Hydro-upgrading catalyst and preparation method thereof

Abstract

The invention discloses a hydro-upgrading catalyst and a preparation method thereof, the hydro-upgrading catalyst is of a spherical core-shell structure formed by taking a Y molecular sieve as a core and aluminum oxide as a shell, and the aluminum oxide shell layer of the hydro-upgrading catalyst contains an active component composed of VIB group metal and VIII group metal. The core-shell structure catalyst is prepared by using the microporous Y molecular sieve and the mesoporous alumina, so that the catalyst has an open pore channel structure in stepped pore distribution, and meanwhile, the active metal is loaded in the alumina shell layer, so that the acid content of the catalyst can be increased, and the acid center of the molecular sieve is prevented from being covered by the active metal. The hydrogenation capacity and the ring opening capacity of the obtained catalyst are highly matched, and the catalyst is suitable for a diesel oil hydrogenation modification process, has the characteristics of high yield of modified diesel oil, excellent product quality and especially low BMCI, and can realize maximum production of a high-quality ethylene cracking raw material from diesel oil.

Description

Technical Field

[0001] The present invention belongs to the technical field of hydrogenation catalyst preparation, and particularly relates to a hydro-upgrading catalyst and a preparation method thereof. Background Art

[0002] Currently, the technology for producing ethylene cracking feedstock from diesel mainly is medium-pressure hydro-upgrading technology. Medium-pressure hydro-upgrading is to appropriately ring-open and crack diesel under medium-pressure conditions, and by changing the hydrocarbon composition structure of diesel, achieve the purpose of improving the quality of diesel products and producing high-quality ethylene cracking feedstock. How to hydrogenate and ring-open aromatics and naphthenes in diesel to convert them into paraffins and enrich them in diesel products, while avoiding excessive cracking, is the key to achieving the maximum production of high-quality ethylene cracking feedstock.

[0003] The microporous-mesoporous composite material that combines the high catalytic activity of microporous molecular sieves with the pore characteristics of mesoporous molecular sieves or alumina can make the microporous molecular sieves and mesoporous molecular sieves or alumina complementary in terms of acidity and pore structure. Patent CN101890363A discloses a preparation method of a mesoporous-microporous core-shell composite molecular sieve catalyst, in which the microporous zeolite is used as the core, and mesoporous silica or aluminosilicate mesoporous silica is used as the shell layer. The obtained composite molecular sieve has a retained zeolite microporous framework, an ordered two-dimensional hexagonal mesoporous structure, and the mesoporous channels are perpendicular to the surface of the zeolite particles, with high pore openness, adjustable thickness of the mesoporous shell layer, and after wrapping the mesoporous shell layer, a high degree of smoothness can be maintained between the mesoporous and microporous.

[0004] Patent CN 114433209A discloses a hydro-upgrading catalyst, a preparation method and an application thereof. The preparation method includes the preparation of a support and the loading of a hydrogenation active metal component. The preparation method of the support includes: mixing an Al-SBA-15 / Y core-shell composite molecular sieve, macroporous alumina and a binder, forming, and then drying and calcining to make a catalyst support. The catalyst is mainly used for hydro-upgrading of inferior catalytic diesel to improve the cetane number of diesel.

[0005] Patent CN 116060113A discloses a straight-run diesel hydro-upgrading catalyst. The catalyst, based on the weight of the catalyst, includes: 70~98 wt% support; 2~30 wt% of an active metal in terms of oxide; the support, based on the mass of the support, includes: 10~20 wt% of an Al-SBA-15 / β core-shell type composite molecular sieve, 35~70wt% amorphous silica-alumina, and 20~45wt% binder component. This catalyst is suitable for hydro-upgrading of straight-run diesel to produce jet fuel, and has the characteristics of high jet fuel yield and good product quality, especially high smoke point.

