Hydrogenation catalysts, their preparation methods and applications

Abstract

This invention relates to the field of hydrorefining, and discloses a hydrogenation catalyst, its preparation method, and its application. The method for preparing the hydrogenation catalyst includes the following steps: (1) impregnating a support with a solution containing an active metal and a quaternary ammonium salt compound, followed by a first calcination to obtain a calcined product; the active metal is selected from at least one group VIII metal and / or at least one group VIB metal, and the support comprises amorphous NiWO4 material and an inorganic heat-resistant matrix; (2) post-treating the calcined product obtained in step (1) with an organic compound, followed by a second calcination to obtain the hydrogenation catalyst, wherein the organic compound is selected from at least one alcohol compound, carboxylic acid compound, and organic amine compound. This method uses amorphous NiWO4 material and an inorganic heat-resistant matrix as a composite support, introducing different types of organic compounds in two steps to improve the activity and stability of the catalyst.

Description

Technical Field

[0001] This invention relates to the technical field of hydrorefining, specifically to a hydrorefining catalyst, its preparation method, and its application. Background Technology

[0002] With increasingly stringent environmental regulations worldwide, the demand for clean fuels is growing. Hydrogenation technology is an effective means of producing clean fuels, and as a result, hydrogenation units are increasingly being installed in major refineries.

[0003] The demand for clean jet fuel is increasing both domestically and internationally. Hydrogenation not only removes mercaptans and sulfur from the feedstock but also allows for deep hydrogenation of jet kerosene, improving its cleanliness. In my country, jet kerosene hydrogenation processes are generally low-pressure processes, requiring high low-temperature catalyst activity. Currently, my country's No. 3 jet fuel standard, GB-6537-2018, requires a total sulfur content of no more than 2000 μg / g. However, with increasingly stringent environmental requirements, the demand for more environmentally friendly low-sulfur jet kerosene products will continue to grow. In the past, straight-run kerosene had a narrow distillation range and low levels of impurities such as sulfur and nitrogen, allowing for the production of high-quality jet kerosene with moderate hydrogenation depth. However, in recent years, refineries have been processing more diverse crude oils, with an increased proportion of high-sulfur and high-nitrogen crude oils, leading to increased impurities and types in jet kerosene feedstocks. This has increased the difficulty of jet kerosene production and introduced certain risks to product quality, such as thermal oxidation stability and color stability. Therefore, developing highly active jet fuel hydrogenation catalysts can better address the issues of raw material degradation and product quality improvement, thereby ensuring product quality and extending the operating cycle of the equipment.

[0004] To develop catalysts with higher activity and better desulfurization effects, researchers have explored different methods to prepare various hydrogenation catalysts. Patent application CN113941351A discloses a jet fuel hydrogenation catalyst and its preparation method. By modifying the catalyst with phosphorus and / or boron, the acidity of the catalyst is increased and mesoporous pores are constructed, thereby improving the catalyst's desulfurization capacity. However, the introduction of acidic components can exacerbate carbon deposition during the reaction process and cause some cracking reactions, reducing the liquid yield of the product and negatively impacting the jet fuel hydrogenation process.

[0005] Patent application CN101733151A discloses a catalyst for hydrorefining distillate oil. By carbonizing the support with a solution containing an organic solvent, the specific surface area and pore volume of the catalyst can be adjusted by changing the carbon content, thus improving the hydrodesulfurization activity to some extent. However, during long-term operation, the carbon species in the carbonized support exhibit poor stability and may change to some extent, posing a risk and deficiency to the stability of the catalyst.

[0006] Patent application CN104437571A discloses a hydrodesulfurization catalyst, its preparation method, and its application. The catalyst is prepared by loading a metal onto a titanium oxide-alumina modified support. However, when processing fuels with high sulfur content, such as jet fuel or diesel fuel, the catalyst has a relatively singular active metal and poor hydrogenation capacity. Furthermore, the catalyst's adaptability needs to be improved when dealing with inferior feedstocks. Summary of the Invention

[0007] The purpose of this invention is to overcome the problems of poor sulfidation, low activity, and poor stability of existing hydrogenation catalysts, and to provide a hydrogenation catalyst, its preparation method, and its application. This method uses amorphous NiWO4 material and an inorganic heat-resistant matrix as a composite support, and introduces different types of organic matter in two steps to improve the activity and stability of the catalyst.

[0008] To achieve the above objectives, the first aspect of the present invention provides a method for preparing a hydrogenation catalyst, wherein the method includes the following steps:

[0009] (1) The carrier is impregnated with a solution containing an active metal and a quaternary ammonium salt compound, and then subjected to a first calcination to obtain a calcined product; the active metal is selected from at least one of Group VIII metals and / or at least one of Group VIB metals, and the carrier includes amorphous NiWO4 material and an inorganic heat-resistant matrix;

[0010] (2) The calcination product of step (1) is post-treated with an organic compound and then subjected to a second calcination to obtain a hydrogenation catalyst, wherein the organic compound is selected from at least one of alcohols, carboxylic acids and organic amines.

[0011] Preferably, in step (1), the carbon content in the roasted product is 0.5-2.5% by weight, based on the total amount of the roasted product.

[0012] Preferably, the mass ratio of the organic compound in step (2) to the carbon in the calcination product in step (1) is 1:1-10:1, and more preferably 2:1-8:1.

[0013] A second aspect of the present invention provides a hydrogenation catalyst prepared by the method described in the first aspect.

[0014] The third aspect of this invention provides the application of the hydrogenation catalyst described in the second aspect in the hydrogenation reaction of jet fuel.

[0015] The method provided by this invention uses amorphous NiWO4 material and inorganic heat-resistant matrix as a composite carrier. Compared with directly loading W onto the carrier, it can better eliminate the strong interaction between metal W and the carrier, which is more conducive to the sulfidation of metal W. At the same time, metal Ni and W are connected through oxygen bridges, which is more conducive to the formation of abundant Ni-WS active centers during the sulfidation process.

[0016] The method provided by this invention uses NiWO4 material, which has both high activity and good diffusion channels, to construct a composite support. The NiWO4 material is kept in an amorphous state, giving it a large specific surface area and pore volume. At the same time, active metals are loaded on the support, which can further enhance the interaction between the active metals, exert the synergistic effect between the active metals, and improve the hydrogenation activity.

[0017] The method provided by this invention introduces different types of organic compounds in two steps. The introduction of organic compounds helps to disperse the active metal and avoid its aggregation. The introduction of quaternary ammonium salt compounds helps the active metal to form heteropolyacid acid copolymers, enhancing the synergistic effect between the active metals and facilitating the formation of more Ni-Mo-S active centers. The subsequent introduction of organic compounds can further disperse the active metal and help to form more active centers. At the same time, by introducing different types of organic compounds in two different ways and then calcining them, some residual carbon can be formed on the support, which helps to reduce the aggregation of active metals and improve the activity and stability of the catalyst. Attached Figure Description

[0018] Figure 1 This is the XRD pattern of the NiWO4 material in Example 1 of this invention;

[0019] Figure 2 This is the XRD pattern of the NiWO4 material in Comparative Example 6 of this invention. Detailed Implementation

[0020] The endpoints and any values ​​of the ranges 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 endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0021] The first aspect of this invention provides a method for preparing a hydrogenation catalyst, wherein the method includes the following steps:

[0022] (1) The carrier is impregnated with a solution containing an active metal and a quaternary ammonium salt compound, and then subjected to a first calcination to obtain a calcined product; the active metal is selected from at least one of Group VIII metals and / or at least one of Group VIB metals, and the carrier includes amorphous NiWO4 material and an inorganic heat-resistant matrix;

[0023] (2) The calcination product of step (1) is post-treated with an organic compound and then subjected to a second calcination to obtain a hydrogenation catalyst, wherein the organic compound is selected from at least one of alcohols, carboxylic acids and organic amines.

