Preparation method of hydrogenation catalyst, hydrogenation catalyst and application thereof, and production method of aromatic extraction raw material

Abstract

The invention relates to the field of hydrogenation catalysts, and discloses a preparation method of a hydrogenation catalyst, the hydrogenation catalyst and application thereof, and a production method of an aromatic extraction raw material. The invention relates to a preparation method of a hydrogenation catalyst, which comprises the following steps: (1) loading nickel and alkali metal and / or alkaline earth metal onto a carrier, and then roasting to obtain a modified carrier; (2) loading cobalt, molybdenum and a first organic matter on the modified carrier, and then carrying out hydrothermal treatment and first post-treatment to obtain a catalyst precursor; and (3) loading a second organic matter on the catalyst precursor, and then carrying out hydrogenolysis post-treatment to obtain the catalyst. According to the method, the loading sequence of the active metal is modulated, the stability of the catalyst is improved, the electronic characteristic adjusting effect of alkali metal is utilized, and organic matter is introduced while the active metal is subsequently impregnated, so that the active metal can be better dispersed on a carrier, and better combination between the active metal is realized.

Description

Preparation methods of hydrogenation catalysts, their applications, and production methods of aromatic hydrocarbon extraction feedstocks. Technical Field

[0001] This invention relates to the technical field of hydrogenation catalysts, specifically to a method for preparing a hydrogenation catalyst, as well as the application of the hydrogenation catalyst and a method for producing aromatic extraction feedstock. Background Technology

[0002] Aromatic hydrocarbons play a crucial role in the petrochemical industry. Aromatic hydrocarbons, especially benzene, toluene, and xylene, are among the most important basic raw materials in petrochemical production. They are obtained through processes such as petroleum cracking and reforming, and further transformed into various petrochemical products. The supply of these basic raw materials provides a solid foundation for the development of the petrochemical industry. They are important raw materials for manufacturing polymer materials such as synthetic resins, synthetic rubbers, and synthetic fibers. For example, benzene can be used to manufacture plastics such as polystyrene, while xylene can be used to manufacture polyester fibers. These synthetic materials are widely used in packaging, construction, transportation, electronics, communications, and medical fields, playing a significant role in promoting the development of modern industry. Aromatic hydrocarbons can also be used as solvents or additives. In the coatings, paints, and inks industries, aromatic hydrocarbons, as solvents, can dissolve resins, pigments, and other components to form a uniform coating. Simultaneously, they can also be used as additives for fuels such as gasoline and diesel, improving fuel combustion performance and stability.

[0003] With the continuous advancement and innovation of petrochemical technology, the application fields of aromatics are constantly expanding and deepening. Through advanced technologies such as catalytic cracking and hydrocracking, aromatics can be converted into higher value-added products. This not only improves the utilization efficiency of aromatics but also promotes the industrial upgrading and sustainable development of the petrochemical industry. Therefore, the petrochemical industry should continue to strengthen the research and application of aromatics to drive the sustainable development and progress of the entire industry.

[0004] Selective hydrogenation of catalytic cracking to produce aromatic feedstock is an important petrochemical process. It aims to extract suitable feedstock for aromatic extraction from gasoline obtained through catalytic cracking (such as DCC or RTC processes) by selective hydrogenation. Gasoline obtained from catalytic cracking contains certain amounts of aromatics, gums, and asphaltenes. To produce feedstock suitable for aromatic extraction, these components need to be selectively hydrogenated. The purpose of selective hydrogenation is to hydrogenate and saturate the unsaturated bonds in aromatics while maintaining the stability of the aromatic ring structure, thereby obtaining high-quality aromatic feedstock.

[0005] However, gasoline needs to have a sulfur content of less than 1 ppm before aromatics extraction. Therefore, the catalyst must not only have excellent hydrogenation performance to deeply remove sulfur impurities and saturate all olefins, but also have good aromatics retention capacity to reduce aromatics hydrogenation saturation.

[0006] CN112337488A discloses a method for treating cracked gasoline using a nickel sulfide-based hydrogenation catalyst. The catalyst, prepared with nickel as the main active metal, copper and / or molybdenum as co-active metals, and magnesium-aluminum composite oxide as the dispersion medium, can effectively remove impurities such as sulfur and saturate olefin components in catalytic cracked gasoline. However, the loss of aromatics is relatively high, reaching a loss rate of 10%, and the selectivity of the catalyst needs to be further improved.

[0007] CN108018075A discloses a method for gasoline desulfurization, which can effectively remove sulfur impurities from gasoline and produce high-octane gasoline products. However, for gasoline processing schemes aimed at producing aromatics extraction feedstock, it is difficult to achieve complete olefin saturation.

[0008] CN101724456A discloses a method for producing aromatics extraction feedstock. This method uses two hydrogenation units to process catalytic cracking gasoline to produce aromatics extraction feedstock, effectively reducing the diene value and removing sulfur and nitrogen impurities, thus expanding the range of aromatics feedstocks. However, the catalyst used has poor aromatics selectivity, resulting in an approximately 9.3% reduction in the aromatics content of the product compared to the feedstock. The hydrogenation of aromatics generates a large amount of cycloalkanes, causing aromatics loss and reducing the value of the aromatics extraction feedstock.

[0009] CN103361118A discloses a method for recovering aromatics from gasoline containing olefins and sulfides. The method reduces hydrogen consumption during hydrodesulfurization by extraction and obtains aromatics with higher purity. However, this method is not very adaptable to gasoline feedstocks containing nitrogen oxides and dienes and is not very operable.

[0010] CN101037614A discloses a hydrorefining catalyst, its preparation method, and its application. The catalyst uses molybdenum, cobalt, and nickel as active components, with added additives, and alumina as a support. This catalyst can be used for the two-stage hydrorefining of cracked gasoline, maximizing the hydrogenation of monoolefins while performing hydrodesulfurization. It can adapt to oils with varying sulfur content and high space velocity requirements. However, its adaptability to feedstocks with high nitrogen content, such as catalytic cracked gasoline, needs further investigation. Summary of the Invention

[0011] The purpose of this invention is to overcome the problems existing in the prior art and provide a method for preparing a hydrogenation catalyst, as well as a method for producing hydrogenation catalysts and their applications, and a method for producing aromatic extraction feedstocks. This method improves the stability of the catalyst by adjusting the loading order of the active metals, utilizes the electronic properties of alkali metals for regulation, and introduces organic matter while impregnating the active metals to promote better dispersion of the active metals on the support and achieve better bonding between the active metals.

[0012] To achieve the above objectives, a first aspect of the present invention provides a method for preparing a hydrogenation catalyst, wherein the method includes:

[0013] (1) Nickel and alkali metals and / or alkaline earth metals are loaded onto a support and then calcined to obtain a modified support.

