CN108144602B

CN108144602B - Preparation method of high-wear-resistance micron noble metal loaded silicon oxide carrier catalyst

Info

Publication number: CN108144602B
Application number: CN201611094282.1A
Authority: CN
Inventors: 王树东; 李大卫; 苏宏久; 李晓彤; 杨晓野
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2016-12-02
Filing date: 2016-12-02
Publication date: 2020-11-10
Anticipated expiration: 2036-12-02
Also published as: CN108144602A

Abstract

The invention discloses a preparation method of a high-wear-resistance micron noble metal loaded silicon oxide carrier catalyst. The method mainly comprises the steps of premixing silicon oxide powder, acid, additives, dispersing agents, silica sol and the like which are impregnated with precious metal active components, injecting mixed glue into a high-temperature oil column through a jet flow generator with a certain aperture for aging and forming, and then washing, drying and roasting to obtain the micron spherical metal supported catalyst with high wear resistance. The catalyst obtained by the method has a structure with mesoporous characteristics (the aperture is adjustable, the dimension is 2-50 nm, and the specific surface area is 200-450 m)²The pore volume is between 0.5 and 1.5 mL/g), and the wear resistance is high, and the dispersion degree of the contained noble metal is high. In addition, the hydrogenation catalyst prepared by the method has controllable particle size of 30-100 microns, and is high in uniformity and suitable for heterogeneous catalytic reaction in a fluidized bed reactor.

Description

Preparation method of high-wear-resistance micron noble metal loaded silicon oxide carrier catalyst

Technical Field

The invention relates to a preparation method of a noble metal catalyst, in particular to a preparation method of a high-wear-resistance micron noble metal loaded silicon oxide carrier catalyst.

Background

The preparation method of the catalyst and the preparation conditions thereof have a considerable influence on the performance thereof. The change of the preparation method can change the structure, the composition, the particle size and the dispersity of the catalyst, and further influence the activity of the catalyst. At present, noble metal catalysts in industry are mostly prepared by an impregnation method, an ion exchange method and a chemical deposition precipitation method. The main idea is how to perform further noble metal loading on the already shaped support. The active ingredient is generally prepared by being present on the surface of a carrier. For the catalyst of the general fluidized bed process, the attrition resistance of the catalyst and the loss prevention of the noble metal are the key factors for improving the activity and stability of the catalyst. However, according to the conventional preparation method, the loss of noble metal which is an active component on the surface of the catalyst due to collision and friction between the catalysts is inevitable, so that the subsequent reaction efficiency is reduced.

The active component is wrapped in inorganic oxide such as silicon oxide, and the core-shell type structure catalyst can be formed. Due to the structural particularity of the catalyst, the core-shell structure catalyst can realize controllable catalytic reaction, protect active components in the core from being corroded by the external environment through a shell layer, and solve the problems of agglomeration of the active components and the like, so that the catalyst can realize high activity, high stability and high selectivity.

A metal load type catalyst with a core-shell structure belongs to inorganic-inorganic core-shell structure composite particles. Inorganic-inorganic core-shell structured composite particles, the inorganic layer of which is covered is typically silica, metal sulfides, titania, zirconia, and some noble metals. The silicon oxide has the properties of adjustable specific surface and pore volume, thereby playing an important role in the fields of catalysis and separation. Pores with a pore size of less than 2nm are called micropores according to the definition of the international institute of pure and applied chemistry (IUPAC); mesopores (or mesopores) with a pore size of 2 to 50 nm; macropores with a pore diameter of more than 50nm are known. Because the pore canal has important influence on the diffusion of substances, the preparation of the silicon oxide with specific pore diameter has very important significance on the selectivity of the catalytic process and the separation efficiency of separation and purification.

In the field of heterogeneous catalytic reactions, the nature of the pore structure of the catalyst and its support is an important factor in determining the performance of the catalyst. The pore structure parameters of the catalyst and the carrier thereof comprise specific surface area, pore diameter, pore volume and the like, which can directly influence the activity of the catalyst and the mass transfer of each substance in a reaction system, thereby determining the service performance of the catalyst. The method can control macroscopic parameters such as morphology, size and uniformity of material particles while adjusting pore structures of the catalyst and the carrier thereof, and can expand the application range of the prepared material particles.

