A hydrogenation catalyst and its preparation method

Abstract

The present disclosure relates to a hydrogenation catalyst and a preparation method thereof. The hydrogenation catalyst comprises a porous support and an active element component supported on the porous support. The porous support is prepared by: pre-oxidizing asphalt powder to obtain pre-oxidized asphalt powder; uniformly mixing the pre-oxidized asphalt powder, an aluminum source, an organic carbon source, and water to obtain a mixed slurry, wherein the aluminum source contains aluminum oxide powder and / or an aluminum oxide powder precursor; and the organic carbon source comprises at least one of a cellulose ether, an ene alcohol polymer, or a sugar compound; hydrothermally treating the mixed slurry to obtain a hydrothermal product; drying the hydrothermal product, and heat-treating the dried hydrothermal product to obtain the porous support. The hydrogenation catalyst has high hydrogenation activity.

Description

Technical Field

[0001] The technical field of catalysts particularly relates to a hydrogenation catalyst and a preparation method thereof. Background Art

[0002] When a carbon support is used to prepare a hydrogenation catalyst, the interaction between the carbon support and the active metal component is weak. Therefore, the prepared hydrogenation catalyst has a high hydrogenation activity. Moreover, for discarded hydrogenation catalysts, the active metal component can be recovered by burning the support.

[0003] However, the hydrogenation activity of existing carbon-supported hydrogenation catalysts is still low. Summary of the Invention

[0004] The purpose of the present disclosure is to provide a hydrogenation catalyst and a preparation method thereof.

[0005] In order to achieve the above object, the present disclosure provides a hydrogenation catalyst, which includes a porous support and an active element component supported on the porous support;

[0006] The porous carrier is prepared by the following method:

[0007] pre-oxidizing the asphalt powder to obtain pre-oxidized asphalt powder;

[0008] The pre-oxidized asphalt powder, an aluminum source, an organic carbon source and water are mixed to obtain a mixed slurry, wherein the aluminum source contains aluminum oxide powder and / or an aluminum oxide powder precursor; and the organic carbon source includes at least one of cellulose ether, enol polymer or sugar compound;

[0009] subjecting the mixed slurry to hydrothermal treatment to obtain a hydrothermal product;

[0010] The hydrothermal product is dried, and the dried hydrothermal product is heat-treated to obtain the porous carrier.

[0011] Optionally, the prepared porous carrier includes an alumina core and a porous carbon layer distributed on the outer surface of the alumina core and the inner wall of the pores. Based on the total weight of the porous carrier, the content of the alumina core is 15 to 38 weight%, preferably 22 to 36 weight%; the content of the porous carbon layer is 62 to 85 weight%, preferably 64 to 78 weight%.

[0012] Optionally, the specific surface area of ​​the porous carrier is 150 to 1200 m 2 / g, pore volume is 0.5~1.3cm 3 / g, pore size is 3 to 30 nm.

[0013] Optionally, the porous carbon layer of the prepared porous carrier contains carbon, oxygen, hydrogen, sulfur and nitrogen. Based on the total weight of the porous carbon layer, the carbon content is 80-95 weight%, preferably 85-91 weight%; the oxygen content is 3-8 weight%, preferably 4-7 weight%; the hydrogen content is 0.1-2 weight%, preferably 0.5-1.5 weight%; the sulfur content is 1-8 weight%, preferably 2-6 weight%; the nitrogen content is 0.5-3 weight%, preferably 1-2 weight%.

[0014] Optionally, the alumina core of the prepared porous support contains a modifying element, and the modifying element is selected from at least one of group IIIA, IVA, VA, IIA, IIB, IIIB or IVB elements;

[0015] Based on the total weight of the alumina core, the content of the modifying element is 0.1 to 10 weight % in terms of element.

[0016] Optionally, the modifying element is selected from at least one of phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium or zirconium;

[0017] Based on the total weight of the alumina core, the content of the modifying element is 0.3 to 5 weight % in terms of element.

[0018] Optionally, the active element component includes a first active metal element and a second active metal element. Based on the total weight of the active element component, the content of the first active metal element is 0.5 to 10 weight percent, and the content of the second active metal element is 4 to 40 weight percent. The first active metal element is selected from at least one of the Group VIII metal elements, and the second active metal element is selected from at least one of the Group VIB metal elements.

[0019] Optionally, based on the total weight of the hydrogenation catalyst, the content of the porous carrier is 50 to 95% by weight, and the content of the active element component is 5 to 50% by weight.

[0020] Optionally, the hydrogenation catalyst further contains an organic auxiliary agent, which is selected from at least one of organic acids and / or ammonium salts thereof, organic alcohols and sugar compounds, and the molar ratio of the organic auxiliary agent to the first active metal element is (0.3-2):1.

[0021] Optionally, the organic acid is selected from at least one of trans-1,2-cyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxylic acid, glycolic acid, tartaric acid and malic acid;

[0022] The organic alcohol is at least one selected from glycerol, ethylene glycol, polyethylene glycol, trimethylolethane, pentaerythritol, xylitol and sorbitol;

[0023] The sugar compound is selected from at least one of triose, tetrose, pentose, D-glucose, D-galactose, D-mannose, D-fructose and sucrose.

[0024] Optionally, when preparing the porous carrier, the amount of the aluminum source used is 1 to 30 parts by weight, preferably 5 to 25 parts by weight, relative to 100 parts by weight of the pre-oxidized asphalt powder, calculated as alumina; the amount of the organic carbon source used is 1 to 60 parts by weight, preferably 10 to 50 parts by weight; the amount of water used is 25 to 1000 parts by weight, preferably 50 to 500 parts by weight.

[0025] Optionally, the aluminum source further contains an auxiliary agent, the auxiliary agent contains a modifying element, and the modifying element is selected from at least one of the elements of Group IIIA, IVA, VA, IIA, IIB, IIIB or IVB;

[0026] The content of the modifying element is 0.1 to 10 wt % based on the total dry weight of the aluminum source, calculated as the element.

[0027] Optionally, the modifying element is at least one selected from phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium and zirconium;

[0028] The content of the modifying element is 0.3 to 5 weight % based on the total dry weight of the aluminum source, calculated as the element.

[0029] Optionally, the organic carbon source used to prepare the porous carrier is a sugar compound, and the sugar compound includes at least one of sucrose, glucose, ribose, fructose or starch.

[0030] Optionally, the particle size of the pre-oxidized asphalt powder used to prepare the porous carrier is 1 to 10,000 μm, preferably 1 to 250 μm; the particle size of the aluminum source is 1 to 150 μm, preferably 1 to 75 μm.

