A hollow hierarchical porous hs-1 molecular sieve encapsulated bimetallic catalyst, a preparation method and use thereof

Abstract

The application discloses a preparation method of a hollow multi-level hole HS-1 molecular sieve encapsulated bimetallic catalyst, which comprises the following steps: (1) mixing a silicon source and a template agent in water; (2) calcining; (3) preparing an active metal impregnation solution; (4) impregnating S-1 molecular sieve powder in the active metal impregnation solution; (5) drying; (6) calcining; (7) dissolving in an alkaline solution; (8) standing; and (9) calcining. The application further discloses the hollow multi-level hole HS-1 molecular sieve encapsulated bimetallic catalyst and the use of the bimetallic catalyst in the preparation of liquid hydrocarbon fuel through high-selectivity hydrogenation and deoxidization of fatty acid methyl ester.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, specifically relating to a hollow hierarchical porous HS-1 molecular sieve-encapsulated bimetallic catalyst, its preparation method, and its use in the highly selective hydrogenation and deoxygenation of fatty acid methyl esters to produce liquid hydrocarbon fuels. Background Technology

[0002] The rapid development of the world economy has led to severe energy depletion and environmental pollution problems, making the development of green, renewable, and clean alternative energy sources an urgent priority. Vegetable oils are the only naturally occurring long-chain hydrocarbon compounds in nature, primarily composed of saturated and unsaturated triglycerides and fatty acid methyl esters, with fatty acid carbon chain lengths ranging from C4 to C6. 32 Liquid hydrocarbon fuels (gasoline C5-C60) can be obtained by hydrogenation, selective cracking, and isomerization. 12 Kerosene C9~C 15 Diesel C 10 ~C 22 However, unrefined vegetable oils contain a large amount of oxygen-containing compounds, resulting in problems such as high viscosity, strong corrosiveness, low calorific value, and poor stability. Therefore, hydrorefining is necessary to reduce oxygen content and improve fuel quality. Vegetable oil hydrorefining involves removing oxygen in the form of H2O, CO, and CO2 under a hydrogen atmosphere and the action of a heterogeneous catalyst. Depending on the deoxygenation pathway, it is divided into three routes: hydrodeoxygenation (HDO), hydrodecarbonylation (DCO), and decarboxylation (DCO2). In HDO, oxygen in the vegetable oil reacts with hydrogen to remove it with H2O, yielding n-alkanes with the same carbon chain length as the fatty acids. In the DCO pathway, oxygen is removed in the form of CO and H2O. In the DCO2 pathway, oxygen is removed in the form of CO2. x The deoxygenation of alkanes via the (DCO and DCO2) pathways results in alkanes with one less carbon atom than fatty acids, leading to resource depletion. Furthermore, the CO produced causes environmental pollution, and the release of CO2 exacerbates the greenhouse effect. Therefore, HDO is the preferred deoxygenation pathway for the hydrorefining of vegetable oils.

[0003] Bifunctional catalysts supported on molecular sieves (ZSM-5, Beta, SAPO-11) with noble metals (Pt, Pd) have exhibited excellent deoxygenation activity and selective cracking capabilities in vegetable oils, and are widely used in the hydrorefining of vegetable oils. However, the inherent microporous structure of molecular sieves restricts the mass transfer of large fatty acid molecules, exacerbating the cracking reaction and resulting in low liquid-phase product yields; moreover, the deoxygenation pathway in noble metal catalysts is primarily DCO. x The HDO pathway is the primary method, exhibiting extremely low selectivity. Furthermore, the selective cracking ability of single precious metals is weak, with diesel oil being the main reaction product and extremely low selectivity for gasoline and kerosene. Therefore, this invention is proposed. Summary of the Invention