[0024] The preparation method provided by this invention uses amorphous NiWO4 material as part of the support. The amorphous NiWO4 material acts as an active center and constructs diffusion channels, while strengthening the interaction between active metals nickel and tungsten, solving the problem of difficult sulfidation after the interaction of active metal tungsten with the support. The support is prepared by composite preparation of NiWO4 material and active alumina material to obtain a metal-containing catalyst support with rich specific surface area. The solution of quaternary ammonium salt compound is loaded on the support. On the one hand, the addition of organic matter can promote the formation of heteropolyacid salts of active metals, producing a certain synergistic effect. On the other hand, some active metals are loaded onto NiWO4 material. After subsequent sulfidation treatment, the interaction between active metals is enhanced, forming more active centers. Furthermore, by introducing different types of organic matter in two different ways and calcining them, some residual carbon can be formed on the support, which helps to reduce the aggregation of active metals and improve the activity and stability of the catalyst.

[0025] In this invention, there is no particular limitation on the type of active metal; any active metal conventionally defined in the art is applicable to this invention. Preferably, the active metal is selected from Ni and / or Mo, and more preferably Ni and Mo.

[0026] In this invention, the selection range of sources for the active metal is relatively wide, as long as the required active metal can be provided. Preferably, the active metal is provided by a precursor of each active metal, more preferably by a soluble compound selected from each active metal, and even more preferably by at least one selected from nickel nitrate, nickel chloride, basic nickel carbonate and nickel sulfate, and at least one selected from ammonium molybdate, sodium molybdate and molybdenum oxide.

[0027] In this invention, the activity and stability of the hydrogenation catalyst are improved by controlling the amount of active metal. Preferably, the amount of the active metal precursor is such that the content of Ni in the prepared hydrogenation catalyst is 0.1-10% by weight (calculated as oxide) and the content of Mo is 5-30% by weight (calculated as oxide). Wherein, Ni is calculated as NiO and Mo as MoO3.

[0028] In this invention, there is no particular limitation on the amount of carrier used. Preferably, the mass ratio of the Ni precursor (calculated as oxide) to the amorphous NiWO4 material is 1:3 to 1:30.

[0029] In this invention, preferably, the method further includes introducing a phosphorus-containing compound in step (1). In this invention, the phosphorus-containing compound is introduced as an auxiliary agent to dissolve the active metal precursor (e.g., the active metal precursor oxide molybdenum oxide). In this invention, the selection range of phosphorus-containing compounds is relatively wide; phosphorus-containing compounds conventionally defined in the art are all applicable to this invention. Preferably, the phosphorus-containing compound is selected from at least one of phosphoric acid, orthophosphate, metaphosphate, hypophosphite, hydrogen phosphate, dihydrogen phosphate, and alkylphosphonic acid. In this invention, there is no particular limitation on the amount of phosphorus-containing compound used, as long as it can dissolve the active metal precursor. Preferably, the molar ratio of the Mo precursor to the phosphorus-containing compound, calculated as oxide, is 1:1 to 5:1.

[0030] In this invention, the introduction of quaternary ammonium salt compounds helps active metals form heteropolyacid acid salt copolymers, enhances the synergistic effect between active metals, and further facilitates the formation of active centers. This invention does not specifically limit the types of quaternary ammonium salt compounds; all quaternary ammonium salt compounds conventionally defined in the art are applicable to this invention. Preferably, in step (1), the quaternary ammonium salt compound is selected from C4-C20 quaternary ammonium salt compounds, preferably selected from at least one of tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, dodecyltrimethylammonium bromide, and hexadecyltrimethylammonium bromide, and more preferably at least one of tetrabutylammonium bromide, dodecyltrimethylammonium bromide, and hexadecyltrimethylammonium bromide.

[0031] In this invention, the synergistic effect between the active metals is enhanced by adjusting the amount of quaternary ammonium salt compounds and active metals, thereby improving the activity and stability of the hydrogenation catalyst. Preferably, in step (1), the molar ratio of the quaternary ammonium salt compound to the active metal Ni (based on elemental composition) is 0.3:1-3:1, more preferably 0.5:1-2:1.

[0032] In this invention, there are no particular limitations on the impregnation method for active metals and quaternary ammonium salt compounds; for example, the pore saturation impregnation method can be used to impregnate the support. According to a specific embodiment of the invention, based on the water absorption rate and mass of the support, a metal impregnation solution of a predetermined volume is prepared. The metal impregnation solution is then poured into the support in three portions and stirred thoroughly. After obtaining the pore-saturated impregnated catalyst, it is then dried.

[0033] In this invention, the amorphous NiWO4 material has a smaller average grain size, which can improve the sulfidation performance of the hydrogenation catalyst. Preferably, in step (1), the average grain size of the amorphous NiWO4 material is 2-5 nm.

[0034] In this invention, the average grain size of the amorphous NiWO4 material refers to the average size of the grains formed by the aggregation of NiWO4 material during the synthesis process.

[0035] In this invention, the average grain size of amorphous NiWO4 material was measured by high-resolution transmission electron microscopy (HRTEM). The specific test conditions were as follows: the sample was characterized using a Tecnai G2 F20 S-TWIN high-resolution transmission electron microscope (HRTEM) manufactured by FEI, with an accelerating voltage of 200kV. The size of the grains in the sample was observed. For the sample that needed to be statistically analyzed, 30-50 photos were taken, and the grain size in the photos was statistically analyzed and the average was calculated.

[0036] In this invention, the metal composition of amorphous NiWO4 material is determined by elemental analysis. The specific test conditions are as follows: an X-ray fluorescence spectrometer from Rigaku Electric Industries, Ltd. of Japan is used to quantitatively analyze the elemental content using the external standard method. The powder sample is pressed into a tablet, and the laser voltage is 50kV and the laser current is 50mA.

[0037] In this invention, the crystal structure of amorphous NiWO4 material was determined by XRD. The specific test conditions were as follows: the sample was characterized by XRD using a Bruker D5005 diffractometer with Cu Kα rays (λ = 0.154 nm), tube voltage 40 kV, tube current 30 mA, scanning range 5°-70°, step size 0.013°, and 1 step per second. The phase composition of the sample was analyzed and determined using a JCPDS-based method.

[0038] In this invention, the amorphous NiWO4 material is in an amorphous crystalline state. It should be noted that, from... Figure 1 As can be seen, amorphous means that NiWO4 material does not show obvious diffraction peaks in the XRD characterization pattern and does not have a clear crystal structure. XRF can be used to analyze the metal composition and element ratio of the material to determine its possible structural formula. Combined with the weak XRD diffraction peaks, its amorphous structure can be determined.

[0039] In this invention, the amorphous NiWO4 material maintains an amorphous crystalline state, resulting in a large specific surface area and pore volume. Using it as part of a support in the preparation of a hydrogenation catalyst can improve its hydrogenation activity. Preferably, the specific surface area of ​​the amorphous NiWO4 material is 200-300 m² / g. 2 / g, pore volume is 0.5-1mL / g.

[0040] In this invention, the specific surface area and pore volume of the amorphous NiWO4 material were measured using the N2 physical adsorption-desorption (BET) method. The specific test conditions were as follows: N2 isothermal adsorption-desorption was employed, and the specific surface area and pore volume of the sample were calculated using conventional BET and BJH methods. Before analysis, the sample was dried at 120°C for 3 hours, and then dehydrated and degassed at 300°C.

[0041] In this invention, there is no particular limitation on the source of the amorphous NiWO4 material. For example, it can be obtained commercially or prepared using methods conventionally defined in the art. Preferably, in step (1), the amorphous NiWO4 material is prepared by the following method: preparing a NiWO4 precursor using a solid-state reaction method and / or a precipitation method, followed by hydrothermal treatment to obtain the amorphous NiWO4 material. The hydrothermal treatment conditions include: a temperature of 120-240℃ and a time of 2-48h. Preferably, the hydrothermal treatment conditions include: a temperature of 140-220℃ and a time of 12-36h.