[0031] Optionally, the asphalt powder used to prepare the porous carrier includes petroleum asphalt powder and / or coal asphalt powder, and the asphalt powder contains polycyclic aromatic hydrocarbons. Based on the total weight of the asphalt powder, the content of the polycyclic aromatic hydrocarbons is 70 to 100 weight%, preferably 85 to 100 weight%.

[0032] Optionally, the conditions of the hydrothermal treatment include: a temperature of 80 to 250° C., preferably 100 to 200° C., and a time of 0.5 to 48 hours, preferably 4 to 24 hours.

[0033] The present disclosure also provides a method for preparing any one of the above-mentioned hydrogenation catalysts, the method comprising:

[0034] impregnating the porous carrier with an aqueous solution containing the organic auxiliary agent and a compound containing the active element component to obtain a mixed slurry;

[0035] The mixed slurry is dried to obtain the hydrogenation catalyst.

[0036] Through the above technical solution, the hydrogenation catalyst provided by the present disclosure includes a porous support and an active element component supported on the porous support. Since the porous support used has a large specific surface area and pore volume, it can support a large amount of active element components. Therefore, the hydrogenation catalyst has a high hydrogenation activity and can be used for the hydroprocessing of petroleum fractions and residual oils, as well as the hydrogenation process of chemical raw materials and products.

[0037] Other features and advantages of the present disclosure will be described in detail in the following detailed description. DETAILED DESCRIPTION

[0038] The following describes the specific embodiments of the present disclosure in detail. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present disclosure, and are not intended to limit the present disclosure.

[0039] The first aspect of the present disclosure provides a hydrogenation catalyst, which includes a porous carrier and an active element component loaded on the porous carrier; the porous carrier is prepared by the following method: pre-oxidizing asphalt powder to obtain pre-oxidized asphalt powder; mixing the pre-oxidized asphalt powder, an aluminum source, an organic carbon source and water to obtain a mixed slurry, wherein the aluminum source contains alumina powder and / or an alumina powder precursor; the organic carbon source includes at least one of cellulose ether, enol polymer or sugar compound; hydrothermally treating the mixed slurry to obtain a hydrothermal product; drying the hydrothermal product, and heat-treating the dried hydrothermal product to obtain the porous carrier.

[0040] In the present disclosure, the hydrogenation catalyst provided by the present disclosure includes a porous support and an active element component loaded on the porous support, wherein an organic carbon source is added during the preparation of the porous support and a hydrothermal treatment is adopted. The hydrothermal treatment process can significantly increase the specific surface area of ​​the organic carbon source. Therefore, the porous support has a large specific surface area and pore volume and can load more active element components. Therefore, the hydrogenation catalyst has a high hydrogenation activity and can be used for the hydroprocessing of petroleum fractions and residual oils and the hydrogenation process of chemical raw materials and products.

[0041] In the present disclosure, specifically, pre-oxidation of asphalt powder during the preparation of a porous carrier can increase the melting point of the asphalt powder, preventing the asphalt powder from melting during the subsequent hydrothermal treatment and failing to form a porous structure. The pre-oxidation treatment of the asphalt powder can be performed by placing the asphalt powder in an oxygen-containing atmosphere, raising the temperature of the asphalt powder from room temperature to 120-400°C at a heating rate of 0.1-10°C / minute, and maintaining the constant temperature for 0.1-48 hours to obtain the pre-oxidized asphalt powder.

[0042] In the aluminum source used to prepare the porous carrier, the aluminum oxide powder precursor can generate aluminum oxide powder during heat treatment, and its specific type can be selected within a certain range. For example, the aluminum oxide powder precursor can be pseudo-boehmite powder.

[0043] According to the present disclosure, the prepared porous carrier may include an alumina core and a porous carbon layer distributed on the outer surface of the alumina core and the inner wall of the pores. Based on the total weight of the porous carrier, the content of the alumina core may be 15 to 38 weight%, preferably 22 to 36 weight%; the content of the porous carbon layer may be 62 to 85 weight%, preferably 64 to 78 weight%.

[0044] In the present disclosure, specifically, the prepared porous carrier is composed of an alumina core and a porous carbon layer. The alumina and the porous carbon layer are compounded in a specific proportion and a specific spatial structure to achieve the effect of 1+1>2. Therefore, the porous carrier has a larger specific surface area and pore volume.

[0045] According to the present disclosure, the specific surface area of ​​the porous carrier can be 150 to 1200 m 2 / g, and the pore volume can be 0.5~1.3cm 3 / g, and the pore size can be 3 to 30 nm.

[0046] According to the present disclosure, the porous carbon layer of the prepared porous carrier may contain carbon, oxygen, hydrogen, sulfur and nitrogen. Based on the total weight of the porous carbon layer, the content of the carbon element may be 80 to 95 weight%, preferably 85 to 91 weight%; the content of the oxygen element may be 3 to 8 weight%, preferably 4 to 7 weight%; the content of the hydrogen element may be 0.1 to 2 weight%, preferably 0.5 to 1.5 weight%; the content of the sulfur element may be 1 to 8 weight%, preferably 2 to 6 weight%; the content of the nitrogen element may be 0.5 to 3 weight%, preferably 1 to 2 weight%.

[0047] According to the present disclosure, the alumina core of the prepared porous carrier may contain a modifying element, and the modifying element is selected from at least one of group IIIA, IVA, VA, IIA, IIB, IIIB or IVB elements; based on the total weight of the alumina core, the content of the modifying element may be 0.1 to 10 weight % in terms of the element.

[0048] Preferably, the modifying element can be selected from at least one of phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium or zirconium; based on the total weight of the alumina core, the content of the modifying element can be 0.3 to 5 weight %.

[0049] According to the present disclosure, the active element component may include a first active metal element and a second active metal element. Based on the total weight of the active element component, the content of the first active metal element may be 0.5-10% by weight, preferably 1-6% by weight; the content of the second active metal element may be 4-40% by weight, preferably 5-35% by weight; wherein the first active metal element may be selected from at least one of the metal elements of Group VIII, and the second active metal element may be selected from at least one of the metal elements of Group VIB. As needed, during the catalyst preparation process, auxiliary elements such as phosphorus and boron may be introduced. For example, phosphorus may be introduced into the metal impregnation solution so that the phosphorus content, calculated as P2O5, is 0.5-10% by weight, preferably 1-8% by weight, based on the total amount of the catalyst.

[0050] According to the present disclosure, the relative amounts of the porous support and the active element component can vary within a certain range. For example, based on the total weight of the hydrogenation catalyst, the content of the porous support can be 50 to 95 weight %, and the content of the active element component can be 5 to 50 weight %.