[0006] Patent CN 116060108 A discloses a diesel hydro-upgrading catalyst, its preparation method and application. The catalyst includes: based on the weight of the catalyst, the content of the active metal is 3.9 - 45 wt% calculated as the oxide; the content of the carrier is 55 - 96.1 wt%; the carrier includes: based on the total mass of the carrier, 10 - 23 wt% of Al-SBA-15 / β zeolite, 45 - 70 wt% of macroporous alumina, and 20 - 35 wt% of the binder component. This catalyst is applicable to diesel hydro-upgrading, especially suitable for inferior diesel with high sulfur and nitrogen contents and complex molecular structures, and has characteristics such as high yield of target products and good product quality.

[0007] Patent CN 116408142 A discloses a diesel selective hydrocracking and ring-opening catalyst, its preparation method and application. The diesel selective hydrocracking and ring-opening catalyst includes a carrier and a metal hydrogenation active component. The carrier includes a (USY + HMS) composite mesoporous zeolite. The diesel selective hydrocracking and ring-opening catalyst of this invention can effectively convert straight-run diesel for high-efficient production of ethylene cracking raw materials, and has great industrial application value in integrated refining and chemical enterprises.

[0008] Patent CN 116603563 A discloses a double-shelled core-shell structured hierarchical pore nickel-based catalyst, its preparation method and application. The catalyst is composed of a core phase and a first shell layer and a second shell layer sequentially coated on the outside of the core phase; the core phase is a zeolite, the first shell layer is mesoporous silica, and the core phase and the first shell layer form a hierarchical pore structure; the second shell layer is nickel or an oxide of nickel, and the content of nickel is 1 - 20 wt% of the total mass of the catalyst. This invention realizes the construction of the hierarchical pore structure and the effective series connection of active sites, and shows excellent catalytic performance in the hydrodesulfurization reaction.

[0009] As can be seen from the content disclosed in the above prior art, in the related research on the preparation of catalysts with a core-shell structure, the catalyst preparation generally adopts the method of first preparing the support and then impregnating the active metal. The steps for preparing the support with a core-shell structure are complex, requiring multiple steps of reaction, and it is difficult to control the stability of the product properties. In addition, during the impregnation process, the active metal will enter the zeolite pores, covering the acid centers, resulting in a decrease in the ring-opening ability of the catalyst, causing a mismatch between the hydrogenation ability and the ring-opening ability of the catalyst. Moreover, secondary calcination is required after impregnation, which has the disadvantages of a long process and high energy consumption. At the same time, most of the raw materials for these catalysts are heavy catalytic diesel, and the products are mainly naphtha and diesel, or aviation kerosene is produced from straight-run diesel, and there is less research on using high-quality ethylene cracking raw materials as the target product. Although Patent CN 116408142A uses straight-run diesel as the raw material to produce ethylene cracking raw materials, the obtained naphtha and tail oil have a relatively high BMCI, the reforming effect is limited, and the catalyst preparation also uses the impregnation method, which has the disadvantages of insufficient ring-opening ability of the catalyst and high preparation cost. The double-shell core-shell graded pore nickel-based catalyst constructed in Patent CN 116603563A has an effective series connection of a stepped pore structure and active sites, but its hydrogenation active phase is distributed in the outermost layer in a bulk phase on the catalyst, resulting in low utilization rate of the active metal, and multiple carbon-based compounds need to be added to form a separation layer, and the preparation process is cumbersome. Therefore, it is necessary to improve the catalyst preparation method, improve the catalyst performance, produce the largest amount of high-quality ethylene cracking raw materials, realize the high-value utilization of straight-run diesel, solve the current problem of diesel surplus and ethylene raw material shortage in China, and help refineries achieve "reducing oil and increasing chemicals". Summary of the Invention

[0010] In view of the deficiencies of the prior art, the present invention provides a diesel hydro-upgrading catalyst capable of producing more high-quality ethylene raw materials and its preparation method. By preparing a core-shell structure catalyst from microporous Y zeolite and mesoporous alumina, the catalyst has an open pore structure with a stepped pore distribution. At the same time, the active metal is loaded in the alumina shell layer, which can increase the acid amount of the catalyst and prevent the acid centers of the zeolite from being covered by the active metal. The obtained catalyst has a highly matched hydrogenation ability and ring-opening ability, is suitable for the diesel hydro-upgrading process, has the characteristics of high reformed diesel yield, excellent product quality, especially low BMCI, and can realize the maximum production of high-quality ethylene cracking raw materials from diesel.