[0014] (2) Cobalt, molybdenum and the first organic compound are loaded onto a modified support, and then subjected to hydrothermal treatment and a first post-treatment to obtain a catalyst precursor;

[0015] (3) The second organic compound is loaded onto the catalyst precursor and then subjected to hydrogenolysis to obtain the catalyst.

[0016] A second aspect of the present invention provides a hydrogenation catalyst prepared by the method described in the first aspect.

[0017] The third aspect of this invention provides the application of the hydrogenation catalyst described in the second aspect in the gasoline hydrogenation reaction.

[0018] A fourth aspect of the present invention provides a method for producing aromatic extraction feedstock, wherein the method includes: hydrogenating the feedstock in the presence of a catalyst, wherein the catalyst is the hydrogenation catalyst of claim 12, and the feedstock is gasoline feedstock.

[0019] Compared with the prior art, the present invention achieves the following outstanding technical effects:

[0020] The method of this invention adjusts the bonding state between the active metal and the support by using different impregnation sequences, and utilizes alkali metals and / or alkaline earth metals to regulate the electronic properties of the active metal. By leveraging the synergistic effect of multiple active metals, the competition and selection among the catalyst's hydrodesulfurization, olefin saturation, and aromatic hydrogenation are improved, thereby enhancing the catalyst's aromatic selectivity.

[0021] The method of the present invention, through the addition of organic matter twice, can, on the one hand, modulate the binding state between active metals, which helps to exert the synergistic effect between active metals; on the other hand, through hydrogenolysis, the organic matter forms highly condensed organic matter at specific positions of the support and active metals, which effectively regulates the selectivity of the catalyst.

[0022] The method of the present invention preferably utilizes ultrasonic impregnation to improve the dispersion of active metals on the carrier; furthermore, it utilizes a hydrothermal environment to promote the micro-carbonization of organic matter, which encapsulates and blocks the active metals, reduces the disordered aggregation and growth of metal oxides during calcination, and enhances the dispersibility of active metals.

[0023] The method of the present invention, using the catalyst of the present invention, can effectively utilize gasoline feedstock containing high aromatics to obtain aromatic extraction feedstock with high aromatic retention and qualified sulfur impurities through hydrogenation. It has a very good selective effect in desulfurization, deeply removing sulfur impurities. It achieves the goal of effectively removing sulfur impurities and saturated olefin components from gasoline feedstock while reducing the occurrence of aromatic component hydrogenation reaction and improving aromatic retention. Detailed Implementation

[0024] 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.

[0025] The first aspect of this invention provides a method for preparing a hydrogenation catalyst, wherein the method includes:

[0026] (1) Nickel and alkali metals and / or alkaline earth metals are loaded onto a support and then calcined to obtain a modified support.

[0027] (2) Cobalt, molybdenum and the first organic compound are loaded onto a modified support, and then subjected to hydrothermal treatment and a first post-treatment to obtain a catalyst precursor;

[0028] (3) The second organic compound is loaded onto the catalyst precursor and then subjected to hydrogenolysis to obtain the catalyst.

[0029] The method of this invention adjusts the bonding state between the active metal and the support by using different impregnation sequences, and utilizes alkali metals and / or alkaline earth metals to regulate the electronic properties of the active metal. By leveraging the synergistic effect of multiple active metals, the competition and selection among the catalyst's hydrodesulfurization, olefin saturation, and aromatic hydrogenation are improved, thereby enhancing the catalyst's aromatic selectivity.

[0030] The method of the present invention, through the addition of organic matter twice, can, on the one hand, modulate the binding state between active metals, which helps to exert the synergistic effect between active metals; on the other hand, through hydrogenolysis, the organic matter forms highly condensed organic matter at specific positions of the support and active metals, which effectively regulates the selectivity of the catalyst.

[0031] The method of the present invention preferably utilizes ultrasonic impregnation to improve the dispersion of active metals on the carrier; furthermore, it utilizes a hydrothermal environment to promote the micro-carbonization of organic matter, which encapsulates and blocks the active metals, reduces the disordered aggregation and growth of metal oxides during calcination, and enhances the dispersibility of active metals.

[0032] In this invention, the type of carrier is not particularly limited. Preferably, in step (1), the carrier is a porous material, preferably selected from at least one of alumina, silicon oxide, alumina-silicon oxide, titanium oxide, alumina-titanium oxide, silicon oxide-zirconium oxide, silicon oxide-thorium oxide, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium oxide, titanium oxide-zirconium oxide, silicon oxide-alumina-thorium oxide, silicon oxide-alumina-titanium oxide, and silicon oxide-alumina-zirconium oxide.

[0033] In this invention, the type of alkali metal is not particularly limited. Preferably, in step (1), the alkali metal is selected from at least one of Li, Na, and K, and preferably K.

[0034] In this invention, the type of alkaline earth metal is not particularly limited. Preferably, in step (1), the alkaline earth metal is selected from at least one of Ca, Mg, Sr and Ba, and more preferably Ca and / or Mg.

[0035] In this invention, the specific operation method of the impregnation method in step (1) is not particularly limited. Preferably, step (1) includes:

[0036] (1-1) Nickel is loaded onto the support by impregnation to obtain a nickel-containing support precursor, and then a first calcination is performed to obtain a nickel-containing support;

[0037] (1-2) An alkali metal and / or alkaline earth metal are loaded onto a nickel-containing support by an impregnation method to obtain a nickel-, alkali metal and / or alkaline earth metal support precursor, which is then subjected to a second calcination to obtain a modified support.

[0038] In this invention, preferably, nickel is saturated or supersaturated with a metal salt solution to impregnate the carrier.

[0039] In this invention, the type of nickel metal salt is not particularly limited, as long as nickel element can be provided. Preferably, the nickel metal salt is selected from at least one of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride, and nickel sulfate.

[0040] In this invention, high-temperature calcination effectively reduces the proportion of metallic nickel on the carrier surface. The metallic nickel binds to the carrier and penetrates the carrier structure to form spinel, further reducing its surface proportion. Preferably, in step (1-1), compared to the nickel-to-aluminum ratio n1 on the nickel-containing carrier precursor surface, the variation ratio n2 of the nickel-to-aluminum ratio on the nickel-containing carrier surface is 10-40%, for example, it can be 10%, 15%, 20%, 25%, 30%, 35%, or 40%.

[0041] In this invention, X-ray photoelectron spectroscopy (XPS) is used to characterize and analyze the samples. Specific testing conditions are as follows: XPS analysis of the samples was performed using a Thermo Scientific ESCALab250 X-ray photoelectron spectrometer. The excitation source was non-monochromatic Al Kα X-rays with a power of 300 W. The baseline vacuum of the analysis chamber was approximately 3 × 10⁻⁶. -7 Pa. Energy correction was performed using the C1s peak (284.6 eV). During testing, the sample was uniformly coated onto the indium foil of the sample holder, and then the sample holder was placed in the preparation chamber of the XPS instrument. After 8 hours of gas extraction, the sample was introduced into the analysis chamber. The accompanying analysis software was used to perform peak fitting on the energy spectrum data of the elements to obtain the elemental proportions on the sample surface. The change ratio was then calculated as (1-n2 / n1)×100%.