[0051] According to the present disclosure, the hydrogenation catalyst may further contain an organic additive, which may be selected from at least one of an organic acid and / or its ammonium salt, an organic alcohol, and a saccharide compound. The molar ratio of the organic additive to the first active metal element may be (0.3-2):1. The organic additive can uniformly disperse the active element component in the porous support, thereby further enhancing the hydrogenation activity of the hydrogenation catalyst.

[0052] According to the present disclosure, the organic acid can be selected from at least one of trans-1,2-cyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxylic acid, glycolic acid, tartaric acid and malic acid; the organic alcohol can be selected from at least one of glycerol, ethylene glycol, polyethylene glycol, trimethylolethane, pentaerythritol, xylitol and sorbitol; the sugar compound can be selected from at least one of triose, tetrose, pentose, D-glucose, D-galactose, D-mannose, D-fructose and sucrose.

[0053] According to the present disclosure, when preparing the porous carrier, the amount of asphalt powder, aluminum source, organic carbon source and water can vary within a certain range. For example, relative to 100 parts by weight of the pre-oxidized asphalt powder, the amount of the aluminum source can be 1 to 30 parts by weight, preferably 5 to 25 parts by weight, calculated as alumina; the amount of the organic carbon source can be 1 to 60 parts by weight, preferably 10 to 50 parts by weight; the amount of water can be 25 to 1000 parts by weight, preferably 50 to 500 parts by weight.

[0054] According to the present disclosure, the aluminum source may further contain an auxiliary agent, the auxiliary agent containing a modifying element, the modifying element being selected from at least one of group IIIA, IVA, VA, IIA, IIB, IIIB or IVB elements; based on the total dry weight of the aluminum source, the content of the modifying element may be 0.1 to 10 wt % in terms of the element.

[0055] Preferably, the modifying element can be selected from at least one of phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium and zirconium; based on the total dry weight of the aluminum source, the content of the modifying element can be 0.3 to 5 weight % in terms of the element.

[0056] The method for determining the dry basis content involved in the embodiments of the present disclosure is as follows: alumina or an alumina precursor is heated to 600°C at a heating rate of 4°C / minute in a muffle furnace under an air atmosphere, and then maintained at 600°C for 4 hours. The percentage of the weight of the product after calcination to the weight before calcination is the dry basis content.

[0057] In the present disclosure, specifically, the auxiliary agent can be a water-soluble compound of a modifying element, for example, it can be boric acid, ammonium borate, ammonium metaborate, ammonium tetraborate, phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, boric acid, ammonium tetraborate, silica sol, silicon tetrachloride, ammonium fluorosilicate and ethyl orthosilicate, magnesium nitrate, magnesium acetate, magnesium sulfate, basic magnesium carbonate, magnesium chloride, zinc nitrate, zinc acetate, zinc sulfate, basic zinc carbonate, zinc chloride, lanthanum nitrate, lanthanum carbonate, lanthanum chloride, cerium nitrate, cerium carbonate, cerium chloride, titanium sulfate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate, zirconium nitrate, zirconyl nitrate and zirconium oxychloride, etc.

[0058] Among them, the method of introducing the auxiliary agent into the aluminum source can be selected within a certain range. For example, the compound containing the auxiliary agent component can be prepared into an aqueous solution, and the aqueous solution can be introduced into the aluminum source synthesis process; it can also be contacted with the aluminum source, impregnated or mixed into a slurry, and then dried at a temperature of 60°C-180°C and a time of 0.5 hour-24 hours; it can also be calcined at a condition of 300°C-1200°C and a time of 1-24 hours.

[0059] Preferably, the organic carbon source used to prepare the porous carrier may be a sugar compound, and the sugar compound may include at least one of sucrose, glucose, ribose, fructose or starch.

[0060] According to the present disclosure, when preparing the porous carrier, in order to enable the pre-oxidized asphalt powder, aluminum source and organic carbon source to be mixed more quickly and better, preferably, the particle size of the pre-oxidized asphalt powder used to prepare the porous carrier can be 1 to 10,000 μm, preferably 1 to 250 μm; the particle size of the aluminum source can be 1 to 150 μm, preferably 1 to 75 μm.

[0061] According to the present disclosure, when preparing the porous carrier, the asphalt powder can be selected within a certain range. For example, the asphalt powder used to prepare the porous carrier may include petroleum asphalt powder and / or coal asphalt powder. The asphalt powder may contain polycyclic aromatic hydrocarbons. Based on the total weight of the asphalt powder, the content of the polycyclic aromatic hydrocarbons may be 70 to 100 weight%, preferably 85 to 100 weight%.

[0062] Furthermore, when preparing the porous carrier, the heat treatment of the dried hydrothermal product to obtain the porous carrier may include: in an oxygen-containing atmosphere, raising the temperature of the dried hydrothermal product from room temperature to 120-400°C at a heating rate of 0.1-10°C / minute, and performing a first heat treatment for 0.1-48 hours to obtain a first intermediate product; in an inert atmosphere, raising the temperature of the first intermediate product to 400-950°C at a heating rate of 0.1-10°C / minute, and performing a second heat treatment for 0.1-24 hours to obtain a second intermediate product; in an oxygen-containing atmosphere, raising the temperature of the second intermediate product to 700-1000°C at a heating rate of 0.1-10°C / minute, and performing a third heat treatment for 0.1-12 hours to obtain the porous carrier.

[0063] The oxygen-containing atmosphere contains an oxygen-containing gas or a mixture of an oxygen-containing gas and an inert gas, the inert atmosphere contains an inert gas, the oxygen-containing gas is selected from at least one of oxygen, carbon dioxide, carbon monoxide or water vapor, and the inert gas is selected from at least one of nitrogen, argon or helium.

[0064] Furthermore, the flow rate of the oxygen-containing gas stream during the first heat treatment can be 1 to 80 liters / hour, the flow rate of the inert gas stream during the second heat treatment can be 1 to 80 liters / hour, and the flow rate of the oxygen-containing gas stream during the third heat treatment can be 1 to 80 liters / hour.

[0065] According to the present disclosure, the conditions of the hydrothermal treatment can vary within a certain range. For example, the conditions of the hydrothermal treatment can include: a temperature of 80 to 250°C, preferably 100-200°C, and a time of 0.5 to 48 hours, preferably 4 to 24 hours.