[0042] In this invention, there is no particular limitation on the preparation method of NiWO4 precursor. For example, it can also be prepared by conventional preparation methods defined in the art, such as solid-phase reaction method or precipitation method.

[0043] This invention does not particularly limit the specific operation method and conditions of the solid-state reaction method. According to a specific embodiment of this invention, the solid-state reaction method includes: mixing Ni metal precursor and W metal precursor and then subjecting them to a first heat treatment. This invention has a wide range of conditions for the first heat treatment. Preferably, the conditions for the first heat treatment include: a temperature of 120-200°C and a time of 12-48 hours.

[0044] This invention does not particularly limit the specific operation method and conditions of the precipitation method. According to another specific embodiment of this invention, the precipitation method includes: dissolving the Ni metal precursor and the W metal precursor separately in a solvent (preferably water) to obtain a Ni metal precursor solution and a W metal precursor solution; then mixing the W metal precursor solution and the Ni metal precursor solution for a second heat treatment. This invention allows for a wide range of conditions for the second heat treatment. Preferably, the conditions for the second heat treatment include a temperature of 50-100°C. In this invention, the second heat treatment is carried out under stirring conditions. This invention does not particularly limit the conditions for the second stirring; those skilled in the art can select the appropriate method based on actual conditions. This invention does not particularly limit the amount of solvent used; those skilled in the art can select the appropriate amount based on actual conditions.

[0045] In this invention, there is no particular limitation on the type of Ni precursor, as long as Ni element can be provided. Preferably, the Ni metal precursor is a Ni-soluble compound, and more preferably, it is selected from at least one of nickel nitrate, nickel chloride, basic nickel carbonate, and nickel sulfate.

[0046] In this invention, there is no particular limitation on the type of precursor for W, as long as W element can be provided. Preferably, the W metal precursor is a soluble compound of W, and more preferably, it is selected from at least one of ammonium metatungstate, sodium tungstate, and ammonium tungstate.

[0047] In this invention, there is no particular limitation on the amount of Ni metal precursor and W metal precursor. Preferably, the molar ratio of the Ni-containing metal precursor to the W-containing metal precursor is 1:5 to 5:1, based on elemental composition.

[0048] In this invention, a wide range of inorganic heat-resistant matrix types can be selected. Preferably, the inorganic heat-resistant matrix is ​​selected from at least one of alumina, zirconium oxide, oxidized state, and silicon oxide, with alumina being the most preferred.

[0049] In this invention, the preparation method of the carrier is not particularly limited. Preferably, the amorphous NiWO4 material and the inorganic heat-resistant matrix are molded. The molding method is not particularly limited; for example, forced mechanical mixing can be used. The amount of amorphous NiWO4 material and the inorganic heat-resistant matrix is ​​not particularly limited, as long as the carrier can be obtained. Preferably, the mass ratio of the amorphous NiWO4 material to the inorganic heat-resistant matrix is ​​1:2 to 1:20.

[0050] In this invention, preferably, the method further includes step (1) performing a first drying treatment before the first calcination. In this invention, the selection range for the conditions of the first drying is relatively wide. Preferably, the conditions of the first drying include: a temperature of 60-200℃, preferably 80-150℃, a time of 1-8 hours, preferably 2-6 hours, and a pressure of 0.01-0.1 MPa, preferably 0.05-0.1 MPa. In this invention, preferably, the first drying is carried out in an air atmosphere.

[0051] In this invention, by controlling the carbon content in the calcination product of step (1), some residual carbon is formed on the support, which helps to reduce the aggregation of active metals and improve the activity and stability of the catalyst. Preferably, in step (1), based on the total amount of the calcination product, the carbon content in the calcination product is 0.5-2.5% by weight, preferably 0.8-2% by weight.

[0052] In this invention, the carbon content is determined by infrared absorption method. The specific test conditions are as follows: the carbon content in the sample is determined by using HORIBA's EMIA-920V. The sample and flux are placed together in a high-frequency induction furnace and oxygen is introduced for combustion. The generated CO2 gas flows through the infrared absorption cell and absorbs infrared energy. The carbon content can be obtained from the change in energy.

[0053] In this invention, low-temperature calcination is employed to avoid excessively strong interactions between the active metal and the support caused by high-temperature calcination, which facilitates the subsequent sulfidation of the active metal. Simultaneously, during the low-temperature calcination stage, the metal salt decomposes to form corresponding metal oxides, while quaternary ammonium salt compounds partially decompose, retaining a certain proportion of carbon species to modify the support. This allows the catalyst to cooperate with subsequent organic compounds, enhancing its activity. Preferably, in step (1), the conditions for the first calcination include a temperature of 180-350℃ and a time of 1-8 hours; more preferably, in step (1), the conditions for the first calcination include a temperature of 230-300℃ and a time of 2-6 hours.

[0054] In this invention, preferably, the first calcination is carried out in an air atmosphere. The advantage of carrying out the first calcination in an air atmosphere is that it effectively converts the active metal from the form of metal salts into the form of oxides, while simultaneously partially oxidizing and decomposing organic matter, effectively controlling the carbon content.

[0055] In this invention, preferably, the pressure of the first calcination is 0.1-0.5 MPa.

[0056] In this invention, there is no particular limitation on the type of alcohol compound. Preferably, in step (2), the alcohol compound is selected from at least one of ethylene glycol, glycerol, diethylene glycol, and butanediol.

[0057] In this invention, there is no particular limitation on the type of carboxylic acid compound. Preferably, in step (2), the carboxylic acid compound is selected from at least one of citric acid, acetic acid, oxalic acid, aminotriacetic acid, 1,2-cyclohexanediaminetetraacetic acid, aminotriacetic acid, malic acid, and maleic acid.

[0058] In this invention, there is no particular limitation on the type of organic amine compound. Preferably, in step (2), the organic amine compound is ethylenediamine and / or ethylenediaminetetraacetic acid.

[0059] In this invention, preferably, in step (2), the post-treatment includes: impregnating the calcined product of step (1) with a solution containing at least one of alcohols, carboxylic acids, and organic amines using an impregnation method. In this invention, the impregnation method for the organic compounds is not particularly limited; for example, a pore-saturated impregnation method can be used to impregnate the carrier. According to a specific embodiment of this invention, based on the water absorption rate and mass of the calcined product, an organic impregnation solution of a predetermined volume is prepared, and the organic impregnation solution is poured into the carrier in three portions and stirred thoroughly. After obtaining the catalyst with pore-saturated impregnation, it is then dried.

[0060] In this invention, the carbon content on the support is controlled by introducing organic matter in steps, which helps to reduce the aggregation of active metals and improve the activity and stability of the catalyst. Preferably, the mass ratio of the organic compound in step (2) to the carbon in the calcination product in step (1) is 1:1-10:1, and more preferably 2:1-8:1.

[0061] In this invention, preferably, the method further includes step (2) performing a second drying treatment before the second calcination. In this invention, the selection range for the first drying conditions is relatively wide. Preferably, the conditions for the second drying include: a temperature of 60-200℃, preferably 80-150℃, a time of 1-8 hours, preferably 2-6 hours, and a pressure of 0.01-0.1 MPa, preferably 0.05-0.1 MPa. In this invention, preferably, the second drying is carried out in an air atmosphere.

[0062] In this invention, the second calcination is carried out at a low temperature, which helps to further disperse the active metal, form more active centers, and improve the activity and stability of the catalyst. Preferably, in step (2), the conditions for the second calcination include: a temperature of 180-350℃ and a time of 1-8h; more preferably, in step (2), the conditions for the second calcination include: a temperature of 200-280℃ and a time of 2-6h.