[0042] In this invention, the conditions for the first roasting are not particularly limited. Preferably, in step (1-1), the conditions for the first roasting include: a temperature of 500-700℃ and a time of 1-8 hours; preferably, in step (1-1), the conditions for the first roasting include: a temperature of 550-650℃ and a time of 2-6 hours.

[0043] In this invention, preferably, the first calcination is carried out in an oxygen-containing atmosphere, and more preferably in an air atmosphere.

[0044] In this invention, preferably, step (1-1) further includes: heat-treating the nickel-containing carrier precursor before the first calcination. In this invention, preferably, the heat treatment is a first drying treatment, the conditions of which include: a temperature of 40-180°C, preferably 60-160°C, and a time of 1-8 hours, preferably 2-6 hours.

[0045] In this invention, preferably, alkali metals and / or alkaline earth metals are saturated or supersaturated impregnated with the carrier in the form of metal salt solutions.

[0046] In this invention, the types of alkali metal and / or alkaline earth metal salts are not particularly limited, as long as the alkali metal and / or alkaline earth metal elements can be provided. Preferably, the alkali metal and / or alkaline earth metal salts can be one or more of the corresponding nitrates, acetates, basic carbonates, and chlorides.

[0047] In this invention, preferably, in steps (1-2), compared to the ratio m1 of alkali metal and / or alkaline earth metal to aluminum on the surface of the nickel-containing, alkali metal and / or alkaline earth metal carrier precursor, the ratio m2 of alkali metal and / or alkaline earth metal to aluminum on the modified carrier surface varies by 10-40%, for example, it can be 10%, 15%, 20%, 25%, 30%, 35%, or 40%. High-temperature calcination effectively modulates the characteristics of the carrier surface, further reducing the number of highly reactive, coordinatingly unsaturated aluminum atoms on the carrier surface, thus altering the surface properties.

[0048] In this invention, X-ray photoelectron spectroscopy (XPS) is used to characterize and analyze the samples. Specific testing conditions are as follows: XPS analysis of the samples was performed using a Thermo Scientific ESCALab250 X-ray photoelectron spectrometer. The excitation source was non-monochromatic Al Kα X-rays with a power of 300 W. The baseline vacuum of the analysis chamber was approximately 3 × 10⁻⁶. -7 Pa. Energy correction was performed using the C1s peak (284.6 eV). During testing, the sample was uniformly coated onto the indium foil of the sample holder, and then the sample holder was placed in the preparation chamber of the XPS instrument. After 8 hours of gas extraction, the sample was introduced into the analysis chamber. The accompanying analysis software was used to perform peak fitting on the energy spectrum data of the elements to obtain the elemental proportions on the sample surface. The change ratio was then calculated as (1-m2 / m1)×100%.

[0049] In this invention, preferably, in step (1-2), the conditions for the second roasting include: a temperature of 300-500℃ and a time of 1-8 hours; preferably, in step (1-2), the conditions for the second roasting include: a temperature of 330-450℃ and a time of 2-6 hours.

[0050] In this invention, preferably, the second calcination is carried out in an oxygen-containing atmosphere, and more preferably in an air atmosphere.

[0051] In this invention, preferably, step (1-2) further includes: heat-treating the nickel-, alkali metal-, and / or alkaline earth metal-containing carrier precursor before the second calcination. In this invention, preferably, the heat treatment is a second drying treatment, the conditions of which include: a temperature of 40-180°C, preferably 60-160°C, and a time of 1-8 hours, preferably 2-6 hours.

[0052] In this invention, preferably, step (2) further includes using an impregnation method to introduce a phosphorus-containing compound, cobalt, molybdenum and a first organic compound onto a modified support.

[0053] In this invention, preferably, the phosphorus-containing compound is selected from at least one of phosphoric acid, metaphosphoric acid, hypophosphoric acid, and phosphorous acid.

[0054] In this invention, preferably, the molar ratio of phosphorus-containing compound to molybdenum atoms, calculated as elements, is 0.1:1 to 1:1, more preferably 0.2:1 to 0.6:1.

[0055] In this invention, the type of the first organic compound is not particularly limited. Preferably, in step (2), the first organic compound is selected from at least one of alcohols, acids, and amines.

[0056] In this invention, preferably, the alcohol compound is selected from at least one of ethylene glycol, glycerol, diethylene glycol, and butanediol.

[0057] In this invention, preferably, the 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, preferably, the amine compound is selected from at least one of ethylenediamine and / or EDTA and its ammonium salt.

[0059] In this invention, preferably, in step (2), the molar ratio of cobalt atoms to the first organic compound based on carbon is 0.1:1-2:1, more preferably 0.5:1-0.8:1.

[0060] In this invention, preferably, the cobalt and molybdenum are prepared as a mixed solution containing metallic cobalt and molybdenum using their respective metal salts.

[0061] In this invention, preferably, the cobalt metal salt is selected from at least one of cobalt nitrate, cobalt acetate, basic cobalt carbonate, cobalt chloride, and cobalt sulfate.

[0062] In this invention, preferably, the metal salt of molybdenum is selected from at least one of ammonium molybdate, ammonium paramolybdate, ammonium phosphomolybdate, and molybdenum oxide.

[0063] In this invention, the order of addition of the first organic compound is not particularly limited. For example, the first organic compound can be added to the prepared mixed solution containing cobalt and molybdenum, or added to the solvent used to prepare the mixed solution in advance. The addition of the first organic compound can complex with the active metals, promote the binding of active metals cobalt and molybdenum, and enhance the synergistic effect between the active metals.

[0064] In this invention, preferably, the impregnation method in step (2) is saturated impregnation or supersaturated impregnation.

[0065] In this invention, preferably, the impregnation method in step (2) is performed under ultrasonic conditions. Ultrasonic impregnation can effectively promote the uniform dispersion of active metals on the carrier, improve the uniformity of the dispersion of active metals on the carrier, and at the same time, through the action of ultrasonic impregnation, strengthen the chemical force combination between active metals and carriers, avoiding the situation in conventional impregnation methods where there is more active metal on the outer surface of the carrier and less in the interior.

[0066] In this invention, the conditions for ultrasonic treatment are not particularly limited. Preferably, the ultrasonic conditions include: an ultrasonic frequency of 20-60 kHz and an ultrasonic duration of 1-5 hours; more preferably, the ultrasonic conditions include: an ultrasonic frequency of 25-45 kHz and an ultrasonic duration of 2-4 hours.

