Hydrogenation catalyst as well as preparation method and application thereof

Abstract

The invention relates to a hydrogenation catalyst as well as a preparation method and application thereof. The hydrogenation catalyst comprises a magnesium modified mesoporous carbon material and an active metal component loaded on the magnesium modified mesoporous carbon material, the metal element of the active metal component is selected from at least one of a VIII group metal element and a VIB group metal element; on the basis of the total weight of the magnesium modified mesoporous carbon material, the content of the magnesium element on the magnesium modified mesoporous carbon material is 0.1-5 wt%. The hydrogenation catalyst provided by the invention takes the magnesium modified mesoporous carbon material as the carrier, and the mesoporous carbon material has the characteristics of regular pore structure, high porosity, large specific surface area and the like, and can promote the contact between the raw material and the active center as the catalyst carrier; after the mesoporous carbon material is modified by magnesium, active components are loaded, so that the hydrodesulfurization selectivity of a catalyst for sulfur-containing compounds difficult to remove is improved.

Description

Technical Field

[0001] This invention belongs to the field of petrochemicals, specifically relating to a hydrogenation catalyst, its preparation method, and its application. Background Technology

[0002] Porous materials possess advantages such as large specific surface area, tunable particle size, thermal stability, chemical inertness, and biocompatibility, leading to their widespread application in fields such as biomolecule adsorption and separation, double-layer capacitors, catalyst supports, and wastewater treatment. Carbon materials, in particular, exhibit weak interactions with metal components, and their large specific surface area is beneficial for enhancing the hydrogenation activity of catalysts and facilitating metal recovery, thus attracting considerable attention.

[0003] CN1104174A discloses a method for preparing activated carbon using asphalt as raw material. The method involves mixing asphalt, which has been crushed into powder, with extrusion aids, binders, etc., and then subjecting the mixture to anti-melting, carbonization, and activation treatments. The resulting activated carbon product has the characteristics of high mechanical strength, good adsorption performance, and low ash content.

[0004] CN111437871A discloses a method for preparing an acidic carbon-supported hydrodesulfurization catalyst. This method involves introducing molecular sieves onto the surface of a carbon-based material and then loading active components to obtain an acidic hydrodesulfurization catalyst that can inhibit the growth of active centers and molecular sieve crystals, avoid side reactions caused by excessive concentration of Brønsted acid, and reduce the formation of carbon deposits.

[0005] However, existing hydrotreating catalysts do not show high selectivity for hydrodesulfurization of difficult-to-remove sulfur-containing compounds when hydrotreating oil products. Summary of the Invention

[0006] The purpose of this invention is to further improve the selectivity of hydrodesulfurization for difficult-to-remove sulfur-containing compounds.

[0007] To achieve the above objectives, a first aspect of the present invention provides a hydrogenation catalyst comprising a magnesium-modified mesoporous carbon support and an active metal component supported on the magnesium-modified mesoporous carbon support; the active metal component comprises at least one Group VIII metal element and at least one Group VIB metal element; the magnesium-modified mesoporous carbon support comprises a mesoporous carbon material and magnesium-containing compounds distributed in the pores and / or on the surface of the mesoporous carbon material; based on the total weight of the magnesium-modified mesoporous carbon support, the magnesium content on the magnesium-modified mesoporous carbon support is 0.1-5% by weight; and the specific surface area of ​​the magnesium-modified mesoporous carbon support is 200-1000 m². 2 / g, pore volume 0.6-1.8 cm³ 3 / g, with a pore size of 5-20 nm.

[0008] Optionally, the magnesium content on the magnesium-modified mesoporous carbon support is 0.2-4% by weight; the specific surface area of ​​the magnesium-modified mesoporous carbon support is 250-900 m². 2 / g, pore volume 0.7-1.6 cm³ 3 / g, with a pore size of 6-16 nm; optionally, based on the total weight of the hydrogenation catalyst, the content of the Group VIII metal element, calculated as oxide, is 0.1-10% by weight, preferably 1-6% by weight; the content of the Group VIB metal element is 3-40% by weight, preferably 5-36% by weight; optionally, the Group VIII metal element is selected from at least one of iron, cobalt and nickel; the Group VIB metal element is selected from at least one of molybdenum and tungsten.

[0009] Optionally, the mesoporous carbon material contains carbon, oxygen, hydrogen, sulfur, and nitrogen. Based on the total weight of the mesoporous carbon material, the carbon content is 80-96% by weight, preferably 82-94% by weight; the oxygen content is 1-12% by weight, preferably 2-10% by weight; the hydrogen content is 0.5-2% by weight, preferably 0.6-1.6% by weight; the sulfur content is 0.01-8% by weight, preferably 0.1-7.5% by weight; and the nitrogen content is 0.01-3% by weight, preferably 0.05-2% by weight.

[0010] A second aspect of the present invention provides a method for preparing a hydrogenation catalyst, the method comprising: S1. Impregnate the mesoporous carbon material with a magnesium-containing solution, and then subject the impregnated mesoporous carbon material to a first drying and a first calcination to obtain magnesium-modified mesoporous carbon material. S2. Impregnate the magnesium-modified mesoporous carbon material with a solution of the precursor containing the active metal component, and subject the obtained catalyst precursor to a second drying or sequentially subject the catalyst precursor to a second drying and a second calcination to obtain a hydrogenation catalyst; wherein the metal element in the solution of the precursor containing the active metal component includes at least one Group VIII metal element and at least one Group VIB metal element; the specific surface area of ​​the mesoporous carbon material is 200-800 m². 2 / g, preferably 250-800m 2 / g; pore volume is 0.6-1.6 cm³ 3 / g, preferably 0.7-1.6 cm 3 / g; the pore size is 5-16 nm, preferably 6-16 nm.

[0011] Optionally, the magnesium source in the magnesium-containing solution is selected from one or more of magnesium acetate, magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium carbonate, and basic magnesium carbonate; Optionally, in step S2, the method is selected from unsaturated impregnation, saturated impregnation, and excess impregnation, such that, on a dry basis and based on the total weight of the hydrogenation catalyst, the content of the Group VIII metal element is 0.1-10% by weight, and the content of the Group VIB metal element is 3-40% by weight.

[0012] Optionally, the mesoporous carbon material is prepared by a method comprising the following steps: mixing pitch powder and metal salt powder to obtain a first mixture; subjecting the first mixture to a first heat treatment to obtain a mesoporous carbon material precursor; subjecting the mesoporous carbon material precursor to a first acid wash and a first washing filtration to remove metal ions to obtain a first material; or, mixing the mesoporous carbon material precursor with pitch powder to obtain a second mixture; subjecting the second mixture to a second heat treatment to obtain an intermediate material; subjecting the intermediate material to a second acid wash and a second washing filtration to remove metal ions to obtain a second material; and subjecting the first material or the second material to a drying treatment to obtain the mesoporous carbon material; wherein the metal element in the metal salt is selected from one or more of Group VIII, Group IIA, Group IB, and Group IIB metal elements; and the processing atmosphere of the first heat treatment and the second heat treatment includes oxygen-containing compounds and inert gases.

[0013] Optionally, in the first mixture, relative to 100 parts by weight of the asphalt powder, the amount of the metal salt, calculated as oxides, is 80-500 parts by weight, preferably 100-450 parts by weight; in the second mixture, the weight ratio of the mesoporous carbon material precursor to the asphalt powder is 100-600:100, preferably 150-500:100; the particle size of the asphalt powder is 1-10000 μm, preferably 1-1000 μm, more preferably 1-150 μm; the particle size of the metal salt is 1-10000 μm, preferably 1-1000 μm. More preferably, the metal element in the metal salt is selected from at least one of iron, cobalt, nickel, magnesium, calcium, copper, and zinc; the metal salt is selected from one or more of basic carbonates, sulfates, acetates, and citrates; preferably, based on the total weight of the asphalt powder, the content of polycyclic aromatic hydrocarbons is 70-100% by weight, preferably 85-100% by weight; preferably, the asphalt powder is selected from one or more of petroleum asphalt powder, coal tar powder, ethylene tar pitch powder, pre-oxidized petroleum asphalt powder, pre-oxidized coal tar pitch powder, and pre-oxidized ethylene tar pitch powder.

[0014] Optionally, the conditions for the first and second heat treatments include: a gas flow rate of 1-200 L / h, a heating rate of 0.1-10℃ / min, a heat treatment temperature of 25-1000℃, preferably 400-1000℃, and a treatment time of 0.1-48 hours; preferably, the first and second heat treatments each independently include a first stage of heat treatment and a second stage of heat treatment; the first stage of heat treatment is carried out in an atmosphere containing oxygen-containing compounds, wherein the oxygen-containing compounds are selected from at least one of water vapor, carbon dioxide, and carbon monoxide; the conditions for the first stage of heat treatment include: a gas flow rate of... The flow rate is 1-200 L / h, the heating rate is 0.1-10℃ / min, the temperature is 25-850℃, preferably 400-850℃, and the time is 0.1-48 hours; the second stage of heat treatment is carried out in an inert gas atmosphere, the inert gas including at least one of nitrogen, argon and helium; the conditions of the second stage of heat treatment include: gas flow rate of 1-200 L / h, heating rate of 0.1-10℃ / min, temperature of 550-1000℃, and time of 0.1-48 hours.