[0004] To improve the selectivity of the HDO deoxygenation pathway and the catalytic controllability of different fuel components in the products, this invention synthesizes a hollow hierarchical porous silicalite-1 (HS-1) molecular sieve-encapsulated PtM (M = Co, Mo, Cu, Sn) bimetallic catalyst (PtM@HS-1) using an alkali-treated recrystallization method. Metal M serves as a promoter to tune the electronic state of metal Pt, thereby improving the HDO pathway selectivity and enhancing the catalyst's selective cracking capability. Hydrodeoxygenation was carried out using a fixed-bed reactor with a vegetable oil model compound, fatty acid methyl ester, as the raw material. The hollow hierarchical porous structure of HS-1 promotes the diffusion of large molecular reactants and inhibits the agglomeration and sintering of the active metal. Compared with Pt@HS-1, the bimetallic PtM@HS-1 catalyst of this invention exhibits higher HDO pathway selectivity, achieving controllable adjustment of different fuel components in the liquid hydrocarbon fuel products.

[0005] The technical solution of the present invention is as follows:

[0006] The first aspect of this invention discloses a method for preparing a bimetallic catalyst encapsulated in a hollow hierarchical porous HS-1 molecular sieve, comprising the following steps:

[0007] (1) Mix the silicon source and template agent evenly in water; then crystallize at a certain temperature for a certain time and separate to obtain a solid; crystallize in an oven at 140-190℃ for 24-96h, preferably, the crystallization temperature is 170℃ and the crystallization time is 72h;

[0008] (2) After drying the solid obtained in (1), it is calcined at high temperature for a period of time to obtain solid powder; it is dried at 80-130℃ for 5-16h, and calcined in a muffle furnace at 500-600℃ for 3-10h. The solid powder is collected and recorded as S-1 molecular sieve; preferably, the drying temperature is 110℃ and the calcination temperature is 550℃.

[0009] (3) Dissolve an appropriate amount of Pt source in water, and then add one of Co source, Mo source, Cu source or Sn source, and mix evenly to obtain an active metal impregnation solution; preferably, the Pt source is chloroplatinic acid hexahydrate, the Co source is cobalt nitrate, the Mo source is ammonium molybdate, the Cu source is copper nitrate, and the Sn source is tin chloride.

[0010] (4) Add S-1 molecular sieve powder to the active metal impregnation solution obtained in (3) and impregnate for a period of time;

[0011] (5) Evaporate the product of (4) to remove moisture to obtain a solid, and then dry it at a certain temperature for a period of time; use a rotary evaporator to remove excess moisture, and then use a vacuum pump to evacuate the vacuum, with a rotation speed of 90 rpm and a rotary evaporation temperature of about 50°C; dry at 80-130°C for 5-16 hours; preferably, the drying temperature is 110°C and the drying time is 12 hours.

[0012] (6) The solid material dried in (5) is calcined at a certain temperature for a period of time to obtain solid powder;

[0013] (7) Dissolve the solid powder obtained in (6) in an alkaline solution with a concentration of 0.2-0.8 mol / L and mix for a period of time; wherein the mass ratio of solid powder to alkaline solution is 1:10 to 1:30.

[0014] (8) Let the mixture from (7) stand at a certain temperature for a period of time;

[0015] (9) After drying the solid product obtained in (8), calcinate it at a certain temperature for a period of time to obtain the solid powder, which is the hollow multi-level porous HS-1 molecular sieve encapsulated bimetallic catalyst; after drying in a forced-air drying oven at a temperature of 80-190℃ for 10-96h, cool it to room temperature, centrifuge it, collect the solid and calcine it; preferably, the standing temperature is 170℃ and the time is 24h.

[0016] Preferably, in step (1), the silicon source is one or more of water glass, sodium silicate, methyl orthosilicate, ethyl orthosilicate, or silica sol; the template agent is one or more of tetrapropylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetraethylammonium bromide; the crystallization temperature is 140-190℃, and the time is 24-96h.

[0017] Preferably, in step (3), the Pt source is one or more of tetraammineplatinum nitrate, chloroplatinic acid hexahydrate, potassium chloroplatinate, or platinum chloride; the Co source is one or more of cobalt sulfate, cobalt acetate, cobalt nitrate, or cobalt chloride; the Mo source is one or two of ammonium molybdate or molybdenum chloride; the Cu source is one or more of copper sulfate, copper nitrate, or copper acetate; and the Sn source is one or more of tin acetate, tin chloride, or stannous sulfate.