[0066] In the present disclosure, the closed reactor can be any reactor that can realize the hydrothermal reaction, for example, a high-pressure reactor, etc. The reaction can be carried out under static conditions or under stirring conditions, and the hydrothermal treatment is preferably carried out under stirring conditions.

[0067] The second aspect of the present disclosure provides a method for preparing any one of the above-mentioned hydrogenation catalysts, comprising: impregnating the porous carrier with an aqueous solution containing the organic auxiliary agent and a compound containing the active element component to obtain a mixed slurry; and drying the mixed slurry to obtain the hydrogenation catalyst.

[0068] The present disclosure is further illustrated by the following examples, but the present disclosure is not limited thereto. Unless otherwise specified, the raw materials, reagents, instruments and equipment involved in the examples of the present disclosure can be purchased.

[0069] The pseudo-boehmite powder involved in the embodiments of the present disclosure has a dry basis weight of 70%. When introducing the modifying element, a compound containing an auxiliary component is formulated into an aqueous solution, and the aqueous solution is contacted with alumina powder and / or alumina powder precursor, impregnated or mixed into a slurry, and then dried at a temperature of 120°C for 12 hours. When an alumina powder precursor is used, only drying is performed without calcination. When an alumina powder precursor is used (a product obtained by heating the alumina powder precursor to 600°C at a heating rate of 4°C / minute in a muffle furnace under an air atmosphere and then maintaining the temperature at 600°C for 4 hours), drying is followed by calcination at 450°C for 8 hours.

[0070] The porous support was prepared as follows:

[0071] Preparation Example 1

[0072] (1) 1000 g of asphalt was weighed and placed in a closed tubular furnace. Under the condition of air flow of 80 L / h, the temperature was raised from room temperature to 360°C at a heating rate of 5°C / min and maintained at 360°C for 4 hours to obtain pre-oxidized asphalt. The temperature of the pre-oxidized asphalt was lowered to room temperature and crushed to obtain pre-oxidized asphalt powder.

[0073] (2) 500 g of the pre-oxidized asphalt powder (particle size 1-250 μm), 50 g of methylcellulose, 10 g of glucose, and 50 g of pseudo-boehmite powder (70% by weight on a dry basis, particle size 1-75 μm) were weighed and mixed with 3600 g of deionized water and stirred to obtain a mixed slurry. The aluminum source (pseudo-boehmite powder) contained a modifying element (phosphorus) modified using ammonium phosphate as a raw material. The content of the modifying element (phosphorus) was 2.2 wt % based on the total dry weight of the aluminum source.

[0074] (3) The mixed slurry was transferred to a 5-liter stainless steel polytetrafluoroethylene-lined autoclave with stirring function, sealed, heated to 100°C, and subjected to constant temperature hydrothermal treatment for 12 hours under stirring to obtain a hydrothermal product. The temperature of the hydrothermal product was cooled to room temperature and then dried in a forced air oven at 120°C for 48 hours to obtain a dried hydrothermal product.

[0075] (4) Take 200 g of the dried hydrothermal product and place it in a closed tube furnace. Under the condition of air flow and air flow rate of 40 liters / hour, the temperature of the mixed material is raised from room temperature to 120°C at a heating rate of 3°C / min, and kept at 120°C for 18 hours. Then, it is raised to 200°C at a heating rate of 0.2°C / min and kept at this temperature for 4 hours. Then, it is raised to 240°C at a heating rate of 0.2°C / min and kept at this temperature for 8 hours. Then, it is raised to 280°C at a heating rate of 0.2°C / min and kept at this temperature for 8 hours. Then, it is raised to 300°C at a heating rate of 0.2°C / min and kept at this temperature for 2 hours. The first intermediate product was obtained when the air was switched to nitrogen with a nitrogen flow rate of 40 liters / hour, and the temperature of the first intermediate product was raised to 700°C at a heating rate of 3°C / minute, and maintained at 700°C for a constant temperature heat treatment for 2 hours to obtain a second intermediate product. Finally, the nitrogen was switched to carbon dioxide with a carbon dioxide flow rate of 40 liters / hour, and the temperature of the second intermediate product was raised to 950°C at a heating rate of 5°C / minute, and maintained at 950°C for a constant temperature heat treatment for 4 hours to obtain a porous support S1. Based on the total weight of the porous support S1, the content of the alumina core was 24% by weight, and the content of the porous carbon layer was 76% by weight.

[0076] Based on the total weight of the porous carbon layer, the carbon content, oxygen content, hydrogen content, sulfur content, and nitrogen content are 89.07 weight %, 4.35 weight %, 0.61 weight %, 4.79 weight %, and 1.18 weight % respectively; based on the total weight of the alumina core, the content of the modifying element (phosphorus) is 2.2 weight % respectively.

[0077] The specific surface area of ​​the porous carrier S1 was determined to be 545 m 2 / g, pore volume is 0.78cm 3 / g.

[0078] Preparation Example 2

[0079] (1) 1000 g of asphalt was weighed and placed in a closed tubular furnace. Under the condition of air flow of 80 L / h, the temperature was raised from room temperature to 360°C at a heating rate of 5°C / min and maintained at 360°C for 4 hours to obtain pre-oxidized asphalt. The temperature of the pre-oxidized asphalt was lowered to room temperature and crushed to obtain pre-oxidized asphalt powder.

[0080] (2) Weigh 500 g of the above-mentioned pre-oxidized asphalt powder (particle size of 1 to 250 μm), 50 g of methyl cellulose, 10 g of glucose and 50 g of pseudo-boehmite powder (dry basis content of 70% by weight, particle size of 1 to 75 μm), mix with 3600 g of deionized water and stir evenly to obtain a mixed slurry.

[0081] (3) The mixed slurry was transferred to a 5-liter stainless steel polytetrafluoroethylene-lined autoclave with stirring function, sealed, heated to 100°C, and subjected to constant temperature hydrothermal treatment for 12 hours under stirring to obtain a hydrothermal product. The temperature of the hydrothermal product was cooled to room temperature and then dried in a forced air oven at 120°C for 48 hours to obtain a dried hydrothermal product.

[0082] (4) 200 g of the dried hydrothermal product was placed in a sealed tube furnace. Under the condition of air flow at 40 liters / hour, the temperature of the hydrothermal product was raised from room temperature to 240°C at a heating rate of 5°C / min, and maintained at 240°C for 8 hours to obtain a first intermediate product. Then, the air was switched to nitrogen, and the nitrogen flow was controlled at 40 liters / hour. The temperature of the first intermediate product was raised to 700°C at a heating rate of 3°C / min, and maintained at 700°C for 2 hours to obtain a second intermediate product. Finally, the nitrogen was switched to carbon dioxide, and the carbon dioxide flow was controlled at 40 liters / hour. The temperature of the second intermediate product was raised to 950°C at a heating rate of 5°C / min, and maintained at 950°C for 4 hours to obtain a porous support S2. Based on the total weight of the porous support S2, the content of the alumina core was 26% by weight, and the content of the porous carbon layer was 74% by weight.

