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 comprises an alumina core and a porous carbon layer distributed on the outer surface of the alumina core and the inner wall of the pores. The alumina core comprises 10 to 40% by weight, preferably 20 to 30% by weight, based on the total weight of the porous support; the porous carbon layer comprises 60 to 90% by weight, preferably 70 to 80% by weight. The hydrogenation catalyst provided by the present disclosure comprises a porous support and an active element component supported on the porous support. Since the porous support has a large specific surface area and pore volume, it can support a large amount of active element components. Therefore, the hydrogenation catalyst has high hydrogenation activity and can be used in the hydroprocessing of petroleum fractions and residual oils, as well as in the hydrogenation of chemical raw materials and products.

Description

Technical Field

[0001] The present disclosure relates to the field of catalyst technology, and particularly 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 object of the present disclosure is to provide a hydrogenation catalyst and a method for preparing the same.

[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] In which, the 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 10 to 40 weight%, preferably 20 to 30 weight%; the content of the porous carbon layer is 60 to 90 weight%, preferably 70 to 80 weight%.

[0007] 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.

[0008] Optionally, the porous carbon layer of the porous carrier contains carbon, oxygen, hydrogen, sulfur and nitrogen. Based on the total weight of the porous carbon layer, the carbon content is 83 to 95 weight%, preferably 85 to 91 weight%; the oxygen content is 2 to 6 weight%, preferably 3 to 5 weight%; the hydrogen content is 0.1 to 1 weight%, preferably 0.5 to 0.8 weight%; the sulfur content is 1 to 8 weight%, preferably 2 to 6 weight%; and the nitrogen content is 0.5 to 3 weight%, preferably 1 to 2 weight%.

[0009] Optionally, the alumina core of the 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;

[0010] 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.

[0011] Optionally, the modifying element is selected from at least one of phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium or zirconium;

[0012] 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.

[0013] 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.

[0014] 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.

[0015] 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.

[0016] 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;

[0017] The organic alcohol is at least one selected from glycerol, ethylene glycol, polyethylene glycol, trimethylolethane, pentaerythritol, xylitol and sorbitol;

[0018] The sugar compound is selected from at least one of triose, tetrose, pentose, D-glucose, D-galactose, D-mannose, D-fructose and sucrose.

[0019] The present disclosure also provides a method for preparing a hydrogenation catalyst, the method comprising:

[0020] Mixing asphalt powder, an aluminum source, and a binder to obtain a mixed material, wherein the aluminum source contains aluminum oxide powder and / or an aluminum oxide powder precursor, and the binder includes at least one of cellulose ether, starch, or ene alcohol polymer;

[0021] heat-treating the mixed material to obtain a porous carrier;

[0022] The compound containing active element components is loaded onto the porous carrier and dried to obtain the hydrogenation catalyst.

[0023] 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;

[0024] 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.

[0025] Optionally, the modifying element is selected from at least one of phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium and zirconium;

[0026] 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.

[0027] Optionally, relative to 100 parts by weight of the asphalt powder, the amount of the aluminum source is 1 to 20 parts by weight, preferably 3 to 15 parts by weight, calculated as alumina; the amount of the binder is 1 to 20 parts by weight, preferably 5 to 15 parts by weight.

[0028] Optionally, the particle size of the asphalt powder is 1 to 1000 μm, preferably 1 to 250 μm; the particle size of the aluminum source is 1 to 150 μm, preferably 1 to 75 μm.

[0029] Optionally, the asphalt powder 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%.

[0030] Optionally, the mixed material is subjected to heat treatment to obtain a porous carrier, comprising:

[0031] In an oxygen-containing atmosphere, the temperature of the mixed material is raised from room temperature to 120-400° C. at a heating rate of 0.1-10° C. / min, and a first heat treatment is performed for 0.1-48 hours to obtain a first intermediate material;

[0032] Under an inert atmosphere, raising the temperature of the first intermediate material to 400-950° C. at a heating rate of 0.1-10° C. / min, and performing a second heat treatment for 0.1-24 hours to obtain a second intermediate material;

[0033] In an oxygen-containing atmosphere, the temperature of the second intermediate material is raised to 700-1000° C. at a heating rate of 0.1-10° C. / min, and a third heat treatment is performed for 0.1-12 hours to obtain the porous support.

[0034] Optionally, the step of loading the compound containing active element components onto the porous carrier comprises:

[0035] The porous carrier is impregnated with an aqueous solution containing an organic auxiliary agent and the compound containing the active element component, so that the compound containing the active element component is loaded on the porous carrier.

[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] A first aspect of the present disclosure provides a hydrogenation catalyst, which includes a porous support and an active element component supported on the porous support; wherein the porous support 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, and based on the total weight of the porous support, the content of the alumina core is 10 to 40 weight%, preferably 20 to 30 weight%; the content of the porous carbon layer is 60 to 90 weight%, preferably 70 to 80 weight%.

[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 the porous support is composed of an alumina core and a porous carbon layer, and 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 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] 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.