[0063] In this invention, preferably, the pressure of the second calcination is 0.1-0.5 MPa.

[0064] In this invention, preferably, in step (2), the second calcination is carried out under an inert atmosphere, and more preferably, the inert atmosphere is selected from at least one of nitrogen, helium, and argon. The advantage of carrying out the second calcination under an inert atmosphere in this invention is that it effectively controls the degree of decomposition of organic matter and adjusts the carbon content on the catalyst.

[0065] A second aspect of the present invention provides a hydrogenation catalyst prepared by the method described in the first aspect.

[0066] The third aspect of this invention provides the application of the hydrogenation catalyst described in the second aspect in the hydrogenation reaction of jet fuel.

[0067] The hydrogenation catalyst provided by this invention has significant advantages in terms of diffusion channels and hydrogenation activity, and performs well in the hydrodesulfurization of jet fuel.

[0068] In this invention, there are no particular limitations on the types and contents of the components in the jet fuel, and the jet fuel conventionally defined in the art is applicable to this invention.

[0069] The method provided by this invention can effectively remove sulfur impurities, especially mercaptan impurities, from jet fuel at relatively low temperatures.

[0070] In this invention, the selection range of conditions for the hydrogenation reaction is relatively wide. Preferably, the conditions for the hydrogenation reaction include: a reaction temperature of 230-300℃, a reaction pressure of 1-4 MPa, and a volume hourly space velocity of 2-6 h⁻¹. -1 The hydrogen-to-oil volume ratio is 50:1-200:1.

[0071] In this invention, preferably, the hydrogenation catalyst is subjected to sulfidation treatment before the reaction. The method of sulfidation is not particularly limited, as long as it can transform the active metal on the catalyst from an oxidized state to a sulfidated state. For example, the sulfidation method can be dry sulfidation or wet sulfidation. The sulfidation conditions are not particularly limited in this invention, and those skilled in the art can choose according to actual needs.

[0072] The present invention will be described in detail below through embodiments. Unless otherwise specified, all embodiments described below are derived from commercially available products.

[0073] To illustrate the features of the present invention, both the examples and comparative examples used commercial alumina powder from the same batch of industrial production, manufactured by Changling Branch of China Petrochemical Catalyst Co., Ltd., with the grade RPB-90.

[0074] In this invention, the carbon content is determined by infrared absorption method.

[0075] In this invention, the average grain size of the amorphous NiWO4 material was measured by high-resolution transmission electron microscopy (HRTEM).

[0076] The crystal structure of amorphous NiWO4 material was determined by XRD.

[0077] The specific surface area and pore volume of the amorphous NiWO4 material were determined by the N2 physical adsorption-desorption (BET) method.

[0078] Example 1

[0079] (1) Take 24g of nickel chloride hexahydrate and 33g of sodium tungstate dihydrate, and dissolve them separately in deionized water. After heating the sodium tungstate solution to 60℃, add the nickel chloride solution dropwise to form a suspension. Transfer the suspension to a hydrothermal reactor for hydrothermal treatment at 180℃ for 24 hours. After hydrothermal treatment, obtain amorphous NiWO4 material for later use. The XRD pattern is shown below. Figure 1 As shown, from Figure 1 As can be seen, no obvious diffraction peaks were formed, indicating that no obvious crystal structure was formed and the NiWO4 material remained in an amorphous state.

[0080] (2) Take 20g of the prepared NiWO4 material and 100g of commercial alumina powder and mix them evenly by mechanical mixing. After molding, it is used as a composite carrier.

[0081] (3) Take 120g of the above composite support, weigh 7g of basic nickel carbonate, 22g of molybdenum oxide, 6g of 85% phosphoric acid and 13g of tetrabutylammonium bromide, dissolve them by heating and stirring with deionized water, make up the volume according to the saturated water absorption rate of the composite support, impregnate the composite support with the solution for 2 hours, the air atmosphere pressure is 0.1MPa, dry at 120℃ for 4 hours, then heat to 280℃ and calcine at low temperature for 4 hours at a pressure of 0.15MPa to obtain catalyst sample M loaded with active metal, and determine its carbon content to be 1.52%;

[0082] (4) Weigh 12.16g of citric acid, dissolve it with deionized water by stirring, and make up the volume according to the saturated water absorption rate of sample M. Impregnate the catalyst sample M loaded with active metal with this solution for 2 hours, with an air atmosphere pressure of 0.1MPa. After drying at 120℃ for 4 hours, switch to nitrogen and heat to 265℃ for low-temperature calcination for 4 hours at a pressure of 0.15MPa to obtain catalyst C1.

[0083] Before using the catalyst, a pre-sulfurization treatment is performed. The pre-sulfurization treatment conditions include: the catalyst is subjected to programmed temperature sulfurization treatment under an atmosphere of 1 volume% H2S and 99 volume% H2. The temperature program is to increase the temperature from 20°C to 300°C at a rate of 1°C / min, hold the temperature for 3 hours, and the gas volume flow rate per hour is 200 times the catalyst volume ratio.

[0084] The hydrodesulfurization activity of this catalyst was evaluated using a 20 mL fixed-bed reactor. The evaluation process conditions were as follows: inlet temperatures of 240℃, 260℃, and 280℃; reaction pressure of 1.6 MPa; hydrogen-to-oil volume ratio of 60; and volume hourly space velocity of 4 h⁻¹. -1 After stabilizing for 24 hours, samples were taken to analyze the sulfur content of the product. The desulfurization rate was calculated by the difference between the sulfur content of the product and the raw material. The higher the desulfurization rate, the better the activity of the catalyst.

[0085] The specific surface area and pore volume of the catalyst were calculated using N2 isothermal adsorption-desorption and conventional BET and BJH methods. The degree of sulfidation of the active metal in the sulfidated catalyst was characterized by XPS. The larger the specific surface area and pore volume of the catalyst, the richer the diffusion channels. The higher degree of sulfidation of the sulfidated catalyst indicates that the active metal utilization rate of the catalyst is higher and there are relatively more active centers.

[0086] The properties of the raw materials are shown in Table 1, the analysis of amorphous NiWO4 materials is shown in Table 2, the analysis and characterization results of the catalyst are shown in Table 3, and the evaluation results are shown in Table 4.

[0087] Example 2

[0088] (1) Take 22g of nickel chloride hexahydrate and 38g of sodium tungstate dihydrate, dissolve them in deionized water respectively. After heating the sodium tungstate solution to 70°C, add the nickel chloride solution dropwise to form a suspension. Transfer the suspension to a hydrothermal reactor for hydrothermal treatment. The hydrothermal conditions are 160°C and 36 hours. After hydrothermal treatment, amorphous NiWO4 material is obtained for later use. The NiWO4 material in Example 2 has the same amorphous state as that in Example 1.

[0089] (2) Take 20g of the prepared NiWO4 material and 100g of commercial alumina powder and mix them evenly by mechanical mixing. After molding, it is used as a composite carrier.

[0090] (3) Take 120g of the above composite support, weigh 7g of basic nickel carbonate, 22g of molybdenum oxide, 6g of 85% phosphoric acid and 13g of tetrabutylammonium bromide, dissolve them by heating and stirring with deionized water, make up the volume according to the saturated water absorption rate of the composite support, impregnate the composite support with the solution for 2 hours, the air atmosphere pressure is 0.1MPa, dry at 120℃ for 4 hours, then heat to 280℃ and calcine at low temperature for 4 hours at a pressure of 0.15MPa to obtain catalyst sample M loaded with active metal, and determine its carbon content to be 1.48%;

[0091] (4) Weigh 11.84 g of citric acid and dissolve it with deionized water by stirring. Make up the volume according to the saturated water absorption rate of sample M. Impregnate the catalyst sample M loaded with active metal with this solution for 2 hours. The air atmosphere pressure is 0.1 MPa. After drying at 120°C for 4 hours, switch to nitrogen and heat to 265°C for low-temperature calcination for 4 hours at a pressure of 0.15 MPa to obtain catalyst C2.