[0015] Optionally, the acids used for the first and second pickling processes are each independently selected from one or more of hydrochloric acid solution, sulfuric acid solution, nitric acid solution, acetic acid solution, and phosphoric acid solution; the acid solution contains H... + The molar concentration of the substance is 0.1-10 mol / L; optionally, the conditions for the first pickling and the second pickling include: a temperature of 20-100℃ and a time of 0.5-24 hours; the washing liquid for the first washing and the second washing is deionized water; the conditions for the drying treatment include: a temperature of 20-200℃ and a time of 0.5-24 hours; optionally, the method further includes: collecting the filtrate from the first pickling and the first filtration washing process to obtain a first filtrate mixture; or, collecting the filtrate from the second pickling and the second filtration washing process to obtain a second filtrate mixture; subjecting the first filtrate mixture or the second filtrate mixture to heating concentration treatment and cooling filtration treatment to obtain recovered metal salt; and mixing the recovered metal salt with asphalt powder.

[0016] Optionally, in step S1, the conditions for the first drying include: a drying temperature of 60-200 ℃ and a drying time of 0.5-10 hours; the first calcination is carried out in an inert gas atmosphere; the conditions for the first calcination include: a calcination temperature of 350-800 ℃, a heating rate of 0.1-10 ℃ / min, and a calcination time of 0.5-10 hours; the conditions for the second drying include: a drying temperature of 60-200 ℃, preferably 100-150 ℃; a drying time of 0.5-10 hours, preferably 4-8 hours; the second calcination is carried out in air or an inert atmosphere; the conditions for the second calcination include: a calcination temperature of 350-800 ℃, preferably 350-550 ℃; a heating rate of 0.1-10 ℃ / min; and a calcination time of 0.5-10 hours, preferably 4-8 hours.

[0017] Optionally, the solution containing the precursor of the active metal component further includes an organic compound; the molar ratio of the organic compound to the active metal component (calculated as oxide) is 0.1-0.6:1; the organic compound is selected from one or more of organic acids or their ammonium salts, organic alcohols, and sugars; wherein 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; and / or the organic alcohol is at least one of glycerol, ethylene glycol, polyethylene glycol, trimethylolethane, pentaerythritol, xylitol, and sorbitol; and / or the sugar is selected from at least one of triose, tetroose, pentose, D-glucose, D-galactose, D-mannose, D-fructose, and sucrose.

[0018] A third aspect of the present invention provides a method for hydrotreating oil, the method comprising: In the presence of hydrogen and a sulfiding agent, the oil is contacted with the hydrotreating catalyst of the first aspect of the present invention or the hydrotreating catalyst prepared by the method of the second aspect of the present invention for hydrotreating; preferably, the hydrotreating conditions include: a reaction temperature of 150-450 °C; a hydrogen partial pressure of 0.1-18 MPa; and a liquid hourly space velocity of 0.1-10 h⁻¹. -1 The hydrogen-to-oil volume ratio is 10-1000; the sulfur content in the oil is 100-20000 μg / g.

[0019] Through the above technical solution, the hydrogenation catalyst provided by the present invention uses magnesium-modified mesoporous carbon material as a support. The mesoporous carbon material has the characteristics of regular pore structure, high porosity and large specific surface area. As a catalyst support, it can improve the selectivity of the catalyst for hydrogenation desulfurization of difficult-to-remove sulfur-containing compounds.

[0020] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0021] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0022] A first aspect of the present invention provides a hydrogenation catalyst comprising a magnesium-modified mesoporous carbon support and an active metal component supported on the magnesium-modified mesoporous carbon support; the active metal component comprises at least one Group VIII metal element and at least one Group VIB metal element; the magnesium-modified mesoporous carbon support comprises a mesoporous carbon material and magnesium-containing compounds distributed in the pores and / or on the surface of the mesoporous carbon material; based on the total weight of the magnesium-modified mesoporous carbon support, the magnesium content on the magnesium-modified mesoporous carbon support is 0.1-5% by weight; and the specific surface area of ​​the magnesium-modified mesoporous carbon support is 200-1000 m². 2 / g, pore volume 0.6-1.8 cm³ 3 / g, with a pore size of 5-20 nm.

[0023] The hydrogenation catalyst provided by this invention uses magnesium-modified mesoporous carbon material as a support. Mesoporous carbon material has the characteristics of regular pore structure, high porosity and large specific surface area. As a catalyst support, it can improve the selectivity of the catalyst for hydrogenation desulfurization of difficult-to-remove sulfur-containing compounds.

[0024] In some embodiments of the present invention, the magnesium content on the magnesium-modified mesoporous carbon support is 0.2-4% by weight.

[0025] In some embodiments of the present invention, the specific surface area of ​​the magnesium-modified mesoporous carbon support is 250-900 m². 2 / g, pore volume 0.7-1.6 cm³ 3 / g, with a pore size of 6-16 nm. The carbon support provided by this invention is a magnesium-modified mesoporous carbon material with a large pore size, which can reduce the mass transfer resistance of the catalyst and improve its activity.

[0026] In some embodiments of the present invention, the content of the magnesium-modified mesoporous carbon support is 50-97% by weight, preferably 60-90% by weight, based on the total weight of the hydrogenation catalyst.

[0027] In some embodiments of the present invention, the mesoporous carbon material contains carbon, oxygen, hydrogen, sulfur, and nitrogen. Specifically, based on the total weight of the mesoporous carbon material, the elemental content is as follows: carbon content is 80-96% by weight, preferably 82-94% by weight; oxygen content is 1-12% by weight, preferably 2-10% by weight; hydrogen content is 0.5-2% by weight, preferably 0.6-1.6% by weight; sulfur content is 0.01-8% by weight, preferably 0.1-7.5% by weight; and nitrogen content is 0.01-3% by weight, preferably 0.05-2% by weight.

[0028] In some embodiments of the present invention, based on the total weight of the hydrogenation catalyst and calculated as oxides, the content of the Group VIII metal element is 0.1-10% by weight, preferably 1-6% by weight, more preferably 1-5% by weight; the content of the Group VIB metal element is 3-40% by weight, preferably 5-36% by weight, more preferably 6-30% by weight.

[0029] In some embodiments of the present invention, the Group VIII metal element is selected from at least one of iron, cobalt, and nickel.

[0030] In some embodiments of the present invention, the Group VIB metal element is selected from at least one of molybdenum and tungsten.

[0031] A second aspect of the present invention provides a method for preparing a hydrogenation catalyst, the method comprising: S1. Impregnate the mesoporous carbon material with a magnesium-containing solution, and then subject the impregnated mesoporous carbon material to a first drying and a first calcination to obtain magnesium-modified mesoporous carbon material. S2. Impregnate the magnesium-modified mesoporous carbon material with a solution of the precursor containing the active metal component, and subject the obtained catalyst precursor to a second drying or sequentially subject the catalyst precursor to a second drying and a second calcination to obtain a hydrogenation catalyst; wherein the metal element in the solution of the precursor containing the active metal component includes at least one Group VIII metal element and at least one Group VIB metal element.

[0032] In some embodiments of the present invention, the specific surface area of ​​the mesoporous carbon material is 200-800 m². 2 / g, preferably 250-800m 2 / g; pore volume is 0.6-1.6 cm³ 3 / g, preferably 0.7-1.6 cm 3 / g; the pore size is 5-16 nm, preferably 6-16 nm.

[0033] In some embodiments of the present invention, the magnesium source in the magnesium-containing solution is selected from one or more of magnesium acetate, magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium carbonate, and basic magnesium carbonate.

[0034] In some embodiments of the present invention, in step S1, the conditions for the first drying include: a drying temperature of 60-200°C and a drying time of 0.5-10 hours.

[0035] In some embodiments of the present invention, the first calcination is carried out under an inert gas atmosphere; specifically, the atmosphere for the first calcination may be selected from at least one of nitrogen, argon, helium, carbon dioxide, and water vapor. The conditions for the first calcination include: a calcination temperature of 350-800 °C, a heating rate of 0.1-10 °C / min, and a calcination time of 0.5-10 hours.

[0036] In some embodiments of the present invention, in step S2, the amount of the solution containing the active component element is 600-2000 mL relative to 1000 g of the magnesium-modified mesoporous carbon material. In the present invention, the method of impregnating the magnesium-modified mesoporous carbon material with the solution containing the precursor of the active metal component is not particularly limited, provided that the compound of the metal component is sufficiently introduced into the carrier; for example, an unsaturated impregnation method, a saturated impregnation method, or an excess liquid impregnation method can be used.