[0067] In this invention, preferably, in step (2), the hydrothermal treatment conditions include: a temperature of 80-260℃ and a time of 1-8 hours; preferably, in step (2), the hydrothermal treatment conditions include: a temperature of 100-200℃ and a time of 2-6 hours. Through hydrothermal treatment, organic matter can be micro-carbonized to a certain extent using the hydrothermal environment, which can encapsulate and block active metals, reduce the disordered aggregation and growth of metal oxides during calcination, and enhance the dispersibility of active metals.

[0068] In this invention, the active metal is transformed from a metal salt to an active metal oxide through a calcination process, thereby enhancing the interaction between the active metal and the support. Preferably, in step (2), the conditions for the first post-treatment include: a temperature of 300-500°C and a time of 1-8 hours; more preferably, in step (2), the conditions for the first post-treatment include: a temperature of 350-450°C and a time of 2-6 hours.

[0069] In this invention, preferably, the first post-processing is carried out in an oxygen-containing atmosphere, and more preferably in an air atmosphere.

[0070] In this invention, the type of the second organic compound in step (3) can be the same as or different from the first organic compound, which will not be elaborated here.

[0071] In this invention, preferably, in step (3), the molar ratio of cobalt atoms to the second organic compound based on carbon is 0.1:1-1:1, more preferably 0.2:1-0.8:1.

[0072] In this invention, preferably, the organic material is used to saturate or supersaturate the catalyst precursor in the form of a solution.

[0073] In this invention, in step (3), the carbon content in the catalyst is 0.3-0.8% by weight, preferably 0.4-0.7% by weight. Through heat treatment in a hydrogen atmosphere, organic matter on the catalyst can be effectively dehydrogenated, while retaining a specific range of carbon deposits. Highly condensed organic matter is formed at specific positions on the support and active metal, which effectively regulates the selectivity of the catalyst.

[0074] In this invention, the carbon content is measured by infrared absorption. The specific test conditions are as follows: the sample and the co-solvent are placed together in a high-frequency induction furnace, oxygen is introduced for combustion, and the generated CO2 gas flows through the infrared absorption cell to absorb infrared energy. The carbon content can be obtained from the change in energy.

[0075] In this invention, preferably, in step (3), the conditions for the post-hydrogenolysis treatment include: a temperature of 300-500℃ and a time of 1-8 hours; preferably, in step (3), the conditions for the post-hydrogenolysis treatment include: a temperature of 350-450℃ and a time of 2-6 hours. Through heat treatment in a hydrogen atmosphere, organic matter on the catalyst can be effectively removed by hydrogenolysis, while retaining a specific range of carbon deposits. Highly condensed organic matter is formed at specific positions on the support and active metal, effectively regulating the selectivity of the catalyst.

[0076] In this invention, preferably, in step (3), the post-hydrogenation treatment is carried out under a hydrogen-containing atmosphere;

[0077] In this invention, preferably, the hydrogen content in the hydrogen-containing atmosphere is 40-100% by volume, based on the total amount of hydrogen in the atmosphere, and more preferably 60-100% by volume.

[0078] In this invention, preferably, the amounts of nickel, alkali metals and / or alkaline earth metals, molybdenum and cobalt are such that, based on the total weight of the catalyst and in terms of oxides, the content of nickel is 0.1-10%, the content of cobalt is 0.1-10%, the content of molybdenum is 5-30%, and the content of alkali metals and / or alkaline earth metals is 0.1-10%.

[0079] A second aspect of the present invention provides a hydrogenation catalyst prepared by the method described in the first aspect.

[0080] The third aspect of this invention provides the application of the hydrogenation catalyst described in the second aspect in the gasoline hydrogenation reaction.

[0081] A fourth aspect of the present invention provides a method for producing aromatic extraction feedstock, wherein the method includes: hydrogenating the feedstock in the presence of a catalyst, wherein the catalyst is the hydrogenation catalyst described in the second aspect, and the feedstock is gasoline feedstock.

[0082] In this invention, preferably, the gasoline feedstock is selected from at least one of catalytic cracking gasoline, catalytic cracking gasoline, steam cracking gasoline, coking gasoline, and reformed gasoline.

[0083] In this invention, preferably, the conditions for the hydrogenation reaction include: a reaction temperature of 180-360°C, a reaction pressure of 1-4 MPa, and a volume hourly space velocity of 1-4 h⁻¹. -1 The hydrogen-to-oil volume ratio is 100-600; preferably, the reaction temperature is 240-360℃, the reaction pressure is 2-3.6MPa, and the volume hourly space velocity is 2-4h. -1 The hydrogen-to-oil volume ratio is 300-500.

[0084] In this invention, the hydrogenation catalyst needs to undergo a sulfidation reaction before the gasoline hydrogenation reaction. The reasons for sulfidation and the conventional sulfidation methods are well known to those skilled in the art. Specific sulfidation methods can be divided into two types: dry sulfidation and wet sulfidation. This invention does not impose any special restrictions on the sulfidation process. If dry sulfidation is used, a combination of hydrogen sulfide and hydrogen can be employed. If wet sulfidation is used, sulfur-containing compounds such as carbon disulfide and dimethyl disulfide can be used as sulfiding agents. The sulfidation reaction is carried out through programmed temperature increases to obtain the maximum hydrogenation activity of the catalyst.

[0085] To illustrate the features of this invention, both the examples and comparative examples used commercial alumina supports from the same batch industrially produced by Zibo Qimao Catalyst Co., Ltd., with a specific surface area of ​​263 m². 2 / g, pore volume is 0.70cm³ 3 / g.

[0086] In this invention, X-ray photoelectron spectroscopy (XPS) is used to characterize and analyze the samples. Specific testing conditions are as follows: XPS analysis of the samples was performed using a Thermo Scientific ESCALab250 X-ray photoelectron spectrometer. The excitation source was non-monochromatic Al Kα X-rays with a power of 300 W. The baseline vacuum of the analysis chamber was approximately 3 × 10⁻⁶. -7 Pa. Energy correction was performed using the C1s peak (284.6 eV). During testing, the sample was uniformly coated on the indium foil of the sample holder, and then the sample holder was placed in the preparation chamber of the XPS instrument. After 8 hours of gas extraction, the sample was introduced into the analysis chamber. Peak fitting was performed on the energy spectrum data of the elements to obtain the elemental proportions on the sample surface.

[0087] In this invention, the carbon content is measured by infrared absorption. The specific test conditions are as follows: the sample and the co-solvent are placed together in a high-frequency induction furnace, oxygen is introduced for combustion, and the generated CO2 gas flows through the infrared absorption cell to absorb infrared energy. The carbon content can be obtained from the change in energy.

