Hydrogenation catalyst, preparation method and use therefor, and oil product hydrotreating method

Abstract

A hydrogenation catalyst, a preparation method and use therefor, and an oil product hydrotreating method. The hydrogenation catalyst comprises a carrier and an active component. The carrier comprises a nickel-aluminum alloy. The active component comprises a sulfur-containing organic molybdenum compound. The hydrogenation catalyst has high hydrotreating capacity for inferior raw oil products.

Description

Hydrogenation catalyst, preparation method and application thereof, and oil product hydrogenation treatment method

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Chinese patent application 202311494116.0 filed on November 10, 2023, the contents of which are incorporated herein by reference. Technical Field

[0003] The present invention belongs to the field of hydrogenation catalysts and relates to a hydrogenation catalyst and a preparation method and application thereof. Background Art

[0004] The limited nickel content of traditional alumina-nickel-molybdenum hydrogenation catalysts limits their hydrogenation activity. For processing feedstocks with high aromatics content, traditional hydrogenation catalysts not only require high temperatures and pressures but are also prone to coking and carbon deposition.

[0005] CN103861596A discloses a method for preparing a nickel-based hydrogenation catalyst. This method involves dissolving a soluble salt of the active component nickel and a soluble salt of an auxiliary agent in water to form a mixed aqueous solution of nickel and the auxiliary agent. This solution is then added to a reactor in parallel with a soluble salt of a precipitant. When the reactor temperature reaches a certain temperature, a carrier is added, the reaction is maintained for a period of time, and the nickel-based catalyst is obtained through washing, drying, and reduction. This catalyst has the advantages of mild reaction conditions, high catalytic activity, and high selectivity for the target product, and is therefore widely applicable in actual industrial production. However, this hydrogenation catalyst is not suitable for processing heavy and low-quality oils.

[0006] CN113019371A discloses a skeletal nickel catalyst precursor, a skeletal nickel catalyst, and a preparation method thereof. The catalyst is prepared by adding three alloy particles of varying particle size and composition to a uniform slurry, followed by activation and post-treatment. The catalyst has a wide particle size distribution and exhibits magnetic synergy between particles of varying particle sizes. However, this catalyst also struggles to effectively remove heteroatoms from oil products, limiting its application.

[0007] Summary of the Invention

[0008] In order to overcome the problem that the hydrogenation processing capacity of the existing hydrogenation catalyst needs to be further improved, the present invention provides a hydrogenation catalyst and its preparation method and application, as well as an oil product hydrogenation processing method. The hydrogenation catalyst provided by the present invention has a strong hydrogenation processing capacity for inferior raw oil products.

[0009] A first aspect of the present invention provides a hydrogenation catalyst, which includes a carrier and an active component, wherein the carrier includes a nickel-aluminum alloy and the active component includes a sulfur-containing organic molybdenum compound.

[0010] By combining sulfur-containing organic molybdenum compounds with nickel-aluminum alloys, sulfur-containing molybdenum species combine with nickel to form Ni-Mo-S active sites, providing hydrogenation centers, improving the utilization rate of molybdenum and the hydrogenation activity of the catalyst, and thus being more conducive to improving the catalyst's hydrogenation processing capacity.

[0011] Preferably, the sulfur-containing organic molybdenum compound is a dialkyl dithiophosphate molybdenum and / or a dialkyl dithiocarbamate molybdenum, more preferably, the dialkyl dithiophosphate molybdenum is selected from at least one of diisopropyl dithiophosphate molybdenum, dibutyl dithiophosphate molybdenum, diisooctyl dithiophosphate molybdenum, diisobutyl dithiophosphate molybdenum, dipropyl dithiophosphate molybdenum, dipentyl dithiophosphate molybdenum, dihexyl dithiophosphate molybdenum and diheptyl dithiophosphate molybdenum; more preferably, preferably, the dialkyl dithiocarbamate molybdenum is selected from at least one of diisopropyl dithiocarbamate molybdenum, dibutyl dithiocarbamate molybdenum, dipentyl dithiocarbamate molybdenum, dihexyl dithiocarbamate molybdenum, diheptyl dithiocarbamate molybdenum and dioctyl dithiocarbamate molybdenum.

[0012] Preferably, the carrier comprises a silicon-modified nickel-aluminum alloy, and more preferably comprises an organosilicon-modified nickel-aluminum alloy.

[0013] Preferably, based on the total dry weight of the hydrogenation catalyst, the content of Al calculated as aluminum oxide is 62% to 85%, preferably 68% to 80%, the content of Ni calculated as nickel oxide is 8% to 18%, preferably 9% to 15%, the content of molybdenum calculated as molybdenum trioxide is 6% to 18%, preferably 8% to 17%, and the content of silicon calculated as silicon dioxide is 0.2% to 3%, preferably 0.5% to 2%.

[0014] Preferably, the hydrogenation catalyst further contains a metal promoter, wherein the metal is selected from at least one of Group IA, IIA, IIIA, IB and IIB metals.

[0015] A second aspect of the present invention provides a method for preparing a hydrogenation catalyst, the method comprising:

[0016] The sulfur-containing organic molybdenum compound is loaded on the nickel-aluminum alloy by an impregnation method and then dried.

[0017] The third aspect of the present invention provides a hydrogenation catalyst prepared by the method described in the second aspect.

[0018] The fourth aspect of the present invention provides use of the hydrogenation catalyst described in the first aspect or the third aspect in the hydrogenation of oil products.

[0019] A fifth aspect of the present invention provides a method for hydrotreating an oil product, the method comprising: contacting the oil product with the hydrogenation catalyst described in the first aspect or the third aspect under hydrotreating conditions.

[0020] Compared with the prior art, the catalyst of the present invention has the following advantages:

[0021] (1) The hydrogenation catalyst of the present invention uses nickel-aluminum alloy as a carrier material for the catalytic substrate and is combined with a sulfur-containing organic molybdenum compound as an active component. The sulfur-containing molybdenum species combines with nickel to form Ni-Mo-S active sites, providing hydrogenation centers, thereby improving the utilization rate of molybdenum and the hydrogenation activity of the catalyst.

[0022] (2) The hydrogenation catalyst of the present invention has higher hydrogenation activity than the molybdenum species obtained from the oxidized state after sulfidation and the unsupported MoS2 particles.

[0023] (3) The preparation process of the hydrogenation catalyst of the present invention is simple, and after the active components are introduced, it can be used after activation. DETAILED DESCRIPTION

[0024] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0025] In the present invention, unless otherwise explicitly stated, percentages and contents are all based on mass.

[0026] A first aspect of the present invention provides a hydrogenation catalyst, which includes a carrier and an active component, wherein the carrier includes a nickel-aluminum alloy and the active component includes a sulfur-containing organic molybdenum compound.

[0027] In the present invention, the nickel-aluminum alloy and the sulfur-containing organic molybdenum compound have a wide range of choices. The nickel-aluminum alloy and the sulfur-containing organic molybdenum compound have conventional definitions in the art, and there is no particular limitation on their sources. They can be purchased commercially or prepared in-house, and any feasible method can be used for preparation.

[0028] The sulfur-containing organo-molybdenum compound of the present invention can be any of the various oil-soluble sulfur-containing organo-molybdenum compounds commonly used in the art. Preferably, the sulfur-containing organo-molybdenum compound is a molybdenum dialkyl dithiophosphate and / or a molybdenum dialkyl dithiocarbamate (MoDTC). The present invention allows for a wide range of selection of the alkyl group in the sulfur-containing organo-molybdenum compound, which can be an alkyl group (straight or branched) with 1 to 13 carbon atoms, including but not limited to methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, n-octyl, and isooctyl.