In the catalytic reaction process, in order to make the catalyst fully exert efficiency, the conditions of the particle shape, the particle size and the like of the catalyst in the reactor are in the optimal state, and the efficiency of the catalyst can be improved to the maximum extent. For silica, when used as a catalyst or a catalyst carrier, the silica is usually shaped into a bar, a column, a raschig ring, a honeycomb, a sphere, or the like. When the spherical silicon oxide is used as a fixed bed catalyst or a catalyst carrier, because the particles are contacted with each other in points, the resistance of a bed layer can be reduced, and the mass transfer and catalytic effects are greatly improved; when the volume of the reactor is constant and the catalyst is filled as much as possible, the spherical shape is the most suitable shape (generally, when spherical particles are filled in the reactor, the volume of the space occupied by the particles can reach 70%, and the volume of cylindrical particles with the same diameter and height can only reach 63-68%). When the catalyst is used as a fluidized bed catalyst or a catalyst carrier, the fine spherical particles are beneficial to the diffusion of substances, the catalytic reaction speed is improved, the heat transfer is also convenient, the reaction temperature is controlled, the reaction temperature can be close to the optimum temperature range, and meanwhile, the wear resistance of the spherical particles is also good.

The existing methods for preparing spherical catalysts include spray drying, spherical size stabilization, microemulsion, rotation forming and the like. Patent CN1660489A is a copper series methanol synthesis catalyst prepared by a spray drying method, and the method has the defect of high feeding and discharging temperature. The method for preparing spherical catalyst by spherical granule finishing in the prior art generally adds peptizer and forming auxiliary agent into materials. The peptizing agent is generally nitric acid, citric acid, acetic acid or tartaric acid, etc. The forming assistant is sesbania powder, polyethylene glycol, etc. The cylindrical bar extruded through the cylindrical orifice plate has poor adhesion and rheological property, so that the forming efficiency is not high. CN101497044B discloses a tooth-sphere heavy oil hydrotreating catalyst and a preparation method thereof. Preparation of alumina carrier precursor: adding peptizing agent, pore-expanding agent and forming aid into aluminum hydroxide, uniformly mixing, adding deionized water and nitric acid, and uniformly mixing to obtain a soft block-shaped plastic body; the peptizing agent is nitric acid, citric acid, acetic acid or tartaric acid or a mixture of any two or more of the above. Therefore, strong interaction between strong acid and alumina tends to occur, which causes severe loss of pore volume and specific surface area, and reduces the pore volume and specific surface area of the final catalyst.

Disclosure of Invention

The invention aims to solve the technical problem of providing a preparation method of a micron-sphere noble metal loaded silica carrier catalyst with high wear resistance, wherein the catalyst has the characteristics of high dispersion degree of active components, adjustable catalyst pore diameter, high wear resistance, high activity and good stability. In addition, the second technical problem to be solved by the invention is to provide a one-step preparation method of the core-shell type particle metal supported catalyst with the micron spherical metal active component coated, and the method is simple and easy to implement, has high efficiency and is easy to realize large-scale production.

In order to solve the two technical problems, the preparation method of the high-wear-resistance micron noble metal loaded silica carrier catalyst comprises the following steps:

(1) firstly, loading a noble metal active component on a silicon oxide carrier to obtain solid powder;

(2) adding the powder obtained in the step (1) into silica sol with a certain concentration, and then adding acid, a dispersing agent, an additive and organic amine to fully mix to form slurry;

(3) injecting the mixed slurry obtained in the step (2) into a high-temperature oil column through a jet generator with a certain aperture for molding;

(4) and (4) aging the product obtained in the step (3) in an oil column, and washing, drying and roasting to obtain the metal supported catalyst.

In the step (1), the noble metal is mainly one or more of Pd, Pt, Au, Rh and Ru, and the mass ratio of the noble metal to the silicon oxide powder is 0.1-5%.

The particle size of the silicon oxide powder selected in the step (1) is preferably 2-15 μm.

It is known that the particle size of the added silica powder has a great influence on the strength of the micron silica particles, and when the particle size is larger than 10 μm, firstly micron silica gel particles with small particles cannot be prepared, and secondly, the mechanical strength of the prepared silica gel particles is poor, so that the later application is difficult to meet. Therefore, the preferred silicon oxide powder of the present invention has a particle size of 2 to 15 μm.