[0088] Example 1

[0089] (1) Take 100g of the above-mentioned industrial alumina carrier, weigh 19g of nickel nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of the alumina carrier, impregnate the carrier with this solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 550℃ for 4 hours to obtain nickel-containing carrier A. Then weigh 8.3g of magnesium nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of nickel-containing carrier A, impregnate carrier A with this solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 400℃ for 4 hours to obtain nickel and magnesium-containing carrier B (modified carrier).

[0090] (2) Weigh 2.5g of basic cobalt carbonate, 21g of molybdenum oxide, 6.5g of phosphoric acid and 3.3g of citric acid and add them to 50ml of deionized water. Heat and stir to dissolve evenly. After cooling, make up the volume according to the saturated water absorption rate of the nickel and magnesium carrier B. Use this solution to impregnate the carrier B in an ultrasonic instrument with a frequency of 33kHz for 3 hours to obtain catalyst C1. Put catalyst C1 into a 200mL hydrothermal reactor and hydrothermally treat it at 120℃ for 4 hours to obtain catalyst C2. Treat catalyst C2 at 400℃ in air atmosphere for 4 hours to obtain catalyst C3 (catalyst precursor).

[0091] (3) Take 3.3g of citric acid and add it to 50ml of deionized water. Make up the volume according to the saturated water absorption rate of catalyst C3. Impregnate catalyst C3 with this solution for 2 hours, dry at 120℃ for 4 hours, and treat at 350℃ for 4 hours under normal pressure hydrogen atmosphere to obtain catalyst D1.

[0092] The catalyst activity and aromatic saturation performance were evaluated using a 100 mL fixed-bed reactor. Sulfidation treatment was required before the evaluation. The sulfidation process involved preparing a sulfidated oil containing 2% CS2 by mass, with atmospheric top oil as the carry oil. The catalyst bed was wetted with the sulfidated oil before reaching 150°C. The temperature was then increased to 230°C at a rate of 20°C / hour and held for 6 hours. Finally, the temperature was increased to 300°C at a rate of 15°C / hour and held for 4 hours. After sulfidation, the catalyst was switched to a different feedstock (catalytic cracking gasoline) for activity evaluation, examining the catalyst's desulfurization and aromatic saturation selectivity. The evaluation process conditions were: inlet temperature 320°C, reaction pressure 3.2 MPa, hydrogen-to-oil volume ratio 400, and volume hourly space velocity (VHSV) 2 h⁻¹. -1 The evaluation period was 240 hours, with samples taken every 24 hours to analyze the sulfur and aromatic content of the products. The average value was taken as the final activity result. The properties of the crude oil and catalytic cracking feedstock are shown in Tables 1 and 2, the catalyst-related analysis data are shown in Table 3, and the evaluation data are shown in Table 4.

[0093] Example 2

[0094] (1) Take 100g of the above-mentioned industrial alumina carrier, weigh 12g of nickel acetate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of the alumina carrier, impregnate the carrier with the solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 650℃ for 4 hours to obtain nickel-containing carrier A; then weigh 8.3g of magnesium nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of nickel-containing carrier A, impregnate carrier A with the solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 400℃ for 4 hours to obtain nickel and magnesium-containing carrier B.

[0095] (2) Weigh 2.5g of basic cobalt carbonate, 21g of molybdenum oxide, 6.5g of phosphoric acid and 3.3g of citric acid and add them to 50ml of deionized water. Heat and stir to dissolve evenly. After cooling, make up the volume according to the saturated water absorption rate of the nickel and magnesium carrier B. Use this solution to impregnate the carrier B in an ultrasonic instrument with a frequency of 40kHz for 3 hours to obtain catalyst C1. Put catalyst C1 into a 200mL hydrothermal reactor and hydrothermally treat it at 120℃ for 4 hours to obtain catalyst C2. Treat catalyst C2 at 400℃ in air atmosphere for 4 hours to obtain catalyst C3.

[0096] (3) Take 3.3g of citric acid and add it to 50ml of deionized water. Make up the volume according to the saturated water absorption rate of catalyst C3. Impregnate catalyst C3 with this solution for 2 hours, dry at 120℃ for 4 hours, and treat at 300℃ for 6 hours under normal pressure hydrogen atmosphere to obtain catalyst D2.

[0097] The evaluation conditions for the catalyst were the same as in Example 1. The relevant analytical data of the catalyst are shown in Table 3, and the evaluation data are shown in Table 4.

[0098] Example 3

[0099] (1) Take 100g of the above-mentioned industrial alumina carrier, weigh 15g of nickel nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of the alumina carrier, impregnate the carrier with the solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 550℃ for 4 hours to obtain nickel-containing carrier A; then weigh 8.3g of magnesium nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of nickel-containing carrier A, impregnate carrier A with the solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 450℃ for 4 hours to obtain nickel and magnesium-containing carrier B.

[0100] (2) Weigh 5.0g of basic cobalt carbonate, 21g of molybdenum oxide, and 6.5g of phosphoric acid into 50ml of deionized water, heat and stir to dissolve evenly, cool and add 6.5g of citric acid and continue stirring for 2 hours. Make up the volume according to the saturated water absorption rate of the nickel and magnesium carrier B, and impregnate the carrier B with the solution in an ultrasonic instrument at a frequency of 33kHz for 3 hours to obtain catalyst C1. Put catalyst C1 into a 200mL hydrothermal reactor and hydrothermally treat it at 120℃ for 4 hours to obtain catalyst C2. Treat catalyst C2 at 400℃ in air atmosphere for 4 hours to obtain catalyst C3.

[0101] (3) Take 3.3g of citric acid and add it to 50ml of deionized water. Make up the volume according to the saturated water absorption rate of catalyst C3. Impregnate catalyst C3 with this solution for 2 hours, dry at 120℃ for 4 hours, and treat at 350℃ for 4 hours under normal pressure hydrogen atmosphere to obtain catalyst D3.

[0102] The evaluation conditions for the catalyst were the same as in Example 1. The relevant analytical data of the catalyst are shown in Table 3, and the evaluation data are shown in Table 4.

[0103] Example 4

[0104] (1) Take 100g of the above-mentioned industrial alumina carrier, weigh 19g of nickel nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of the alumina carrier, impregnate the carrier with the solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 550℃ for 4 hours to obtain nickel-containing carrier A; then weigh 12.4g of magnesium nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of nickel-containing carrier A, impregnate carrier A with the solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 330℃ for 4 hours to obtain nickel and magnesium-containing carrier B.

