that the ball mills adopted in the two ball mills in the step (2) are both liquid nitrogen cooling ball mills, and the ball milling tank is WC (wolfram carbide) with controllable atmosphereLining, agate grinding ball.
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