[0083] Based on the total weight of the porous carbon layer, the carbon content, oxygen content, hydrogen content, sulfur content, and nitrogen content are 88.28 weight %, 4.67 weight %, 0.58 weight %, 5.38 weight %, and 1.09 weight %.

[0084] The specific surface area of ​​the porous carrier S2 was determined to be 516 m 2 / g, pore volume is 0.75cm 3 / g.

[0085] Preparation Example 3

[0086] (1) 1000 g of asphalt was weighed and placed in a closed tubular furnace. Under the condition of air flow of 80 L / h, the temperature was raised from room temperature to 350°C at a heating rate of 5°C / min and maintained at 350°C for 8 hours to obtain pre-oxidized asphalt. The temperature of the pre-oxidized asphalt was lowered to room temperature and crushed to obtain pre-oxidized asphalt powder.

[0087] (2) Weigh 500 g of the above-mentioned pre-oxidized asphalt powder (particle size of 1 to 250 μm), 50 g of methyl cellulose, 10 g of glucose and 28 g of pseudo-boehmite powder (dry basis content of 70% by weight, particle size of 1 to 75 μm), mix with 3600 g of deionized water and stir evenly to obtain a mixed slurry.

[0088] (3) The mixed slurry was transferred to a 5-liter stainless steel polytetrafluoroethylene-lined autoclave with stirring function, sealed, heated to 120°C, and subjected to constant temperature hydrothermal treatment for 8 hours under stirring to obtain a hydrothermal product. The temperature of the hydrothermal product was cooled to room temperature and then dried in a forced air oven at 120°C for 48 hours to obtain a dried hydrothermal product.

[0089] (4) 200 g of the dried hydrothermal product was placed in a sealed tube furnace. Under the condition of air flow at 40 liters / hour, the temperature of the hydrothermal product was raised from room temperature to 300°C at a heating rate of 5°C / min, and maintained at 300°C for 4 hours to obtain a first intermediate product. Then, the air was switched to nitrogen, and the nitrogen flow was controlled at 40 liters / hour. The temperature of the first intermediate product was raised to 700°C at a heating rate of 3°C / min, and maintained at 700°C for 2 hours to obtain a second intermediate product. Finally, the nitrogen was switched to carbon dioxide, and the carbon dioxide flow was controlled at 40 liters / hour. The temperature of the second intermediate product was raised to 980°C at a heating rate of 5°C / min, and maintained at 980°C for 3 hours to obtain a porous support S3. Based on the total weight of the porous support S3, the content of the alumina core was 23% by weight, and the content of the porous carbon layer was 77% by weight.

[0090] Based on the total weight of the porous carbon layer, the carbon content is 89.29 weight %, the oxygen content is 4.13 weight %, the hydrogen content is 0.59 weight %, the sulfur content is 4.71 weight %, and the nitrogen content is 1.28 weight %.

[0091] The specific surface area of ​​the porous carrier S3 was determined to be 479 m 2 / g, pore volume is 0.74cm 3 / g.

[0092] Preparation Example 4

[0093] (1) 1000 g of asphalt was weighed and placed in a closed tubular furnace. Under the condition of air flow of 80 liters per hour, the temperature was raised from room temperature to 400°C at a heating rate of 5°C per minute and maintained at 400°C for 2 hours to obtain pre-oxidized asphalt. The temperature of the pre-oxidized asphalt was lowered to room temperature and crushed to obtain pre-oxidized asphalt powder.

[0094] (2) Weigh 500 g of the above-mentioned pre-oxidized asphalt powder (particle size of 1 to 250 μm), 50 g of methyl cellulose, 50 g of glucose and 30 g of pseudo-boehmite powder (dry basis content of 70% by weight, particle size of 1 to 75 μm) calcined at 600°C for 4 hours, mix with 3600 g of deionized water and stir evenly to obtain a mixed slurry.

[0095] (3) The mixed slurry was transferred to a 5-liter stainless steel polytetrafluoroethylene-lined autoclave with stirring function, sealed, heated to 180°C, and subjected to constant temperature hydrothermal treatment for 4 hours under stirring to obtain a hydrothermal product. The temperature of the hydrothermal product was cooled to room temperature and then dried in a forced air oven at 120°C for 48 hours to obtain a dried hydrothermal product.

[0096] (4) 200 g of the dried hydrothermal product was placed in a sealed tube furnace. Under the condition of air flow at 40 liters / hour, the temperature of the hydrothermal product was raised from room temperature to 350°C at a heating rate of 5°C / min, and maintained at 350°C for 4 hours to obtain a first intermediate product. Then, the air was switched to nitrogen, and the nitrogen flow was controlled at 40 liters / hour. The temperature of the first intermediate product was raised to 700°C at a heating rate of 3°C / min, and maintained at 700°C for 3 hours to obtain a second intermediate product. Finally, the nitrogen was switched to carbon dioxide, and the carbon dioxide flow was controlled at 40 liters / hour. The temperature of the second intermediate product was raised to 940°C at a heating rate of 5°C / min, and maintained at 940°C for 8 hours to obtain a porous support S4. Based on the total weight of the porous support S4, the content of the alumina core was 28% by weight, and the content of the porous carbon layer was 72% by weight.

[0097] Based on the total weight of the porous carbon layer, the carbon content is 88.78 weight %, the oxygen content is 4.85 weight %, the hydrogen content is 0.72 weight %, the sulfur content is 4.17 weight %, and the nitrogen content is 1.48 weight %.

[0098] The specific surface area of ​​the porous carrier S4 was determined to be 459 m 2 / g, pore volume is 0.73cm 3 / g.

[0099] Preparation Example 5

[0100] Porous support S5 was prepared according to the method of Preparation Example 2, except that, in the preparation of porous support S5, the amount of aluminum source (pseudo-boehmite powder) was 1 part by weight, and the amount of organic carbon source (methylcellulose + glucose) was 1 part by weight, calculated as alumina, relative to 100 parts by weight of asphalt powder. Based on the total weight of porous support S5, the content of the alumina core was 34% by weight, and the content of the porous carbon layer was 66% by weight.

[0101] The specific surface area of ​​the porous carrier S5 was determined to be 319 m 2 / g, pore volume is 0.69cm 3 / g.