[0042] According to the present disclosure, the porous carbon layer of the porous carrier may contain carbon, oxygen, hydrogen, sulfur and nitrogen. Based on the total weight of the porous carbon layer, the carbon content may be 83 to 95% by weight, preferably 85 to 91% by weight; the oxygen content may be 2 to 6% by weight, preferably 3 to 5% by weight; the hydrogen content may be 0.1 to 1% by weight, preferably 0.5 to 0.8% by weight; the sulfur content may be 1 to 8% by weight, preferably 2 to 6% by weight; and the nitrogen content may be 0.5 to 3% by weight, preferably 1 to 2% by weight.

[0043] According to the present disclosure, the alumina core of the porous carrier may contain a modifying element, and the modifying element may be 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.

[0044] 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 %.

[0045] 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 first active metal element may be present in an amount of 0.5-10% by weight, preferably 1-6% by weight; the second active metal element may be present in an amount of 4-40% by weight, preferably 5-35% by weight. The first active metal element may be selected from at least one of the Group VIII metal elements, and the second active metal element may be selected from at least one of the Group VIB metal elements. As needed, additives such as phosphorus and boron may be introduced during catalyst preparation. 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.

[0046] 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 %.

[0047] 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.

[0048] 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.

[0049] The second aspect of the present disclosure provides a method for preparing a hydrogenation catalyst, which comprises: mixing asphalt powder, an aluminum source and a binder to obtain a mixture, wherein the aluminum source contains alumina powder and / or an alumina powder precursor, and the binder comprises at least one of cellulose ether, starch or ene alcohol polymer; heat-treating the mixture to obtain a porous carrier; loading a compound containing an active element component onto the porous carrier, and drying the mixture to obtain the hydrogenation catalyst.

[0050] In the present disclosure, specifically, the alumina powder precursor can generate alumina powder during heat treatment, and its specific type can be selected within a certain range. Exemplarily, the alumina powder precursor can be pseudo-boehmite powder.

[0051] Preferably, the binder is cellulose ether, and the cellulose ether may include at least one of methyl cellulose, hydroxyethyl methyl cellulose and hydroxypropyl methyl cellulose.

[0052] The method for preparing the hydrogenation catalyst provided by the present disclosure has the advantages of simple process flow, low cost and good environmental protection, and is suitable for industrial large-scale production.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] According to the present disclosure, when preparing the porous carrier, the amount of asphalt powder, aluminum source and adhesive can vary within a certain range. For example, relative to 100 parts by weight of the asphalt powder, the amount of the aluminum source can be 1 to 20 parts by weight, preferably 3 to 15 parts by weight, calculated as alumina; the amount of the adhesive can be 1 to 20 parts by weight, preferably 5 to 15 parts by weight.

[0058] According to the present disclosure, when preparing the porous carrier, in order to enable the asphalt powder, aluminum source and adhesive to be mixed faster and better, preferably, the asphalt powder and aluminum source can have a smaller particle size. For example, the particle size of the asphalt powder can be 1 to 1000 μm, preferably 1 to 250 μm; the particle size of the aluminum source can be 1 to 150 μm, preferably 1 to 75 μm.

[0059] In the present disclosure, specifically, in order to further improve the uniformity of mixing, when mixing asphalt powder, aluminum source and adhesive, the aluminum source and adhesive can be first made into a paste slurry, and then the asphalt powder is mixed with the prepared paste slurry, and finally stirred or extruded.

[0060] According to the present disclosure, the asphalt powder used to prepare the porous carrier can be selected within a certain range. For example, the asphalt powder can include petroleum asphalt powder and / or coal asphalt powder. The asphalt powder can contain polycyclic aromatic hydrocarbons (PAHs). The PAH content can be 70-100% by weight, preferably 85-100% by weight, based on the total weight of the asphalt powder. Furthermore, the asphalt powder can be obtained by physically pulverizing asphalt solids.

[0061] According to the present disclosure, the mixed material is subjected to heat treatment to obtain a porous carrier, which may include: in an oxygen-containing atmosphere, raising the temperature of the mixed material 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 material; in an inert atmosphere, raising the temperature of the first intermediate material 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 material; in an oxygen-containing atmosphere, raising the temperature of the second intermediate material 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.

[0062] 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.

[0063] 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.

[0064] According to the present disclosure, loading the compound containing active element components onto the porous carrier may include: impregnating the porous carrier with an aqueous solution containing an organic auxiliary agent and the compound containing active element components, so that the compound containing active element components is loaded onto the porous carrier.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] Prepare the porous support as follows:

[0069] Preparation Example 1

[0070] Weigh 50 grams of methyl cellulose, add 260 milliliters of an aqueous solution containing 50 grams of pseudo-boehmite powder (dry basis content of 70 weight percent, particle size of 1 to 75 μm), stir and mix evenly, and then let stand for 2 hours. Then add 500 grams of asphalt powder (particle size of 1 to 250 μm), stir and mix evenly to obtain a mixture. Take 200 grams of the above-mentioned mixture and place it in a closed tube furnace. Under the condition of air ventilation and an air flow rate of 40 liters / hour, the temperature of the above-mentioned mixture is raised from room temperature to 120°C at a heating rate of 3°C / min, and maintained at 120°C for 18 hours, then raised to 200°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 4 hours, then raised to 240°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 8 hours, then raised to 280°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 8 hours, then raised to 300°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 2 hours. , obtaining a first intermediate material; then, switching the air to nitrogen, and controlling the nitrogen flow rate to 40 liters / hour, raising the temperature of the first intermediate material to 700°C at a heating rate of 3°C / minute, and maintaining a constant temperature of 700°C for heat treatment for 2 hours, to obtain a second intermediate material; finally, switching the nitrogen to carbon dioxide gas, and controlling the carbon dioxide gas flow rate to 40 liters / hour, raising the temperature of the second intermediate material to 960°C at a heating rate of 5°C / minute, and maintaining a constant temperature of 960°C for heat treatment for 4 hours, to obtain a porous carrier S1;