[0029] Preferably, the dialkyl dithiophosphate molybdenum is selected from at least one of diisopropyl dithiophosphate molybdenum, dibutyl dithiophosphate molybdenum, diisooctyl dithiophosphate molybdenum, diisobutyl dithiophosphate molybdenum, dipropyl dithiophosphate molybdenum, dipentyl dithiophosphate molybdenum, dihexyl dithiophosphate molybdenum and diheptyl dithiophosphate molybdenum, more preferably at least one of diisopropyl dithiophosphate molybdenum, dibutyl dithiophosphate molybdenum and diisooctyl dithiophosphate molybdenum.

[0030] Preferably, the dialkyl dithiocarbamate molybdenum is selected from at least one of diisopropyl dithiocarbamate, dibutyl dithiocarbamate, dipentyl dithiocarbamate, dihexyl dithiocarbamate, diheptyl dithiocarbamate and dioctyl dithiocarbamate, more preferably dibutyl dithiocarbamate and / or diisopropyl dithiocarbamate.

[0031] In the present invention, the nickel and aluminum content in the nickel-aluminum alloy can be selected within a wide range. Preferably, based on the total amount of the nickel-aluminum alloy, the aluminum content, calculated as the element, is 50% to 95% by weight, and the nickel content, calculated as the element, is 5% to 50% by weight. More preferably, based on the total amount of the nickel-aluminum alloy, the aluminum content, calculated as the element, is 70% to 90% by weight, and the nickel content, calculated as the element, is 10% to 30% by weight. This preferred embodiment not only allows the nickel and sulfur-containing organomolybdenum compound to effectively combine to improve the hydrogenation performance of the catalyst, but also prevents the nickel content in the nickel-aluminum alloy from being too high.

[0032] According to a preferred embodiment of the present invention, based on the total dry weight of the hydrogenation catalyst, the content of Al calculated as aluminum oxide is 63% to 86%, preferably 69% to 81%, the content of Ni calculated as nickel oxide is 8% to 20%, preferably 9% to 16%, and the content of molybdenum calculated as molybdenum trioxide is 6% to 20%, preferably 8% to 18%.

[0033] In the present invention, the dry basis measurement method of the hydrogenation catalyst is as follows: in an air atmosphere, the catalyst is heated from 120°C at 3.0°C per minute to 420°C, and then calcined for 4.0 hours. Thereafter, the temperature is increased by 3.0°C per minute and calcined at 550°C for 2.0 hours. The obtained object is analyzed in a dry environment.

[0034] The content of each component on a dry basis can be determined using atomic emission spectrometry (ICP-AES) analysis, specifically using an OPTIMA 7000DV atomic emission spectrometer manufactured by PE. In a typical solution preparation process, 0.1 g of sample is dissolved in a mixture of 3 HCl:1 HNO3:0.5 HF by volume. This mixture is then diluted with deionized water to a volume sufficient to maintain the concentration of the element being measured between 1 and 10 ppm, thereby increasing the accuracy of the measurement data.

[0035] The method for analyzing metal organic compounds in catalysts can be used to analyze the product by XPS, and the test conditions of the XPS include: light source: Mg Kα, energy step size: 0.05eV, scanning range: 200-250eV (molybdenum), 280-300eV (carbon). When analyzing the valence state of molybdenum, it is considered that the molybdenum species with a 3d5 / 2 orbital binding energy of 227-228eV is a 0-valent molybdenum species, the molybdenum species with a 3d5 / 2 orbital binding energy of 228-229eV is a +2-valent molybdenum species, the molybdenum species with a 3d5 / 2 orbital binding energy of 229-231eV is a +4-valent molybdenum species, and the molybdenum species with a 3d5 / 2 orbital binding energy greater than 231eV is a +5- or +6-valent molybdenum species.

[0036] The 3d5 / 2 orbital of organometallic molybdenum is between 227 and 229 eV, indicating a valence range of 0 to +2 for molybdenum species. Other metal organic compounds, such as Ga, Zn, Mg, and Cu, are tested using similar methods to elemental molybdenum. Analysis revealed that the valence states of these metal additives are organic species with a valence range of 0 to +1, confirming the presence of sulfur-containing organometallic molybdenum compounds.

[0037] According to the present invention, preferably, the support comprises a silicon-modified nickel-aluminum alloy, preferably an organosilicon-modified nickel-aluminum alloy. Using this preferred embodiment, the use of a modified nickel-aluminum alloy as a catalytic substrate in the catalyst can provide a large amount of activated hydrogen, providing conditions for hydrogen transfer, and in combination with a sulfur-containing organic molybdenum compound, particularly a dialkyl dithiophosphate molybdenum and / or an alkyl dithiocarbamate molybdenum as an active component. The sulfur-containing molybdenum species combines with nickel to form more Ni-Mo-S active sites, providing hydrogenation centers, further improving the utilization rate of molybdenum and the hydrogenation activity of the catalyst.

[0038] According to the present invention, the organosilicon is preferably selected from alkoxysilanes. The alkoxysilanes of the present invention may contain alkoxy groups, and the number of alkoxy groups may be 1 to 4. The organosilicon may be at least one of trialkoxysilanes, alkyltrialkoxysilanes, dialkyldialkoxysilanes, trialkylalkoxysilanes, and tetraalkoxysilanes.

[0039] The alkyl group refers to a linear or branched alkyl group, and the number of carbon atoms in the alkyl group is preferably 1 to 8. Examples of the alkyl group with 1 to 8 carbon atoms include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-octyl, isooctyl, and the like.

[0040] The alkoxy group refers to a group in which an oxygen atom is attached to the end of a linear or branched alkyl group, and the number of carbon atoms in the alkoxy group is preferably 1 to 8. The alkoxy group with 1 to 8 carbon atoms includes, but is not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and the like.

[0041] More preferably, the alkoxysilane is at least one selected from methyltrimethoxysilane, triethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, butyltriethoxysilane and octyltriethoxysilane.

[0042] According to the present invention, preferably, the content of the organosilicon compound in the hydrogenation catalyst calculated as SiO2 is 0.2% to 3%, preferably 0.5% to 2%, based on the total dry weight of the hydrogenation catalyst.

[0043] In this preferred embodiment, in the hydrogenation catalyst, based on the total dry weight of the hydrogenation catalyst, the content of Al calculated as aluminum oxide is 62% to 85%, preferably 68% to 80%, the content of Ni calculated as nickel oxide is 8% to 18%, preferably 9% to 15%, the content of molybdenum calculated as molybdenum trioxide is 6% to 18%, preferably 8% to 17%, and the content of silicon calculated as silicon dioxide is 0.2% to 3%, preferably 0.5% to 2%.

[0044] According to the present invention, preferably, the hydrogenation catalyst may further contain various metal and / or non-metal additives that are beneficial to improving the hydrogenation performance of the catalyst.

[0045] Preferably, the hydrogenation catalyst further contains a metal promoter, wherein the metal is selected from at least one of Group IA, IIA, IIIA, IB and IIB metals.

[0046] The Group IA metals include but are not limited to Na, K, and Rb.

[0047] The Group IIA metals include, but are not limited to, Mg, Ca, and Sr.

[0048] The Group IIIA metals include, but are not limited to, Al, Ga, and In.

[0049] The Group IB metals include but are not limited to Cu and Ag.

[0050] The Group IIB metals include but are not limited to Zn and Cd.

[0051] According to the present invention, preferably, the metal is selected from at least one of Zn, Ga, Mg and Cu, more preferably Zn and / or Ga. This embodiment is more conducive to the coordination effect between the metal additive and the sulfur-containing organic molybdenum compound.

[0052] Preferably, the metal adjuvant is a metal organic compound, such as an oil-soluble metal organic compound.