[0102] Preparation Example 6

[0103] Porous support S6 was prepared according to the method of Preparation Example 2, except that, in the preparation of porous support S6, the amount of aluminum source (alumina) was 30 parts by weight, and the amount of organic carbon source (glucose) was 60 parts by weight, calculated as alumina, relative to 100 parts by weight of pitch powder. Based on the total weight of porous support S6, the content of the alumina core was 38% by weight, and the content of the porous carbon layer was 62% by weight.

[0104] The specific surface area of ​​the porous carrier S6 was determined to be 345 m 2 / g, pore volume is 0.68cm 3 / g.

[0105] Preparation Example 7

[0106] Porous support S7 was prepared according to the method of Preparation Example 2, except that the amount of aluminum source (alumina) used in the preparation of porous support S7 was 5 parts by weight, and the amount of organic carbon source (glucose + sucrose) used was 10 parts by weight, calculated as alumina, relative to 100 parts by weight of pitch powder. Based on the total weight of porous support S7, the content of the alumina core was 22% by weight, and the content of the porous carbon layer was 78% by weight.

[0107] The specific surface area of ​​the porous carrier S7 was determined to be 489 m 2 / g, pore volume is 0.74cm 3 / g.

[0108] Preparation Example 8

[0109] Porous support S8 was prepared according to the method of Preparation Example 2, except that the aluminum source (alumina + pseudo-boehmite powder) was used in an amount of 25 parts by weight, and the organic carbon source (glucose + fructose) was used in an amount of 50 parts by weight, calculated as alumina, relative to 100 parts by weight of the asphalt powder. Based on the total weight of porous support S8, the alumina core content was 36% by weight, and the porous carbon layer content was 64% by weight.

[0110] The specific surface area of ​​the porous carrier S8 was determined to be 510 m 2 / g, pore volume is 0.73cm 3 / g.

[0111] Preparation Example 9

[0112] The porous carrier S9 was prepared according to the method of Preparation Example 1, with the following difference: when preparing the porous carrier S9, the aluminum source (alumina powder) contained a modifying element (zirconium), and zirconium nitrate was used as the raw material for modification. Based on the total dry weight of the aluminum source, the content of the modifying element (zirconium) was 0.1 wt % in terms of element.

[0113] The specific surface area of ​​the porous carrier S9 was determined to be 528 m 2 / g, pore volume is 0.76cm 3 / g.

[0114] Preparation Example 10

[0115] The porous carrier S10 was prepared according to the method of Preparation Example 1, with the following difference: when preparing the porous carrier S10, the aluminum source (pseudo-boehmite powder) contained a modifying element (silicon), and the modification was carried out using silica sol as a raw material. Based on the total dry weight of the aluminum source, the content of the modifying element (silicon) was 10 wt % in terms of element.

[0116] The specific surface area of ​​the porous carrier S10 was determined to be 535 m 2 / g, pore volume is 0.77cm 3 / g.

[0117] Preparation Example 11

[0118] The porous carrier S11 was prepared according to the method of Preparation Example 1, with the following difference: when preparing the porous carrier S11, the aluminum source (pseudo-boehmite powder) contained a modifying element (magnesium), and was modified using magnesium acetate as a raw material. Based on the total dry weight of the aluminum source, the content of the modifying element (magnesium) was 0.3 wt % in terms of element.

[0119] The specific surface area of ​​the porous carrier S11 was determined to be 540 m 2 / g, pore volume is 0.76cm 3 / g.

[0120] Preparation Example 12

[0121] The porous carrier S12 was prepared according to the method of Preparation Example 1, with the following difference: when preparing the porous carrier S12, the aluminum source (pseudo-boehmite powder) contained modifying elements (lanthanum and cerium), and was modified using lanthanum nitrate and cerium nitrate as raw materials. Based on the total dry weight of the aluminum source, the content of the modifying elements (3.8 weight% of lanthanum and 1.2 weight% of cerium) was 5 weight%.

[0122] The specific surface area of ​​the porous carrier S12 was determined to be 532 m 2 / g, pore volume is 0.75cm 3 / g.

[0123] Preparation Example 13

[0124] The porous carrier S13 was prepared according to the method of Preparation Example 1, with the following difference: when preparing the porous carrier S13, the aluminum source (pseudo-boehmite powder) contained a modifying element (boron), and was modified using boric acid as a raw material. Based on the total dry weight of the aluminum source, the content of the modifying element (boron) was 1.6 wt % in terms of element.

[0125] The specific surface area of ​​the porous carrier S13 was determined to be 545 m 2 / g, pore volume is 0.77cm 3 / g.

[0126] Preparation Example 14

[0127] The porous carrier S14 was prepared according to the method of Preparation Example 1, with the following difference: when preparing the porous carrier S14, the aluminum source (aluminum oxide powder) contained a modifying element (zinc), and was modified using zinc nitrate as the raw material. Based on the total dry weight of the aluminum source, the content of the modifying element (zinc) was 2.3 wt % in terms of element.

[0128] The specific surface area of ​​the porous carrier S14 was determined to be 552 m 2 / g, pore volume is 0.77cm 3 / g.

[0129] Preparation Example 15

[0130] The porous carrier S15 was prepared according to the method of Preparation Example 1, with the following difference: when preparing the porous carrier S15, the aluminum source (pseudo-boehmite powder) contained a modifying element (titanium), and was modified using titanium sulfate as the raw material. Based on the total dry weight of the aluminum source, the content of the modifying element (titanium) was 4.2 wt % in terms of element.

[0131] The specific surface area of ​​the porous carrier S15 was determined to be 549 m 2 / g, pore volume is 0.76cm 3 / g.

[0132] Comparative Preparation Example 1

[0133] The porous carrier DT1 was prepared according to the method of Preparation Example 1, except that, when preparing the porous carrier DT-1, the mixed slurry was prepared by mixing 500 g of pre-oxidized asphalt powder (particle size of 1 to 250 μm), 50 g of methyl cellulose, 10 g of glucose and 3600 g of deionized water and stirring them evenly.

[0134] The specific surface area of ​​the prepared porous carrier DT-1 is 232 m 2 / g, pore volume is 0.18cm 3 / g.

[0135] Comparative Preparation Example 2

[0136] The porous carrier DT2 was prepared according to the method of Preparation Example 1, except that, when preparing the porous carrier DT-2, the mixed slurry was prepared by mixing 500 g of pseudo-boehmite powder (dry basis content of 70 weight %), 50 g of methyl cellulose, 10 g of glucose and 3600 g of deionized water and stirring them evenly.