[0092] The evaluation conditions for the catalyst were the same as in Example 1. The analysis of amorphous NiWO4 material is shown in Table 2, the analysis and characterization results of the catalyst are shown in Table 3, and the evaluation results data are shown in Table 4.

[0093] Example 3

[0094] (1) Take 26g of nickel nitrate and 23g of ammonium metatungstate, mix and grind them into powder, and then heat them. The treatment conditions are 180°C and 24 hours. Then transfer them to a hydrothermal reactor for hydrothermal treatment. The hydrothermal conditions are 180°C and 24 hours. After hydrothermal treatment, amorphous NiWO4 material is obtained for later use. The NiWO4 material in Example 3 has the same amorphous state as that in Example 1.

[0095] (2) Take 20g of the prepared NiWO4 material and 100g of commercial alumina powder and mix them evenly by mechanical mixing. After molding, it is used as a composite carrier.

[0096] (3) Take 120g of the above composite support, weigh 7g of basic nickel carbonate, 22g of molybdenum oxide, 6g of 85% phosphoric acid and 13g of tetrabutylammonium bromide, dissolve them by heating and stirring with deionized water, make up the volume according to the saturated water absorption rate of the composite support, impregnate the composite support with the solution for 2 hours, the air atmosphere pressure is 0.1MPa, dry at 120℃ for 4 hours, then heat to 280℃ and calcine at low temperature for 4 hours at a pressure of 0.15MPa to obtain catalyst sample M loaded with active metal, and determine its carbon content to be 1.51%;

[0097] (4) Weigh 12.08g of citric acid and dissolve it with deionized water by stirring. Make up the volume according to the saturated water absorption rate of sample M. Impregnate the catalyst sample M loaded with active metal with this solution for 2 hours. The air atmosphere pressure is 0.1MPa. After drying at 120℃ for 4 hours, switch to nitrogen and heat to 265℃ for low-temperature calcination for 4 hours at a pressure of 0.15MPa to obtain catalyst C3.

[0098] The evaluation conditions for the catalyst were the same as in Example 1. The analysis of amorphous NiWO4 material is shown in Table 2, the analysis and characterization results of the catalyst are shown in Table 3, and the evaluation results data are shown in Table 4.

[0099] Example 4

[0100] (1) Take 24g of nickel chloride hexahydrate and 33g of sodium tungstate dihydrate, dissolve them in deionized water respectively. After heating the sodium tungstate solution to 60°C, add the nickel chloride solution dropwise to form a suspension. Transfer the suspension to a hydrothermal reactor for hydrothermal treatment. The hydrothermal conditions are 180°C and 24 hours. After hydrothermal treatment, amorphous NiWO4 material is obtained for later use. The NiWO4 material in Example 4 has the same amorphous state as that in Example 1.

[0101] (2) Take 15g of the prepared NiWO4 material and 100g of commercial alumina powder and mix them evenly by mechanical mixing. After molding, it is used as a composite carrier.

[0102] (3) Take 115g of the above composite support, weigh 9g of basic nickel carbonate, 26g of molybdenum oxide, 7g of 85% phosphoric acid and 16g of tetrabutylammonium bromide, dissolve them by heating and stirring with deionized water, make up the volume according to the saturated water absorption rate of the composite support, impregnate the composite support with the solution for 2 hours, the air atmosphere pressure is 0.1MPa, dry at 120℃ for 4 hours, then heat to 280℃ and calcine at low temperature for 4 hours at 0.15MPa to obtain catalyst sample M loaded with active metal, and determine its carbon content to be 1.60%;

[0103] (4) Weigh 9.6g of citric acid and dissolve it with deionized water by stirring. Make up the volume according to the saturated water absorption rate of sample M. Impregnate the catalyst sample M with the solution for 2 hours. The air atmosphere pressure is 0.1MPa. After drying at 120℃ for 4 hours, switch to nitrogen and heat to 265℃ for low-temperature calcination for 4 hours at a pressure of 0.15MPa to obtain catalyst C4.

[0104] The evaluation conditions for the catalyst were the same as in Example 1. The analysis of amorphous NiWO4 material is shown in Table 2, the analysis and characterization results of the catalyst are shown in Table 3, and the evaluation results data are shown in Table 4.

[0105] Example 5

[0106] (1) Take 24g of nickel chloride hexahydrate and 33g of sodium tungstate dihydrate, dissolve them in deionized water respectively. After heating the sodium tungstate solution to 60°C, add the nickel chloride solution dropwise to form a suspension. Transfer the suspension to a hydrothermal reactor for hydrothermal treatment. The hydrothermal conditions are 180°C and 24 hours. After hydrothermal treatment, amorphous NiWO4 material is obtained for later use. The NiWO4 material in Example 5 has the same amorphous state as that in Example 1.

[0107] (2) Take 20g of the prepared NiWO4 material and 100g of commercial alumina powder and mix them evenly by mechanical mixing. After molding, it is used as a composite carrier.

[0108] (3) Take 120g of the above composite support, weigh 7g of basic nickel carbonate, 22g of molybdenum oxide, 6g of 85% phosphoric acid and 19g of dodecyltrimethylammonium bromide, dissolve them by heating and stirring with deionized water, make up the volume according to the saturated water absorption rate of the composite support, impregnate the composite support with the solution for 2 hours, the air atmosphere pressure is 0.1MPa, dry at 120℃ for 4 hours, then heat to 280℃ and calcine at low temperature for 4 hours at a pressure of 0.15MPa to obtain catalyst sample M loaded with active metal, and determine its carbon content to be 1.86%;

[0109] (4) Weigh 13.02 g of glycerol and dissolve it with deionized water. Make up the volume according to the saturated water absorption rate of sample M. Impregnate the catalyst sample M loaded with active metal with this solution for 2 hours. The air atmosphere pressure is 0.1 MPa. After drying at 120°C for 4 hours, switch to nitrogen and heat to 265°C for low-temperature calcination for 4 hours at a pressure of 0.15 MPa to obtain catalyst C5.

[0110] The evaluation conditions for the catalyst were the same as in Example 1. The analysis of amorphous NiWO4 material is shown in Table 2, the analysis and characterization results of the catalyst are shown in Table 3, and the evaluation results data are shown in Table 4.

[0111] Example 6

[0112] (1) Take 24g of nickel chloride hexahydrate and 33g of sodium tungstate dihydrate, dissolve them in deionized water respectively. After heating the sodium tungstate solution to 60°C, add the nickel chloride solution dropwise to form a suspension. Transfer the suspension to a hydrothermal reactor for hydrothermal treatment. The hydrothermal conditions are 180°C and 24 hours. After hydrothermal treatment, amorphous NiWO4 material is obtained for later use. The NiWO4 material in Example 6 has the same amorphous state as that in Example 1.

[0113] (2) Take 20g of the prepared NiWO4 material and 100g of commercial alumina powder and mix them evenly by mechanical mixing. After molding, it is used as a composite carrier.

[0114] (3) Take 120g of the above composite support, weigh 7g of basic nickel carbonate, 22g of molybdenum oxide, 6g of 85% phosphoric acid and 13g of tetrabutylammonium bromide, dissolve them by heating and stirring with deionized water, make up the volume according to the saturated water absorption rate of the composite support, impregnate the composite support with the solution for 2 hours, the air atmosphere pressure is 0.1MPa, dry at 120℃ for 4 hours, then heat to 300℃ and calcine at low temperature for 3 hours at a pressure of 0.15MPa to obtain catalyst sample M loaded with active metal, and determine its carbon content to be 1.22%;

[0115] (4) Weigh 12.2g of citric acid, dissolve it with deionized water, and make up the volume according to the saturated water absorption rate of sample M. Impregnate the catalyst sample M loaded with active metal with this solution for 2 hours, with an air atmosphere pressure of 0.1MPa. After drying at 150℃ for 3 hours, switch to nitrogen and heat to 255℃ for low-temperature calcination for 6 hours at a pressure of 0.1MPa to obtain catalyst C6.