[0018] Preferably, in step (4) S-1, the mass ratio of molecular sieve powder to active metal impregnation solution is 1:5 to 1:20; wherein the loading of metal Pt is 0.5 to 5 wt%, and the loading of other metals is 0.5 to 5 wt%; more preferably, the solid-liquid ratio is 1:10, the loading of metal Pt is 1 wt%, and the loading of other metals is 1 wt%.

[0019] Preferably, the roasting temperature in step (6) is 400-600℃ and the roasting time is 3-10h; preferably, the roasting temperature is 450℃ and the roasting time is 4h.

[0020] Preferably, in step (7), the alkali source is one or more of tetrapropylammonium hydroxide, tetraethylammonium hydroxide, sodium hydroxide, potassium hydroxide, or sodium carbonate; the mixture is stirred at 800 rpm for 0.2-2 hours at room temperature; preferably, the alkali source is tetrapropylammonium hydroxide, the solid-liquid ratio is 1:20, and the stirring time is 0.5 hours.

[0021] Preferably, in step (9), the drying temperature is 80-130℃ and the time is 5-16h, and the calcination temperature is 500-600℃ and the time is 3-10h; more preferably, the drying temperature is 110℃ and the drying time is 12h; the calcination temperature is 550℃ and the calcination time is 8h.

[0022] The second aspect of this invention discloses a hollow multi-level porous HS-1 molecular sieve encapsulated bimetallic catalyst prepared by the aforementioned preparation method.

[0023] The third aspect of this invention discloses the use of the hollow hierarchical porous HS-1 molecular sieve-encapsulated bimetallic catalyst for the highly selective hydrodeoxygenation of fatty acid methyl esters to prepare liquid hydrocarbon fuels.

[0024] Preferably, the method for using a hollow hierarchical porous HS-1 molecular sieve to encapsulate a bimetallic catalyst for the highly selective hydrodeoxygenation of fatty acid methyl esters to produce liquid hydrocarbon fuels includes the following steps:

[0025] (A) The prepared hollow multi-level porous HS-1 molecular sieve encapsulated bimetallic catalyst is pressed into 20-40 mesh particles. The catalyst particles are fixed in the middle of a stainless steel reaction tube with quartz wool at both ends. The two ends of the reaction tube are filled with silicon carbide and installed on a fixed bed reactor.

[0026] (B) In a hydrogen atmosphere, the temperature is raised to 300-500℃ for 2-6 hours; preferably, the reduction temperature is 450℃ and the reduction time is 4 hours.

[0027] Before using a fixed-bed reactor, nitrogen gas is used to adjust the pressure of the fixed-bed reactor to 5 MPa for leak testing. If there is no significant change in the pressure of the fixed-bed reactor within 0.5 hours, it indicates that the device is well sealed.

[0028] (C) Prepare the raw materials for the fatty acid methyl ester reaction by dissolving the fatty acid methyl ester in a hydrocarbon solvent; wherein the fatty acid methyl ester is one or more of methyl palmitate, methyl stearate or methyl oleate, and the hydrocarbon solvent is one or more of cyclopentane, cyclohexane, decane or dodecane; preferably, the hydrocarbon solvent is cyclohexane;

[0029] (D) After the catalyst reduction is complete, adjust the reaction pressure to 2-5 MPa, the reaction temperature to 200-400℃, the hydrogen-to-oil ratio to 200-800 NmL / mL, and the feed mass hourly space velocity (WHSV) to 2-20 h⁻¹. -1 ;

[0030] (E) Collect the product after hydrogenation reaction in (D), which is the liquid hydrocarbon fuel; gasoline, kerosene and diesel fuel can be obtained by simple distillation and cutting of the liquid hydrocarbon fuel.