[0037] In some embodiments of the present invention, the content of the precursor of the group VIII metal element in the solution containing the active metal component, calculated as oxide, is 0.5-200 g / L, and the content of the precursor of the group VIB metal element is 15-800 g / L.

[0038] In some specific embodiments of the present invention, the precursor of the Group VIB metal element is selected from at least one of the soluble compounds and oxides of the Group VIB metal element, such as at least one of molybdic acid, secondary molybdic acid, molybdate, secondary molybdate, tungstic acid, metatungstic acid, ethyl metatungstic acid, tungstate, metatungstate and ethyl metatungstate.

[0039] In some specific embodiments of the present invention, the precursor of the Group VIII metal element is selected from at least one of the soluble compounds and oxides of the Group VIII metal element, such as at least one of nickel nitrate, cobalt nitrate, nickel acetate, cobalt acetate, basic nickel carbonate, basic cobalt carbonate, nickel chloride, and cobalt chloride.

[0040] In this invention, the method for obtaining the hydrogenation catalyst by heat treatment of the catalyst precursor can be simply drying, or it can be drying and calcining the catalyst precursor sequentially.

[0041] In some embodiments of the present invention, the conditions for the second drying include: a drying temperature of 60-200 ℃, preferably 100-150 ℃; and a drying time of 0.5-10 hours, preferably 4-8 hours.

[0042] In some embodiments of the present invention, the second calcination is carried out in air or an inert atmosphere; specifically, the inert atmosphere is selected from at least one of nitrogen, argon, helium, carbon dioxide, and water vapor. The conditions for the second calcination may include: a calcination temperature of 350-800 °C, preferably 350-550 °C; a heating rate of 0.1-10 °C / min; and a calcination time of 0.5-10 hours, preferably 4-8 hours.

[0043] In some embodiments of the present invention, the mesoporous carbon material is prepared by a method comprising the following steps: Asphalt powder and metal salt powder are mixed to obtain a first mixture; the first mixture is subjected to a first heat treatment to obtain a mesoporous carbon material precursor. The mesoporous carbon material precursor is subjected to a first acid wash and a first washing filtration to remove metal ions, resulting in a first material; or, the mesoporous carbon material precursor is mixed with asphalt powder to obtain a second mixture; the second mixture is subjected to a second heat treatment to obtain an intermediate material, and the intermediate material is subjected to a second acid wash and a second washing filtration to remove metal ions, resulting in a second material. The first material or the second material is dried to obtain a mesoporous carbon material.

[0044] The metal element in the metal salt is selected from one or more of Group VIII, Group IIA, Group IB, and Group IIB metal elements.

[0045] The processing atmosphere of the first heat treatment and the second heat treatment includes oxygen-containing compounds and inert gases.

[0046] In some embodiments of the present invention, in the first mixture, the amount of the metal salt, based on oxides, is 80-500 parts by weight relative to 100 parts by weight of the asphalt powder, preferably 100-450 parts by weight; in the second mixture, the weight ratio of the mesoporous carbon material precursor to the asphalt powder is 100-600:100, preferably 150-500:100.

[0047] In some embodiments of the present invention, the particle size of the asphalt powder is 1-10000 μm, preferably 1-1000 μm, and more preferably 1-150 μm.

[0048] In some embodiments of the present invention, the particle size of the metal salt is 1-10000 μm, preferably 1-1000 μm, and more preferably 1-150 μm.

[0049] In some embodiments of the present invention, the metal element in the metal salt is selected from at least one of iron, cobalt, nickel, magnesium, calcium, copper and zinc; preferably, the metal salt is a water-soluble salt, and the metal salt is selected from one or more of basic carbonates, sulfates, acetates and citrates.

[0050] The asphalt powder may include at least one of petroleum asphalt powder, coal tar powder, ethylene tar pitch powder, etc., as well as pre-oxidized petroleum asphalt powder, pre-oxidized coal tar powder, and pre-oxidized ethylene tar pitch powder. Compared to petroleum asphalt powder and coal tar powder, ethylene tar pitch powder has relatively lower sulfur and nitrogen content, resulting in lower sulfur and nitrogen content in the carbon materials prepared from it.

[0051] Preferably, in order to obtain carbon materials in higher yield, the asphalt powder contains polycyclic aromatic hydrocarbons (PAHs); based on the total weight of the asphalt powder, the PAH content can be 70-100% by weight, preferably 85-100% by weight. The PAH content is determined by a four-component analysis method.

[0052] The method for preparing mesoporous carbon materials of the present invention may further include a pre-oxidation treatment step of asphalt powder. Specifically, when pre-oxidizing asphalt powder, the asphalt powder can be placed in an oxygen-containing atmosphere, and the temperature of the asphalt powder can be raised from room temperature to 120-400°C at a heating rate of 0.1-10°C / min, and maintained at a constant temperature for 0.1-48 hours to obtain pre-oxidized asphalt powder.

[0053] In some embodiments of the present invention, the conditions for the first heat treatment and the second heat treatment include: a gas flow rate of 1-200 L / h, a heating rate of 0.1-10℃ / min, a heat treatment temperature of 25-1000℃, preferably 400-1000℃, and a treatment time of 0.1-48 hours.

[0054] The first and second heat treatments can both employ a single-stage temperature ramp, or both can employ a multi-stage temperature ramp, or the first heat treatment can employ a single-stage temperature ramp and the second heat treatment can employ a multi-stage temperature ramp, or the first heat treatment can employ a multi-stage temperature ramp and the second heat treatment can employ a single-stage temperature ramp. When the first and second heat treatments employ a single-stage temperature ramp, it is preferable to conduct them in the atmosphere containing the oxygen compound.

[0055] In some embodiments of the present invention, the oxygen-containing compound is selected from at least one of water vapor, carbon dioxide, and carbon monoxide; the inert gas includes at least one of nitrogen, argon, and helium.

[0056] Preferably, the first heat treatment and the second heat treatment each independently include a first heat treatment stage and a second heat treatment stage.

[0057] In some specific embodiments of the present invention, the first stage of heat treatment is carried out in an atmosphere containing an oxygen-containing compound, wherein the oxygen-containing compound is selected from at least one of water vapor, carbon dioxide, and carbon monoxide; the conditions of the first stage of heat treatment include: a gas flow rate of 1-200 L / h, a heating rate of 0.1-10 °C / min, a temperature of 25-850 °C, preferably 400-850 °C, and a time of 0.1-48 hours.

[0058] In some specific embodiments of the present invention, the second stage of heat treatment is carried out in an inert gas atmosphere, wherein the inert gas includes at least one of nitrogen, argon and helium; the conditions of the second stage of heat treatment include: gas flow rate of 1-200 L / h, heating rate of 0.1-10 °C / min, temperature of 550-1000 °C, and time of 0.1-48 hours.

[0059] The first stage of heat treatment and / or the second stage of heat treatment can be carried out by a single-stage temperature rise or by a multi-stage temperature rise.

[0060] In some embodiments of the present invention, the acid solutions used for the first pickling and the second pickling are each independently selected from one or more of hydrochloric acid solution, sulfuric acid solution, nitric acid solution, acetic acid solution and phosphoric acid solution.

[0061] Wherein, the acid solution contains H + The molar concentration of the substance is 0.1-10 mol / L, and the acid solution contains H. + The ratio of the amount of substance of the metal ion to the product of the amount of substance of the metal ion and the absolute value of the valence state of the metal ion is 1-3.

[0062] In some embodiments of the present invention, the conditions for the first pickling and the second pickling respectively include: a temperature of 20-100°C and a time of 0.5-24 hours.

[0063] The washing solutions for the first and second washes are deionized water.

[0064] In some embodiments of the present invention, the method further includes: collecting the filtrate from the first pickling and the first filtration washing process to obtain a first filtrate mixture; or, collecting the filtrate from the second pickling and the second filtration washing process to obtain a second filtrate mixture; The first filtrate mixture or the second filtrate mixture is subjected to heating concentration and cooling filtration to obtain the recovered metal salt; the recovered metal salt is then mixed with asphalt powder.

[0065] In some embodiments of the present invention, the weight ratio of the mesoporous carbon material precursor to the asphalt powder in the second mixture is 100-600:100, preferably 150-500:100.

[0066] In some embodiments of the present invention, the precursor solution containing the active metal component further includes an organic compound; the molar ratio of the organic compound to the active metal component (calculated as oxide) is 0.1-0.6:1. The organic compound is selected from one or more of organic acids or their ammonium salts, organic alcohols, and sugar compounds.

[0067] In some preferred embodiments of the present invention, 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.