[0116] The evaluation conditions for the catalyst were the same as in Example 1. The analysis of amorphous NiWO4 material is shown in Table 2, the analysis and characterization results of the catalyst are shown in Table 3, and the evaluation results data are shown in Table 4.

[0117] Example 7

[0118] (1) Take 24g of nickel chloride hexahydrate and 33g of sodium tungstate dihydrate, dissolve them in deionized water respectively. After heating the sodium tungstate solution to 60°C, add the nickel chloride solution dropwise to form a suspension. Transfer the suspension to a hydrothermal reactor for hydrothermal treatment. The hydrothermal conditions are 180°C and 24 hours. After hydrothermal treatment, amorphous NiWO4 material is obtained for later use. The NiWO4 material in Example 7 has the same amorphous state as that in Example 1.

[0119] (2) Take 20g of the prepared NiWO4 material and 100g of commercial alumina powder and mix them evenly by mechanical mixing. After molding, it is used as a composite carrier.

[0120] (3) Take 120g of the above composite support, weigh 8g of basic nickel carbonate, 21g of molybdenum oxide, 6g of 85% phosphoric acid and 14g of hexadecyltrimethylammonium bromide, dissolve them by heating and stirring with deionized water, make up the volume according to the saturated water absorption rate of the composite support, impregnate the composite support with the solution for 2 hours, the air atmosphere pressure is 0.1MPa, dry at 120℃ for 4 hours, then heat to 230℃ and calcine at low temperature for 4 hours at a pressure of 0.15MPa to obtain catalyst sample M loaded with active metal, and determine its carbon content to be 1.92%;

[0121] (4) Weigh 9.6g of citric acid and dissolve it with deionized water by stirring. Make up the volume according to the saturated water absorption rate of sample M. Impregnate the catalyst sample M loaded with active metal with this solution for 2 hours. The air atmosphere pressure is 0.1MPa. After drying at 120℃ for 4 hours, switch to nitrogen and heat to 210℃ for low-temperature calcination for 4 hours at a pressure of 0.15MPa to obtain catalyst C7.

[0122] The evaluation conditions for the catalyst were the same as in Example 1. The analysis of amorphous NiWO4 material is shown in Table 2, the analysis and characterization results of the catalyst are shown in Table 3, and the evaluation results data are shown in Table 4.

[0123] Example 8

[0124] (1) Take 24g of nickel chloride hexahydrate and 33g of sodium tungstate dihydrate, dissolve them in deionized water respectively. After heating the sodium tungstate solution to 60°C, add the nickel chloride solution dropwise to form a suspension. Transfer the suspension to a hydrothermal reactor for hydrothermal treatment. The hydrothermal conditions are 180°C and 24 hours. After hydrothermal treatment, amorphous NiWO4 material is obtained for later use. The NiWO4 material in Example 8 has the same amorphous state as that in Example 1.

[0125] (2) Take 20g of the prepared NiWO4 material and 100g of commercial alumina powder and mix them evenly by mechanical mixing. After molding, it is used as a composite carrier.

[0126] (3) Take 120g of the above composite support, weigh 7g of basic nickel carbonate, 22g of molybdenum oxide, 6g of 85% phosphoric acid and 13g of tetrabutylammonium bromide, dissolve them by heating and stirring with deionized water, make up the volume according to the saturated water absorption rate of the composite support, impregnate the composite support with the solution for 2 hours, the air atmosphere pressure is 0.1MPa, dry at 120℃ for 4 hours, then heat to 190℃ and calcine at low temperature for 4 hours at a pressure of 0.15MPa to obtain catalyst sample M loaded with active metal, and determine its carbon content to be 2.10%;

[0127] (4) Weigh 16.8g of citric acid, dissolve it with deionized water, and make up the volume according to the saturated water absorption rate of sample M. Impregnate the catalyst sample M loaded with active metal with this solution for 2 hours, with an air atmosphere pressure of 0.1MPa. After drying at 120℃ for 4 hours, switch to nitrogen and heat to 320℃ for low-temperature calcination for 4 hours at a pressure of 0.15MPa to obtain catalyst C8.

[0128] The evaluation conditions for the catalyst were the same as in Example 1. The analysis of amorphous NiWO4 material is shown in Table 2, the analysis and characterization results of the catalyst are shown in Table 3, and the evaluation results data are shown in Table 4.

[0129] Comparative Example 1

[0130] (1) Take 100g of commercial alumina powder and use it as a carrier. Weigh 7g of basic nickel carbonate, 22g of molybdenum oxide, 6g of 85% phosphoric acid and 13g of tetrabutylammonium bromide. Dissolve them by heating and stirring with deionized water. Make up the volume according to the saturated water absorption rate of the carrier. Impregnate the carrier with the solution for 2 hours. The air atmosphere pressure is 0.1MPa. After drying at 120℃ for 4 hours, the temperature is raised to 280℃ and calcined at low temperature for 4 hours at a pressure of 0.15MPa to obtain catalyst sample M with active metal supported. The carbon content is determined to be 1.50%.

[0131] (2) Weigh 12g of citric acid and dissolve it with deionized water by stirring. Make up the volume according to the saturated water absorption rate of sample M. Impregnate the catalyst sample M loaded with active metal with this solution for 2 hours. The air atmosphere pressure is 0.1MPa. After drying at 120℃ for 4 hours, switch to nitrogen and heat to 265℃ for low-temperature calcination for 4 hours at a pressure of 0.15MPa to obtain catalyst D1.

[0132] The evaluation conditions for the catalyst were the same as in Example 1. The analysis of NiWO4 material is shown in Table 2, the analysis and characterization results of the catalyst are shown in Table 3, and the evaluation results data are shown in Table 4.

[0133] Comparative Example 2

[0134] (1) Take 24g of nickel chloride hexahydrate and 33g of sodium tungstate dihydrate, dissolve them in deionized water respectively. After heating the sodium tungstate solution to 60°C, add the nickel chloride solution dropwise to form a suspension. Transfer the suspension to a hydrothermal reactor for hydrothermal treatment. The hydrothermal conditions are 180°C and 24 hours. After hydrothermal treatment, amorphous NiWO4 material is obtained for later use. The NiWO4 material in Comparative Example 2 has a similar amorphous state to that in Example 1.

[0135] (2) Take 100g of commercial alumina powder, weigh 7g of basic nickel carbonate, 22g of molybdenum oxide, 6g of 85% phosphoric acid and 13g of tetrabutylammonium bromide, dissolve them by heating and stirring with deionized water, make up the volume according to the saturated water absorption rate of commercial alumina powder, impregnate the alumina powder with the solution for 2 hours, dry it in air at 120℃ for 4 hours, and then calcine it at 280℃ for 4 hours to obtain catalyst sample M loaded with active metal, and determine its carbon content to be 1.52%.

[0136] (3) Weigh 12.16g of citric acid, dissolve it in deionized water by stirring, and make up the volume according to the saturated water absorption rate of sample M. Impregnate the catalyst sample M supported on active metal with this solution for 2 hours, with an air atmosphere pressure of 0.1MPa, dry at 120℃ for 4 hours, switch to nitrogen and heat to 265℃ for low-temperature calcination for 4 hours at a pressure of 0.15MPa to obtain a catalyst sample containing NiMo.

[0137] (4) Take 20g of the prepared NiWO4 material and mix it evenly with the above NiMo catalyst sample. After molding, catalyst D2 is prepared.