[0031] The beneficial effects of this invention are:

[0032] This invention prepares a hollow hierarchical porous HS-1 molecular sieve-encapsulated PtM bimetallic catalyst (PtM@HS-1, M=C) by recrystallization after alkali treatment. O ( / Mo / Mn / Sn). The PtM@HS-1 catalyst of this invention exhibits higher active metal dispersion, improving the catalyst's selective cracking capability. It is used for the highly selective hydrodeoxygenation of fatty acid methyl esters to produce liquid hydrocarbon fuels, achieving controllable adjustment of gasoline, kerosene, and diesel products in the reaction of fatty acid methyl ester hydrorefining to liquid hydrocarbon fuels; and significantly suppressing the DCOx deoxygenation pathway, enhancing the HDO pathway selectivity, thus realizing the highly selective hydrodeoxygenation of fatty acid methyl esters to produce liquid hydrocarbon fuels. Compared with Pt@HS-1, the bimetallic PtM@HS-1 catalyst of this invention exhibits higher HDO pathway selectivity. Attached Figure Description

[0033] Figure 1 Transmission electron microscopy images of the Pt@HS-1(a) and PtCo@HS-1(b) catalysts. Detailed Implementation

[0034] To make the objectives and technical solutions of this invention clearer, detailed descriptions are provided below in conjunction with specific embodiments. These embodiments are intended to illustrate the content of this invention and not to further limit the scope of protection of this invention. The processes, conditions, reagents, experimental methods, etc., used in the implementation, except as specifically mentioned below, are all common knowledge and general knowledge in the field, and this invention does not impose any particular limitations. Experimental methods in the embodiments that do not specify specific conditions are generally performed under conventional conditions or according to the manufacturer's recommendations. Unless otherwise stated, all technical terms and scientific terms used in this specification have the same meaning as commonly understood by those skilled in the art to which this invention pertains. However, in case of conflict, this specification, including the definitions, shall prevail.

[0035] Example: Synthesis of PtCo@HS-1, the steps are as follows:

[0036] (1) Weigh 16.0g of tetraethyl orthosilicate, 18.6g of tetrapropylammonium hydroxide solution and 39.5g of ultrapure water and mix them. Stir in a water bath at 35℃ for 12h. Transfer the resulting clear solution into a 100mL stainless steel crystallization vessel with a polytetrafluoroethylene liner. Place it in a 170℃ oven for static crystallization for 72h. Remove it and cool it to room temperature. Centrifuge to separate and collect the solid. Wash it three times with distilled water. Dry it in a 110℃ oven for 12h. Then place it in a muffle furnace and heat it to 550℃ at a rate of 1℃ / min for 6h. Collect the product, namely S-1 molecular sieve.

[0037] (2) Weigh a measured amount of chloroplatinic acid hexahydrate and dissolve it in 30 mL of water. After complete dissolution, add an appropriate amount of cobalt nitrate to control the loading of Pt and Co in the final catalyst to be 1 wt%. Add 3 g of the synthesized S-1 molecular sieve and stir at 800 rpm for 8 h at room temperature. After stirring, fix the molecular sieve sample onto a rotary evaporator to remove excess water. Set the rotation speed to 90 rpm and the evaporation temperature to 50 °C. Then, place the evaporated molecular sieve in an oven and dry it at 110 °C for 6 h. Finally, transfer it to a muffle furnace and calcine it at 450 °C for 4 h. Collect the product and record it as PtCo / S-1 catalyst.

[0038] (3) Weigh 3g of the calcined catalyst powder and place it in 60mL of 0.50M tetrapropylammonium hydroxide aqueous solution at a solid-liquid ratio of 20. Stir for 30min to mix evenly, then place it in a 100mL hydrothermal crystallization vessel and statically treat it in a 170℃ oven for 24h. Remove it and allow it to cool naturally to room temperature, then centrifuge and wash it three times with distilled water. Dry it overnight in a 110℃ oven and then calcine it in a muffle furnace at a temperature of 450℃ at a rate of 1℃ / min for 4h. Collect the powder, which is the PtCo@HS-1 catalyst. Finally, use a powder tablet press to press the synthesized catalyst into 20-40 mesh particles.