[0011] To achieve the above object, the present invention adopts the following technical solutions: A hydro-upgrading catalyst is a spherical core-shell structure with Y zeolite as the core and alumina as the shell, and the alumina shell layer contains an active component composed of a Group VIB metal and a Group VIII metal.

[0012] Further, in the catalyst, the thickness of the alumina shell layer is 10-90% of the radius of the catalyst.

[0013] Further, based on the total mass of 100 wt%, the content of alumina (dry basis) in the catalyst is 20 - 80 wt%, the content of Y zeolite (dry basis) is 5 - 35 wt%, the content of Group VIB metal oxide is 8 - 30 wt%, and the content of Group VIII metal oxide is 1 - 12 wt%.

[0014] The preparation method of the hydro-upgrading catalyst comprises the following steps: (1) Mix Y zeolite with shaping adjuvants evenly to obtain powder A, and mix alumina precursor with active metal precursor and shaping adjuvants evenly to obtain powder B; (2) Feed powder A into a sugar coating machine, spray a peptizing agent to form spheres. When the average particle size of the wet spheres reaches an appropriate size, switch powder A to powder B and feed it into the sugar coating machine, continue to spray the peptizing agent to form spheres. When the average particle size of the wet spheres reaches an appropriate size, the sphere forming ends; (3) After subjecting the obtained wet spheres to curing, drying and calcination, the hydro-upgrading catalyst is obtained.

[0015] Further, the Y zeolite in step (1) can be a commercial product or a product prepared by a conventional method.

[0016] Further, the alumina precursor in step (1) is selected from one or more of amorphous aluminum hydroxide, gibbsite, boehmite, pseudoboehmite, and preferably pseudoboehmite. It can be a commercially available product or a product prepared by any method in the prior art.

[0017] Further, the active metal precursor in step (1) is composed of a compound containing a Group VIB metal element and a compound containing a Group VIII metal element.

[0018] Furthermore, the compound containing a Group VIB metal element is one or several of molybdic acid, paramolybdic acid, ammonium molybdate, ammonium paramolybdate, molybdenum trioxide, tungstic acid, metatungstic acid, ammonium tungstate, ammonium metatungstate, tungsten trioxide; the compound containing a Group VIII metal element is one or more of inorganic acid salts or organic acid salts containing a Group VIII metal element, wherein the inorganic acid salt can be basic carbonate, nitrate, phosphate, carbonate, halate; the organic acid salt can be acetate, oxalate, citrate, formate, tartrate.

[0019] Further, the shaping adjuvants in step (1) are selected from one or more of sesbania powder, starch, methyl cellulose, polyacrylamide, and polycarboxylic acid, and the addition amount is 0.1 - 5% of the dry basis mass of the corresponding Y zeolite or alumina precursor.

[0020] Further, the peptizing agent described in step (2) is various peptizing agents commonly used in the art, which may be aluminum sol and / or silica sol, or inorganic acid and / or organic acid solution, wherein the mass concentration of the inorganic acid and / or organic acid is 1-20%. The inorganic acid may be one or more of nitric acid, phosphoric acid, hydrochloric acid, and sulfuric acid, preferably nitric acid, and the organic acid may be one or more of oxalic acid, acetic acid, and citric acid.

[0021] Further, the curing temperature in step (3) is 10-50 °C, and the time is 4-72 h.

[0022] Further, the drying temperature in step (3) is 50-200 °C, and the time is 1-24 h.