[0068] In some preferred embodiments of the present invention, the organic alcohol is at least one selected from glycerol, ethylene glycol, polyethylene glycol, trimethylolethane, pentaerythritol, xylitol, and sorbitol.

[0069] In some preferred embodiments of the present invention, the carbohydrate compound is selected from at least one of triose, tetroose, pentose, D-glucose, D-galactose, D-mannose, D-fructose and sucrose.

[0070] A third aspect of the present invention provides a method for hydrotreating oil, the method comprising: In the presence of hydrogen and a sulfiding agent, the oil is contacted with the hydrogenation catalyst provided in the first aspect of the present invention or the hydrogenation catalyst provided in the second aspect of the present invention for hydrogenation treatment.

[0071] In some embodiments of the present invention, the vulcanizing agent may be a mixture of a sulfur-containing compound and a hydrocarbon oil. The sulfur-containing compound and the hydrocarbon oil are conventional sulfur-containing compounds and hydrocarbon oils that have undergone hydrogenation catalyst sulfidation in the art. For example, the sulfur-containing compound may be selected from at least one of CS2, dimethyl disulfide, dimethyl sulfide, tert-butyl polysulfide, and ethanethiol, and the hydrocarbon oil may be selected from C5-C4. 18 It is one or more of the following: organic hydrocarbons, gasoline distillate, jet fuel distillate, and diesel distillate. The sulfiding agent may also be a mixture of hydrogen gas and hydrogen sulfide.

[0072] In some embodiments of the present invention, the oil is selected from at least one of catalytic cracking gasoline, straight-run gasoline, coking gasoline, kerosene, catalytic cracking diesel, straight-run diesel, coking diesel, viscosity-reducing diesel, solvent-refined oil, wax paste, under-wax oil, Fischer-Tropsch synthetic oil, coal liquefaction oil, light deasphalted oil, and heavy deasphalted oil.

[0073] In some embodiments of the present invention, the conditions for the hydrogenation treatment include: a reaction temperature of 150-450 °C; a hydrogen partial pressure of 0.1-18 MPa; and a liquid hourly space velocity of 0.1-10 h⁻¹. -1 The hydrogen-to-oil volume ratio is 10-1000; the sulfur content in the oil is 100-20000 μg / g.

[0074] The present invention will be further described in detail below through embodiments, but the invention is not limited thereto. All raw materials used in the embodiments are commercially available.

[0075] In this embodiment of the invention, the ammonium metatungstate contains 91.4 wt% WO3; and the basic nickel carbonate contains 51 wt% NiO.

[0076] The method for pre-oxidizing asphalt powder includes the following steps: Weigh 1000 grams of asphalt and place it in a tube furnace. Under the condition of air circulation and an air flow rate of 180 liters / hour, raise the temperature from room temperature to 360°C at a heating rate of 1°C / minute, and maintain the temperature at 360°C for 4 hours to obtain pre-oxidized asphalt. Then, lower the temperature of the pre-oxidized asphalt to room temperature and pulverize it to obtain pre-oxidized asphalt powder.

[0077] Preparation Example 1 This preparation example illustrates the method for preparing the mesoporous carbon material of the present invention, including the following steps: (1) Weigh 100g of petroleum asphalt powder and mix it evenly with 505g of magnesium acetate to obtain a first mixture. Place the first mixture in a tube furnace, pass carbon dioxide through it, and perform a first heat treatment. After cooling to room temperature, a mesoporous carbon material precursor is obtained. The conditions of the first heat treatment include: the gas flow rate of carbon dioxide is 160 liters / hour; the temperature is raised from room temperature to 700 ℃ at a rate of 5 ℃ / minute; and the treatment time is 2 hours. (2) The mesoporous carbon material precursor obtained in step (1) is mixed with hydrochloric acid, and deionized water is added to dilute it to 4000 ml. The mixture is stirred at 80°C for 6 hours and acid washed to obtain the first material. The first material is filtered and washed with deionized water until neutral. The resulting filter cake is dried in a forced-air drying oven at 120°C for 6 hours. The amount of hydrochloric acid (mass fraction of 36%) is 473 g. The mesoporous carbon material obtained after drying is labeled as S1.

[0078] Preparation Example 2 This preparation example illustrates the method for preparing the mesoporous carbon material of the present invention, including the following steps: (1) Weigh 100g of petroleum asphalt powder and mix it evenly with 505g of basic magnesium carbonate to obtain the first mixture. Place the first mixture in a tube furnace, pass carbon dioxide through it, control the gas flow rate to 160 liters / hour, raise it to 700℃ at 5℃ / minute, and keep it at 700℃ for 2 hours for constant temperature heat treatment; after cooling to room temperature, the mesoporous carbon material precursor is obtained. (2) Add 805 g of glacial acetic acid to the mesoporous carbon material precursor obtained in step (1), then add deionized water to dilute to 4000 ml, stir at 80°C for 6 hours to obtain the first material; filter and wash the first material with deionized water until neutral. Dry the obtained filter cake in a forced-air oven at 120°C for 6 hours. The mesoporous carbon material obtained after drying is labeled as S2.

[0079] Preparation Example 3 This preparation example illustrates the method for preparing the mesoporous carbon material of the present invention, including the following steps: (1) Weigh 100g of pre-oxidized petroleum asphalt powder and mix it evenly with 675g of magnesium acetate to obtain the first mixture. Place the first mixture in a tube furnace, pass carbon dioxide through it, control the gas flow rate to 190L / hour, raise it to 700℃ at 2℃ / min, and keep it at 700℃ for 2 hours for constant temperature heat treatment; after cooling to room temperature, mesoporous carbon material precursor is obtained. (2) Add 922 g of hydrochloric acid (mass fraction of 36%) to the mesoporous carbon material precursor obtained in step (1), then add deionized water to dilute to 4000 ml, stir at 80°C for 6 hours to obtain the first material; filter and wash the first material with deionized water until neutral, and dry the resulting filter cake in a forced-air drying oven at 120°C for 6 hours. The mesoporous carbon material obtained after drying is labeled as S3.

[0080] Preparation Example 4 This preparation example illustrates the method for preparing the mesoporous carbon material of the present invention, including the following steps: (1) Weigh 100g of petroleum asphalt powder and mix it evenly with 505g of magnesium acetate to obtain the first mixture. Place the first mixture in a tube furnace, pass nitrogen gas through it, control the gas flow rate to 160 liters / hour, raise the temperature to 700℃ at 5℃ / minute, and keep it at 700℃ for 2 hours for constant temperature heat treatment; after cooling to room temperature, the mesoporous carbon material precursor is obtained. (2) Add 473 g of hydrochloric acid (mass fraction of 36%) to the mesoporous carbon material precursor obtained in step (1), then add deionized water to dilute to 4000 ml, stir at 80°C for 6 hours to obtain the first material; filter and wash the first material with deionized water until neutral, and dry the resulting filter cake in a forced-air drying oven at 120°C for 6 hours. The mesoporous carbon material obtained after drying is labeled as S4.

[0081] Preparation Example 5 This preparation example illustrates the method for preparing the mesoporous carbon material of the present invention, including the following steps: (1) Weigh 100g of petroleum asphalt powder and mix it evenly with 955g of magnesium acetate to obtain the first mixture. Place the first mixture in a tube furnace, pass carbon dioxide through it, control the gas flow rate at 160L / hour, raise it to 700℃ at 5℃ / min, and maintain it at 700℃ for 2 hours. After cooling to room temperature, a mesoporous carbon material precursor is obtained. Weigh the required petroleum asphalt powder according to the weight ratio of the mesoporous carbon material precursor to petroleum asphalt powder of 150:100. Mix the obtained mesoporous carbon material precursor and petroleum asphalt powder evenly to obtain the second mixture. Place the second mixture in a tube furnace, pass carbon dioxide through it, control the gas flow rate at 160L / hour, raise it to 800℃ at 5℃ / min, and maintain it at 800℃ for 2 hours. Cool the product to room temperature to obtain the intermediate material. (2) Add 1330 g of glacial acetic acid to the intermediate material obtained in step (1), then add deionized water to dilute to 4000 ml, stir at 80°C for 6 hours to obtain the second material; filter and wash the second material with deionized water until neutral. The obtained filter cake is dried in a forced-air oven at 120°C for 6 hours. The mesoporous carbon material obtained after drying is labeled as S5.