Although the support required for the present invention is silica powder, it may also include alumina, titania, zirconia, ceria, zinc oxide, magnesia, etc., or a mixture of the above oxides. In addition, the size of the silica particles required in this patent is 2-15 μm, but for other oxides or oxide mixtures, the size may be larger or smaller.

The noble metal can be loaded on the silicon oxide powder by one of the methods of dipping, ion exchange, chemical deposition and precipitation, vapor deposition and the like.

In the step (2), the solid powder obtained in the step (1) is added in the whole slurry in a mass ratio of 10-50%.

If the amount of the added silica powder is less than 10%, the silica microspheres are difficult to mold. Conversely, if the silica powder is added in an amount of more than 50%, the viscosity of the suspension is too high to eject the balls.

The silica sol of step (2) contains SiO₂The mass fraction of the particles is 20-40%, and the particle size of the particles is 2-50 nm; and the mass proportion of the used silica sol in the whole slurry is 10-60%.

Furthermore, the particle size of the silica sol added has a relatively large influence on the mechanical strength of the catalyst prepared. In general, the smaller the particle size of the silica sol, the higher the mechanical strength of the particles; on the contrary, the mechanical strength of the microparticles may be deteriorated. The size of silica particles in the silica sol preferred by the invention is 2-50 nm, and the silica sol adopted by the invention can be alkaline silica sol or acidic silica sol.

In the step (2), the acid is one or more of inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid and the like and organic acid such as salicylic acid, acetic acid, oxalic acid, citric acid and the like.

The dispersing agent in the step (2) is one or a mixture of more of methanol, ethanol, isopropanol, amine acetate, ammonium citrate, polyethylene glycol and polymaleic acid, and the adding amount of the dispersing agent is 0.1-5% of the proportion of the solid mass in the slurry system.

In the step (2), the organic amine is mainly one or more of ethylenediamine, ethanolamine, triethylene diamine, diethylene triamine, hexamethylene tetramine and urea. The mass ratio of the solid mass to the organic amine in the slurry system is 1: 0.05-0.2.

The additive in the step (2) is one or more of wollastonite, kaolin, silicon carbide fiber, glass fiber and talcum powder, and the addition amount of the additive is SiO in a slurry system₂0.1-5% of the mass fraction.

The forming oil in the step (3) is one or more of vacuum pump oil, transformer oil, paraffin oil, solvent oil, vegetable oil and mineral oil C10-C13 mixed straight-chain paraffin, and the temperature of the oil column is controlled to be 80-150 ℃.

The aperture of the jet generator nozzle formed in the step (3) is 0.1-1.0 mm; the jet speed is preferably 0.1-10 m/s.

The aging time in the step (4) is 3-24 hr.

The micron spherical metal-loaded catalyst with high wear resistance, prepared by the invention, has spherical silica particles with the aperture of 2-50 nm and the specific surface area of 200-450 m²The pore volume is 0.5 to 1.5 ml/g. The diameter of the single particle of the catalyst is 30-100 μm.

The micron spherical core-shell type particle metal supported catalyst prepared by the invention has the following advantages: the core active component is wrapped in the silicon oxide shell layer, so that the active component has higher dispersity and more concentrated particle size distribution; meanwhile, the silicon oxide shell layer has a mesoporous structure with appropriate specific surface area and pore volume, so that the catalyst has high activity, selectivity and stability. The catalyst is suitable for slurry bed reactors in the process of preparing hydrogen peroxide by anthraquinone hydrogenation, and is also suitable for the processes of liquid phase hydrogenation and gas phase FCC processes of other slurry beds.

Drawings

Figure 1 is a TEM photograph of the catalyst prepared in example 1,

FIG. 2 shows the results of evaluation of hydrogenation performance of the catalyst of example 1;

figure 3 is a TEM photograph of the catalyst prepared in example 2,

FIG. 4 shows the results of evaluation of hydrogenation performance of the catalyst of example 2;

figure 5 is a TEM photograph of the catalyst prepared in example 3,

FIG. 6 shows the results of evaluating the hydrogenation performance of the catalyst of example 3;

figure 7 is a TEM photograph of the catalyst prepared in example 4,

FIG. 8 shows the results of evaluating the hydrogenation performance of the catalyst of example 4;

figure 9 is a TEM photograph of the catalyst prepared in example 5,

FIG. 10 shows the results of evaluating the hydrogenation performance of the catalyst of example 5;

figure 11 is a TEM photograph of the catalyst prepared in example 6,

FIG. 12 shows the results of evaluating the hydrogenation performance of the catalyst of example 6.