[0137] The specific surface area of ​​the prepared porous carrier DT-2 is 169m 2 / g, pore volume is 0.71cm 3 / g.

[0138] Comparative Preparation Example 3

[0139] The porous carrier DT3 was prepared according to the method of Preparation Example 1, except that: when preparing the porous carrier DT-3, the mixed slurry was not subjected to hydrothermal treatment. After the mixed slurry was directly dried, 200 grams was placed in a closed tube furnace for subsequent heat treatment.

[0140] It has been determined that the specific surface area of ​​alumina is 265m 2 / g, pore volume is 0.72cm 3 / g.

[0141] Comparative Preparation Example 4

[0142] The porous carrier DT4 was prepared according to the method of Preparation Example 1, except that: when preparing the porous carrier DT-4, the asphalt was not pre-oxidized, and the asphalt was directly used to prepare the mixed slurry, and subsequent hydrothermal treatment and heat treatment were performed.

[0143] The specific surface area of ​​the prepared porous carrier DT-4 is 213 m 2 / g, pore volume is 0.72cm 3 / g.

[0144] Comparative Preparation Example 5

[0145] The porous carrier DT5 was prepared according to the method of Preparation Example 1, except that: when preparing the porous carrier DT-5, the mixed slurry was prepared by mixing 500 grams of pre-oxidized asphalt powder (particle size of 1 to 250 μm), 50 grams of methyl cellulose, 10 grams of glucose, 7.35 grams of titanium sulfate and 3600 grams of deionized water and stirring them evenly.

[0146] The specific surface area of ​​the prepared porous carrier DT-5 is 201m 2 / g, pore volume is 0.17cm 3 / g.

[0147] Catalyst preparation:

[0148] Examples 1-15

[0149] 175 mL of an aqueous solution containing 5.29 g of phosphoric acid (85%), 38.65 g of molybdenum trioxide, 15.78 g of basic nickel carbonate (NiO content 51%), 1.86 g of phosphotungstic acid, 1.13 g of cobalt nitrate, 20.32 g of citric acid, 3.21 g of ethylene glycol and 2.13 g of propylene glycol was used to impregnate porous supports S1-S15, respectively. The amount of each porous support was 200 g. After stirring evenly, the mixture was allowed to stand for 2 h and dried at 120°C for 4 h to obtain hydrogenation catalysts C1-C15.

[0150] Comparative Examples 1-5

[0151] 175 mL of an aqueous solution containing 5.29 g of phosphoric acid (85%), 38.65 g of molybdenum trioxide, 15.78 g of basic nickel carbonate (NiO content 51%), 1.86 g of phosphotungstic acid, 1.13 g of cobalt nitrate, 20.32 g of citric acid, 3.21 g of ethylene glycol and 2.13 g of propylene glycol was used to impregnate the porous carriers DT1-DT5, respectively. The amount of each porous carrier was 200 g. After stirring evenly, the mixture was allowed to stand for 2 h and dried at 120°C for 4 h to obtain hydrogenation catalysts D1-D5.

[0152] Test Case

[0153] The hydrodesulfurization activities of hydrogenation catalysts C1-C15 and D1-D5 were evaluated using straight-run kerosene (total sulfur 2956 μg / g) as the reaction feedstock.

[0154] The evaluation apparatus was a fixed-bed hydrogenation reactor, with a catalyst particle size of 20-30 mesh and a catalyst dosage of 20 grams. Hydrogen was passed through the reactor in a single pass. Prior to the reaction, the catalyst was pre-sulfided with straight-run kerosene containing 2% CS2. The sulfidation conditions included a pressure of 1.6 MPa, a hydrogen-to-oil volume ratio of 80:1, and a mass space velocity of 4 h / min. -1 , temperature 310℃, time 4 hours. After sulfurization, the feed was switched to straight-run kerosene. The reaction conditions included: reaction temperature 260℃, mass space velocity 4h -1 , reaction pressure 1.6 MPa, hydrogen to oil ratio 80:1. After 6 days of reaction at 260°C, samples were taken for analysis, and the relative hydrodesulfurization activities of the hydrogenation catalysts were calculated. The results are shown in Table 1.

[0155] Table 1 Comparison of catalytic performance of various hydrogenation catalysts

[0156]

[0157]

[0158] As can be seen from Table 1, the hydrogenation catalyst provided by the present disclosure has a high hydrodesulfurization activity.

[0159] The preferred embodiments of the present disclosure are described in detail above. However, the present disclosure is not limited to the specific details of the above embodiments. Within the technical concept of the present disclosure, various simple modifications can be made to the technical solutions of the present disclosure, and these simple modifications all fall within the scope of protection of the present disclosure.

[0160] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present disclosure will not further describe various possible combinations.

[0161] In addition, the various embodiments of the present disclosure may be arbitrarily combined, and as long as they do not violate the concept of the present disclosure, they should also be regarded as the contents disclosed by the present disclosure.

Claims

1. A hydrogenation catalyst, characterized in that The hydrogenation catalyst includes a porous support and an active element component supported on the porous support; The porous carrier is prepared by the following method: pre-oxidizing the asphalt powder to obtain pre-oxidized asphalt powder; The pre-oxidized asphalt powder, an aluminum source, an organic carbon source and water are mixed to obtain a mixed slurry, wherein the aluminum source contains aluminum oxide powder and / or an aluminum oxide powder precursor; and the organic carbon source includes at least one of cellulose ether, enol polymer or sugar compound; subjecting the mixed slurry to hydrothermal treatment to obtain a hydrothermal product; Drying the hydrothermal product and heat-treating the dried hydrothermal product to obtain the porous carrier; The conditions of the hydrothermal treatment include: a temperature of 80 to 250°C and a time of 0.5 to 48 hours; The heat treatment includes: in an oxygen-containing atmosphere, raising the temperature of the dried hydrothermal product from room temperature to 120-400°C at a heating rate of 0.1-10°C / minute, and performing a first heat treatment for 0.1-48 hours to obtain a first intermediate product; in an inert atmosphere, raising the temperature of the first intermediate product to 400-950°C at a heating rate of 0.1-10°C / minute, and performing a second heat treatment for 0.1-24 hours to obtain a second intermediate product; in an oxygen-containing atmosphere, raising the temperature of the second intermediate product to 700-1000°C at a heating rate of 0.1-10°C / minute, and performing a third heat treatment for 0.1-12 hours.

2. The hydrogenation catalyst according to claim 1, characterized in that The prepared porous carrier includes an alumina core and a porous carbon layer distributed on the outer surface of the alumina core and the inner wall of the pores. Based on the total weight of the porous carrier, the content of the alumina core is 15 to 38 weight percent; the content of the porous carbon layer is 62 to 85 weight percent.