[0105] (2) Weigh 2.5g of basic cobalt carbonate, 21g of molybdenum oxide, 8.0g of phosphoric acid and 5.0g of citric acid and add them to 50ml of deionized water. Heat and stir to dissolve evenly. After cooling, make up the volume according to the saturated water absorption rate of the nickel and magnesium carrier B. Use this solution to impregnate the carrier B in an ultrasonic instrument with a frequency of 33kHz for 3 hours to obtain catalyst C1. Put catalyst C1 into a 200mL hydrothermal reactor and hydrothermally treat it at 120℃ for 4 hours to obtain catalyst C2. Treat catalyst C2 at 450℃ in air atmosphere for 2 hours to obtain catalyst C3.

[0106] (3) Take 3.3g of citric acid and add it to 50ml of deionized water. Make up the volume according to the saturated water absorption rate of catalyst C3. Impregnate catalyst C3 with this solution for 2 hours, dry at 120℃ for 4 hours, and treat at 350℃ for 4 hours under normal pressure hydrogen atmosphere to obtain catalyst D4.

[0107] The evaluation conditions for the catalyst were the same as in Example 1. The relevant analytical data of the catalyst are shown in Table 3, and the evaluation data are shown in Table 4.

[0108] Example 5

[0109] (1) Take 100g of the above-mentioned industrial alumina carrier, weigh 19g of nickel nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of the alumina carrier, impregnate the carrier with the solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 500℃ for 4 hours to obtain nickel-containing carrier A; then weigh 3.8g of calcium nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of nickel-containing carrier A, impregnate carrier A with the solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 400℃ for 4 hours to obtain carrier B containing nickel and calcium.

[0110] (2) Weigh 2.5g of basic cobalt carbonate, 21g of molybdenum oxide, 6.5g of phosphoric acid, and 1.5g of ethylene glycol and add them to 50ml of deionized water. Heat and stir to dissolve evenly. After cooling, make up the volume according to the saturated water absorption rate of the nickel and calcium carrier B. Use this solution to impregnate carrier B in an ultrasonic instrument with a frequency of 45kHz for 3 hours to obtain catalyst C1. Put catalyst C1 into a 200mL hydrothermal reactor and hydrothermally treat it at 180℃ for 4 hours to obtain catalyst C2. Treat catalyst C2 at 400℃ in air atmosphere for 4 hours to obtain catalyst C3.

[0111] (3) Take 3.3g of citric acid and add it to 50ml of deionized water. Make up the volume according to the saturated water absorption rate of catalyst C3. Impregnate catalyst C3 with this solution for 2 hours, dry at 120℃ for 4 hours, and treat at 350℃ for 4 hours under normal pressure hydrogen atmosphere to obtain catalyst D5.

[0112] The evaluation conditions for the catalyst were the same as in Example 1. The relevant analytical data of the catalyst are shown in Table 3, and the evaluation data are shown in Table 4.

[0113] Example 6

[0114] (1) Take 100g of the above-mentioned industrial alumina carrier, weigh 19g of nickel nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of the alumina carrier, impregnate the carrier with the solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 550℃ for 4 hours to obtain nickel-containing carrier A; then weigh 8.3g of magnesium nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of nickel-containing carrier A, impregnate carrier A with the solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 400℃ for 4 hours to obtain nickel and magnesium-containing carrier B.

[0115] (2) Weigh 8.0g of basic cobalt carbonate, 25g of molybdenum oxide, 7.9g of phosphoric acid and 4.7g of citric acid and add them to 50ml of deionized water. Heat and stir to dissolve evenly. After cooling, make up the volume according to the saturated water absorption rate of the nickel and magnesium carrier B. Use this solution to impregnate the carrier B in an ultrasonic instrument with a frequency of 33kHz for 3 hours to obtain catalyst C1. Put catalyst C1 into a 200mL hydrothermal reactor and hydrothermally treat it at 100℃ for 6 hours to obtain catalyst C2. Treat catalyst C2 at 400℃ in air atmosphere for 4 hours to obtain catalyst C3.

[0116] (4) Take 5g of citric acid and add it to 50ml of deionized water. Make up the volume according to the saturated water absorption rate of catalyst C3. Impregnate catalyst C3 with this solution for 2 hours, dry at 120℃ for 4 hours, and treat at 380℃ for 3 hours under normal pressure hydrogen atmosphere to obtain catalyst D6.

[0117] The evaluation conditions for the catalyst were the same as in Example 1. The relevant analytical data of the catalyst are shown in Table 3, and the evaluation data are shown in Table 4.

[0118] Example 7

[0119] (1) Take 100g of the above-mentioned industrial alumina carrier, weigh 19g of nickel nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of the alumina carrier, impregnate the carrier with this solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 550℃ for 4 hours to obtain nickel-containing carrier A. Then weigh 8.3g of magnesium nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of nickel-containing carrier A, impregnate carrier A with this solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 400℃ for 4 hours to obtain nickel and magnesium-containing carrier B (modified carrier).

[0120] (2) Weigh 2.5g of basic cobalt carbonate, 21g of molybdenum oxide, 6.5g of phosphoric acid and 3.3g of citric acid and add them to 50ml of deionized water. Heat and stir to dissolve evenly. After cooling, make up the volume according to the saturated water absorption rate of the nickel and magnesium carrier B. Use this solution to impregnate the carrier B in an ultrasonic instrument at a frequency of 20kHz for 1.5 hours to obtain catalyst C1. Put catalyst C1 into a 200mL hydrothermal reactor and hydrothermally treat it at 120℃ for 4 hours to obtain catalyst C2. Treat catalyst C2 at 400℃ in air atmosphere for 4 hours to obtain catalyst C3 (catalyst precursor).

[0121] (3) Take 3.3g of citric acid and add it to 50ml of deionized water. Make up the volume according to the saturated water absorption rate of catalyst C3. Impregnate catalyst C3 with this solution for 2 hours, dry at 120℃ for 4 hours, and treat at 350℃ for 4 hours under normal pressure hydrogen atmosphere to obtain catalyst D7.

[0122] The evaluation conditions for the catalyst were the same as in Example 1. The relevant analytical data of the catalyst are shown in Table 3, and the evaluation data are shown in Table 4.

[0123] Example 8

[0124] (1) Take 100g of the above-mentioned industrial alumina carrier, weigh 19g of nickel nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of the alumina carrier, impregnate the carrier with this solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 550℃ for 4 hours to obtain nickel-containing carrier A. Then weigh 8.3g of magnesium nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of nickel-containing carrier A, impregnate carrier A with this solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 400℃ for 4 hours to obtain nickel and magnesium-containing carrier B (modified carrier).

[0125] (2) Weigh 2.5g of basic cobalt carbonate, 21g of molybdenum oxide, 6.5g of phosphoric acid and 3.3g of citric acid and add them to 50ml of deionized water. Heat and stir to dissolve evenly. After cooling, make up the volume according to the saturated water absorption rate of the nickel and magnesium carrier B. Use this solution to impregnate the carrier B in an ultrasonic instrument with a frequency of 33kHz for 3 hours to obtain catalyst C1. Put catalyst C1 into a 200mL hydrothermal reactor and hydrothermally treat it at 120℃ for 4 hours to obtain catalyst C2. Treat catalyst C2 at 400℃ in air atmosphere for 4 hours to obtain catalyst C3 (catalyst precursor).