[0082] Preparation Example 6 This preparation example illustrates the method for preparing the mesoporous carbon material of the present invention, including the following steps: (1) Weigh 100g of petroleum asphalt powder and mix it evenly with 905g of magnesium acetate to obtain the first mixture. Place the first mixture in a tube furnace, pass carbon dioxide through it, control the gas flow rate at 160L / h, raise the temperature to 700℃ at 5℃ / min, and maintain the temperature at 700℃ for 2 hours to obtain the first stage product. Pass nitrogen through the first stage product, control the gas flow rate at 160L / h, raise the temperature to 900℃ at 5℃ / min, and maintain the temperature at 900℃ for 1 hour to obtain the second stage product. Cool the second stage product to room temperature to obtain the mesoporous carbon material precursor. Mix the mesoporous carbon material precursor with petroleum asphalt powder. Weigh the required petroleum asphalt powder at a weight ratio of 400:100; mix the obtained mesoporous carbon material precursor with the petroleum asphalt powder evenly to obtain a second mixture; place the second mixture in a tube furnace, pass carbon dioxide through it, control the gas flow rate at 160 liters / hour, raise the temperature to 700°C at 5°C / minute, and maintain the temperature at 700°C for 4 hours to obtain the first stage product; pass nitrogen through the first stage product, control the gas flow rate at 160 liters / hour, raise the temperature to 900°C at 5°C / minute, and maintain the temperature at 900°C for 3 hours to obtain the second stage product; cool the second stage product to room temperature to obtain the intermediate material. (2) Add 1276 g of hydrochloric acid (mass fraction of 36%) to the intermediate material obtained in step (1), then add deionized water to dilute to 4000 ml, stir at 80°C for 6 hours to obtain the second material; filter and wash the second material with deionized water until neutral. Dry the obtained filter cake in a forced-air oven at 120°C for 6 hours. The mesoporous carbon material obtained after drying is labeled as S6.

[0083] Preparation Example 7 This preparation example illustrates the method for preparing the mesoporous carbon material of the present invention, including the following steps: (1) Weigh 100g of petroleum asphalt powder and mix it evenly with 1205g of magnesium acetate to obtain the first mixture. Place the first mixture in a tube furnace, pass carbon dioxide through it, control the gas flow rate at 160L / hour, raise it to 700℃ at 5℃ / min, and keep it at 700℃ for 2 hours to obtain the first stage product. Then, pass nitrogen through the first stage product, control the gas flow rate at 160L / hour, raise it to 900℃ at 5℃ / min, and keep it at 900℃ for 2 hours to obtain the second stage product. Cool the second stage product to room temperature. After cooling to room temperature, the mesoporous carbon material precursor is obtained. (2) Add 806 g of glacial acetic acid to the mesoporous carbon material precursor obtained in step (1), then add deionized water to dilute to 4000 ml, stir at 80°C for 6 hours to obtain the first material; filter and wash the first material with deionized water until neutral. Dry the obtained filter cake in a forced-air oven at 120°C for 6 hours. The mesoporous carbon material obtained after drying is labeled as S7.

[0084] Preparation Example 8 This preparation example illustrates the method for preparing the mesoporous carbon material of the present invention, including the following steps: (1) Weigh 100g of petroleum asphalt powder and mix it evenly with 1205g of magnesium acetate to obtain the first mixture. Place the first mixture in a tube furnace, pass carbon dioxide through it, control the gas flow rate to 160L / hour, raise it to 700℃ at 5℃ / min, and keep it at 700℃ for 2 hours for constant temperature heat treatment; after cooling to room temperature, mesoporous carbon material precursor is obtained. (2) Add 806 g of glacial acetic acid to the mesoporous carbon material precursor obtained in step (1), then add deionized water to dilute to 4000 mL, stir at 80 °C for 6 hours to obtain an intermediate product; filter and wash the intermediate product with deionized water until neutral; collect all the filtrate in a beaker, heat and concentrate it in an 80 °C water bath until the relative density of the hot solution is 1.25-1.26, cool, and filter to obtain crystals. Mix the obtained crystals with 100 g of pitch powder to obtain a third mixture, place the third mixture in a tube furnace, pass carbon dioxide, control the gas flow rate to 160 L / h, raise it to 700 °C at 5 °C / min, and maintain it at 700 °C for 2 hours; after cooling to room temperature, obtain the mesoporous carbon material intermediate; (3) Add 806 g of glacial acetic acid to the mesoporous carbon material intermediate obtained in step (2), then add deionized water to dilute to 4000 ml, stir at 80°C for 6 hours to obtain the third material; filter and wash the third material with deionized water until neutral. Dry the obtained filter cake in a forced-air drying oven at 120°C for 6 hours. The mesoporous carbon material obtained after drying is labeled as S8.

[0085] Preparation Example 9 This preparation example illustrates the method for preparing the mesoporous carbon material of the present invention, including the following steps: (1) Weigh 100g of pre-oxidized petroleum asphalt powder and mix it evenly with 505g of magnesium acetate to obtain a first mixture. Place the first mixture in a tube furnace, pass carbon dioxide through it, and perform a first heat treatment. After cooling to room temperature, a mesoporous carbon material precursor is obtained. The conditions of the first heat treatment include: the gas flow rate of carbon dioxide is 1 L / h; the temperature is raised from room temperature to 400 ℃ at a rate of 0.5 ℃ / min; the treatment time is 40 hours; then, the gas flow rate of carbon dioxide is changed to 200 L / h, and the temperature is raised to 550 ℃ at a rate of 5 ℃ / min; the treatment time is 2 hours; finally, the gas flow rate of carbon dioxide is changed to 100 L / h; the temperature is raised to 700 ℃ at a rate of 10 ℃ / min; the treatment time is 1 hour. (2) The mesoporous carbon material precursor obtained in step (1) is mixed with 473 g of hydrochloric acid (mass fraction of 36%), and deionized water is added to dilute to 4000 ml. The mixture is stirred at 80 °C for 6 hours and acid washed to obtain the first material. The first material is filtered and washed with deionized water until neutral. The resulting filter cake is dried in a forced-air drying oven at 120 °C for 6 hours. The mesoporous carbon material obtained after drying is labeled as S9.

[0086] Preparation Example 10 This preparation example illustrates the method for preparing the mesoporous carbon material of the present invention, including the following steps: (1) Weigh 100g of petroleum asphalt powder and mix it evenly with 1505g of magnesium acetate, 101g of iron acetate, 52g of basic nickel carbonate and 7g of cobalt citrate to obtain the first mixture. Place the first mixture in a tube furnace, pass carbon dioxide through it, control the gas flow rate at 160L / hour, raise the temperature to 700℃ at 5℃ / min, and keep it at 700℃ for 2 hours for constant temperature heat treatment. After cooling to room temperature, the mesoporous carbon material precursor is obtained. (2) Add 2000 g of hydrochloric acid (mass fraction 36%) to the mesoporous carbon material precursor obtained in step (1), then add deionized water to dilute to 4000 mL, stir at 80 °C for 6 hours to obtain the first material; filter and wash the first material with deionized water until neutral. Dry the obtained filter cake in a forced-air drying oven at 120 °C for 6 hours. The mesoporous carbon material obtained after drying is labeled as S10.

[0087] Preparation Example 11 The method for preparing mesoporous carbon materials in this preparation example is basically similar to that in Preparation Example 6, except that the pitch powder raw material is ethylene tar pitch powder. The resulting mesoporous carbon material is labeled as S11.

[0088] Comparative Preparation Example 1 Referring to the method described in Example 1 of Patent Document 93120049.0, 100 grams of petroleum asphalt powder (passed through a 100-mesh sieve) was mixed with 3 grams of guar gum powder. 8 grams of polyvinyl alcohol were dissolved in 92 grams of water. After complete dissolution, 40 grams of this solution was added to the mixture of petroleum asphalt powder and guar gum powder and thoroughly mixed. The mixture was then extruded using an extruder. After molding, it was dried at 120°C for 2 hours to obtain material A. Material A was placed in a tube furnace and heated to 240°C at a rate of 0.2°C / min, then kept at this temperature in air for 8 hours to obtain material B. Material B was carbonized at 700°C under nitrogen for 2 hours, and then activated at 900°C under a steam / nitrogen atmosphere for 1 hour to obtain activated carbon product, labeled DT-1.

[0089] The probable pore size, specific surface area, and pore volume of the carbon materials prepared in Preparation Examples 1-11 and Comparative Preparation Example 1 were tested, and the test results are shown in Table 1. The elemental composition of the carbon materials prepared in Preparation Examples 1-11 was tested, and the test results are shown in Table 2.

[0090] Table 1

[0091] Table 2

[0092] Example 1 This embodiment illustrates the preparation method of the hydrogenation catalyst of the present invention, including the following steps: (1) Preparation of magnesium-modified mesoporous carbon materials Weigh 5.80 g of magnesium acetate tetrahydrate, add 160 mL of deionized water, and stir until homogeneous. Impregnate 120 g of the mesoporous carbon material S1 obtained in Example 1 with this solution for 2 hours, then dry at 120 °C for 4 hours. In a tube furnace, heat to 550 °C at 5 °C / min and treat with nitrogen for 4 hours. Magnesium-modified mesoporous carbon material is obtained, and the resulting sample is labeled CX-1. The properties of CX-1 are shown in Table 3.