[0053] According to the present invention, preferably, the metal additive is a metal zinc organic compound and / or a metal gallium organic compound. Further preferably, the metal zinc organic compound is zinc dialkyldithiophosphate and / or zinc dialkyldithiocarbamate; and the metal gallium organic compound is at least one of triethylgallium, triisopropylgallium, tri-tert-butylgallium, gallium acetylacetonate, gallium ethoxide, and gallium isopropoxide.

[0054] The selection range of the organic ligand coordinated with zinc in the zinc dialkyldithiophosphate and / or zinc dialkyldithiocarbamate can be the same as that for the molybdenum dialkyldithiophosphate and / or molybdenum dialkyldithiocarbamate described above, and the present invention will not be repeated here. Preferably, the metal zinc organic compound is selected from at least one of dibutyldithiophosphate, zinc diisooctyldithiophosphate, and zinc diethyldithiocarbamate.

[0055] In the catalyst provided by the present invention, the use of organometallic gallium compounds, since gallium and aluminum are in the same element group, can also bind to nickel and interact with the supported organic molybdenum species, which is beneficial for enhancing hydrogenation activity. Furthermore, organometallic gallium compounds can form strong Ga-N triple bonds with nitrogen, which strongly interacts with nitrides in oil products, significantly enhancing hydrodenitrogenation activity.

[0056] In the catalyst provided by the present invention, when a metallic zinc organic compound is used, since the metallic zinc organic compound and the sulfur-containing organic molybdenum compound have similar physical and chemical properties, their distribution patterns on the surface of the nickel-aluminum alloy carrier are similar and their distribution positions are close, thus avoiding phase separation of zinc and molybdenum, making the hydrogenation effect, especially the hydrodesulfurization effect, more obvious.

[0057] Preferably, based on the total dry weight of the hydrogenation catalyst, the content of the metal promoter in the hydrogenation catalyst in terms of metal oxide is 1.5% to 7%, preferably 2% to 5.5%.

[0058] The present invention has a wide range of pore volume selection for the hydrogenation catalyst. Preferably, the pore volume of the hydrogenation catalyst is 0.1 to 1 cm 3 / g, preferably 0.15 to 0.6 cm 3 / g.

[0059] According to a preferred embodiment of the present invention, the average pore diameter of the hydrogenation catalyst is 4 to 15 nm, preferably 6 to 12 nm.

[0060] According to a preferred embodiment of the present invention, in the hydrogenation catalyst, the pore volume of pores with a diameter of 0 to 3 nm accounts for 1% to 10% of the total pore volume, preferably 2% to 5%. The catalyst in the preferred embodiment is more conducive to mass transfer and diffusion of reactant molecules.

[0061] According to some embodiments of the present invention, the pore volume of 0-3 nm pores and the total pore volume of the catalyst are determined using a nitrogen isothermal adsorption-desorption method.

[0062] A second aspect of the present invention provides a method for preparing a hydrogenation catalyst, the method comprising:

[0063] The sulfur-containing organic molybdenum compound is loaded on the nickel-aluminum alloy by an impregnation method and then dried.

[0064] The selection range of the types of sulfur-containing organic molybdenum compound and nickel-aluminum alloy in the method provided by the present invention can be the same as the selection range of the first aspect mentioned above, and the present invention will not be repeated here.

[0065] Preferably, the pore volume of the nickel-aluminum alloy is 0.4 to 1.0 cm 3 / g, preferably with a pore volume of 0.5 to 0.9 cm 3 / g, the average pore diameter is 4-12 nm, preferably 6-10 nm, wherein the volume proportion of pores smaller than 3.0 nm is not higher than 20%, preferably 5-10%.

[0066] The present invention has a wide range of particle size selection for the nickel-aluminum alloy, and can be adaptively selected according to the actual application environment. Preferably, the average particle size of the nickel-aluminum alloy is 1 to 8 mm, preferably 2 to 5 mm.

[0067] According to the method provided by the present invention, preferably, the method further comprises silicon-modifying the nickel-aluminum alloy with a silicon-containing compound, preferably silicon-modifying the nickel-aluminum alloy with an organic silicon-containing compound.

[0068] Preferably, the silicon-containing compound is selected from alkylsilane and / or alkoxysilane, more preferably alkoxysilane. The selection range of the type of alkoxysilane can be the same as the selection range of the first aspect above, and the present invention will not be repeated here.

[0069] Preferably, the organosilicon modification is such that the organosilicon compound content in the hydrogenation catalyst obtained is 0.2% to 3%, preferably 0.5% to 2%, calculated as silicon dioxide, based on the total dry weight of the hydrogenation catalyst.

[0070] The present invention provides a wide range of options for the specific operation of silicon modification. Specifically, silicon modification of the nickel-aluminum alloy may include contacting the nickel-aluminum alloy with a silicon-containing compound. The silicon modification may be performed by mixing the silicon-containing compound with a solvent, contacting the nickel-aluminum alloy with the silicon-containing compound, and then drying to remove the solvent. Alternatively, the nickel-aluminum alloy and the silicon-containing compound may be solid-phase dry-mixed or performed by vapor deposition.

[0071] According to a preferred embodiment of the present invention, the silicon modification of the nickel-aluminum alloy includes: contacting the nickel-aluminum alloy with a gaseous silicon-containing compound to perform silicon modification. This preferred embodiment is more conducive to ensuring that the silicon-containing compound is preferentially blocked in the pores of the catalyst, thereby optimizing the pore structure of the nickel-aluminum alloy catalyst and preventing subsequent deposition of molybdenum metal in the pores. At the same time, the silicon, especially the organosilicon, on the surface of the nickel-aluminum alloy can effectively segment the nickel surface, preventing the aggregation of molybdenum species on the nickel surface.

[0072] According to the present invention, preferably, when the nickel-aluminum alloy is contacted with the silicon-containing compound in the gas phase, a carrier gas can also be introduced at the same time. The present invention has no special limitation on the selection range of the carrier gas, as long as it does not participate in the reaction. Preferably, the carrier gas is at least one of nitrogen, helium, argon, and neon.

[0073] Preferably, the silicon modification conditions include: temperature of 160-400°C, preferably 180-350°C, time of 1-10 hours, preferably 2-8 hours, flow rate of the silicon-containing compound in the gas phase of 1-20 mL / min·g -1 Nickel-aluminum alloy, preferably 3-15 mL / min·g -1 Nickel-aluminum alloy; the partial pressure of the silicon-containing compound in the gas phase is 0.02 to 1 MPa, preferably 0.05 to 0.5 MPa.

[0074] According to a specific embodiment of the present invention, before the silicon-containing compound in the gas phase is introduced, the temperature is first increased according to the boiling point of the silicon-containing compound used. The specific temperature can be adjusted according to the boiling point of the corresponding silicon-containing compound.

[0075] According to the present invention, preferably, the method further comprises vacuuming the nickel-aluminum alloy before the silicon modification and performing a displacement treatment after the silicon modification. This method is more conducive to the deposition of alkoxysilane on the pores of the nickel-aluminum alloy support.

[0076] Preferably, the conditions for the vacuum treatment include: a temperature of 50 to 200° C., preferably 80 to 150° C.; a vacuum degree of 0.05 torr torr, preferably 0.1 torr torr; and a treatment time of 2 to 10 hours torr, preferably 4 to 8 hours.

[0077] Preferably, the replacement treatment is performed using an inert gas, and the conditions for the replacement treatment include: the flow rate of the inert gas is 0.5 to 5 mL / min·g -1 Nickel-aluminum alloy, preferably 1-4 mL / min·g -1 For nickel-aluminum alloy, the replacement time is 0.5 to 8 hours, preferably 1 to 4 hours, and the temperature is 100 to 400° C., preferably 150 to 350° C. The inert gas is preferably selected from at least one of nitrogen, helium, argon, and neon.