[0071] The aluminum source (pseudo-boehmite powder) contains a modifying element (phosphorus) and is modified using ammonium dihydrogen phosphate. The phosphorus content is 2% by weight, calculated as the element, based on the total dry weight of the aluminum source. The alumina core and the porous carbon layer comprise 25% by weight, respectively, based on the total weight of the porous support S1.

[0072] Based on the total weight of the porous carbon layer, the carbon content, oxygen content, hydrogen content, sulfur content, and nitrogen content are 89.38 weight%, 3.45 weight%, 0.52 weight%, and 5.33 weight%, respectively. Based on the total weight of the alumina core, the content of the modifying element (phosphorus) is 2 weight%.

[0073] The specific surface area of ​​the porous carrier S1 was determined to be 586 m 2 / g, pore volume 0.79cm 3 / g, and the average pore diameter is 5.39nm.

[0074] Preparation Example 2

[0075] Weigh 50 grams of methyl cellulose, add 260 milliliters of an aqueous solution containing 50 grams of pseudo-boehmite powder (dry basis content of 70 weight percent, particle size of 1 to 75 μm), stir and mix evenly, and then let stand for 2 hours. Then add 500 grams of asphalt powder (particle size of 1 to 250 μm), stir and mix evenly to obtain a mixture. Take 200 grams of the above-mentioned mixture and place it in a closed tube furnace. Under the condition of air ventilation and an air flow rate of 40 liters / hour, the temperature of the above-mentioned mixture is raised from room temperature to 120°C at a heating rate of 5°C / min, and maintained at 120°C for 18 hours, then raised to 200°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 4 hours, then raised to 240°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 8 hours, then raised to 280°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 8 hours, then raised to 300°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 2 hours. , obtaining a first intermediate material; then, the air was switched to nitrogen, with the nitrogen flow rate controlled at 40 liters / hour, and the temperature of the first intermediate material 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, obtaining a second intermediate material; finally, the nitrogen was switched to carbon dioxide, with the carbon dioxide flow rate controlled at 40 liters / hour, and the temperature of the second intermediate material was raised to 960°C at a heating rate of 5°C / minute, and maintained at 960°C for a constant temperature heat treatment for 4 hours, obtaining a porous support S2. Based on the total weight of the porous support S2, the content of the alumina core was 27% by weight, and the content of the porous carbon layer was 73% by weight.

[0076] Based on the total weight of the porous carbon layer, the carbon content is 88.78 weight %, the oxygen content is 3.78 weight %, the hydrogen content is 0.48 weight %, the sulfur content is 5.84 weight %, and the nitrogen content is 1.12 weight %.

[0077] The specific surface area of ​​the porous carrier S2 was determined to be 546 m 2 / g, pore volume 0.76cm 3 / g, and the average pore diameter is 5.57nm.

[0078] Preparation Example 3

[0079] Weigh 50 grams of methyl cellulose, add 230 milliliters of an aqueous solution containing 26 grams of pseudo-boehmite powder (dry basis content of 70 weight%, particle size of 1 to 75 μm), stir and mix evenly, and let it stand for 2 hours. Then, add 500 grams of asphalt powder (particle size of 1 to 250 μm), stir and mix evenly to obtain a mixed material. 200 g of the above-mentioned mixed material was placed in a sealed tube furnace. Under the condition of air flow and an air flow rate of 40 liters / hour, the temperature of the above-mentioned mixed material was increased from room temperature to 280°C at a heating rate of 5°C / minute, and maintained at 280°C for 12 hours to obtain a first intermediate material. Then, the air was switched to nitrogen, and the nitrogen flow rate was controlled to 40 liters / hour. The temperature of the above-mentioned first intermediate material was increased to 700°C at a heating rate of 3°C / minute, and maintained at 700°C for 2 hours to obtain a second intermediate material. Finally, the nitrogen was switched to carbon dioxide gas, and the carbon dioxide flow rate was controlled to 40 liters / hour. The temperature of the above-mentioned second intermediate material was increased to 980°C at a heating rate of 5°C / minute, 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 22% by weight, and the content of the porous carbon layer was 78% by weight.

[0080] Based on the total weight of the porous carbon layer, the carbon content is 89.65 weight %, the oxygen content is 3.25 weight %, the hydrogen content is 0.54 weight %, the sulfur content is 5.21 weight %, and the nitrogen content is 1.35 weight %.

[0081] The specific surface area of ​​the porous carrier S3 was determined to be 530 m 2 / g, pore volume is 0.72cm 3 / g, and the average pore diameter is 5.43nm.