[0023] Further, the calcination temperature in step (3) is 400-750 °C, and the time is 1-8 h.

[0024] The hydro-upgrading catalyst can be used for diesel hydro-upgrading.

[0025] In the present invention, by preparing a core-shell structured catalyst from microporous Y zeolite and mesoporous alumina, the catalyst has an open pore structure with a stepped pore distribution. During the diesel hydro-upgrading process, large molecules such as naphthenes and aromatics in diesel can be adsorbed on the mesoporous layer first and undergo pre-hydrocracking. Subsequently, the larger molecules generated can quickly enter the microporous Y zeolite for ring-opening reaction, thus effectively solving the diffusion problem of large molecule reactants in the catalyst pores. Moreover, the pore structure with micro-mesoporous distribution also provides a smooth pore for the cracking products to quickly detach from the catalyst surface, avoiding secondary deep cracking reactions. At the same time, in the present invention, the active metal is loaded in the alumina shell layer, which can not only increase the acid amount of the catalyst, avoid the coverage of the acid centers of the zeolite by the active metal, but also maintain the smoothness of the zeolite pores, further promoting the products after ring-opening to quickly diffuse out from the acid centers, avoiding side reactions such as secondary cracking, and effectively improving the yield of upgraded diesel. In addition, the hydrogenation ability and ring-opening ability of the obtained catalyst are highly matched, and it has the characteristics of high yield of upgraded diesel, excellent product quality, especially low BMCI, and can achieve the maximum production of high-quality ethylene cracking raw materials from diesel.

[0026] Compared with the prior art, the present invention has the following remarkable advantages: (1) Compared with the prior catalyst preparation technology, the catalyst prepared by the present invention has a highly matched hydrogenation ability and ring-opening ability, and can effectively avoid overcracking reactions during the straight-run diesel upgrading process. While maintaining a relatively high yield of upgraded diesel, it can significantly reduce BMCI, thus achieving the maximum production of high-quality ethylene cracking raw materials.

[0027] (2) The acid amount of the catalyst of the present invention can be flexibly controlled. Compared with the conventional method of first preparing a support and then impregnating an active metal, under the condition of the same acid amount, the amount of Y zeolite used can be reduced, thereby reducing the raw material cost of the catalyst.

[0028] (3) The preparation method of the present invention is simple, the process flow is short, and no secondary calcination is required, reducing the production cost of the catalyst. Detailed implementation manners

[0029] A hydro-upgrading catalyst has a spherical core-shell structure with a Y zeolite as the core and alumina as the shell, and the alumina shell layer contains an active component composed of a Group VIB metal and a Group VIII metal. Among them, the thickness of the alumina shell layer is 10-90% of the radius of the spherical catalyst.

[0030] Based on the total mass of 100 wt%, the content of alumina (dry basis) in the catalyst is 20-80 wt%, the content of Y zeolite (dry basis) is 5-35 wt%, the content of Group VIB metal oxide is 8-30 wt%, and the content of Group VIII metal oxide is 1-12 wt%.

[0031] The preparation method of the hydro-upgrading catalyst includes the following steps: (1) Mix Y-type zeolite and shaping auxiliary materials evenly to obtain powder A, and mix an alumina precursor, a compound containing a Group VIB metal element, a compound containing a Group VIII metal element, and shaping auxiliary materials evenly to obtain powder B; (2) Feed powder A into a sugar coating machine, spray a peptizing agent at a rate of 5-30 mL / min to form spheres. When the average wet ball diameter reaches an appropriate size, switch powder A to powder B and feed it into the sugar coating machine, and continue to spray the peptizing agent to form spheres. When the average wet ball diameter reaches an appropriate size, the sphere forming ends; (3) Cure the obtained wet balls at 10-50 °C for 4-72 h, then dry them at 50-200 °C for 1-24 h, and then calcine them at 400-750 °C for 1-8 h to obtain the hydro-upgrading catalyst.