[0126] (3) Take 3.3g of citric acid and add it to 50ml of deionized water. Make up the volume according to the saturated water absorption rate of catalyst C3. Impregnate catalyst C3 with this solution for 2 hours, dry at 120℃ for 4 hours, and treat at 450℃ for 1.5 hours under an atmosphere of 60% hydrogen gas and 40% nitrogen gas to obtain catalyst D8.

[0127] The evaluation conditions for the catalyst were the same as in Example 1. The relevant analytical data of the catalyst are shown in Table 3, and the evaluation data are shown in Table 4.

[0128] Example 9

[0129] (1) Take 100g of the above-mentioned industrial alumina carrier, weigh 19g of nickel nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of the alumina carrier, impregnate the carrier with this solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 500℃ for 2 hours to obtain nickel-containing carrier A. Then weigh 8.3g of magnesium nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of nickel-containing carrier A, impregnate carrier A with this solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 400℃ for 4 hours to obtain nickel and magnesium-containing carrier B (modified carrier).

[0130] (2) Weigh 2.5g of basic cobalt carbonate, 21g of molybdenum oxide, 6.5g of phosphoric acid and 3.3g of citric acid and add them to 50ml of deionized water. Heat and stir to dissolve evenly. After cooling, make up the volume according to the saturated water absorption rate of the nickel and magnesium carrier B. Use this solution to impregnate the carrier B in an ultrasonic instrument with a frequency of 33kHz for 3 hours to obtain catalyst C1. Put catalyst C1 into a 200mL hydrothermal reactor and hydrothermally treat it at 120℃ for 4 hours to obtain catalyst C2. Treat catalyst C2 at 400℃ in air atmosphere for 4 hours to obtain catalyst C3 (catalyst precursor).

[0131] (3) Take 3.3g of citric acid and add it to 50ml of deionized water. Make up the volume according to the saturated water absorption rate of catalyst C3. Impregnate catalyst C3 with this solution for 2 hours, dry at 120℃ for 4 hours, and treat at 350℃ for 4 hours under normal pressure hydrogen atmosphere to obtain catalyst D9.

[0132] The evaluation conditions for the catalyst were the same as in Example 1. The relevant analytical data of the catalyst are shown in Table 3, and the evaluation data are shown in Table 4.

[0133] Example 10

[0134] (1) Take 100g of the above-mentioned industrial alumina carrier, weigh 19g of nickel nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of the alumina carrier, impregnate the carrier with this solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 550℃ for 4 hours to obtain nickel-containing carrier A. Then weigh 8.3g of magnesium nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of nickel-containing carrier A, impregnate carrier A with this solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 300℃ for 2 hours to obtain nickel and magnesium-containing carrier B (modified carrier).

[0135] (2) Weigh 2.5g of basic cobalt carbonate, 21g of molybdenum oxide, 6.5g of phosphoric acid and 3.3g of citric acid and add them to 50ml of deionized water. Heat and stir to dissolve evenly. After cooling, make up the volume according to the saturated water absorption rate of the nickel and magnesium carrier B. Use this solution to impregnate the carrier B in an ultrasonic instrument with a frequency of 33kHz for 3 hours to obtain catalyst C1. Put catalyst C1 into a 200mL hydrothermal reactor and hydrothermally treat it at 120℃ for 4 hours to obtain catalyst C2. Treat catalyst C2 at 400℃ in air atmosphere for 4 hours to obtain catalyst C3 (catalyst precursor).

[0136] (3) Take 3.3g of citric acid and add it to 50ml of deionized water. Make up the volume according to the saturated water absorption rate of catalyst C3. Impregnate catalyst C3 with this solution for 2 hours, dry at 120℃ for 4 hours, and treat at 350℃ for 4 hours under normal pressure hydrogen atmosphere to obtain catalyst D10.

[0137] The evaluation conditions for the catalyst were the same as in Example 1. The relevant analytical data of the catalyst are shown in Table 3, and the evaluation data are shown in Table 4.

[0138] Comparative Example 1

[0139] (1) Take 100g of the above-mentioned industrial alumina carrier, weigh 19g of nickel nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of the alumina carrier, impregnate the carrier with this solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 550℃ for 4 hours to obtain nickel-containing carrier A. Then weigh 8.3g of magnesium nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of nickel-containing carrier A, impregnate carrier A with this solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 400℃ for 4 hours to obtain nickel and magnesium-containing carrier B (modified carrier).

[0140] (2) Weigh 2g of cobalt nitrate, 25g of ammonium metatungstate, 6.5g of phosphoric acid and 3.3g of citric acid and add them to 50ml of deionized water. Heat and stir to dissolve evenly. After cooling, make up the volume according to the saturated water absorption rate of the nickel and magnesium carrier B. Use this solution to impregnate the carrier B in an ultrasonic instrument with a frequency of 33kHz for 3 hours to obtain catalyst C1. Put catalyst C1 into a 200mL hydrothermal reactor and hydrothermally treat it at 120℃ for 4 hours to obtain catalyst C2. Treat catalyst C2 at 400℃ in air atmosphere for 4 hours to obtain catalyst C3 (catalyst precursor).

[0141] (3) Take 3.3g of citric acid and add it to 50ml of deionized water. Make up the volume according to the saturated water absorption rate of catalyst C3. Impregnate catalyst C3 with this solution for 2 hours, dry at 120℃ for 4 hours, and treat at 350℃ for 4 hours under normal pressure hydrogen atmosphere to obtain catalyst F1.

[0142] The evaluation conditions for the catalyst were the same as in Example 1. The relevant analytical data of the catalyst are shown in Table 3, and the evaluation data are shown in Table 4.

[0143] Comparative Example 2

[0144] (1) Take 100g of the above-mentioned industrial alumina carrier, dry it at 120℃ for 4 hours, and calcine it at 550℃ for 4 hours to obtain carrier A. Then weigh 8.3g of magnesium nitrate, add it to 50ml of deionized water, stir to dissolve evenly, make up the volume according to the saturated water absorption rate of carrier A, impregnate carrier A with this solution for 2 hours, dry it at 120℃ for 4 hours, and calcine it at 400℃ for 4 hours to obtain magnesium-containing carrier B (modified carrier).