[0078] According to the method provided by the present invention, preferably, the method further comprises loading a metal additive on the nickel-aluminum alloy by an impregnation method, wherein the metal is selected from at least one of Group IA, IIA, IIIA, IB and IIB metals.

[0079] In the method provided by the present invention, the selection range of the types of the metal and the metal additive can be the same as the selection range of the first aspect mentioned above, and the present invention will not be repeated here.

[0080] In the method provided by the present invention, the impregnation method is not particularly limited and can be either isovolumetric impregnation or supersaturated impregnation. When the method further includes introducing a metal additive, the sulfur-containing organomolybdenum compound and the metal additive can be simultaneously introduced into the nickel-aluminum alloy by co-impregnation or separately introduced into the nickel-aluminum alloy by stepwise impregnation. The order of introduction is not particularly limited.

[0081] Preferably, the sulfur-containing organic molybdenum compound and the metal promoter are introduced into the nickel-aluminum alloy by co-impregnation.

[0082] According to the method provided by the present invention, preferably, the method comprises impregnating the nickel-aluminum alloy with an impregnation solution containing a sulfur-containing organic molybdenum compound and an optional metal additive, and then performing the drying. The preparation method of the impregnation solution is well known to those skilled in the art.

[0083] The present invention has a wide range of choices for the solvent in the impregnation liquid, as long as it can provide the required environment for impregnation. Preferably, the solvent in the impregnation liquid is an organic solvent, more preferably selected from C1-C10 alkanes and / or alcohols, and further preferably selected from at least one of n-hexane, n-heptane, n-octane, n-nonane, cyclohexane, ethanol, methanol and isopropanol.

[0084] According to the present invention, preferably, the concentrations of the sulfur-containing organic molybdenum compound and the metal additive in the impregnation solution are independently 0.1 to 3 mol / L.

[0085] Preferably, the amount of the metal promoter is such that the content of the metal promoter in the prepared hydrogenation catalyst, calculated as metal oxide, is 1.5% to 7%, preferably 2% to 5.5%, based on the total dry weight of the hydrogenation catalyst.

[0086] According to the present invention, preferably, the amounts of the sulfur-containing organo-molybdenum compound and the nickel-aluminum alloy are used such that the content of the sulfur-containing organo-molybdenum compound in the resulting hydrogenation catalyst, calculated as molybdenum trioxide, is 6% to 18%, preferably 8% to 17%, based on the total weight of the hydrogenation catalyst on a dry basis. Based on this disclosure, those skilled in the art will know how to control the content of the sulfur-containing organo-molybdenum compound in the resulting hydrogenation catalyst during the impregnation process, which can be determined by pore saturation impregnation.

[0087] According to the present invention, when the nickel-aluminum alloy does not include silicon modification, preferably, the amount of sulfur-containing organic molybdenum compound and nickel-aluminum alloy used is such that in the prepared hydrogenation catalyst, based on the total dry weight of the hydrogenation catalyst, the content of Al calculated as aluminum oxide is 63% to 86%, preferably 69% to 81%, the content of Ni calculated as nickel oxide is 8% to 20%, preferably 9% to 16%, and the content of molybdenum calculated as molybdenum trioxide is 6% to 20%, preferably 8% to 18%.

[0088] According to the present invention, when the nickel-aluminum alloy includes silicon modification, preferably, the amount of sulfur-containing organic molybdenum compound and nickel-aluminum alloy used is such that in the prepared hydrogenation catalyst, based on the total dry weight of the hydrogenation catalyst, the content of Al calculated as aluminum oxide is 62% to 85%, preferably 68% to 80%, the content of Ni calculated as nickel oxide is 8% to 18%, preferably 9% to 15%, the content of molybdenum calculated as molybdenum trioxide is 6% to 18%, preferably 8% to 17%, and the content of silicon calculated as silicon dioxide is 0.2% to 3%, preferably 0.5% to 2%.

[0089] According to a preferred embodiment of the present invention, the drying is vacuum drying, and more preferably the drying conditions include: a vacuum degree of 0.5 to 5 torr, preferably 1 to 3 torr, a drying temperature of 60 to 150° C., preferably 70 to 120° C., and a drying time of 2 to 120 hours, preferably 4 to 8 hours.

[0090] According to a particularly preferred embodiment of the present invention, the preparation method of the hydrogenation catalyst comprises:

[0091] (1) vacuuming the nickel-aluminum alloy, introducing gaseous alkoxysilane for silicon modification, and then introducing inert gas for displacement treatment to obtain a silicon-modified nickel-aluminum alloy carrier;

[0092] (2) preparing an impregnation solution containing a sulfur-containing organic molybdenum compound and a metal promoter, impregnating the solution onto the silicon-modified nickel-aluminum alloy support obtained in step (1), and drying the solution to obtain a hydrogenation catalyst;

[0093] Wherein, the sulfur-containing organic molybdenum compound is dialkyl molybdenum dithiophosphate and / or dialkyl molybdenum dithiocarbamate.

[0094] The third aspect of the present invention provides a hydrogenation catalyst prepared by the method described in the second aspect.

[0095] A fourth aspect of the present invention provides the use of the hydrogenation catalyst described in the first or third aspects in oil hydrogenation, more preferably in oil hydrorefining. The catalyst provided by the present invention is applied to oil hydrogenation, exhibiting good hydrogenation processing capacity and stability. The selection of different metal promoter components also provides the catalyst provided by the present invention with additional advantages. For example, when a metal gallium organocompound is used as a metal promoter in the catalyst, the catalyst is particularly suitable for oil hydrodenitrogenation. When a metal zinc organocompound is used as a metal promoter in the catalyst, the catalyst is particularly suitable for oil hydrodesulfurization.

[0096] In the present invention, the hydrorefining has the conventional meaning in the art. For example, the hydrorefining includes but is not limited to hydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation, hydrodemetallization, and saturated hydrogenation of olefins and aromatics.

[0097] A fifth aspect of the present invention provides a method for hydrotreating an oil product, the method comprising: contacting the oil product with the hydrogenation catalyst described in the first aspect or the third aspect under hydrotreating conditions.

[0098] The hydroprocessing method provided by the present invention can be carried out in a fixed bed reactor, a fluidized bed reactor or an ebullating bed reactor, preferably in a fixed bed reactor.

[0099] The oil product can be selected from a wide range and can be any oil product that requires hydrotreatment conventionally in the art. Preferably, the oil product is selected from at least one of diesel, wax oil and residual oil.

[0100] Preferably, the oil product is a secondary processing oil.

[0101] Preferably, the oil product has a nitrogen content of 300 to 3000 μg / g, a sulfur content of 2000 to 30000 μg / g, and an aromatic hydrocarbon content of 15 wt% to 80 wt%, preferably 30 wt% to 70 wt%.

[0102] The range of selection of hydrotreatment conditions is relatively wide. Preferably, the hydrotreatment conditions include: reaction hydrogen pressure of 2-20 MPa, preferably 6-16 MPa, hydrogen-oil volume ratio of 200:1-1500:1, preferably 500:1-1200:1, volume space velocity of 0.2-3h -1 , preferably 0.5 to 2 hours -1 The reaction temperature is 240-420°C, preferably 280-400°C.

[0103] According to the hydroprocessing method provided by the present invention, the oil product can be subjected to a one-stage hydroprocessing using the catalyst provided by the present invention, or can be subjected to a multi-stage hydroprocessing according to specific needs.

[0104] In a single-stage hydroprocessing process, the hydroprocessing catalyst preferably includes a first hydroprocessing catalyst and a second hydroprocessing catalyst (the loading volume ratio of the first and second hydroprocessing catalysts can be selected within a wide range, for example, 10-90:10-90). The metal promoter in the first hydroprocessing catalyst is a zinc-metal organic compound, while the metal promoter in the second hydroprocessing catalyst is a gallium-metal organic compound. This preferred embodiment is more conducive to removing sulfur and nitrogen from low-quality oil products.