[0093] (2) Preparation of hydrogenation catalyst Weigh 5.02 g of citric acid monohydrate, add 80 mL of deionized water, and heat and stir until homogeneous; add 6.97 g of nickel nitrate; continue heating and stirring until clear and transparent; then add 19.42 g of ammonium metatungstate (containing 91.4 wt% WO3), and continue heating and stirring until clear and transparent; cool and dilute to 120 mL. Impregnate 100 g of CX-1 support with this solution for 2 hours, then dry at 120 °C for 4 hours to obtain catalyst C1. The properties of catalyst C1 are shown in Table 4.

[0094] Examples 2-8 The methods for preparing hydrogenation catalysts in Examples 2-8 are basically similar to those in Example 1, except that the carbon materials used for magnesium modification in step (1) are the mesoporous carbon materials S2-S8 prepared in Examples 2-8. The resulting magnesium-modified mesoporous carbon materials are designated as CX-2 to CX-8, and their properties are shown in Table 3.

[0095] The corresponding catalysts are designated as C2-C8, and their properties are shown in Table 4.

[0096] Example 9 This embodiment illustrates the preparation method of the hydrogenation catalyst of the present invention, including the following steps: (1) Preparation of magnesium-modified mesoporous carbon materials Weigh 2.91 g of magnesium acetate tetrahydrate, add 160 mL of deionized water, and stir until homogeneous. Impregnate 120 g of the mesoporous carbon material S5 prepared in Example 5 with this solution for 2 hours, then dry at 120 °C for 4 hours. In a tube furnace, heat to 550 °C at 5 °C / min and treat with nitrogen for 4 hours. Magnesium-modified mesoporous carbon material is obtained, and the resulting sample is labeled CX-9. The properties of CX-9 are shown in Table 3.

[0097] (2) Preparation of hydrogenation catalyst Weigh 5.02 g of citric acid monohydrate, add 80 mL of deionized water, and heat and stir until homogeneous; add 6.97 g of nickel nitrate; continue heating and stirring until clear and transparent; then add 19.42 g of ammonium metatungstate (containing 91.4 wt% WO3), and continue heating and stirring until clear and transparent; cool and dilute to 120 mL. Impregnate 100 g of CX-9 support with this solution for 2 hours, then dry at 120 °C for 4 hours to obtain catalyst C9. The properties of catalyst C9 are shown in Table 4.

[0098] Example 10 This embodiment illustrates the preparation method of the hydrogenation catalyst of the present invention, including the following steps: (1) Preparation of magnesium-modified mesoporous carbon materials Weigh 11.65 g of magnesium acetate tetrahydrate, add 160 mL of deionized water, and stir well. Impregnate 120 g of the mesoporous carbon material S5 (Preparation Example 5) with this solution for 2 hours, then dry at 120 °C for 4 hours. In a tube furnace, raise the temperature to 550 °C at 5 °C / min and treat with nitrogen for 4 hours. Magnesium-modified mesoporous carbon material is obtained, and the resulting sample is labeled CX-10. The properties of CX-10 are shown in Table 3.

[0099] (2) Preparation of hydrogenation catalyst Weigh 5.02 g of citric acid monohydrate, add 80 mL of deionized water, and heat and stir until homogeneous; add 6.97 g of nickel nitrate; continue heating and stirring until clear and transparent; then add 19.42 g of ammonium metatungstate (containing 91.4 wt% WO3), and continue heating and stirring until clear and transparent; cool and dilute to 120 mL. Impregnate 100 g of CX-10 support with this solution for 2 hours, then dry at 120 °C for 4 hours to obtain catalyst C10. The properties of catalyst C10 are shown in Table 4.

[0100] Example 11 This embodiment illustrates the preparation method of the hydrogenation catalyst of the present invention, including the following steps: (1) Preparation of magnesium-modified mesoporous carbon materials Weigh 18.36 g of magnesium acetate tetrahydrate, add 160 mL of deionized water, and stir until homogeneous. Impregnate 120 g of the mesoporous carbon material S5 obtained in Example 5 with this solution for 2 hours, then dry at 120 °C for 4 hours. In a tube furnace, heat to 550 °C at 5 °C / min and treat with nitrogen for 4 hours. Magnesium-modified mesoporous carbon material is obtained, and the resulting sample is labeled CX-11. The properties of CX-11 are shown in Table 3.

[0101] (2) Preparation of hydrogenation catalyst Weigh 5.02 g of citric acid monohydrate, add 80 mL of deionized water, and heat and stir until homogeneous; add 6.97 g of nickel nitrate; continue heating and stirring until clear and transparent; then add 19.42 g of ammonium metatungstate (containing 91.4 wt% WO3), and continue heating and stirring until clear and transparent; cool and dilute to 120 mL. Impregnate 100 g of CX-11 support with this solution for 2 hours, then dry at 120 °C for 4 hours to obtain catalyst C11. The properties of catalyst C11 are shown in Table 4.

[0102] Example 12 This embodiment illustrates the preparation method of the hydrogenation catalyst of the present invention, including the following steps: (1) Preparation of magnesium-modified mesoporous carbon materials Weigh 25.01 g of magnesium acetate tetrahydrate, add 160 mL of deionized water, and stir until homogeneous. Impregnate 120 g of the mesoporous carbon material S5 obtained in Example 5 with this solution for 2 hours, then dry at 120 °C for 4 hours. In a tube furnace, heat to 550 °C at 5 °C / min and treat with nitrogen for 4 hours. Magnesium-modified mesoporous carbon material is obtained, and the resulting sample is labeled CX-12. The properties of CX-12 are shown in Table 3.

[0103] (2) Preparation of hydrogenation catalyst Weigh 5.02 g of citric acid monohydrate, add 80 mL of deionized water, and heat and stir until homogeneous; add 6.97 g of nickel nitrate; continue heating and stirring until clear and transparent; then add 19.42 g of ammonium metatungstate (containing 91.4 wt% WO3), and continue heating and stirring until clear and transparent; cool and dilute to 120 mL. Impregnate 100 g of CX-12 support with this solution for 2 hours, then dry at 120 °C for 4 hours to obtain catalyst C12. The properties of catalyst C12 are shown in Table 4.

[0104] Example 13 The preparation method of the hydrogenation catalyst in this embodiment is basically similar to that in Example 12, except that: Step (2) involves: weighing 11.89 g of citric acid monohydrate, adding 80 mL of deionized water, and heating and stirring until homogeneous; adding 8.25 g of basic nickel carbonate (containing 51% by weight NiO); continuing to heat and stir until clear and transparent; then adding 42.66 g of ammonium metatungstate (containing 91.4% by weight WO3), and continuing to heat and stir until clear and transparent; cooling and adjusting the volume to 120 mL. Impregnating 100 g of CX-12 support with this solution for 2 hours, followed by drying at 120 °C for 4 hours, yields catalyst C13. The properties of catalyst C13 are shown in Table 4.

[0105] Example 14 The preparation method of the hydrogenation catalyst in this embodiment is basically similar to that in Example 1, except that: Step (2) involves: measuring 80 mL of deionized water and adding 6.97 g of nickel nitrate; heating and stirring until clear and transparent; then adding 19.42 g of ammonium metatungstate (containing 91.4% wt% WO3), and continuing to heat and stir until clear and transparent; cooling and adjusting the volume to 120 mL. After impregnating 100 g of CX-1 support with this solution for 2 hours, the solution was dried at 120 °C for 4 hours to obtain catalyst C14. The properties of catalyst C14 are shown in Table 4.

[0106] Example 15 The preparation method of the hydrogenation catalyst in this embodiment is basically similar to that in Example 1, except that: Step (2) involves: measuring 80 mL of deionized water and adding 6.97 g of nickel nitrate; heating and stirring until clear and transparent; then adding 19.42 g of ammonium metatungstate (containing 91.4% wt% WO3), and continuing to heat and stir until clear and transparent; cooling and adjusting the volume to 120 mL. 100 g of CX-1 support was impregnated with this solution for 2 hours, dried at 120°C with forced air for 4 hours, then placed in a tube furnace under nitrogen gas, heated to 400°C at 5°C / min, and then calcined at 400°C for 5 hours to obtain catalyst C15. The properties of catalyst C15 are shown in Table 4.

[0107] Example 16 The method for preparing the hydrogenation catalyst in this embodiment is basically similar to that in Example 1, except that: the carbon material used for magnesium modification in step (1) is the mesoporous carbon material S9 prepared in Example 9; the obtained magnesium-modified mesoporous carbon material is denoted as CX-13, and its properties are shown in Table 3.

[0108] The corresponding catalyst is designated C16, and its properties are shown in Table 4.