[0082] Preparation Example 4

[0083] Weigh 50 grams of methyl cellulose, add 240 milliliters of an aqueous solution containing 30 grams of pseudo-boehmite powder (dry basis content of 70 weight%, particle size of 1 to 75 μm) calcined at 600°C for 4 hours, stir and mix evenly, and let stand for 2 hours. Then, add 500 grams of asphalt powder (particle size of 1 to 250 μm), stir and mix evenly to obtain a mixed material. 200 g of the above-mentioned mixed material was placed in a sealed tube furnace. Under the condition of air flow and an air flow rate of 40 liters / hour, the temperature of the above-mentioned mixed material was increased from room temperature to 280°C at a heating rate of 5°C / minute, and maintained at 280°C for 12 hours to obtain a first intermediate material. Then, the air was switched to nitrogen, and the nitrogen flow rate was controlled to 40 liters / hour. The temperature of the above-mentioned first intermediate material was increased to 700°C at a heating rate of 3°C / minute, and maintained at 700°C for 3 hours to obtain a second intermediate material. Finally, the nitrogen was switched to carbon dioxide gas, and the carbon dioxide flow rate was controlled to 40 liters / hour. The temperature of the above-mentioned second intermediate material was increased to 940°C at a heating rate of 5°C / minute, 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 29% by weight, and the content of the porous carbon layer was 71% by weight.

[0084] Based on the total weight of the porous carbon layer, the carbon content is 89.09 weight %, the oxygen content is 4.12 weight %, the hydrogen content is 0.63 weight %, the sulfur content is 4.58 weight %, and the nitrogen content is 1.58 weight %.

[0085] The specific surface area of ​​the porous carrier S4 was determined to be 482 m 2 / g, pore volume is 0.79cm 3 / g, and the average pore diameter is 6.56nm.

[0086] Preparation Example 5

[0087] 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 binder (methylcellulose) 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 35% by weight, and the content of the porous carbon layer was 65% by weight.

[0088] The specific surface area of ​​the porous carrier S5 is 326m 2 / g, pore volume is 0.69cm 3 / g, and the average pore diameter is 8.47nm.

[0089] Preparation Example 6

[0090] 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 20 parts by weight, and the amount of binder (starch) was 20 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 40% by weight, and the content of the porous carbon layer was 60% by weight.

[0091] The specific surface area of ​​the porous carrier S6 is 338m 2 / g, pore volume is 0.66cm 3 / g, and the average pore diameter is 7.81nm.

[0092] Preparation Example 7

[0093] 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 3 parts by weight, and the amount of binder (enol polymer) used was 5 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 23% by weight, and the content of the porous carbon layer was 77% by weight.

[0094] The specific surface area of ​​the porous carrier S7 is 452 m 2 / g, pore volume is 0.73cm 3 / g, and the average pore diameter is 6.46nm.

[0095] Preparation Example 8

[0096] Porous support S8 was prepared according to the method of Preparation Example 2, except that the amount of aluminum source (alumina + pseudo-boehmite powder) and binder (methylcellulose) used in the preparation of porous support S8 was 15 parts by weight, calculated as alumina, relative to 100 parts by weight of asphalt powder. Based on the total weight of porous support S8, the content of the alumina core was 37% by weight, and the content of the porous carbon layer was 63% by weight.

[0097] The specific surface area of ​​the porous carrier S8 is 428m 2 / g, pore volume is 0.75cm 3 / g, and the average pore diameter is 7.01nm.

[0098] Preparation Example 9

[0099] The porous support S9 was prepared according to the method of Preparation Example 1, except that: when preparing the porous support S9, the aluminum source (aluminum oxide powder) contained a modifying element (zirconium), and zirconyl nitrate was used as a raw material for modification. The content of the modifying element (zirconium) was 0.1% by weight based on the total dry weight of the aluminum source. The specific surface area of ​​the porous support S9 was 551 m 2 / g, pore volume is 0.77cm 3 / g, and the average pore diameter is 5.59nm.

[0100] Preparation Example 10

[0101] The porous support S10 was prepared according to the method of Preparation Example 1, except that: when preparing the porous support S10, the aluminum source (pseudo-boehmite powder) contained a modifying element (silicon), and silica sol was used as a raw material for modification. The content of the modifying element (silicon) was 10% by weight based on the total dry weight of the aluminum source. The specific surface area of ​​the porous support S10 was 556 m 2 / g, pore volume is 0.78cm 3 / g, and the average pore diameter is 5.61nm.

[0102] Preparation Example 11

[0103] The porous carrier S11 was prepared according to the method of Preparation Example 1, except that: in the preparation of the porous carrier S11, the aluminum source (pseudo-boehmite powder) contained a modifying element (magnesium), and magnesium nitrate was used as a raw material for modification. The content of the modifying element (magnesium) was 0.3% by weight, calculated as the element, based on the total dry weight of the aluminum source. The specific surface area of ​​the porous carrier S11 was 562 m 2 / g, pore volume is 0.77cm 3 / g, and the average pore diameter is 5.48nm.

[0104] Preparation Example 12

[0105] The porous carrier S12 was prepared according to the method of Preparation Example 1, except that: when preparing the porous carrier S12, the aluminum source (pseudo-boehmite powder) contained modifying elements (lanthanum and cerium), and lanthanum nitrate and cerium nitrate were used as raw materials for modification. The content of the modifying elements (2 wt% of lanthanum and 3 wt% of cerium) was 5 wt% based on the total dry weight of the aluminum source. The specific surface area of ​​the porous carrier S12 was 552 m 2 / g, pore volume is 0.76cm 3 / g, and the average pore diameter is 5.51nm.