[0105] When multi-stage hydroprocessing is used, as long as at least one of the stages uses the catalyst provided by the present invention, the hydroprocessing results can be further improved. The catalysts used in the other stages can be various hydroprocessing catalysts commonly used in the art, and can also be the hydroprocessing catalyst provided by the present invention.

[0106] Preferably, the method comprises:

[0107] (1) subjecting the oil product to a first hydrogenation reaction with a first hydrogenation catalyst;

[0108] (2) subjecting the product obtained from the first hydrogenation reaction to a second hydrogenation reaction with a second hydrogenation catalyst;

[0109] Wherein, at least one of the first hydrogenation catalyst and the second hydrogenation catalyst is selected from the hydrogenation catalyst provided by the present invention; preferably, the first hydrogenation catalyst and the second hydrogenation catalyst are each independently the hydrogenation catalyst provided by the present invention.

[0110] In the present invention, the loading volume ratio of the first hydrogenation catalyst to the second hydrogenation catalyst can be selected in a wide range, for example, 10-90:10-90.

[0111] Preferably, the metal promoter in the first hydrogenation catalyst is a metal zinc organic compound, and the metal promoter in the second hydrogenation catalyst is a metal gallium organic compound. This preferred embodiment is more conducive to removing sulfur and nitrogen from low-quality oil products.

[0112] Preferably, the reaction temperature of the first hydrogenation reaction is 280-390°C, and the reaction temperature of the second hydrogenation reaction is 290-400°C.

[0113] Furthermore, the hydrogenation catalyst of the present invention only needs to be activated before use. Preferably, the activation conditions include: hydrogen pressure of 0.1-1 MPa, preferably 0.2-0.8 MPa, treatment temperature of 80-250°C, preferably 120-200°C, treatment time of 0.5-5 h, preferably 1-3 h, and hydrogen flow rate of 3-15 mL / h·g -1 Hydrogenation catalyst, preferably 5-10 mL / h·g -1 Hydrogenation catalyst.

[0114] The preparation process and product performance of the method of the present invention are further illustrated below in conjunction with examples and comparative examples, but the following examples do not constitute a limitation of the method of the present invention.

[0115] In the hydrogenation catalysts of the following examples and comparative examples, the content of each component on a dry basis of the catalysts was determined by ICP-AES, and the specific conditions were as described above.

[0116] The specific surface area, average pore diameter and pore volume were obtained by nitrogen isothermal adsorption-desorption method.

[0117] Two nickel-aluminum alloys are selected in the embodiments and comparative examples of the present invention.

[0118] The properties of nickel aluminum alloy-I include: average grain size 4.1mm, pore volume 0.72cm 3 / g, the average pore diameter of the carrier is 8.3nm, the volume of pores less than 3nm is 7.6%, the mass fraction of Al is 83.6%, and the mass fraction of Ni is 16.4%.

[0119] The properties of NiAl-II include: average grain size 3.2 mm, pore volume 0.68 cm 3 / g, the average pore size of the carrier is 7.5nm, the volume of pores smaller than 3nm is 8.1%, the mass fraction of Al is 80.1%, and the mass fraction of Ni is 19.9%.

[0120] Example 1

[0121] 100.0 g of nickel-aluminum alloy-I particles were placed in a vacuum drying oven, the vacuum degree was controlled at 0.2 torr, the temperature was 80° C., and the treatment time was 4.0 hours.

[0122] The temperature of the vacuum drying oven was raised to 220° C., and nitrogen and methyltrimethoxysilane gas were introduced therein. The partial pressure of the methyltrimethoxysilane gas was 0.1 MPa, the gas flow rate (excluding nitrogen, the same below) was 400 mL / min, and the gas introduction time was 3 hours.

[0123] The drying oven temperature was adjusted to 160° C., and the drying oven was replaced with nitrogen at a rate of 200 mL / min for 1 hour. The obtained modified nickel-aluminum alloy carrier was recorded as L-1.

[0124] 20.0 g of diisopropyl molybdenum dithiophosphate, 6.0 g of dibutyl zinc dithiophosphate, and 70.0 g of n-heptane were prepared to prepare an impregnation solution Q-1.

[0125] L-1 was impregnated with Q-1 and then vacuum dried at 70°C with a vacuum degree of 1.0 torr for 4 hours. The resulting catalyst was designated Cat-1.

[0126] Example 2

[0127] 100.0 g of nickel-aluminum alloy-I particles were placed in a vacuum drying oven, the vacuum degree was controlled at 0.4 torr, the temperature was 100° C., and the treatment time was 5.0 hours.

[0128] The temperature of the vacuum drying oven was raised to 240° C., and nitrogen and triethoxysilane were introduced therein. The gas partial pressure of triethoxysilane was 0.1 MPa, the gas flow rate was 450 mL / min, and the gas introduction time was 4.0 hours.

[0129] The drying oven temperature was adjusted to 170° C., and the drying oven was replaced with nitrogen at a rate of 200 mL / min for 1.5 hours. The obtained modified nickel-aluminum alloy carrier was recorded as L-2.

[0130] 25.0 g of dibutyl dithiophosphate molybdenum oxysulfide, 8.0 g of diisooctyl dithiophosphate zinc, and 70.0 g of n-octane were prepared to prepare impregnation solution Q-2.

[0131] L-2 was impregnated with Q-2 and then vacuum dried at 90°C with a vacuum degree of 1.0 torr for 4 hours. The resulting catalyst was designated Cat-2.

[0132] Example 3

[0133] 100.0 g of nickel-aluminum alloy-I particles were placed in a vacuum drying oven, the vacuum degree was controlled at 0.5 torr, the temperature was 120° C., and the treatment time was 5.0 hours.

[0134] The temperature of the vacuum drying oven was raised to 270° C., and nitrogen and isobutyltriethoxysilane were introduced therein. The gas partial pressure of isobutyltriethoxysilane was 0.1 MPa, the gas flow rate was 500 mL / min·, and the gas introduction time was 5.0 hours.

[0135] The drying box temperature was adjusted to 200° C., and the drying box was replaced with nitrogen at a rate of 200 mL / min for 2.0 hours. The obtained modified nickel-aluminum alloy carrier was recorded as L-3.

[0136] 20.0 g of molybdenum diisopropyldithiocarbamate, 4.0 g of zinc diethyldithiocarbamate, and 70.0 g of n-nonane were prepared to prepare an impregnation solution Q-3.

[0137] L-3 was impregnated with Q-3 and then vacuum dried at 120°C with a vacuum degree of 1.0 torr for 4 hours. The resulting catalyst was designated Cat-3.

[0138] Example 4

[0139] 100.0 g of nickel-aluminum alloy-II carrier particles were placed in a vacuum drying oven, the vacuum degree was controlled at 0.4 torr, the temperature was 100° C., and the treatment time was 5.0 hours.

[0140] The temperature of the vacuum drying oven was raised to 240° C., and nitrogen and triethoxysilane gas were introduced therein. The partial pressure of the triethoxysilane gas was 0.1 MPa, the gas flow rate was 450 mL / min, and the gas introduction time was 4.0 hours.

[0141] The drying box temperature was adjusted to 170° C., and the drying box was replaced with nitrogen at a rate of 200 mL / min for 1.5 hours. The obtained modified nickel-aluminum alloy carrier was recorded as L-4.

[0142] 25.0 g of dibutyl dithiophosphorosulfide molybdenum oxysulfide, 8.0 g of gallium acetylacetonate, 40.0 g of n-heptane and 30.0 g of ethanol were prepared to prepare an impregnation solution Q-4.