[0039] (4) Weigh 1.5g of the compressed 20-40 mesh catalyst and load it into the stainless steel reaction tube of the fixed-bed reactor. Fill both ends with quartz wool and silicon carbide in sequence, and then install it into the fixed-bed reactor. After checking the airtightness with nitrogen, pressurize the device with hydrogen to 3MPa, and set the hydrogen flow rate to 150mL / min. Then, turn on the heating and activate the catalyst by in-situ reduction at 450℃ for 4h.

[0040] (5) After the catalyst reduction is complete, lower the furnace temperature to the catalytic reaction temperature and set the hydrogen flow rate to 100 mL / min. Turn on the high-pressure liquid feed pump and input the fatty acid methyl ester reaction raw material into the reaction tube for catalytic reaction. The solvent is cyclohexane, and the weight hourly space velocity is 6 h⁻¹. -1After the reaction stabilizes, the liquid product is collected through a sampling port after gas-liquid separation, and then quantitatively analyzed using a Shimadzu 2010plus (FID) gas chromatograph; the gas product is collected through a gas sampling bag and quantitatively analyzed using a Shimadzu 2010plus (BID) gas chromatograph.

[0041] Comparative Example: Synthesis of Pt@HS-1. A Pt catalyst encapsulated in hollow HS-1 molecular sieves without the introduction of promoter M (Pt@HS-1) is used as a comparison.

[0042] (1) Weigh 16.0g of tetraethyl orthosilicate, 18.6g of tetrapropylammonium hydroxide solution and 39.5g of ultrapure water and mix them. Stir in a water bath at 35℃ for 12h. Transfer the resulting clear solution into a 100mL stainless steel crystallization vessel with a polytetrafluoroethylene liner. Place it in a 170℃ oven for static crystallization for 72h. Remove it and cool it to room temperature. Centrifuge to separate and collect the solid. Wash it three times with distilled water. Dry it in a 110℃ oven for 12h. Then place it in a muffle furnace and heat it to 550℃ at a rate of 1℃ / min for 6h. Collect the product, namely S-1 molecular sieve.

[0043] (2) Weigh a measured amount of chloroplatinic acid hexahydrate and dissolve it in 30 mL of water until fully dissolved, controlling the Pt loading in the final catalyst to be 1 wt%. Add 3 g of the synthesized S-1 molecular sieve and stir at 800 rpm for 8 h at room temperature. After stirring, fix the molecular sieve sample onto a rotary evaporator to remove excess water, setting the rotation speed to 90 rpm and the evaporation temperature to 50 °C. Next, place the evaporated molecular sieve in an oven and dry at 110 °C for 6 h. Finally, transfer it to a muffle furnace and calcine at 450 °C for 4 h. Collect the product and record it as the Pt / S-1 catalyst.

[0044] (3) Weigh 3g of the calcined catalyst powder and add it to 60mL of 0.50M tetrapropylammonium hydroxide aqueous solution at a solid-liquid ratio of 20. Stir for 30min to mix evenly, then place it in a 100mL hydrothermal crystallization vessel and statically treat it in a 170℃ oven for 24h. Remove it and allow it to cool naturally to room temperature, then centrifuge and wash it three times with distilled water. Dry it overnight in a 110℃ oven and then calcine it in a muffle furnace at a temperature of 450℃ at a rate of 1℃ / min for 4h. Collect the powder, which is the Pt@HS-1 catalyst. Finally, use a powder tablet press to press the synthesized catalyst into 20-40 mesh particles.

[0045] (4) Weigh 1.5g of the compressed 20-40 mesh catalyst and load it into the stainless steel reaction tube of the fixed-bed reactor. Fill both ends with quartz wool and silicon carbide in sequence, and then install it into the fixed-bed reactor. After checking the airtightness with nitrogen, pressurize the device with hydrogen to 3MPa, and set the hydrogen flow rate to 150mL / min. Then, turn on the heating and activate the catalyst by in-situ reduction at 450℃ for 4h.