[0109] Example 17 The method for preparing the hydrogenation catalyst in this embodiment is basically similar to that in Example 1, except that: the carbon material used for magnesium modification in step (1) is the mesoporous carbon material S10 prepared in Preparation Example 10; the obtained magnesium-modified mesoporous carbon material is denoted as CX-14, and its properties are shown in Table 3.

[0110] The corresponding catalyst is designated C17, and its properties are shown in Table 4.

[0111] Example 18 The method for preparing the hydrogenation catalyst in this embodiment is basically similar to that in Example 1, except that: the carbon material used for magnesium modification in step (1) is the mesoporous carbon material S11 prepared in Example 11; the obtained magnesium-modified mesoporous carbon material is denoted as CX-15, and its properties are shown in Table 3.

[0112] The corresponding catalyst is designated C18, and its properties are shown in Table 4.

[0113] Comparative Example 1 The method for preparing the hydrogenation catalyst in this comparative example includes the following steps: (1) Preparation of magnesium-modified mesoporous carbon materials Weigh 5.80 g of magnesium acetate tetrahydrate, add 160 mL of deionized water, and stir well. Impregnate 120 g of the carbon material DT-1 obtained in Comparative Preparation Example 1 with this solution for 2 hours, then dry at 120 °C for 4 hours. In a tube furnace, heat to 550 °C at 5 °C / min and treat with nitrogen for 4 hours. Magnesium-modified carbon material is obtained, and the sample is labeled DCX-1. The properties of magnesium-modified carbon material DCX-1 are shown in Table 3.

[0114] (2) Preparation of hydrogenation catalyst Weigh 5.02 g of citric acid monohydrate, add 80 mL of deionized water, and heat and stir until homogeneous; add 6.97 g of nickel nitrate; continue heating and stirring until clear and transparent; then add 19.42 g of ammonium metatungstate (containing 91.4 wt% WO3), and continue heating and stirring until clear and transparent; cool and dilute to 120 mL. Impregnate 100 g of DCX-1 support with this solution for 2 hours, then dry at 120 °C for 4 hours to obtain the hydrogenation catalyst, denoted as DC1, whose properties are shown in Table 4.

[0115] Comparative Example 2 The method for preparing the hydrogenation catalyst in this comparative example is basically similar to that in Comparative Example 1, except that step (1) is not performed, and the active component is directly impregnated on the carbon material DT-1 support prepared in Comparative Example 1; the prepared catalyst is labeled as DC2; the properties of the catalyst are shown in Table 4.

[0116] Comparative Example 3 The method for preparing the hydrogenation catalyst in this comparative example is basically similar to that in Comparative Example 1, with the following differences: Step (2) involves: measuring 80 mL of deionized water and adding 6.97 g of nickel nitrate; heating and stirring until clear and transparent; then adding 19.42 g of ammonium metatungstate (containing 91.4% wt% WO3), and continuing to heat and stir until clear and transparent; cooling and adjusting the volume to 120 mL. 100 g of DCX-1 support was impregnated with this solution for 2 hours, and then dried at 120°C for 4 hours. The resulting catalyst was labeled DC3; the properties of the catalyst are shown in Table 4.

[0117] Comparative Example 4 The method for preparing the hydrogenation catalyst in this comparative example is basically similar to that in comparative example 3, except that step (1) is not performed, and the active component is directly impregnated on the carbon material DT-1 support prepared in comparative preparation example 1; the prepared catalyst is labeled as DC4; the properties of the catalyst are shown in Table 4.

[0118] Comparative Example 5 The method for preparing the hydrogenation catalyst in this comparative example is basically similar to that in Comparative Example 1, with the following differences: Step (2) involves: measuring 80 mL of deionized water and adding 6.97 g of nickel nitrate; heating and stirring until clear and transparent; then adding 19.42 g of ammonium metatungstate (containing 91.4% wt% WO3), and continuing to heat and stir until clear and transparent; cooling and adjusting the volume to 120 mL. 100 g of DCX-1 support was impregnated with this solution for 2 hours, dried at 120°C with forced air for 4 hours, then placed in a tube furnace under nitrogen gas, heated to 400°C at 5°C / min, and then calcined at 400°C for 5 hours. The resulting catalyst was labeled DC5; the properties of the catalyst are shown in Table 4.

[0119] Comparative Example 6 The method for preparing the hydrogenation catalyst in this comparative example is basically similar to that in comparative example 5, except that step (1) is not performed, and the active component is directly impregnated on the carbon material DT-1 support prepared in comparative preparation example 1; the prepared catalyst is labeled as DC6; the properties of the catalyst are shown in Table 4.

[0120] Comparative Example 7 The method for preparing the hydrogenation catalyst in this comparative example is basically similar to that in Example 1, except that step (1) is not performed, and the active component is directly impregnated on the mesoporous carbon material S1 support obtained in Example 1; the catalyst obtained is labeled as DC7; the properties of the catalyst are shown in Table 4.

[0121] Table 3

[0122] Table 4

[0123] Catalytic performance evaluation The hydrogenation performance of the hydrogenation catalyst of the present invention was evaluated. In the experiment, the model reaction oil used was a mixed oil containing sulfur compounds in n-decane solution, which contained 1 wt% 4,6-dimethyldibenzothiophene, 1 wt% decahydronaphthalene and 2.6 wt% o-xylene.

[0124] The catalyst was crushed into 40-60 mesh particles, and 0.15 g of the crushed catalyst was loaded into the isothermal zone of the microreactor hydrogenation test apparatus. A carbon disulfide / cyclohexane mixture with 5 wt% CS2 was used as the sulfurized oil, with a flow rate of 0.2 mL / min and a hydrogen flow rate of 180 mL / min. Sulfurization was carried out at 360 °C for 3 hours. After sulfurization, when the temperature in the reactor dropped to 260 °C, the sulfurized oil was switched to the model reaction oil, and the catalyst was evaluated for hydrodesulfurization. The hydrodesulfurization reaction conditions included: a reaction temperature of 320 °C, a reaction pressure of 4.0 MPa, a feed rate of 0.2 mL / min, and a hydrogen flow rate of 180 mL / min. After reaching steady state, samples were taken and the product composition was analyzed offline using an Agilent 7890 gas chromatograph.

[0125] The hydrodesulfurization selectivity factor S is calculated based on the ratio of the yields of HYD pathway desulfurization products (dimethyltetrahydrodibenzothiophene, dimethylhexahydrodibenzothiophene, and dimethylcyclohexylbenzene) to DDS pathway desulfurization products (dimethylbiphenyl). Taking the hydrodesulfurization selectivity of the control catalyst DC1 as 100, the relative hydrodesulfurization selectivity of other catalysts can be expressed by the following formula: Relative selectivity = (S QT / S DC1 )×100%, where A QT S, S is the selectivity factor for hydrodesulfurization of other catalysts. DC1 S is the hydrodesulfurization selectivity factor for the reference catalyst. The results are shown in Table 5.

[0126] Table 5

[0127] As can be seen from the experimental results in the table above, the hydrogenation catalyst prepared using the magnesium-modified mesoporous carbon material of the present invention can significantly improve the selectivity for hydrodesulfurization of the difficult-to-remove sulfur-containing compound 4,6-dimethyldibenzothiophene.

[0128] Comparing Example 1 and Comparative Example 7, it can be seen that by introducing magnesium into the mesoporous carbon material, the selectivity of the magnesium-modified hydrogenation catalyst for the hydrodesulfurization of 4,6-dimethyldibenzothiophene is significantly improved.

[0129] The results from Examples 1 and 14-15 show that when organic matter is added to the impregnation solution of the active component, the hydrogenation catalyst obtained by the magnesium-modified mesoporous carbon material has a higher selectivity for hydrodesulfurization of 4,6-dimethyldibenzothiophene. Moreover, when no organic matter is present in the impregnation solution, the desulfurization selectivity of the hydrogenation catalyst is different depending on the heat treatment method of the catalyst precursor.

[0130] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0131] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0132] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A hydrogenation catalyst, characterized in that, The hydrogenation catalyst comprises a magnesium-modified mesoporous carbon support and an active metal component supported on the magnesium-modified mesoporous carbon support; the active metal component comprises at least one Group VIII metal element and at least one Group VIB metal element; the magnesium-modified mesoporous carbon support comprises mesoporous carbon material and magnesium-containing compounds distributed in the pores and / or on the surface of the mesoporous carbon material; based on the total weight of the magnesium-modified mesoporous carbon support, the magnesium content on the magnesium-modified mesoporous carbon support is 0.1-5% by weight; the specific surface area of ​​the magnesium-modified mesoporous carbon support is 200-1000 m². 2 / g, pore volume 0.6-1.8 cm³ 3 / g, with a pore size of 5-20 nm.