[0143] L-4 was impregnated with Q-4 and then vacuum dried at 90°C with a vacuum degree of 1.0 torr for 4 hours. The resulting catalyst was designated Cat-4.

[0144] Example 5

[0145] 100.0 g of nickel-aluminum alloy-II particles were placed in a vacuum drying oven, the vacuum degree was controlled at 0.5 torr, the temperature was 120° C., and the treatment time was 5.0 hours.

[0146] The temperature of the vacuum drying oven was raised to 270° C., and nitrogen and isobutyltriethoxysilane gas were introduced therein. The partial pressure of the isobutyltriethoxysilane gas was 0.1 MPa, the gas flow rate was 500 mL / min, and the gas introduction time was 5.0 hours.

[0147] The temperature of the drying box was adjusted to 200° C., and the drying box was replaced with nitrogen at a rate of 200 mL / min for 2.0 hours. The obtained modified nickel-aluminum alloy carrier was recorded as L-5.

[0148] 20.0 g of molybdenum diisopropyldithiocarbamate, 6.0 g of gallium ethoxide, 40.0 g of n-nonane and 30.0 g of ethanol were prepared to prepare an impregnation solution Q-5.

[0149] L-5 was impregnated with Q-5 and then vacuum dried at 120°C with a vacuum degree of 1.0 torr for 4 hours. The resulting catalyst was designated Cat-5.

[0150] Example 6

[0151] 100.0 g of nickel-aluminum alloy-II particles were placed in a vacuum drying oven, the vacuum degree was controlled at 0.5 torr, the temperature was 120° C., and the treatment time was 5.0 hours.

[0152] The temperature of the vacuum drying oven was raised to 380° C., and nitrogen and n-octyltriethoxysilane gas were introduced therein. The partial pressure of the n-octyltriethoxysilane gas was 0.1 MPa, the gas flow rate was 600 mL / min, and the gas introduction time was 5.0 hours.

[0153] The temperature of the drying box was adjusted to 200° C., and the drying box was replaced with nitrogen at a rate of 200 mL / min for 2.0 hours. The obtained modified nickel-aluminum alloy carrier was recorded as L-6.

[0154] 25.0 g of dibutyl molybdenum dithiocarbamate, 8.0 g of gallium isopropoxide, and 60.0 g of n-decane were prepared to prepare an impregnation solution Q-6.

[0155] L-6 was impregnated with Q-6 and then vacuum dried at 120°C with a vacuum degree of 1.0 torr for 4 hours. The resulting catalyst was designated Cat-6.

[0156] Example 7

[0157] 100.0 g of nickel-aluminum alloy-I particles were placed in a vacuum drying oven, with the vacuum degree controlled at 0.5 torr, the temperature at 120° C., and the treatment time for 5.0 hours. The obtained nickel-aluminum alloy carrier was designated L-7.

[0158] 20.0 g of molybdenum diisopropyldithiocarbamate, 4.0 g of zinc diethyldithiocarbamate, and 75.0 g of n-octane were prepared to prepare an impregnation solution Q-7.

[0159] L-7 was impregnated with Q-7 and then vacuum dried at 120°C with a vacuum degree of 1.0 torr for 4 hours. The resulting catalyst was designated Cat-7.

[0160] Example 8

[0161] 100.0 g of nickel-aluminum alloy-II carrier particles were placed in a vacuum drying oven, with the vacuum degree controlled at 0.5 torr, the temperature at 120° C., and the treatment time for 5.0 hours. The obtained nickel-aluminum alloy carrier was designated L-8.

[0162] 25.0 g of dibutyl molybdenum dithiocarbamate, 8.0 g of gallium isopropoxide, and 60.0 g of n-decane were prepared to prepare an impregnation solution Q-8.

[0163] L-8 was impregnated with Q-8 and then vacuum dried at 120°C with a vacuum degree of 1.0 torr for 4 hours. The resulting catalyst was designated Cat-8.

[0164] Example 9

[0165] The preparation of nickel-aluminum alloy carrier L-1 is the same as that in Example 1.

[0166] 26.0 g of diisopropyl molybdenum dithiophosphate and 70.0 g of n-heptane were used to prepare an impregnation solution Q-9.

[0167] L-1 was impregnated with Q-9 and then vacuum dried at 70°C with a vacuum degree of 1.0 torr for 4 hours. The resulting catalyst was designated Cat-9.

[0168] Example 10

[0169] The preparation of nickel-aluminum alloy carrier L-1 is the same as that in Example 4.

[0170] 33.0 g of dibutyl dithiophosphorosulfide molybdenum oxysulfide, 40.0 g of n-heptane and 30.0 g of ethanol were prepared to prepare an impregnation solution Q-10.

[0171] L-4 was impregnated with Q-10 and then vacuum dried at 90°C with a vacuum degree of 1.0 torr for 4 hours. The resulting catalyst was designated Cat-10.

[0172] Example 11

[0173] 100.0 g of nickel-aluminum alloy-I particles were placed in a vacuum drying oven, the vacuum degree was controlled at 0.2 torr, the temperature was 80° C., and the treatment time was 4.0 hours.

[0174] 60.0 g of trimethylsilane was used to impregnate nickel-aluminum alloy-I. The drying oven temperature was adjusted to 170°C, and then the drying oven was replaced with nitrogen at a rate of 200 mL / min for 1.5 hours. The modified nickel-aluminum alloy carrier was obtained and recorded as L-11.

[0175] 20.0 g of diisopropyl molybdenum dithiophosphate, 6.0 g of dibutyl zinc dithiophosphate, and 70.0 g of n-heptane were prepared to prepare impregnation solution Q-11.

[0176] L-11 was impregnated with Q-11 and then vacuum dried at 70°C with a vacuum degree of 1.0 torr for 4 hours. The resulting catalyst was designated Cat-11.

[0177] Comparative Example 1

[0178] The preparation method of the modified nickel-aluminum alloy carrier L-3 is the same as that in Example 3.

[0179] 20.0 g of molybdenum hexacarbonyl, 7.0 g of zinc octoate, and 70.0 g of toluene were prepared into solution DQ-1.

[0180] L-3 was impregnated with DQ-1 and then vacuum dried at 120°C with a vacuum degree of 1.0 torr for 4 hours to obtain an oxidized catalyst.

[0181] 20.0 g of the above-mentioned oxidized catalyst was weighed and placed in a tubular reactor for conventional sulfidation treatment. The treatment conditions were as follows: the sulfiding liquid was a cyclohexane solution containing 5.0% dimethyl disulfide by mass, the sulfiding liquid dosage was 40.0 g / h, the hydrogen pressure was 4.0 MPa, the hydrogen flow rate was 200 mL / min, the sulfidation temperature was 340° C., and the sulfidation time was 6.0 hours. The resulting catalyst was designated DCT-1.

[0182] Comparative Example 2

[0183] The preparation method of the modified nickel-aluminum alloy carrier L-3 is the same as that in Example 3.

[0184] 12.0 g of molybdenum disulfide powder and 2.0 g of zinc sulfide powder were dissolved in a mixed solution of 40.0 g of n-octane and 30.0 g of DMDS to prepare an impregnation solution, which was recorded as DQ-2.

[0185] L-3 was impregnated with DQ-2 and then vacuum dried at 120°C with a vacuum degree of 1.0 torr for 4 hours. The resulting catalyst was designated DCT-2.

[0186] Comparative Example 3

[0187] The preparation method of the modified nickel-aluminum alloy carrier L-6 is the same as that in Example 6.

[0188] Solution DQ-3 was prepared by taking 22.0 g of molybdenum carbonyl, 6.0 g of gallium ethoxide, 60.0 g of cyclohexane and 10.0 g of ethanol.