[0046] (5) After the catalyst reduction is complete, lower the furnace temperature to the catalytic reaction temperature and set the hydrogen flow rate to 100 mL / min. Turn on the high-pressure liquid feed pump and input the fatty acid methyl ester reaction raw material into the reaction tube for catalytic reaction. The solvent is cyclohexane, and the weight hourly space velocity is 6 h⁻¹. -1 After the reaction stabilizes, the liquid product is collected through a sampling port after gas-liquid separation, and then quantitatively analyzed using a Shimadzu 2010plus (FID) gas chromatograph; the gas product is collected through a gas sampling bag and quantitatively analyzed using a Shimadzu 2010plus (BID) gas chromatograph.

[0047] Figure 1 Transmission electron microscopy images of the Pt@HS-1 and PtCo@HS-1 catalysts. From Figure 1 The synthesized HS-1 molecular sieve exhibits a regular hollow structure and an ordered mesoporous distribution on its surface, which facilitates the diffusion of macromolecular reactants. Furthermore, for the comparative catalyst Pt@HS-1, a distinct metallic Pt particle is observed inside the HS-1 molecular sieve; while for the PtCo@HS-1 catalyst, the active metal is highly dispersed within the hollow structure, providing more active sites and promoting the hydrogenation refining reaction of fatty acid methyl esters.

[0048] The method for using Pt@HS-1 and PtCo@HS-1 catalysts for the highly selective hydrodeoxygenation of fatty acid methyl esters to produce liquid hydrocarbon fuels includes the following steps:

[0049] A fixed-bed reactor was used. Table 1 shows the activity evaluation data for the synthesis of liquid hydrocarbon fuels from methyl stearate using Pt@HS-1 and PtM@HS-1 catalysts. The reaction conditions were: hydrogenation pressure 3 MPa, temperature 360 ​​°C, hydrogen-to-oil ratio 500 N / mL, and weight hourly space velocity 6 h⁻¹. -1 As shown in Table 1, the Pt@HS-1 catalyst exhibits high selectivity for diesel fuel, indicating its relatively weak selective cracking ability. The introduction of additive M improved the selectivity of the PtM@HS-1 catalyst for gasoline and kerosene fuels. PtCo@HS-1 showed the highest selectivity for gasoline and kerosene, reaching 45.04% and 28.62%, respectively. This demonstrates that the introduction of metallic M can enhance the selective cracking ability of the catalyst, achieving controllable adjustment of the selectivity for different fuel components.

[0050] Table 1 Hydrogenation Activity Data of Methyl Stearate

[0051]

[0052] Table 2 shows the deoxygenation pathway selectivity data during the hydrogenation purification of methyl stearate using Pt@HS-1 and PtM@HS-1 catalysts. As shown in Table 2, the Pt@HS-1 catalyst exhibits high DCOx pathway selectivity, but only 14.41% selectivity for HDO. After introducing the promoter M, the selectivity of the PtM@HS-1 catalyst for the HDO pathway is significantly improved, with PtMo@HS-1 showing the highest HDO pathway selectivity at 74.58%. This indicates that introducing the promoter M can regulate the deoxygenation pathway selectivity of the Pt-based catalyst and enhance the HDO pathway selectivity.

[0053] Table 2. Deoxygenation pathway selectivity of different catalysts in the hydrogenation purification of methyl stearate.