Detailed Description

The preparation of the highly attrition resistant spherical highly dispersed noble metal supported catalyst is described in further detail below with reference to the following examples, but it should not be understood that the scope of the present invention as claimed above is limited to the following examples. Unless otherwise indicated, all numbers appearing in the specification and claims of the present invention, such as drying, firing temperatures, operating conditions, mass percentages of compositions, and the like, are not to be understood as being absolutely exact, within the range of error permitted by the well-known art as understood by those of ordinary skill in the art.

The high-wear-resistance micron spherical metal supported catalyst prepared by the invention adopts a specific surface area, a pore size and a pore size distribution of a sample measured on a NOVA2200e type specific surface-pore size distribution instrument of Quanta company in America.

The micron spherical core-shell type particle metal supported catalyst prepared by the invention adopts a JEM-2100 type 200kV high-resolution transmission electron microscope of Japan electron corporation to measure the size of active component particles contained in the catalyst.

The performance evaluation of the catalyst is carried out by producing hydrogen peroxide through anthraquinone hydrogenation and using a slurry bed fully-mixed reactor. The working liquids used for the experimental evaluation are shown in Table 1

TABLE 1 ingredient Table of anthraquinone working fluids

The volume of the slurry bed fully-mixed reactor is 200ml, and a stirring paddle and a gas distributor are arranged in the reactor. A volume of about 1ml of catalyst was taken and placed inside the reactor. The evaluation adopts a continuous feeding and discharging mode, the total liquid flow is 150ml, the feeding speed is 0.3ml/min, and the hydrogen flow is 30 ml/min.

Example 1

(1-1) weighing SiO with an average particle size of 2 μm₂21g of powder, 11.5mL of Pd (NO) with a concentration of 20mg/mL₃)₂The solution was loaded on the SiO in an equal volume impregnation₂Powder coating;

(1-2) taking 15mL of concentrated hydrochloric acid and 126g of 30 wt% alkaline silica sol (wherein the average particle size of silica is 25nm) to be mixed to obtain a slurry main body, adding 15g of hexamethylenetetramine into the slurry, and stirring to fully dissolve the hexamethylenetetramine.

(1-3) selecting a nozzle with the inner diameter of 0.25mm to be installed on a jet flow generator, injecting the slurry obtained in the step (1-2) into 25# transformer oil at the speed of 0.1m/s for forming, standing and aging for 4 hours, separating the formed core-shell catalyst microspheres from the oil, and drying in vacuum at the temperature of 60 ℃ for 12 hours.

(1-4) washing the obtained product to be neutral, then drying the product for 10 hours at 140 ℃, and roasting the product for 12 hours at 550 ℃ to obtain the spherical core-shell type particle metal supported catalyst.

The TEM photograph is shown in FIG. 1, and the result of the evaluation of the hydrogenation performance of the catalyst is shown in FIG. 2.

Example 2

(2-1) weighing SiO with average particle size of 5 μm₂21g of powder, 4.6mL of 20mg/mL Pd (NO)₃)₂The solution was loaded on the SiO in an equal volume impregnation₂Powder coating;

(2-2) taking 15mL of concentrated hydrochloric acid and 126g of 30 wt% alkaline silica sol (wherein the average particle size of the silica is 25nm) to be mixed to obtain a slurry main body, adding 15g of hexamethylenetetramine into the slurry, and stirring to fully dissolve the hexamethylenetetramine.

(2-3) selecting a nozzle with the inner diameter of 0.25mm to be installed on a jet flow generator, injecting the slurry obtained in the step (2-2) into 25# transformer oil at the temperature of 95 ℃ at the speed of 0.1m/s for forming, standing and aging for 4 hours, separating the formed core-shell catalyst microspheres from the oil, and drying in vacuum at the temperature of 60 ℃ for 12 hours.

(2-4) washing the obtained product to be neutral, then drying the product for 10 hours at 140 ℃, and roasting the product for 12 hours at 550 ℃ to obtain the spherical core-shell type particle metal supported catalyst.

The TEM photograph is shown in FIG. 3, and the result of evaluating the hydrogenation performance of the catalyst is shown in FIG. 4.