[0106] Preparation Example 13

[0107] The porous carrier S13 was prepared according to the method of Preparation Example 1, except that: in the preparation of the porous carrier S13, the aluminum source (pseudo-boehmite powder) contained a modifying element (boron), and boric acid was used as a raw material for modification. The content of the modifying element (boron) was 1.5% by weight, calculated as the element, based on the total dry weight of the aluminum source. The specific surface area of ​​the porous carrier S13 was 563 m 2 / g, pore volume is 0.78cm 3 / g, and the average pore diameter is 5.54nm.

[0108] Preparation Example 14

[0109] The porous support S14 was prepared according to the method of Preparation Example 1, except that: in the preparation of the porous support S14, the aluminum source (aluminum oxide powder) contained a modifying element (zinc), and zinc nitrate was used as a raw material for modification. The content of the modifying element (zinc) was 2.5% by weight based on the total dry weight of the aluminum source. The specific surface area of ​​the porous support S14 was 571 m 2 / g, pore volume is 0.78cm 3 / g, and the average pore diameter is 5.46nm.

[0110] Preparation Example 15

[0111] The porous carrier S15 was prepared according to the method of Preparation Example 1, except that: when preparing the porous carrier S15, the aluminum source (pseudo-boehmite powder) contained a modifying element (titanium), titanium sulfate was used as a raw material for modification, and the content of the modifying element (titanium) was 4% by weight based on the total dry weight of the aluminum source. The specific surface area of ​​the porous carrier S15 was 569 m 2 / g, pore volume is 0.77cm 3 / g, and the average pore diameter is 5.41nm.

[0112] Preparation Example 16

[0113] In this preparation example, the aluminum source (commercially available phosphorus-containing pseudo-boehmite powder) contained a modifying element (phosphorus) content of 3% by weight, calculated as the element, based on the total dry weight of the aluminum source. 50 g of methyl cellulose was added to 260 ml of an aqueous solution containing 26 g of phosphorus-containing pseudo-boehmite powder (72% by weight on a dry basis, with a particle size of 1 to 75 μm). The mixture was stirred and mixed thoroughly, then allowed to stand for 2 hours. Then, 500 g of asphalt powder (particle size of 1 to 250 μm) was added and stirred and mixed thoroughly to obtain a mixed material. Take 200 grams of the above-mentioned mixed material and place it in a closed tube furnace. Under the condition of air circulation and an air flow rate of 20 liters / hour, the temperature of the above-mentioned mixed material is raised from room temperature to 120°C at a heating rate of 5°C / min, and maintained at 120°C for heat treatment for 8 hours, and then raised to 320°C at 0.5°C / min and maintained at a constant temperature for 4 hours to obtain the first intermediate material; then, switch the air to nitrogen, and control the nitrogen flow rate to 60 liters / hour, and raise the temperature of the above-mentioned first intermediate material to 550°C at a heating rate of 5°C / min, and maintain a constant temperature of 550°C for heat treatment for 3 hours to obtain the second intermediate material; finally, switch the nitrogen to carbon dioxide gas, and control the carbon dioxide gas flow rate to 40 liters / hour, and raise the temperature of the above-mentioned second intermediate material to 950°C at a heating rate of 5°C / min, and maintain a constant temperature of 950°C for heat treatment for 4 hours to obtain the porous carrier S16. It has been measured that the specific surface area of ​​the porous carrier S16 is 794m 2 / g, pore volume is 0.91cm 3 / g, and the average pore diameter is 4.58nm.

[0114] Preparation Example 17

[0115] In this preparation example, the aluminum source (commercially available phosphorus-containing pseudo-boehmite powder) contained a modifying element (phosphorus) content of 3% by weight, calculated as the element, based on the total dry weight of the aluminum source. 50 g of methyl cellulose was added to 260 ml of an aqueous solution containing 26 g of phosphorus-containing pseudo-boehmite powder (72% by weight on a dry basis, with a particle size of 1 to 75 μm). The mixture was stirred and mixed thoroughly, then allowed to stand for 2 hours. Then, 500 g of asphalt powder (particle size of 1 to 250 μm) was added and stirred and mixed thoroughly to obtain a mixed material. Take 200 grams of the above-mentioned mixed material and place it in a closed tube furnace. Under the condition of air circulation and an air flow rate of 1 liter / hour, the temperature of the above-mentioned mixed material is raised from room temperature to 120°C at a heating rate of 3°C / min, and maintained at 120°C for heat treatment for 8 hours, and then raised to 300°C at 0.2°C / min and maintained at a constant temperature for 4 hours to obtain the first intermediate material; then, switch the air to nitrogen, and control the nitrogen flow rate to 70 liters / hour, and raise the temperature of the above-mentioned first intermediate material to 800°C at a heating rate of 3°C / min, and maintain a constant temperature of 800°C for heat treatment for 2 hours to obtain the second intermediate material; finally, switch the nitrogen to carbon dioxide gas, and control the carbon dioxide gas flow rate to 50 liters / hour, and raise the temperature of the above-mentioned second intermediate material to 950°C at a heating rate of 5°C / min, and maintain a constant temperature of 950°C for heat treatment for 4 hours to obtain the porous carrier S17. It has been measured that the specific surface area of ​​the porous carrier S17 is 1100m 2 / g, pore volume is 0.82cm 3 / g, and the average pore diameter is 2.98nm.