[0032] Among them, the alumina precursor described in step (1) is selected from one or more of amorphous aluminum hydroxide, gibbsite, boehmite, pseudoboehmite, and meta-boehmite. Further, the compound containing a Group VIB metal element in step (1) is one or several of molybdic acid, paramolybdic acid, ammonium molybdate, ammonium paramolybdate, molybdenum trioxide, tungstic acid, metatungstic acid, ammonium tungstate, ammonium metatungstate, and tungsten trioxide; the compound containing a Group VIII metal element is derived from one or more of inorganic acid salts or organic acid salts containing a Group VIII metal element. The shaping auxiliary is selected from one or more of sesbania powder, starch, methylcellulose, polyacrylamide, and polycarboxylic acid, and the addition amount thereof is 0.1-5% of the dry basis mass of the corresponding Y-type molecular sieve or alumina precursor.

[0033] To make the content of the present invention easier to understand, the technical solutions of the present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited thereto.

[0034] Example 1 (1) Weigh 120 g of Y molecular sieve (dry basis 78.7 wt%) and 3 g of sesbania powder, and mix them evenly to obtain powder A1; weigh 500 g of pseudoboehmite (dry basis 71.0 wt%), 83 g of nickel nitrate, 174 g of ammonium metatungstate, and 10 g of sesbania powder, and mix them evenly to obtain powder B1. Add 10 g of citric acid and 15 g of nitric acid to 1000 g of water, stir and mix evenly to obtain a peptizing agent.

[0035] (2) Feed powder A1 into a sugar coating machine at a rate of 8 g / min, and spray the peptizing agent at a rate of 6 mL / min for rolling into balls. When the average wet ball diameter reaches 1.5 mm, stop feeding powder A1; then feed powder B1 into the sugar coating machine at a rate of 10 g / min and continue to spray the peptizing agent for ball forming. When the average wet ball diameter reaches 3.0 mm, the ball forming ends.

[0036] (3) Cure the wet balls at room temperature for 24 h, then dry them at 100 °C for 6 h, and finally calcine them at 550 °C for 4 h to obtain catalyst C1.

[0037] Example 2 (1) Weigh 100 g of Y molecular sieve (dry basis 78.7 wt%) and 3 g of sesbania powder, and mix them evenly to obtain powder A2; weigh 550 g of pseudoboehmite (dry basis 71.0 wt%), 83 g of nickel nitrate, 174 g of ammonium metatungstate, and 11 g of sesbania powder, and mix them evenly to obtain powder B2. Add 10 g of citric acid and 15 g of nitric acid to 1000 g of water, stir and mix evenly to obtain a peptizing agent.

[0038] (2) Feed powder A2 into the sugar coating machine at a rate of 8 g / min, and spray the peptizing agent at a rate of 6 mL / min for rolling into balls. When the average wet ball diameter reaches 1.2 mm, stop feeding powder A2; then feed powder B2 into the sugar coating machine at a rate of 10 g / min and continue to spray the peptizing agent for ball forming. When the average wet ball diameter reaches 3.0 mm, the ball forming ends.

[0039] (3) Cure the wet balls at room temperature for 24 h, then dry them at 100 °C for 6 h, and finally calcine them at 550 °C for 4 h to obtain catalyst C2.

[0040] Example 3 (1) Weigh 130 g of Y zeolite (dry basis 78.7 wt%) and 4 g of talc powder, and mix them evenly to obtain powder A3; weigh 450 g of pseudo-boehmite (dry basis 71.0 wt%), 83 g of nickel nitrate, 174 g of ammonium metatungstate and 9 g of talc powder, and mix them evenly to obtain powder B3. Add 10 g of citric acid and 15 g of nitric acid to 1000 g of water, stir and mix evenly to obtain the peptizing agent.