[0054]

[0055] The embodiments described are merely preferred embodiments of the present invention and are not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. Application of hollow hierarchical pore HS-1 molecular sieve encapsulated bimetallic catalyst in high selectivity hydrodeoxygenation of fatty acid methyl ester to produce liquid hydrocarbon fuel, characterized in that, The hollow hierarchical pore HS-1 molecular sieve encapsulated bimetallic catalyst is PtMo@HS-1; wherein the HDO path selectivity of the PtMo@HS-1 is 74.58%; The method for preparing liquid hydrocarbon fuel by using the PtMo@HS-1 to perform high-selectivity hydrogenation and deoxidation on fatty acid methyl ester comprises the following steps: (A) The prepared hollow hierarchical pore HS-1 molecular sieve encapsulated bimetallic catalyst is pressed into particles with a mesh size of 20-40, quartz wool is used to fix the catalyst particles in the middle of a stainless steel reaction tube, silicon carbide is used to fill the two ends of the reaction tube, and the reaction tube is installed on a fixed bed reactor; (B) The temperature is raised to 450 DEG C in a hydrogen atmosphere and reduced for 4 h; (C) The fatty acid methyl ester reaction raw material is configured, and the fatty acid methyl ester is dissolved in a hydrocarbon solvent; wherein the fatty acid methyl ester is methyl stearate, and the hydrocarbon solvent is cyclohexane; (D) After the catalyst reduction is completed, the reaction pressure is adjusted to 3 MPa, the reaction temperature is 360°C, the hydrogen / oil ratio is 500 NmL / mL, and the feedstock mass hourly space velocity WHSV is 6 h -1 ; (E) The product after the hydrogenation reaction in step (D) is collected, which is the liquid hydrocarbon fuel; The preparation method of the PtMo@HS-1 comprises the following steps: (1) A silicon source and a template agent are uniformly mixed in water, then crystallized at a certain temperature for a certain time, and a solid is separated; (2) The solid obtained in step (1) is dried, then calcined at a high temperature for a period of time to obtain a solid powder, which is S-1 molecular sieve; (3) A proper amount of Pt source is dissolved in water, then Mo source is added, and uniformly mixed to obtain an active metal impregnation solution; (4) The S-1 molecular sieve powder in step (2) is added to the active metal impregnation solution in step (3) for impregnation for a period of time; (5) The product in step (4) is evaporated to remove water to obtain a solid, then dried at a certain temperature for a period of time; (6) The dried solid in step (5) is calcined at a certain temperature for a period of time to obtain a solid powder; (7) The solid powder in step (6) is dissolved in an alkaline solution with a concentration of 0.2-0.8 mol / L, and mixed for a period of time; wherein the mass ratio of the solid powder to the alkaline solution is 1:10-1:30; (8) The mixed product in step (7) is statically placed at a certain temperature for a period of time; (9) The solid product in step (8) is dried, then calcined at a certain temperature for a period of time to obtain a solid powder, which is the hollow hierarchical pore HS-1 molecular sieve encapsulated bimetallic catalyst PtMo@HS-1.

2. Use according to claim 1, characterized in that, In step (1), the silicon source is one or more of water glass, sodium silicate, methyl orthosilicate, ethyl orthosilicate or silica sol; the template agent is one or more of tetrapropylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetraethylammonium bromide; the crystallization temperature is 140-190 DEG C, and the time is 24-96 h.

3. Use according to claim 1, characterized in that, In step (3), the Pt source is one or more of tetraammine platinum nitrate, chloroplatinic acid hexahydrate, potassium chloroplatinate or platinum chloride; the Mo source is one or both of ammonium molybdate or molybdenum chloride.

4. Use according to claim 1, characterized in that, In step (4), the mass ratio of the S-1 molecular sieve powder to the active metal impregnation solution is 1:5-1:20; wherein the loading amount of Pt is 0.5-5 wt%, and the loading amount of other metals is 0.5-5 wt%.

5. The use according to claim 1, characterized in that, In step (6), the calcination temperature is 400-600 DEG C, and the time is 3-10 h.

6. Use according to claim 1, characterized in that, In step (7), the alkaline source in the alkaline solution is one or more of tetrapropylammonium hydroxide, tetraethylammonium hydroxide, sodium hydroxide, potassium hydroxide, or sodium carbonate.

7. Use according to claim 1, characterized in that, Step (9) Drying temperature 80-130℃, time 5-16h, calcination temperature 500-600℃, time 3-10h.

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