[0116] Comparative Preparation Example 1

[0117] The porous support was prepared as follows:

[0118] 500 g of asphalt powder (particle size of 1 to 250 μm) and 50 g of methyl cellulose were stirred and mixed uniformly, then soaked with 260 ml of water and stirred and mixed uniformly, and allowed to stand for 2 hours to obtain a mixed material. Take 200 grams of the above-mentioned mixed material and place it in a closed tube furnace. Under the condition of air circulation and an air flow rate of 40 liters / hour, the temperature of the above-mentioned mixed material is raised from room temperature to 120°C at a heating rate of 5°C / minute, and maintained at 120°C for 48 hours to obtain the first intermediate material; then, switch the air to nitrogen, and control the nitrogen flow rate to 40 liters / hour, and raise the temperature of the above-mentioned first intermediate material to 700°C at a heating rate of 3°C / minute, and maintain 700°C for 2 hours to obtain the second intermediate material; finally, switch the nitrogen to carbon dioxide gas, and control the carbon dioxide gas flow rate to 40 liters / hour, and raise the temperature of the above-mentioned second intermediate material to 960°C at a heating rate of 5°C / minute, and maintain 960°C for 4 hours to obtain the porous carrier DT-1. It has been measured that the specific surface area of ​​the porous carrier DT-1 is 228m 2 / g, pore volume is 0.17cm 3 / g, and the average pore diameter is 2.98nm.

[0119] Comparative Preparation Example 2

[0120] The porous support was prepared as follows:

[0121] 500 g of pseudo-boehmite powder (dry basis content: 70 wt%) and 50 g of methyl cellulose were stirred and mixed uniformly, then soaked with 260 ml of water, stirred and mixed uniformly, and allowed to stand for 2 hours to obtain a mixed material. Take 200 grams of the above-mentioned mixed material and place it in a closed tube furnace. Under the condition of air circulation and an air flow rate of 40 liters / hour, the temperature of the above-mentioned mixed material is raised from room temperature to 120°C at a heating rate of 5°C / minute, and maintained at 120°C for 48 hours to obtain the first intermediate material; then, switch the air to nitrogen, and control the nitrogen flow rate to 40 liters / hour, and raise the temperature of the above-mentioned first intermediate material to 700°C at a heating rate of 3°C / minute, and maintain 700°C for 2 hours to obtain the second intermediate material; finally, switch the nitrogen to carbon dioxide gas, and control the carbon dioxide gas flow rate to 40 liters / hour, and raise the temperature of the above-mentioned second intermediate material to 960°C at a heating rate of 5°C / minute, and maintain 960°C for 4 hours to obtain the porous carrier DT-2. It has been measured that the specific surface area of ​​the porous carrier DT-2 is 168m 2 / g, pore volume is 0.70cm 3 / g, and the average pore diameter is 16.67nm.

[0122] Comparative Preparation Example 3

[0123] The porous support was prepared as follows:

[0124] Weigh 50 grams of methyl cellulose, add 260 milliliters of an aqueous solution containing 50 grams of pseudo-boehmite powder (dry basis content of 70 weight percent, particle size of 1 to 75 μm), stir and mix evenly, and let stand for 2 hours. Then, add 500 grams of asphalt powder (particle size of 1 to 250 μm), stir and mix evenly to obtain a mixed material. Take 200 grams of the above-mentioned mixed material and place it in a closed tube furnace. Under the condition of air circulation and an air flow rate of 40 liters / hour, the temperature of the above-mentioned mixed material is raised from room temperature to 120°C at a heating rate of 5°C / min, and maintained at 120°C for 18 hours, then raised to 200°C at 0.2°C / min and maintained at a constant temperature for 4 hours, then raised to 240°C at 0.2°C / min and maintained at a constant temperature for 8 hours, then raised to 280°C at 0.2°C / min and maintained at a constant temperature for 8 hours, then raised to 300°C at 0.2°C / min and maintained at a constant temperature for 2 hours to obtain the first intermediate material; then, switch the air to carbon dioxide gas, and control the carbon dioxide gas flow rate to 40 liters / hour, raise the temperature of the above-mentioned first intermediate material to 960°C at a heating rate of 5°C / min, and maintain a constant temperature of 960°C for 4 hours to obtain the porous carrier DT-3. It has been measured that the specific surface area of ​​the porous carrier DT-3 is 217m 2 / g, pore volume is 0.75cm 3 / g, and the average pore diameter is 13.82nm.