[0041] (2) Feed powder A3 into the sugar coating machine at a rate of 8 g / min, and spray the peptizing agent at a rate of 6 mL / min for rolling into balls. When the average wet ball diameter reaches 1.7 mm, stop feeding powder A3; then feed powder B3 into the sugar coating machine at a rate of 10 g / min and continue to spray the peptizing agent for ball forming. When the average wet ball diameter reaches 3.0 mm, the ball forming ends.

[0042] (3) Cure the wet balls at room temperature for 24 h, then dry them at 100 °C for 6 h, and finally calcine them at 550 °C for 4 h to obtain catalyst C3.

[0043] Comparative Example 1 (1) Weigh 159.4 g of pseudo-boehmite (dry basis 71.0 wt%) and 38.2 g of Y zeolite (dry basis 78.7 wt%). After mixing them evenly, add the peptizing agent (prepared by adding 10 g of citric acid and 15 g of nitric acid to 1000 g of water and stirring and mixing evenly) for kneading, and use an extrusion machine to extrude the kneaded material into a shape. Dry the extrudate at 120 °C for 6 h, and then calcine it at 550 °C for 4 h to obtain the catalyst support, and measure the water absorption of the support.

[0044] (2) Weigh 71.6 g of the catalyst support, and calculate the volume of the required active metal solution according to its water absorption. Then weigh 13.2 g of nickel nitrate and 27.7 g of ammonium metatungstate, dissolve them in an appropriate amount of water and make up the volume to the required value, and use the impregnation method to load the active metal onto the catalyst support.

[0045] (3) Dry the wet catalyst bars obtained in step (2) at 120 °C for 6 h, and then calcine them at 550 °C for 4 h to obtain catalyst D1.

[0046] Comparative Example 2 (1) Weigh 120 g of Y zeolite (dry basis 78.7 wt%) and 3 g of sesbania powder, and mix them evenly to obtain powder A4; weigh 500 g of pseudo-boehmite (dry basis 71.0 wt%), 10 g of sesbania powder, and mix them evenly to obtain powder B4; weigh 83 g of nickel nitrate, 174 g of ammonium metatungstate and 5 g of sesbania powder, and mix them evenly to obtain powder E. Add 10 g of citric acid and 15 g of nitric acid to 1000 g of water, stir and mix evenly to obtain a peptizing agent.

[0047] (2) Feed powder A4 into a sugar coating machine at a rate of 8 g / min, and spray the peptizing agent at a rate of 6 mL / min for rolling into balls. When the average wet ball diameter reaches 1.5 mm, stop feeding powder A4; then feed powder B4 into the sugar coating machine at a rate of 10 g / min and continue to spray the peptizing agent for ball forming. When the average wet ball diameter reaches 2.7 mm, stop feeding powder B4; finally, feed powder E into the sugar coating machine at a rate of 10 g / min and continue to spray the peptizing agent for ball forming. When the average wet ball diameter reaches 3.0 mm, the ball forming is completed.

[0048] (3) Cure the wet balls at room temperature for 24 h, then dry them at 100 °C for 6 h, and finally calcine them at 550 °C for 4 h to obtain catalyst D2.

[0049] The physical and chemical properties of the catalysts obtained in the examples and comparative examples are listed in Table 1. The acid amount of the catalyst was measured by the NH 3 -TPD method, see ("Research Methods of Solid Catalysts", Petrochemical Industry, 30(12), 2001: 952).

[0050] Table 1 Physical and Chemical Properties of Catalysts

[0051] As can be seen from Table 1, compared with the catalysts prepared in the comparative examples, the catalysts prepared in the examples have a larger pore volume, specific surface area and higher total acid amount because the microporous Y zeolite and mesoporous alumina have a core-shell structure and the active metal components are loaded in the shell layer.

[0052] Application Examples The prepared catalyst was evaluated on a 200 mL fixed-bed hydrotreating pilot plant. Before the evaluation, the catalyst was pre-sulfurized by wet pre-sulfidation. The evaluation conditions were as follows: the reaction temperature of the commercial hydrofining catalyst was 350 °C, the reaction temperature of the hydro-upgrading catalyst was 355 °C, the hydrogen partial pressure was 11 MPa, and the liquid hourly space velocity was 2.0 h -1 , and the hydrogen-oil volume ratio was 800. The properties of the feedstock oil are shown in Table 2.