Example 3

(3-1) weighing SiO with an average of 7 μm₂31g of powder, 15mL of Pd (NO) with a concentration of 20mg/mL₃)₂The solution was loaded on the SiO in an equal volume impregnation₂Powder coating;

(3-2) taking 10ml of concentrated phosphoric acid, 126g of 30 wt% alkaline silica sol (wherein the average particle size of the silicon oxide is 25nm) and 8ml of polyethylene glycol, fully mixing to obtain mixed slurry, and then adding 2.5g (500 meshes) of silicon carbide fiber and 14g of hexamethylenetetramine into the slurry for fully dissolving.

(3-3) selecting a nozzle with a pore diameter of 0.35mm, installing the nozzle on a jet flow generator, injecting the slurry obtained in the step (3-2) into 25# transformer oil at the temperature of 90 ℃ at the speed of 5m/s for forming, separating the formed pellets from the oil, and drying in vacuum at the temperature of 80 ℃ for 16 hours.

(3-3) washing the obtained product to be neutral, then drying the product for 10 hours at 140 ℃, and roasting the product for 12 hours at 550 ℃ to obtain the spherical core-shell type particle metal supported catalyst.

The TEM photograph is shown in FIG. 5, and the result of evaluating the hydrogenation performance of the catalyst is shown in FIG. 6.

Example 4

(4-1) weighing SiO with average particle size of 10 μm₂21g of powder, 1.05mL of Pd (NO) with a concentration of 20mg/mL₃)₂The solution was loaded on the SiO in an equal volume impregnation₂Powder coating;

(4-2) taking 5ml of concentrated hydrochloric acid, 126g of 30 wt% of alkaline silica sol (wherein the average particle size of the silicon oxide is 12nm) and 10ml of isopropanol, fully mixing to obtain slurry, and adding 15g of hexamethylenetetramine into the slurry for fully dissolving.

(4-3) selecting a nozzle with a pore diameter of 0.2mm, installing the nozzle on a jet flow generator, injecting the slurry obtained in the step (4-2) into 25# transformer oil at the temperature of 85 ℃ at the speed of 1m/s for forming, separating the formed pellets from the oil, and drying in vacuum at the temperature of 60 ℃ for 12 hours.

(4-4) washing the obtained product to be neutral, then drying the product for 10 hours at 140 ℃, and roasting the product for 12 hours at 550 ℃ to obtain the spherical core-shell type particle metal supported catalyst.

The TEM photograph is shown in FIG. 7, and the result of evaluating the hydrogenation performance of the catalyst is shown in FIG. 8.

Example 5

(5-1) weighing SiO with an average particle size of 15 μm₂47.1g of powder prepared by mixing 117.75mL of 20mg/mL Pd (NO)₃)₂The solution was loaded on the SiO in an equal volume impregnation₂Powder coating;

(5-2) weighing 15ml of concentrated hydrochloric acid, 126g of 30 wt% alkaline silica sol (wherein the average particle size of the silicon oxide is 12nm) and 5ml of ethanol, fully mixing to obtain slurry, and adding 14g of hexamethylenetetramine into the slurry for fully dissolving.

(5-3) selecting a nozzle with the aperture of 1mm to be installed on a jet flow generator, injecting the slurry obtained in the step (5-3) into 25# transformer oil at the temperature of 95 ℃ at the speed of 2m/s for forming, separating the formed small balls from the oil, and drying in vacuum at the temperature of 80 ℃ for 12 hours.

(5-4) washing the obtained product to be neutral, then drying the product for 20 hours at 110 ℃, and roasting the product for 12 hours at 550 ℃ to obtain the spherical core-shell type particle metal supported catalyst.

The TEM photograph is shown in FIG. 9, and the results of the evaluation of the hydrogenation performance of the catalyst are shown in FIG. 10.

Example 6

(6-1) weighing SiO 5 μm in average₂18.1g of powder, 0.905mL of 20mg/mL Pd (NO)₃)₂The solution was loaded on the SiO in an equal volume impregnation₂Powder coating;

(6-2) weighing 15ml of concentrated hydrochloric acid, 126g of 30 wt% alkaline silica sol (wherein the average particle size of the silicon oxide is 12nm) and 10ml of ethanol, fully mixing to obtain slurry, and adding 14g of hexamethylenetetramine into the slurry for fully dissolving.