[0125] Comparative Preparation Example 4

[0126] The porous support was prepared as follows:

[0127] Weigh 50 grams of methyl cellulose, add 260 milliliters of an aqueous solution containing 50 grams of pseudo-boehmite powder (dry basis content of 70% by weight, particle size of 1 to 75 μm), stir and mix evenly, and then let it stand for 2 hours. Then add 500 grams of asphalt powder (particle size of 1 to 250 μm), stir and mix evenly to obtain a mixed material. Take 200 grams of the above mixed material and place it in a closed tube furnace. Under the condition of nitrogen, control the nitrogen flow rate to 40 liters / hour, increase the temperature of the above mixed material to 700°C at a heating rate of 3°C / minute, and maintain a constant temperature of 700°C for 2 hours to obtain a first intermediate material; finally, switch the nitrogen to carbon dioxide gas, and control the carbon dioxide gas flow rate to 40 liters / hour, increase the temperature of the above first intermediate material to 960°C at a heating rate of 5°C / minute, and maintain a constant temperature of 960°C for 4 hours to obtain a porous carrier DT-4. It has been measured that the specific surface area of ​​the porous carrier DT-4 is 315m 2 / g, pore volume is 0.65cm 3 / g, and the average pore diameter is 8.25nm.

[0128] Comparative Preparation Example 5

[0129] The porous support was prepared as follows:

[0130] (1) Weigh 50 g of methyl cellulose, add 260 ml of an aqueous solution containing 50 g of pseudo-boehmite powder (dry basis content: 70 wt%, particle size: 1-75 μm), stir and mix evenly, let stand for 2 hours, then add 500 g of asphalt powder (particle size: 1-250 μm), stir and mix evenly to obtain a mixed material. Take 200 grams of the above-mentioned mixed material and place it in a closed tube furnace. Under the condition of air circulation and an air flow rate of 40 liters / hour, raise the temperature of the above-mentioned mixed material from room temperature to 120°C at a heating rate of 5°C / min, and keep it at 120°C for 18 hours, then raise it to 200°C at 0.2°C / min and keep it at a constant temperature for 4 hours, then raise it to 240°C at 0.2°C / min and keep it at a constant temperature for 8 hours, then raise it to 280°C at 0.2°C / min and keep it at a constant temperature for 8 hours, then raise it to 300°C at 0.2°C / min and keep it at a constant temperature for 2 hours to obtain the first intermediate material; then, switch the air to nitrogen, and control the nitrogen flow rate to 40 liters / hour, raise the temperature of the above-mentioned first intermediate material to 700°C at a heating rate of 3°C / min, and keep it at 700°C for 2 hours to obtain the carrier DT-5. It has been measured that the specific surface area of ​​the porous carrier DT-5 is 0m 2 / g, pore volume is 0cm 3 / g, and the average pore size is 0nm.

[0131] Comparative Preparation Example 6

[0132] The porous support was prepared as follows:

[0133] 500 g of asphalt powder (particle size of 1-250 μm) and 50 g of methyl cellulose were stirred and mixed uniformly, then impregnated with 260 ml of an aqueous solution containing 7 g of titanium sulfate and stirred and mixed uniformly, and allowed to stand for 2 hours to obtain a mixed material. 200 g of the mixed material was placed in a sealed tube furnace, and under the condition of air flow of 40 liters / hour, the temperature of the mixed material was raised from room temperature to 120°C at a heating rate of 5°C / min, and maintained at 120°C for 18 hours, then raised to 200°C at a heating rate of 0.2°C / min and maintained at this temperature for 4 hours, then raised to 240°C at a heating rate of 0.2°C / min and maintained at this temperature for 8 hours, then raised to 280°C at a heating rate of 0.2°C / min and maintained at this temperature for 8 hours, then raised to 300°C at a heating rate of 0.2°C / min and maintained at this temperature for 2 hours, The first intermediate material is obtained; then, the air is switched to nitrogen, and the nitrogen flow rate is controlled to 40 liters / hour, the temperature of the first intermediate material is raised to 700°C at a heating rate of 3°C / minute, and maintained at 700°C for heat treatment for 2 hours to obtain the second intermediate material; finally, the nitrogen is switched to carbon dioxide gas, and the carbon dioxide flow rate is controlled to 40 liters / hour, the temperature of the second intermediate material is raised to 960°C at a heating rate of 5°C / minute, and maintained at 960°C for heat treatment for 4 hours to obtain the porous carrier DT-6. It has been measured that the specific surface area of ​​the porous carrier DT-6 is 197m 2 / g, pore volume is 0.16cm 3 / g, and the average pore diameter is 3.25nm.

[0134] Catalyst preparation:

[0135] Examples 1-17

[0136] 180 mL of an aqueous solution containing 5.07 g of phosphoric acid (85%), 41.26 g of molybdenum trioxide, 16.85 g of basic nickel carbonate (NiO content 51%), 1.57 g of cobalt nitrate, 22.10 g of citric acid, 2.12 g of ethylene glycol and 3.31 g of propylene glycol was used to impregnate porous supports S1-S17, 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-C17.

[0137] Comparative Examples 1-6

[0138] 180 mL of an aqueous solution containing 5.07 g of phosphoric acid (85%), 41.26 g of molybdenum trioxide, 16.85 g of basic nickel carbonate (NiO content 51%), 1.57 g of cobalt nitrate, 22.10 g of citric acid, 2.12 g of ethylene glycol and 3.31 g of propylene glycol was used to impregnate the porous carriers DT1-DT6, 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-D6.

[0139] Test Case

[0140] The hydrodesulfurization activities of hydrogenation catalysts C1-C17 and D1-D6 were evaluated using straight-run kerosene (total sulfur 3120 μg / g) as the reaction feedstock.