[0053] Table 2 Properties of Feedstock Oil

[0054] The properties of the upgraded diesel oil obtained by treating with the catalysts prepared in the examples and comparative examples are shown in Table 3.

[0055] Table 3 Properties of Upgraded Diesel Oil Obtained by Treating with Each Catalyst

[0056] The results in Table 3 show that compared with the comparative examples, the catalysts prepared in the examples have more excellent performance, higher yield of upgraded diesel oil, lower sulfur and nitrogen contents, and lower BMCI, and are more suitable as high-quality ethylene cracking feedstock.

[0057] The above are only the preferred embodiments of the present invention. All equivalent changes and modifications made according to the scope of the patent application of the present invention shall fall within the scope covered by the present invention.

Claims

1. A hydro-reforming catalyst, characterized in that: The catalyst is a spherical core-shell structure composed of Y molecular sieve as core and alumina as shell, and the alumina shell layer contains active components composed of VIB group metals and VIII group metals.

2. The hydro-reforming catalyst according to claim 1, characterized in that The thickness of the alumina shell layer is 10-90% of the catalyst radius.

3. The hydro-reforming catalyst according to claim 1, characterized in that Based on the total mass of 100 wt%, the content of aluminum oxide in the catalyst is 20-80 wt%, the content of Y molecular sieve is 5-35 wt%, the content of VIB group metal oxide is 8-30 wt%, and the content of VIII group metal oxide is 1-12 wt%.

4. A method for preparing the hydro-reforming catalyst according to claim 1, characterized in that: The steps include: (1) Mixing the Y-type molecular sieve and the molding auxiliary materials uniformly to obtain powder A, and mixing the alumina precursor, the active metal precursor and the molding auxiliary materials uniformly to obtain powder B; (2) conveying powder A to the sugar coating machine, spraying the adhesive agent to form balls, then switching powder A to powder B and conveying it to the sugar coating machine, and continuing to spray the adhesive agent to form balls; (3) The obtained wet bulb is cured, dried and calcined to obtain the hydrogenation reforming catalyst.

5. The method for preparing the hydro-upgrading catalyst according to claim 4, characterized in that: The alumina precursor in step (1) is selected from one or more of amorphous aluminum hydroxide, gibbsite, boehmite, and pseudo-boehmite.

6. The method for preparing the hydro-upgrading catalyst according to claim 4, characterized in that: The active metal precursor in step (1) is composed of a compound containing a metal element of Group VIB and a compound containing a metal element of Group VIII; Among them, the compound containing the metal element of Group VIB is one or more of molybdic acid, paramolybdic acid, ammonium molybdate, ammonium paramolybdate, molybdenum trioxide and tungstic acid, metatungstic acid, ammonium tungstate, ammonium metatungstate, and tungsten trioxide; the compound containing the metal element of Group VIII is derived from one or more of the inorganic acid salt or organic acid salt containing the metal element of Group VIII.

7. The method for preparing the hydro-reforming catalyst according to claim 4, characterized in that: The molding auxiliary material in step (1) is selected from one or more of sesbania powder, starch, methyl cellulose, polyacrylamide, and polycarboxylic acid, and the added amount thereof is 0.1-5% of the dry basis mass of the corresponding Y-type molecular sieve or alumina precursor.

8. The method for preparing the hydro-reforming catalyst according to claim 4, characterized in that: The curing temperature in step (3) is 10-50°C and the curing time is 4-72 hours.

9. The method for preparing the hydro-reforming catalyst according to claim 4, characterized in that: The calcination temperature in step (3) is 400-750°C and the calcination time is 1-8 h.

10. Use of the hydro-reforming catalyst according to claim 1 in diesel hydro-reforming.

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