2. The hydrogenation catalyst according to claim 1, wherein, The magnesium content on the magnesium-modified mesoporous carbon support is 0.2-4% by weight. Optionally, the specific surface area of ​​the magnesium-modified mesoporous carbon support is 250-900 m². 2 / g, pore volume 0.7-1.6 cm³ 3 / g, with a pore size of 6-16 nm; Optionally, based on the total weight of the hydrogenation catalyst and calculated as oxides, the content of the Group VIII metal element is 0.1-10% by weight, preferably 1-6% by weight; the content of the Group VIB metal element is 3-40% by weight, preferably 5-36% by weight. Optionally, the Group VIII metal element is selected from at least one of iron, cobalt, and nickel; and the Group VIB metal element is selected from at least one of molybdenum and tungsten.

3. The hydrogenation catalyst according to claim 1, wherein, The mesoporous carbon material contains carbon, oxygen, hydrogen, sulfur, and nitrogen. Based on the total weight of the mesoporous carbon material, the carbon content is 80-96 wt%, preferably 82-94 wt%; the oxygen content is 1-12 wt%, preferably 2-10 wt%; the hydrogen content is 0.5-2 wt%, preferably 0.6-1.6 wt%; the sulfur content is 0.01-8 wt%, preferably 0.1-7.5 wt%; and the nitrogen content is 0.01-3 wt%, preferably 0.05-2 wt%.

4. A method for preparing a hydrogenation catalyst, characterized in that, The method includes: S1. Impregnate the mesoporous carbon material with a magnesium-containing solution, and then subject the impregnated mesoporous carbon material to a first drying and a first calcination to obtain magnesium-modified mesoporous carbon material. S2. Impregnate the magnesium-modified mesoporous carbon material with a solution containing an active metal component, and subject the obtained catalyst precursor to a second drying or sequentially subject the catalyst precursor to a second drying and a second calcination to obtain a hydrogenation catalyst. The metal elements in the solution of the precursor containing the active metal component include at least one Group VIII metal element and at least one Group VIB metal element; the specific surface area of ​​the mesoporous carbon material is 200-800 m². 2 / g, preferably 250-800m 2 / g; pore volume is 0.6-1.6 cm³ 3 / g, preferably 0.7-1.6 cm 3 / g; the pore size is 5-16 nm, preferably 6-16 nm.

5. The method according to claim 4, wherein, The magnesium source in the magnesium-containing solution is selected from one or more of magnesium acetate, magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium carbonate, and basic magnesium carbonate. Optionally, in step S2, the impregnation is selected from one of unsaturated impregnation, saturated impregnation, and excess impregnation, such that, on a dry basis and based on the total weight of the hydrogenation catalyst, the content of the Group VIII metal element is 0.1-10% by weight, and the content of the Group VIB metal element is 3-40% by weight.

6. The method according to claim 4, wherein, The mesoporous carbon material is prepared by a method comprising the following steps: Asphalt powder and metal salt powder are mixed to obtain a first mixture; the first mixture is subjected to a first heat treatment to obtain a mesoporous carbon material precursor. The mesoporous carbon material precursor is subjected to a first acid wash and a first washing filtration to remove metal ions, resulting in a first material; or, the mesoporous carbon material precursor is mixed with asphalt powder to obtain a second mixture; the second mixture is subjected to a second heat treatment to obtain an intermediate material, and the intermediate material is subjected to a second acid wash and a second washing filtration to remove metal ions, resulting in a second material. The first material or the second material is dried to obtain a mesoporous carbon material. The metal element in the metal salt is selected from one or more of Group VIII, Group IIA, Group IB, and Group IIB metal elements; the processing atmosphere of the first heat treatment and the second heat treatment includes oxygen-containing compounds and inert gases.

7. The method according to claim 6, wherein, In the first mixture, the amount of the metal salt, based on oxides, is 80-500 parts by weight relative to 100 parts by weight of the asphalt powder, preferably 100-450 parts by weight; in the second mixture, the weight ratio of the mesoporous carbon material precursor to the asphalt powder is 100-600:100, preferably 150-500:

100. The particle size of the asphalt powder is 1-10000μm, preferably 1-1000μm, and more preferably 1-150μm; The particle size of the metal salt is 1-10000 μm, preferably 1-1000 μm, more preferably 1-150 μm; the metal element in the metal salt is selected from at least one of iron, cobalt, nickel, magnesium, calcium, copper and zinc; the metal salt is selected from one or more of basic carbonates, sulfates, acetates and citrates. Preferably, based on the total weight of the asphalt powder, the content of polycyclic aromatic hydrocarbons is 70-100% by weight, more preferably 85-100% by weight. Preferably, the asphalt powder is selected from one or more of petroleum asphalt powder, coal tar powder, ethylene tar pitch powder, pre-oxidized petroleum asphalt powder, pre-oxidized coal tar powder, and pre-oxidized ethylene tar pitch powder.

8. The method according to claim 6, wherein, The conditions for the first heat treatment and the second heat treatment include: gas flow rate of 1-200 L / h, heating rate of 0.1-10℃ / min, heat treatment temperature of 25-1000℃, preferably 400-1000℃, and treatment time of 0.1-48 hours; Preferably, the first heat treatment and the second heat treatment each independently include a first stage heat treatment and a second stage heat treatment; the first stage heat treatment is carried out in an atmosphere containing an oxygen-containing compound, wherein the oxygen-containing compound is selected from at least one of water vapor, carbon dioxide, and carbon monoxide; the conditions of the first stage heat treatment include: a gas flow rate of 1-200 L / h, a heating rate of 0.1-10 °C / min, a temperature of 25-850 °C, preferably 400-850 °C, and a time of 0.1-48 hours; the second stage heat treatment is carried out in an inert gas atmosphere, wherein the inert gas includes at least one of nitrogen, argon, and helium; the conditions of the second stage heat treatment include: a gas flow rate of 1-200 L / h, a heating rate of 0.1-10 °C / min, a temperature of 550-1000 °C, and a time of 0.1-48 hours.

9. The method according to claim 6, wherein, The acids used in the first and second pickling processes are each independently selected from one or more of hydrochloric acid solution, sulfuric acid solution, nitric acid solution, acetic acid solution, and phosphoric acid solution; the acid solutions contain H+. + The molar concentration of the substance is 0.1-10 mol / L; optionally, the conditions for the first pickling and the second pickling include: a temperature of 20-100℃ and a time of 0.5-24 hours; the washing solution for the first washing and the second washing is deionized water; the conditions for the drying treatment include: a temperature of 20-200℃ and a time of 0.5-24 hours. Optionally, the method further includes: collecting the filtrate from the first pickling and first filtration washing processes to obtain a first filtrate mixture; or, collecting the filtrate from the second pickling and second filtration washing processes to obtain a second filtrate mixture; subjecting the first filtrate mixture or the second filtrate mixture to heating concentration and cooling filtration to obtain recovered metal salts; and mixing the recovered metal salts with asphalt powder.

10. The method according to claim 4, wherein, In step S1, the conditions for the first drying include: a drying temperature of 60-200 ℃ and a drying time of 0.5-10 hours; the first calcination is carried out in an inert gas atmosphere; the conditions for the first calcination include: a calcination temperature of 350-800 ℃, a heating rate of 0.1-10 ℃ / min, and a calcination time of 0.5-10 hours. The second drying conditions include: a drying temperature of 60-200 ℃, preferably 100-150 ℃; a drying time of 0.5-10 hours, preferably 4-8 hours; and the second calcination is carried out in air or an inert atmosphere. The second calcination conditions include: a calcination temperature of 350-800 ℃, preferably 350-550 ℃; a heating rate of 0.1-10 ℃ / min; and a calcination time of 0.5-10 hours, preferably 4-8 hours.

11. The method according to claim 4, wherein, The solution containing the precursor of the active metal component further includes an organic compound; the molar ratio of the organic compound to the active metal component (calculated as oxide) is 0.1-0.6:1; the organic compound is selected from one or more of organic acids or their ammonium salts, organic alcohols, and sugars; wherein 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; and / or the organic alcohol is at least one of glycerol, ethylene glycol, polyethylene glycol, trimethylolethane, pentaerythritol, xylitol, and sorbitol; and / or the sugar is selected from at least one of triose, tetroose, pentose, D-glucose, D-galactose, D-mannose, D-fructose, and sucrose.

12. A method for hydrotreating oil, characterized in that, The method includes: In the presence of hydrogen and a sulfiding agent, the oil is contacted with the hydrotreating catalyst described in any one of claims 1-3 or the hydrotreating catalyst prepared by the method described in any one of claims 4-11 for hydrotreating. Preferably, the conditions for hydrogenation treatment include: a reaction temperature of 150-450 °C; a hydrogen partial pressure of 0.1-18 MPa; and a liquid hourly space velocity of 0.1-10 h⁻¹. -1 The hydrogen-to-oil volume ratio is 10-1000; the sulfur content in the oil is 100-20000 μg / g.

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