(6-3) A nozzle having a bore diameter of 0.3mm was attached to a jet generator, the slurry obtained in (6-1) was injected into 25# transformer oil at 95 ℃ at a speed of 20m/s for molding, the molded pellets were separated from the oil, and vacuum-dried at 80 ℃ for 12 hours.

(6-4) washing the obtained product to be neutral, then drying the product for 20 hours at 110 ℃, and roasting the product for 12 hours at 550 ℃ to obtain the spherical core-shell type particle metal supported catalyst. The TEM photograph is shown in FIG. 11, and the result of evaluating the hydrogenation performance of the catalyst is shown in FIG. 12.

Claims

1. A preparation method of a high wear-resistant micron noble metal loaded silica carrier catalyst is characterized by comprising the following steps:

(1) firstly, loading a noble metal active component on a silicon oxide carrier to obtain solid powder; wherein the particle size of the silicon oxide powder is 2-15 μm;

(2) adding the powder obtained in the step (1) into silica sol with a certain concentration, and then adding acid, a dispersing agent, an additive and organic amine to fully mix to form slurry; wherein the mass ratio of the solid powder in the whole slurry is 10-50%; SiO contained in silica sol₂The mass fraction of the particles is 20-40%, and the particle size of the particles is 2-50 nm;

2. The method for preparing a micron noble metal supported silica supported catalyst with high abrasion resistance as claimed in claim 1, wherein: in the step (1), the noble metal is one or more of Pd, Pt, Au, Rh or Ru, and the mass ratio of the noble metal to the silicon oxide powder is 0.1-5%.

3. The method for preparing a micron noble metal supported silica supported catalyst with high abrasion resistance as claimed in claim 1, wherein: the mode of loading noble metal on the silicon oxide powder is one of an impregnation method, an ion exchange method, a chemical deposition and precipitation method and a vapor deposition method.

4. The method for preparing a micron noble metal supported silica supported catalyst with high abrasion resistance as claimed in claim 1, wherein: the mass ratio of the silica sol used in the step (2) to the whole slurry is 10-60%; the addition amount of the dispersing agent is 0.1-5% of the mass of the solid in the slurry system; the organic amine accounts for 5-20% of the mass of the solid in the slurry system; the additive accounts for 0.1-5% of the mass fraction of solids in the slurry system.

5. The method for preparing a micron noble metal supported silica supported catalyst with high abrasion resistance as claimed in claim 1, wherein: in the step (2), the acid is one or more of hydrochloric acid, nitric acid, phosphoric acid, other inorganic acids, salicylic acid, acetic acid, oxalic acid, citric acid or other organic acids.

6. The method for preparing a micron noble metal supported silica supported catalyst with high abrasion resistance as claimed in claim 1, wherein: the dispersant in the step (2) is one or more of methanol, ethanol, isopropanol, amine acetate, ammonium citrate, polyethylene glycol and polymaleic acid.

7. The method for preparing a micron noble metal supported silica supported catalyst with high abrasion resistance as claimed in claim 1, wherein: in the step (2), the organic amine is mainly one or more of ethylenediamine, ethanolamine, triethylene diamine, diethylene triamine, hexamethylene tetramine or urea.

8. The method for preparing a micron noble metal supported silica supported catalyst with high abrasion resistance as claimed in claim 1, wherein: the additive in the step (2) is one or more of wollastonite, kaolin, silicon carbide fiber, glass fiber and talcum powder.

9. The method for preparing a micron noble metal supported silica supported catalyst with high abrasion resistance as claimed in claim 1, wherein: the forming oil in the oil column in the step (3) is one or more of vacuum pump oil, transformer oil, paraffin oil, solvent oil, vegetable oil and mineral oil C10-C13 mixed straight-chain paraffin, and the temperature of the oil column is controlled to be 80-150 ℃.

10. The method for preparing a micron noble metal supported silica supported catalyst with high abrasion resistance as claimed in claim 1, wherein: the aperture of the jet generator nozzle formed in the step (3) is 0.1-1.0 mm; the jet speed is preferably 0.1-10 m/s.

11. The method for preparing a micron noble metal supported silica supported catalyst with high abrasion resistance as claimed in claim 1, wherein: the aging time in the step (4) is 3-24 hr.