[0189] L-6 was impregnated with DQ-3 and then vacuum dried at 120°C with a vacuum degree of 1.0 torr for 4 hours to obtain an oxidized catalyst.

[0190] 20.0 g of the above-mentioned oxidized catalyst was weighed and placed in a tubular reactor for conventional sulfidation treatment. The treatment conditions were: the sulfiding liquid was a cyclohexane solution containing 5.0% dimethyl disulfide by mass, the sulfiding liquid dosage was 40.0 g / h, the hydrogen pressure was 4.0 MPa, the hydrogen flow rate was 200 mL / min, the sulfidation temperature was 340° C., and the sulfidation time was 6.0 hours. The resulting catalyst was designated DCT-3.

[0191] Comparative Example 4

[0192] The preparation method of the modified nickel-aluminum alloy carrier L-6 is the same as that in Example 6.

[0193] 13.0 g of molybdenum disulfide powder and 6.0 g of gallium ethoxide were dissolved in a mixed solution of 30.0 g of isopropyl alcohol and 40.0 g of dimethyl disulfide to prepare an impregnation solution designated as DQ-4.

[0194] L-6 was impregnated with DQ-4 and then vacuum dried at 120°C with a vacuum degree of 1.0 torr for 4 hours. The resulting catalyst was designated DCT-4.

[0195] Table 1 Composition (catalyst dry basis) and properties of the catalysts obtained in each embodiment and comparative example

[0196] Test Example 1-8

[0197] The catalysts obtained in Examples 1-11 were graded and loaded (see Table 3). The properties of the secondary processing oil used are shown in Table 2. A fixed bed process was used, and the hydrodesulfurization catalyst and the hydrodenitrogenation catalyst were loaded in sequence according to the flow direction (the loading volume ratio was 1:1).

[0198] Catalyst activation

[0199] 20.0 g of catalysts Cat-1, Cat-2, Cat-3, Cat-4, Cat-5, Cat-6, Cat-7, Cat-8, Cat-9, Cat-10, and Cat-11 were weighed respectively and placed in a tubular reactor. The activation conditions were: temperature 120 ° C, hydrogen pressure 0.5 MPa, hydrogen flow rate 150.0 mL / min, and activation time 2.0 hours.

[0200] Catalyst evaluation

[0201] The evaluation conditions are: hydrogen pressure of 10.0 MPa, hydrogen flow rate of 500 mL / min, oil feed rate of 50.0 g / h, total volume space velocity of the catalyst of 1.0 h -1 The reaction temperature of the desulfurization catalyst bed is 320°C, and the reaction temperature of the denitrification catalyst bed is 350°C. After 1200 hours of reaction, the sample analysis results are shown in Table 3.

[0202] Comparative Test Example 1-2

[0203] The catalysts obtained in Comparative Examples 1-4 were graded and loaded (Table 3). The properties of the secondary processing oil used are shown in Table 2. A fixed-bed process was used, with the hydrodesulfurization catalyst and the hydrodenitrogenation catalyst loaded sequentially in the direction of flow (at a loading volume ratio of 1:1).

[0204] The activation and evaluation of the catalyst were the same as those in Test Examples 1-6.

[0205] Table 2 Properties of crude oil

[0206] Table 3 Evaluation results

[0207] From the results in Table 3, it can be seen that the use of the hydrogenation catalyst of the present invention has good hydrodesulfurization, hydrodenitrogenation and aromatic saturation effects on the treatment of heavy secondary processed crude oil.

Claims

1. A hydrogenation catalyst comprising a carrier and an active component, wherein: The carrier comprises a nickel-aluminum alloy, and the active component comprises a sulfur-containing organic molybdenum compound.

2. The hydrogenation catalyst according to claim 1, wherein The sulfur-containing organic molybdenum compound is dialkyl dithiophosphate molybdenum and / or dialkyl dithiocarbamate molybdenum; Preferably, the dialkyl dithiophosphate molybdenum is selected from at least one of diisopropyl dithiophosphate molybdenum, dibutyl dithiophosphate molybdenum, diisooctyl dithiophosphate molybdenum, diisobutyl dithiophosphate molybdenum, dipropyl dithiophosphate molybdenum, dipentyl dithiophosphate molybdenum, dihexyl dithiophosphate molybdenum and diheptyl dithiophosphate molybdenum; Preferably, the dialkyl dithiocarbamate molybdenum is selected from at least one of diisopropyl dithiocarbamate molybdenum, dibutyl dithiocarbamate molybdenum, dipentyl dithiocarbamate molybdenum, dihexyl dithiocarbamate molybdenum, diheptyl dithiocarbamate molybdenum and dioctyl dithiocarbamate molybdenum.

3. The hydrogenation catalyst according to claim 1 or 2, wherein Based on the total dry weight of the hydrogenation catalyst, the content of Al calculated as aluminum oxide is 63% to 86%, preferably 69% to 81%, the content of Ni calculated as nickel oxide is 8% to 20%, preferably 9% to 16%, and the content of molybdenum calculated as molybdenum trioxide is 6% to 20%, preferably 8% to 18%.

4. The hydrogenation catalyst according to any one of claims 1 to 3, wherein The carrier comprises a silicon-modified nickel-aluminum alloy, preferably an organosilicon-modified nickel-aluminum alloy; Preferably, the organosilicon is selected from alkoxysilanes, more preferably at least one of methyltrimethoxysilane, triethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, butyltriethoxysilane and octyltriethoxysilane; Preferably, based on the total dry weight of the hydrogenation catalyst, the content of Al calculated as aluminum oxide is 62% to 85%, preferably 68% to 80%, the content of Ni calculated as nickel oxide is 8% to 18%, preferably 9% to 15%, the content of molybdenum calculated as molybdenum trioxide is 6% to 18%, preferably 8% to 17%, and the content of silicon calculated as silicon dioxide is 0.2% to 3%, preferably 0.5% to 2%.

5. The hydrogenation catalyst according to any one of claims 1 to 4, wherein The hydrogenation catalyst further contains a metal promoter, wherein the metal is selected from at least one of Group IA, IIA, IIIA, IB and IIB metals, preferably at least one of Zn, Ga, Mg and Cu; Preferably, the metal additive is a metal organic compound, more preferably a metal zinc organic compound and / or a metal gallium organic compound, most preferably triethylgallium, triisopropylgallium, tri-tert-butylgallium, gallium acetylacetonate, ethoxygallium, gallium isopropoxide, dialkyldithiocarbyl, di ... At least one of zinc thiophosphate and zinc dialkyldithiocarbamate.

6. The hydrogenation catalyst according to claim 5, wherein Based on the total dry weight of the hydrogenation catalyst, the content of the metal promoter in the hydrogenation catalyst in terms of metal oxide is 1.5% to 7%, preferably 2% to 5.5%.

7. The hydrogenation catalyst according to any one of claims 1 to 6, wherein The average pore size of the hydrogenation catalyst is 4 to 15 nm, preferably 6 to 12 nm; Preferably, in the hydrogenation catalyst, the pore volume of pores with a diameter of 0 to 3 nm accounts for 1% to 10% of the total pore volume, preferably 2% to 5%.

8. A method for preparing a hydrogenation catalyst, the method comprising: The sulfur-containing organic molybdenum compound is loaded on the nickel-aluminum alloy by an impregnation method and then dried.