[0141] 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 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 60:1, and a mass space velocity of 4 h / min. -1 , temperature 320℃, time 4 hours. After sulfurization, the feed was switched to straight-run kerosene. The reaction conditions included: reaction temperature 250℃, mass space velocity 4h -1 , reaction pressure 1.6 MPa, hydrogen to oil ratio 60:1. After 6 days of reaction at 250°C, samples were taken for analysis, and the relative hydrodesulfurization activities of the hydrogenation catalysts were calculated. The results are shown in Table 1.

[0142] Table 1 Comparison of catalytic performance of various hydrogenation catalysts

[0143]

[0144]

[0145] As can be seen from Table 1, the hydrogenation catalyst provided by the present disclosure has a high hydrodesulfurization activity.

[0146] 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.

[0147] 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.

[0148] 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 support comprises 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 support, the content of the alumina core is 10 to 40% by weight; the content of the porous carbon layer is 60 to 90% by weight. 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 3-30nm; The preparation method of the hydrogenation catalyst comprises: Mixing asphalt powder, an aluminum source, and a binder to obtain a mixed material, wherein the aluminum source contains aluminum oxide powder and / or an aluminum oxide powder precursor, and the binder includes at least one of cellulose ether, starch, or ene alcohol polymer; heat-treating the mixed material to obtain a porous carrier; The compound containing active element components is loaded onto the porous carrier and dried to obtain the hydrogenation catalyst.

2. The hydrogenation catalyst according to claim 1, characterized in that Based on the total weight of the porous support, the content of the alumina core is 20 to 30 weight %; and the content of the porous carbon layer is 70 to 80 weight %.

3. The hydrogenation catalyst according to claim 1, characterized in that The porous carbon layer of the porous carrier contains carbon, oxygen, hydrogen, sulfur and nitrogen. Based on the total weight of the porous carbon layer, the content of the carbon element is 83 to 95 weight %; the content of the oxygen element is 2 to 6 weight %; the content of the hydrogen element is 0.1 to 1 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 %.

4. The hydrogenation catalyst according to claim 3, characterized in that The porous carbon layer of the porous carrier contains carbon, oxygen, hydrogen, sulfur and nitrogen. Based on the total weight of the porous carbon layer, the carbon content is 85-91 weight %; the oxygen content is 3-5 weight %; the hydrogen content is 0.5-0.8 weight %; the sulfur content is 2-6 weight %; and the nitrogen content is 1-2 weight %.

5. The hydrogenation catalyst according to claim 1, characterized in that The alumina core of the porous support 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.

6. The hydrogenation catalyst according to claim 5, 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.

7. 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.

8. The hydrogenation catalyst according to claim 7, 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 %.

9. The hydrogenation catalyst according to claim 7, 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.

10. The hydrogenation catalyst according to claim 9, 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.

11. A method for preparing the hydrogenation catalyst according to any one of claims 1 to 10, characterized in that: The method includes: Mixing asphalt powder, an aluminum source, and a binder to obtain a mixed material, wherein the aluminum source contains aluminum oxide powder and / or an aluminum oxide powder precursor, and the binder includes at least one of cellulose ether, starch, or ene alcohol polymer; heat-treating the mixed material to obtain a porous carrier; loading a compound containing active element components onto the porous carrier and drying the compound to obtain the hydrogenation catalyst; The heat treatment comprises: In an oxygen-containing atmosphere, the temperature of the mixed material is raised from room temperature to 120-400° C. at a heating rate of 0.1-10° C. / min, and a first heat treatment is performed for 0.1-48 hours to obtain a first intermediate material; Under an inert atmosphere, raising the temperature of the first intermediate material to 400-950° C. at a heating rate of 0.1-10° C. / min, and performing a second heat treatment for 0.1-24 hours to obtain a second intermediate material; In an oxygen-containing atmosphere, the temperature of the second intermediate material is raised to 700-1000° C. at a heating rate of 0.1-10° C. / min, and a third heat treatment is performed for 0.1-12 hours to obtain the porous support.

12. The method according to claim 11, 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.

13. The method according to claim 12, 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.

14. The method according to claim 11, characterized in that Relative to 100 parts by weight of the asphalt powder, the amount of the aluminum source is 1 to 20 parts by weight, calculated as alumina; the amount of the binder is 1 to 20 parts by weight.

15. The method according to claim 14, characterized in that Relative to 100 parts by weight of the asphalt powder, the amount of the aluminum source is 3 to 15 parts by weight, calculated as aluminum oxide; the amount of the binder is 5 to 15 parts by weight.

16. The method according to any one of claims 11 to 15, characterized in that The particle size of the asphalt powder is 1 to 1000 μm; the particle size of the aluminum source is 1 to 150 μm.

17. The method according to claim 16, characterized in that The particle size of the asphalt powder is 1 to 250 μm; the particle size of the aluminum source is 1 to 75 μm.

18. The method according to any one of claims 11 to 15, characterized in that The asphalt powder 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.

19. The method according to claim 18, characterized in that Based on the total weight of the asphalt powder, the content of the polycyclic aromatic hydrocarbons is 85 to 100 weight %.

20. The method according to claim 11, characterized in that The step of loading the compound containing the active element component onto the porous carrier comprises: The porous carrier is impregnated with an aqueous solution containing an organic auxiliary agent and the compound containing the active element component, so that the compound containing the active element component is loaded on the porous carrier.

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