[0138] The evaluation conditions for the catalyst were the same as in Example 1. The analysis of NiWO4 material is shown in Table 2, the analysis and characterization results of the catalyst are shown in Table 3, and the evaluation results data are shown in Table 4.

[0139] Comparative Example 3

[0140] (1) Take 24g of nickel chloride hexahydrate and 33g of sodium tungstate dihydrate, dissolve them in deionized water respectively. After heating the sodium tungstate solution to 60°C, add the nickel chloride solution dropwise to form a suspension. Transfer the suspension to a hydrothermal reactor for hydrothermal treatment. The hydrothermal conditions are 180°C and 24 hours. After hydrothermal treatment, amorphous NiWO4 material is obtained for later use. The NiWO4 material in Comparative Example 3 has a similar amorphous state to that in Example 1.

[0141] (2) Take 20g of the prepared NiWO4 material and 100g of commercial alumina powder and mix them evenly by mechanical mixing. After molding, it is used as a composite carrier.

[0142] (3) Take 120g of the above composite support, weigh 7g of basic nickel carbonate, 22g of molybdenum oxide and 6g of 85% phosphoric acid and heat and stir to dissolve them in deionized water. Make up the volume according to the saturated water absorption rate of the composite support, impregnate the composite support with the solution for 2 hours, the air atmosphere pressure is 0.1MPa, dry at 120℃ for 4 hours, then heat to 280℃ and calcine at low temperature for 4 hours at a pressure of 0.15MPa to obtain catalyst sample M loaded with active metal, and determine its carbon content to be 0.24%.

[0143] (4) Weigh 1.92g of citric acid, dissolve it with deionized water, and make up the volume according to the saturated water absorption rate of sample M. Impregnate the catalyst sample M loaded with active metal with this solution for 2 hours, with an air atmosphere pressure of 0.1MPa. After drying at 120℃ for 4 hours, switch to nitrogen and heat to 265℃ for low-temperature calcination for 4 hours at a pressure of 0.15MPa to obtain catalyst D3.

[0144] The evaluation conditions for the catalyst were the same as in Example 1. The analysis of NiWO4 material is shown in Table 2, the analysis and characterization results of the catalyst are shown in Table 3, and the evaluation results data are shown in Table 4.

[0145] Comparative Example 4

[0146] (1) Take 24g of nickel chloride hexahydrate and 33g of sodium tungstate dihydrate, dissolve them in deionized water respectively. After heating the sodium tungstate solution to 60°C, add the nickel chloride solution dropwise to form a suspension. Transfer the suspension to a hydrothermal reactor for hydrothermal treatment. The hydrothermal conditions are 180°C and 24 hours. After hydrothermal treatment, amorphous NiWO4 material is obtained for later use. The NiWO4 material in Comparative Example 4 has a similar amorphous state to that in Example 1.

[0147] (2) Take 20g of the prepared NiWO4 material and 100g of commercial alumina powder and mix them evenly by mechanical mixing. After molding, it is used as a composite carrier.

[0148] (3) Take 120g of the above composite support, weigh 7g of basic nickel carbonate, 22g of molybdenum oxide, 6g of 85% phosphoric acid and 13g of tetrabutylammonium bromide, dissolve them by heating and stirring with deionized water, make up the volume according to the saturated water absorption rate of the composite support, impregnate the composite support with the solution for 2 hours, the air atmosphere pressure is 0.1MPa, dry at 120℃ for 4 hours, then heat to 280℃ and calcine at low temperature for 4 hours at a pressure of 0.15MPa to obtain catalyst D4.

[0149] The evaluation conditions for the catalyst were the same as in Example 1. The analysis of NiWO4 material is shown in Table 2, the analysis and characterization results of the catalyst are shown in Table 3, and the evaluation results data are shown in Table 4.

[0150] Comparative Example 5

[0151] (1) Take 100g of commercial alumina powder and use it as a carrier. Weigh 17g of basic nickel carbonate, 22g of molybdenum oxide, 16g of ammonium metatungstate, 6g of 85% phosphoric acid and 13g of tetrabutylammonium bromide. Dissolve them by heating and stirring with deionized water. Make up the volume according to the saturated water absorption rate of the carrier. Impregnate the carrier with the solution for 2 hours. The air atmosphere pressure is 0.1MPa. After drying at 120℃ for 4 hours, the temperature is raised to 280℃ and calcined at low temperature for 4 hours at a pressure of 0.15MPa to obtain catalyst sample M with active metal supported. The carbon content is determined to be 1.48%.

[0152] (2) Weigh 11.84 g of citric acid and dissolve it with deionized water by stirring. Make up the volume according to the saturated water absorption rate of sample M. Impregnate the catalyst sample M loaded with active metal with this solution for 2 hours. The air atmosphere pressure is 0.1 MPa. After drying at 120°C for 4 hours, switch to nitrogen and heat to 265°C for low-temperature calcination for 4 hours at a pressure of 0.15 MPa to obtain catalyst D5.

[0153] The evaluation conditions for the catalyst were the same as in Example 1. The analysis of NiWO4 material is shown in Table 2, the analysis and characterization results of the catalyst are shown in Table 3, and the evaluation results data are shown in Table 4.

[0154] Comparative Example 6

[0155] (1) Take 24g of nickel chloride hexahydrate and 33g of sodium tungstate dihydrate, dissolve them separately in deionized water. After heating the sodium tungstate solution to 60℃, add the nickel chloride solution dropwise to form a suspension. Transfer the suspension to a hydrothermal reactor for hydrothermal treatment at 280℃ for 48 hours. After hydrothermal treatment, obtain NiWO4 material with obvious crystals for later use. The XRD pattern is shown below. Figure 2 As shown, from Figure 2 As can be seen from the table, the NiWO4 material exhibits typical crystal structure diffraction peaks at 30.9°, 36.5° and 54.5°, indicating good crystallization effect. As can be seen from Table 1, the average grain size of the NiWO4 material in Comparative Example 6 is significantly increased compared to the amorphous NiWO4 material in the examples, while the specific surface area is reduced.

[0156] (2) Take 120g of the above composite carrier, take 20g of the prepared NiWO4 material and 100g of commercial alumina powder and mix them evenly by mechanical mixing. After molding, it is used as a composite carrier.

[0157] (3) Weigh 7g of basic nickel carbonate, 22g of molybdenum oxide, 6g of 85% phosphoric acid and 13g of tetrabutylammonium bromide, dissolve them by heating and stirring with deionized water, make up the volume according to the saturated water absorption rate of the composite support, impregnate the composite support with the solution for 2 hours, the air atmosphere pressure is 0.1MPa, dry at 120℃ for 4 hours, then heat to 280℃ and calcine at low temperature for 4 hours at 0.15MPa to obtain catalyst sample M with active metal supported, and determine its carbon content to be 1.55%;

[0158] (4) Weigh 12.4g of citric acid and dissolve it with deionized water by stirring. Make up the volume according to the saturated water absorption rate of sample M. Impregnate the catalyst sample M loaded with active metal with this solution for 2 hours. The air atmosphere pressure is 0.1MPa. After drying at 120℃ for 4 hours, switch to nitrogen and heat to 265℃ for low-temperature calcination for 4 hours at a pressure of 0.15MPa to obtain catalyst D6.

[0159] The evaluation conditions for the catalyst were the same as in Example 1. The analysis of NiWO4 material is shown in Table 2, the analysis and characterization results of the catalyst are shown in Table 3, and the evaluation results data are shown in Table 4.