3. The hydrogenation catalyst according to claim 2, characterized in that Based on the total weight of the porous support, the content of the alumina core is 22 to 36 weight %; and the content of the porous carbon layer is 64 to 78 weight %.

4. The hydrogenation catalyst according to claim 2, characterized in that The specific surface area of ​​the porous carrier is 150 to 1200 m 2 / g, pore volume of 0.5~1.3 cm 3 / g, pore size is 3 to 30 nm.

5. The hydrogenation catalyst according to any one of claims 1 to 4, characterized in that The porous carbon layer of the prepared porous carrier contains carbon, oxygen, hydrogen, sulfur and nitrogen elements. Based on the total weight of the porous carbon layer, the content of the carbon element is 80 to 95 weight %; the content of the oxygen element is 3 to 8 weight %; the content of the hydrogen element is 0.1 to 2 weight %; the content of the sulfur element is 1 to 8 weight %; and the content of the nitrogen element is 0.5 to 3 weight %.

6. The hydrogenation catalyst according to claim 5, characterized in that Based on the total weight of the porous carbon layer, the content of the carbon element is 85 to 91 weight %; the content of the oxygen element is 4 to 7 weight %; the content of the hydrogen element is 0.5 to 1.5 weight %; the content of the sulfur element is 2 to 6 weight %; and the content of the nitrogen element is 1 to 2 weight %.

7. The hydrogenation catalyst according to any one of claims 1 to 4, characterized in that The alumina core of the prepared porous carrier contains a modifying element, wherein the modifying element is selected from at least one of group IIIA, IVA, VA, IIA, IIB, IIIB or IVB elements; Based on the total weight of the alumina core, the content of the modifying element is 0.1 to 10% by weight.

8. The hydrogenation catalyst according to claim 7, characterized in that The modifying element is selected from at least one of phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium or zirconium; Based on the total weight of the alumina core, the content of the modifying element is 0.3 to 5% by weight.

9. The hydrogenation catalyst according to claim 1, characterized in that The active element component includes a first active metal element and a second active metal element. Based on the total weight of the active element component, the content of the first active metal element is 0.5 to 10 weight percent, and the content of the second active metal element is 4 to 40 weight percent. The first active metal element is selected from at least one of the Group VIII metal elements, and the second active metal element is selected from at least one of the Group VIB metal elements.

10. The hydrogenation catalyst according to claim 9, characterized in that Based on the total weight of the hydrogenation catalyst, the content of the porous carrier is 50 to 95 weight %, and the content of the active element component is 5 to 50 weight %.

11. The hydrogenation catalyst according to claim 9 or 10, characterized in that The hydrogenation catalyst further contains an organic auxiliary agent, which is selected from at least one of organic acids and / or ammonium salts thereof, organic alcohols and sugar compounds. The molar ratio of the organic auxiliary agent to the first active metal element is (0.3-2):

1.

12. The hydrogenation catalyst according to claim 11, characterized in that The organic acid is selected from at least one of trans-1,2-cyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxylic acid, glycolic acid, tartaric acid and malic acid; The organic alcohol is at least one selected from glycerol, ethylene glycol, polyethylene glycol, trimethylolethane, pentaerythritol, xylitol and sorbitol; The sugar compound is selected from at least one of triose, tetrose, pentose, D-glucose, D-galactose, D-mannose, D-fructose and sucrose.

13. The hydrogenation catalyst according to any one of claims 1 to 4, characterized in that When preparing the porous carrier, relative to 100 parts by weight of the pre-oxidized asphalt powder, the amount of the aluminum source used is 1 to 30 parts by weight, the amount of the organic carbon source used is 1 to 60 parts by weight, and the amount of water used is 25 to 1000 parts by weight, calculated as alumina.

14. The hydrogenation catalyst according to claim 13, characterized in that Relative to 100 parts by weight of the pre-oxidized asphalt powder, the amount of the aluminum source is 5 to 25 parts by weight, calculated as aluminum oxide; the amount of the organic carbon source is 10 to 50 parts by weight; and the amount of water is 50 to 500 parts by weight.

15. The hydrogenation catalyst according to any one of claims 1 to 4, characterized in that The aluminum source further contains an auxiliary agent, the auxiliary agent contains a modifying element, and the modifying element is selected from at least one of the elements of Group IIIA, IVA, VA, IIA, IIB, IIIB or IVB; The content of the modifying element is 0.1 to 10 wt % based on the total dry weight of the aluminum source, calculated as the element.

16. The hydrogenation catalyst according to claim 15, characterized in that The modifying element is at least one element selected from phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium and zirconium; The content of the modifying element is 0.3 to 5 wt % based on the total dry weight of the aluminum source, calculated as the element.

17. The hydrogenation catalyst according to any one of claims 1 to 4, characterized in that The organic carbon source used to prepare the porous carrier is a sugar compound, and the sugar compound includes at least one of sucrose, glucose, ribose, fructose or starch.

18. The hydrogenation catalyst according to any one of claims 1 to 4, characterized in that The particle size of the pre-oxidized asphalt powder used to prepare the porous carrier is 1 to 10,000 μm; the particle size of the aluminum source is 1 to 150 μm.

19. The hydrogenation catalyst according to claim 18, characterized in that The particle size of the pre-oxidized asphalt powder used to prepare the porous carrier is 1 to 250 μm; the particle size of the aluminum source is 1 to 75 μm.

20. The hydrogenation catalyst according to any one of claims 1 to 4, characterized in that The asphalt powder used to prepare the porous carrier includes petroleum asphalt powder and / or coal asphalt powder. The asphalt powder contains polycyclic aromatic hydrocarbons. Based on the total weight of the asphalt powder, the content of the polycyclic aromatic hydrocarbons is 70 to 100% by weight.

21. The hydrogenation catalyst according to claim 20, characterized in that Based on the total weight of the asphalt powder, the content of the polycyclic aromatic hydrocarbons is 85 to 100 weight %.

22. The hydrogenation catalyst according to claim 1, characterized in that The conditions of the hydrothermal treatment include: a temperature of 100-200° C. and a time of 4 to 24 hours.

23. A method for preparing the hydrogenation catalyst according to any one of claims 1 to 22, characterized in that: The method includes: impregnating the porous carrier with an aqueous solution containing the organic auxiliary agent and a compound containing the active element component to obtain a mixed slurry; The mixed slurry is dried to obtain the hydrogenation catalyst.

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