9. The method according to claim 8, wherein: The sulfur-containing organic molybdenum compound is dialkyl dithiophosphate molybdenum and / or dialkyl dithiocarbamate molybdenum; Preferably, the dialkyl dithiophosphate molybdenum is selected from at least one of diisopropyl dithiophosphate molybdenum, dibutyl dithiophosphate molybdenum, diisooctyl dithiophosphate molybdenum, diisobutyl dithiophosphate molybdenum, dipropyl dithiophosphate molybdenum, dipentyl dithiophosphate molybdenum, dihexyl dithiophosphate molybdenum and diheptyl dithiophosphate molybdenum; Preferably, the dialkyl dithiocarbamate molybdenum is selected from at least one of diisopropyl dithiocarbamate molybdenum, dibutyl dithiocarbamate molybdenum, dipentyl dithiocarbamate molybdenum, dihexyl dithiocarbamate molybdenum, diheptyl dithiocarbamate molybdenum and dioctyl dithiocarbamate molybdenum.

10. The method according to claim 8 or 9, wherein: Based on the total amount of the nickel-aluminum alloy, the content of aluminum as an element is 50wt% to 95wt%, and the content of nickel as an element is 5wt% to 50wt%; preferably, the content of aluminum as an element is 70wt% to 90wt%, and the content of nickel as an element is 10wt% to 30wt%; Preferably, the pore volume of the nickel-aluminum alloy is 0.4 to 1.0 cm 3 / g, preferably with a pore volume of 0.5 to 0.9 cm 3 / g, the average pore diameter is 4-12nm, preferably 6-10nm, wherein the volume proportion of small pores smaller than 3.0nm is not higher than 20%, preferably 5-10%.

11. The method according to any one of claims 8 to 10, wherein: The amount of sulfur-containing organic molybdenum compound and nickel-aluminum alloy used is such that the content of molybdenum in the prepared hydrogenation catalyst calculated as molybdenum trioxide is 6% to 18%, preferably 8% to 17%, based on the total dry weight of the hydrogenation catalyst.

12. The method according to any one of claims 8 to 11, wherein: The method further comprises silicon-modifying the nickel-aluminum alloy using a silicon-containing compound, preferably silicon-modifying the nickel-aluminum alloy using an organic silicon-containing compound; Preferably, the silicon-containing compound is selected from alkylsilanes and / or alkoxysilanes, more preferably alkoxysilanes; Preferably, the alkoxysilane is at least one of methyltrimethoxysilane, triethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, butyltriethoxysilane and octyltriethoxysilane; Preferably, the organosilicon modification is such that the content of the organosilicon compound in the prepared hydrogenation catalyst calculated as silicon dioxide is 0.2% to 3%, preferably 0.5% to 2%, based on the total dry weight of the hydrogenation catalyst.

13. The method according to claim 12, wherein: The silicon-modifying the nickel-aluminum alloy comprises: contacting the nickel-aluminum alloy with a silicon-containing compound to perform silicon modification; Preferably, the silicon modification of the nickel-aluminum alloy comprises: contacting the nickel-aluminum alloy with a silicon-containing compound in a gas phase to perform silicon modification; Preferably, the silicon modification conditions include: a temperature of 160 to 400°C, preferably 180 to 350°C, a time of 1 to 10 hours, preferably 2 to 8 hours, and a flow rate of the silicon-containing compound in the gas phase of 1 to 20 mL / min·g -1 Nickel-aluminum alloy, preferably 3-15 mL / min·g -1 Nickel aluminum alloy; the partial pressure of the silicon-containing compound in the gas phase is 0.02 to 1 MPa, preferably 0.05 to 0.5 MPa.

14. The method according to claim 12 or 13, wherein: The method further comprises a vacuum treatment performed on the nickel-aluminum alloy before the silicon modification and a replacement treatment performed on the nickel-aluminum alloy after the silicon modification; Preferably, the conditions for the vacuum treatment include: a temperature of 50 to 200° C., preferably 80 to 150° C.; a vacuum degree of 0.05 torr to 1 torr, preferably 0.1 to 0.5 torr; a treatment time of 2 to 10 hours, preferably 4 to 8 hours; Preferably, the replacement treatment is performed using an inert gas, and the conditions of the replacement treatment include: the flow rate of the inert gas is 0.5 to 5 mL / min·g -1 Nickel-aluminum alloy, preferably 1-4 mL / min·g -1 For nickel-aluminum alloy, the replacement time is 0.5 to 8 hours, preferably 1 to 4 hours, and the temperature is 100 to 400°C, preferably 150 to 350°C.

15. The method according to any one of claims 8 to 14, wherein: The method further comprises loading a metal additive on the nickel-aluminum alloy by an impregnation method, wherein the metal is selected from at least one of group IA, IIA, IIIA, IB and IIB metals, preferably at least one of Zn, Ga, Mg and Cu; Preferably, the metal auxiliary agent is a metal organic compound, more preferably at least one of triethylgallium, triisopropylgallium, tri-tert-butylgallium, gallium acetylacetonate, ethoxygallium, gallium isopropoxide, zinc dialkyldithiophosphate and zinc dialkyldithiocarbamate; Preferably, the amount of the metal promoter is such that the content of the metal promoter in the prepared hydrogenation catalyst, calculated as metal oxide, is 1.5% to 7%, preferably 2% to 5.5%, based on the total dry weight of the hydrogenation catalyst.

16. The method according to any one of claims 8 to 15, wherein: The method comprises impregnating a nickel-aluminum alloy with an impregnation solution containing a sulfur-containing organic molybdenum compound and an optional metal promoter, and then performing the drying; Preferably, the solvent in the impregnation solution is an organic solvent, preferably selected from C1-C10 alkanes and / or alcohols, more preferably at least one selected from n-hexane, n-heptane, n-octane, n-nonane, cyclohexane, ethanol, methanol and isopropanol; Preferably, the drying is vacuum drying, and more preferably the drying conditions include: a vacuum degree of 0.5 to 5 torr, preferably 1 to 3 torr, a drying temperature of 60 to 150° C., preferably 70 to 120° C., and a drying time of 2 to 120 hours, preferably 4 to 8 hours.

17. The hydrogenation catalyst prepared by the method according to any one of claims 8 to 16.

18. Use of the hydrogenation catalyst according to any one of claims 1 to 7 and 17 in oil product hydroprocessing; preferably in oil product hydrorefining.

19. A method for hydrotreating an oil product, the method comprising: Under hydroprocessing conditions, contacting the oil product with the hydrogenation catalyst according to any one of claims 1 to 7 and 17 for reaction; Preferably, the oil product is selected from at least one of diesel, wax oil and residual oil; Preferably, the oil product has a nitrogen content of 300 to 3000 μg / g, a sulfur content of 2000 to 30000 μg / g, and an aromatics content of 15 wt% to 80 wt%, preferably 30 wt% to 70 wt%; Preferably, the hydroprocessing conditions include: a reaction hydrogen pressure of 2 to 20 MPa, preferably 6 to 16 MPa, a hydrogen to oil volume ratio of 200:1 to 1500:1, preferably 500:1 to 1200:1, and a volume space velocity of 0.2 to 3 h -1 , preferably 0.5 to 2 hours -1 The reaction temperature is 240-420°C, preferably 280-400°C.

20. The method according to claim 19, wherein: The method includes: (1) subjecting the oil product to a first hydrogenation reaction with a first hydrogenation catalyst; (2) subjecting the product obtained from the first hydrogenation reaction to a second hydrogenation reaction with a second hydrogenation catalyst; Wherein, at least one of the first hydrogenation catalyst and the second hydrogenation catalyst is selected from the hydrogenation catalyst according to any one of claims 1 to 6 and 16; Preferably, the first hydrogenation catalyst and the second hydrogenation catalyst are each independently any one of claims 1-6 and 16 The hydrogenation catalyst; Preferably, the metal promoter in the first hydrogenation catalyst is a metal zinc organic compound; the metal promoter in the second hydrogenation catalyst is a metal gallium organic compound; Preferably, the reaction temperature of the first hydrogenation reaction is 280-390°C, and the reaction temperature of the second hydrogenation reaction is 290-400°C.

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