[0160] Table 1

[0161] Analysis Project Aviation fuel Sulfur content, ppm 2011 Nitrogen content, ppm 2.52 Density, g / mL 0.78558 Refractive index (20℃) 1.4401

[0162] Table 2

[0163] <![CDATA[Specific surface area / (m 2 / g)]]> Pore ​​volume (mL / g) Average particle size (nm) Example 1 275 0.81 3.9 Example 2 272 0.82 3.8 Example 3 271 0.83 3.7 Comparative Example 1 / / / Comparative Example 6 182 0.58 28.2

[0164] Table 3

[0165]

[0166]

[0167] As can be seen from the table above, the composite support prepared using the amorphous NiWO4 material provided by this invention has a larger specific surface area and pore volume, which is beneficial to the subsequent hydrodesulfurization reaction. 4+ ) / n(Mo Total ) and n(W 4+ ) / n(W Total The higher the proportion of ), the easier it is for the active metals Mo and W in the catalyst to sulfide, the higher the utilization rate of the active metals, and the better the hydrogenation activity of the catalyst.

[0168] Table 4

[0169]

[0170]

[0171] As can be seen from the table above, the hydrogenation catalyst prepared by the method of the present invention has higher hydrodesulfurization activity under the same evaluation conditions.

[0172] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing a hydrogenation catalyst, characterized in that, The method includes the following steps: (1) The carrier is impregnated with a solution containing an active metal and a quaternary ammonium salt compound, and then subjected to a first calcination to obtain a calcined product, wherein the carbon content in the calcined product is 0.5-2.5% by weight, based on the total amount of the calcined product; the active metal is selected from at least one of Group VIII metals and / or at least one of Group VIB metals, and the carrier includes amorphous NiWO4 material and an inorganic heat-resistant matrix; (2) The calcination product of step (1) is post-treated with an organic compound and then subjected to a second calcination to obtain a hydrogenation catalyst, wherein the organic compound is selected from at least one of alcohols, carboxylic acids and organic amines.

2. The method according to claim 1, wherein, In step (1), the active metal is selected from Ni and / or Mo.

3. The method according to claim 2, wherein, In step (1), the active metals are Ni and Mo.

4. The method according to claim 3, wherein, In step (1), the active metal is provided by the precursor of each active metal.

5. The method according to claim 4, wherein, In step (1), the precursors of each active metal are provided by soluble compounds of each active metal.

6. The method according to claim 5, wherein, In step (1), the precursors of each active metal are selected from at least one of nickel nitrate, nickel chloride, basic nickel carbonate and nickel sulfate, and at least one of ammonium molybdate, sodium molybdate and molybdenum oxide.

7. The method according to claim 4, wherein, In step (1), the amount of the active metal precursor is such that the content of Ni in the prepared hydrogenation catalyst is 0.1-10% by weight as oxide and the content of Mo in the catalyst is 5-30% by weight as oxide.

8. The method according to claim 2, wherein, In step (1), the mass ratio of the precursor of active metal Ni and amorphous NiWO4 material, calculated as oxides, is 1:3-1:

30.

9. The method according to claim 1, wherein, In step (1), the quaternary ammonium salt compound is selected from C4-C20 quaternary ammonium salt compounds.

10. The method according to claim 9, wherein, In step (1), the quaternary ammonium salt compound is at least one of tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, dodecyltrimethylammonium bromide and hexadecyltrimethylammonium bromide.

11. The method according to claim 10, wherein the quaternary ammonium salt compound is at least one selected from tetrabutylammonium bromide, dodecyltrimethylammonium bromide, and hexadecyltrimethylammonium bromide.

12. The method according to claim 2, wherein, In step (1), the molar ratio of the quaternary ammonium salt compound to the active metal Ni (calculated as an element) is 0.3:1-3:

1.

13. The method according to claim 12, wherein, In step (1), the molar ratio of the quaternary ammonium salt compound to the active metal Ni (calculated as an element) is 0.5:1-2:

1.

14. The method according to any one of claims 1-13, wherein, In step (1), the average grain size of the amorphous NiWO4 material is 2-5 nm.

15. The method according to any one of claims 1-13, wherein, In step (1), the amorphous NiWO4 material is prepared by the following method: NiWO4 precursor is prepared by solid-state reaction method and / or precipitation method, and then hydrothermal treatment is performed to obtain amorphous NiWO4 material. The hydrothermal treatment conditions include: temperature of 120-240℃ and time of 2-48h.

16. The method according to claim 15, wherein, The conditions for the hydrothermal treatment include: a temperature of 140-220℃ and a time of 12-36h.

17. The method according to claim 15, wherein, The NiWO4 precursor is prepared by precipitation of Ni metal precursor and W metal precursor.

18. The method according to claim 17, wherein, The Ni metal precursor is a soluble compound of Ni.

19. The method according to claim 18, wherein, The Ni metal precursor is at least one of nickel nitrate, nickel chloride, basic nickel carbonate, and nickel sulfate.

20. The method of claim 17, wherein, The W metal precursor is a soluble compound of W.

21. The method according to claim 20, wherein, The W metal precursor is at least one of ammonium metatungstate, sodium tungstate, and ammonium tungstate.

22. The method according to claim 17, wherein, The molar ratio of the Ni metal precursor to the W metal precursor is 1:5 to 5:1, based on elemental composition.

23. The method according to claim 1, wherein, In step (1), the inorganic heat-resistant matrix is ​​selected from at least one of alumina, zirconium oxide, titanium oxide and silicon oxide.

24. The method according to claim 23, wherein, In step (1), the inorganic heat-resistant matrix is ​​alumina.

25. The method according to claim 1, wherein, In step (1), the mass ratio of the amorphous NiWO4 material to the inorganic heat-resistant matrix is ​​1:2-1:

20.

26. The method according to claim 1, wherein, In step (1), the carbon content in the calcined product is 0.8-2% by weight.

27. The method according to claim 1, wherein, In step (1), the conditions for the first roasting include: a temperature of 180-350℃ and a time of 1-8h.

28. The method according to claim 27, wherein, In step (1), the conditions for the first roasting include: a temperature of 230-300℃ and a time of 2-6h.

29. The method according to claim 1, wherein, In step (2), the alcohol compound is selected from at least one of ethylene glycol, glycerol, diethylene glycol and butanediol.

30. The method according to claim 1, wherein, In step (2), the carboxylic acid compound is selected from at least one of citric acid, acetic acid, oxalic acid, aminotriacetic acid, 1,2-cyclohexanediaminetetraacetic acid, aminotriacetic acid, malic acid, and maleic acid.

31. The method according to claim 1, wherein, In step (2), the organic amine compound is ethylenediamine and / or ethylenediaminetetraacetic acid.

32. The method according to claim 1, wherein, In step (2), the post-processing includes: impregnating the roasted product of step (1) with a solution containing at least one of alcohols, carboxylic acids and organic amines using an impregnation method.

33. The method according to claim 32, wherein, The mass ratio of the organic compound in step (2) to the carbon in the calcination product in step (1) is 1:1-10:

1.

34. The method according to claim 33, wherein, The mass ratio of the organic compound in step (2) to the carbon in the calcination product in step (1) is 2:1-8:

1.

35. The method according to claim 1, wherein, In step (2), the conditions for the second calcination include: a temperature of 180-350℃ and a time of 1-8h.

36. The method according to claim 35, wherein, In step (2), the conditions for the second roasting include: a temperature of 200-280℃ and a time of 2-6h.

37. The method according to claim 1, wherein, In step (2), the second calcination is carried out under an inert atmosphere, which is selected from at least one of nitrogen, helium and argon.

38. The hydrogenation catalyst prepared by the method of any one of claims 1-37.

39. The application of the hydrogenation catalyst according to claim 38 in the hydrogenation reaction of jet fuel.

40. The application according to claim 39, wherein, The conditions for the hydrogenation reaction include: a reaction temperature of 230-300℃, a reaction pressure of 1-4 MPa, and a volume hourly space velocity of 2-6 h⁻¹. -1 The hydrogen-to-oil volume ratio is 50:1-200:1.

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