[0145] (2) Weigh 19g of nickel nitrate, 2.5g of basic cobalt carbonate, 21g of molybdenum oxide, 6.5g of phosphoric acid, and 3.3g of citric acid and add them to 50ml of deionized water. Heat and stir to dissolve evenly. After cooling, make up the volume according to the saturated water absorption rate of magnesium-containing support B. Use this solution to impregnate support B in an ultrasonic instrument with a frequency of 33kHz for 3 hours to obtain catalyst C1. Put catalyst C1 into a 200mL hydrothermal reactor and hydrothermally treat it at 120℃ for 4 hours to obtain catalyst C2. Treat catalyst C2 at 400℃ in air atmosphere for 4 hours to obtain catalyst C3 (catalyst precursor).

[0146] (3) Take 3.3g of citric acid and add it to 50ml of deionized water. Make up the volume according to the saturated water absorption rate of catalyst C3. Impregnate catalyst C3 with this solution for 2 hours, dry at 120℃ for 4 hours, and treat at 350℃ for 4 hours under normal pressure hydrogen atmosphere to obtain catalyst F2.

[0147] The evaluation conditions for the catalyst were the same as in Example 1. The relevant analytical data of the catalyst are shown in Table 3, and the evaluation data are shown in Table 4.

[0148] Comparative Example 3

[0149] (1) Take 100g of the above-mentioned industrial alumina carrier, weigh 8.3g of magnesium nitrate, add it to 50ml of deionized water, stir and dissolve evenly, adjust the volume according to the saturated water absorption rate of the alumina carrier, impregnate the alumina carrier with the solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 400℃ for 4 hours to obtain magnesium-containing carrier B.

[0150] (2) Weigh 2.5g of basic cobalt carbonate, 21g of molybdenum oxide, 6.5g of phosphoric acid and 3.3g of citric acid and add them to 50ml of deionized water. Heat and stir to dissolve evenly. After cooling, make up the volume according to the saturated water absorption rate of magnesium-containing carrier B. Use this solution to impregnate carrier B in an ultrasonic instrument with a frequency of 33kHz for 3 hours to obtain catalyst C1. Put catalyst C1 into a 200mL hydrothermal reactor and hydrothermally treat it at 120℃ for 4 hours to obtain catalyst C2. Treat catalyst C2 at 400℃ in air atmosphere for 4 hours to obtain catalyst C3.

[0151] (3) Take 3.3g of citric acid and add it to 50ml of deionized water. Make up the volume according to the saturated water absorption rate of catalyst C3. Impregnate catalyst C3 with this solution for 2 hours, dry at 120℃ for 4 hours, and treat at 350℃ for 4 hours under normal pressure hydrogen atmosphere to obtain catalyst F3.

[0152] The evaluation conditions for the catalyst were the same as in Example 1. The relevant analytical data of the catalyst are shown in Table 3, and the evaluation data are shown in Table 4.

[0153] Comparative Example 4

[0154] (1) Take 100g of the above-mentioned industrial alumina carrier, weigh 19g of nickel nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of the alumina carrier, impregnate the carrier with the solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 400℃ for 4 hours to obtain nickel-containing carrier A; then weigh 8.3g of magnesium nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of nickel-containing carrier A, impregnate carrier A with the solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 550℃ for 4 hours to obtain nickel and magnesium-containing carrier B.

[0155] (2) Weigh 2.5g of basic cobalt carbonate, 21g of molybdenum oxide, and 6.5g of phosphoric acid and add them to 50ml of deionized water. Heat and stir to dissolve evenly. After cooling, make up the volume according to the saturated water absorption rate of the nickel and magnesium carrier B. Use this solution to impregnate the carrier B in an ultrasonic instrument with a frequency of 33kHz for 3 hours to obtain catalyst C1. Put catalyst C1 into a 200mL hydrothermal reactor and hydrothermally treat it at 120℃ for 4 hours to obtain catalyst C2. Treat catalyst C2 at 400℃ in air atmosphere for 4 hours to obtain catalyst C3.

[0156] (3) Take 3.3g of citric acid and add it to 50ml of deionized water. Make up the volume according to the saturated water absorption rate of catalyst C3. Impregnate catalyst C3 with this solution for 2 hours, dry at 120℃ for 4 hours, and treat at 350℃ for 4 hours under normal pressure hydrogen atmosphere to obtain catalyst F4.

[0157] The evaluation conditions for the catalyst were the same as in Example 1. The relevant analytical data of the catalyst are shown in Table 3, and the evaluation data are shown in Table 4.

[0158] Comparative Example 5

[0159] (1) Take 100g of the above-mentioned industrial alumina carrier, weigh 19g of nickel nitrate, add it to 50ml of deionized water, stir to dissolve evenly, and make up the volume according to the saturated water absorption rate of the alumina carrier. Impregnate the carrier with this solution for 2 hours, and dry it at 120℃ for 4 hours to obtain nickel-containing carrier A. Then weigh 8.3g of magnesium nitrate, add it to 50ml of deionized water, stir to dissolve evenly, and make up the volume according to the saturated water absorption rate of nickel-containing carrier A. Impregnate carrier A with this solution for 2 hours, dry it at 120℃ for 4 hours, and calcine it at 400℃ for 4 hours to obtain nickel and magnesium-containing carrier B (modified carrier).

[0160] (2) Weigh 2.5g of basic cobalt carbonate, 21g of molybdenum oxide, 6.5g of phosphoric acid and 3.3g of citric acid and add them to 50ml of deionized water. Heat and stir to dissolve evenly. After cooling, make up the volume according to the saturated water absorption rate of the nickel and magnesium carrier B. Use this solution to impregnate the carrier B in an ultrasonic instrument with a frequency of 33kHz for 3 hours to obtain catalyst C1. Put catalyst C1 into a 200mL hydrothermal reactor and hydrothermally treat it at 120℃ for 4 hours to obtain catalyst C2. Treat catalyst C2 at 400℃ in air atmosphere for 4 hours to obtain catalyst C3 (catalyst precursor).

[0161] (3) Take 3.3g of citric acid and add it to 50ml of deionized water. Make up the volume according to the saturated water absorption rate of catalyst C3. Impregnate catalyst C3 with this solution for 2 hours, dry at 120℃ for 4 hours, and treat at 350℃ for 4 hours under normal pressure hydrogen atmosphere to obtain catalyst F5.

[0162] The evaluation conditions for the catalyst were the same as in Example 1. The relevant analytical data of the catalyst are shown in Table 3, and the evaluation data are shown in Table 4.

[0163] Comparative Example 6

[0164] (1) Take 100g of the above-mentioned industrial alumina carrier, weigh 19g of nickel nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of the alumina carrier, impregnate the carrier with this solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 550℃ for 4 hours to obtain nickel-containing carrier A. Then weigh 8.3g of magnesium nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of nickel-containing carrier A, impregnate carrier A with this solution for 2 hours, and dry at 120℃ for 4 hours to obtain nickel and magnesium-containing carrier B (modified carrier).

[0165] (2) Weigh 2.5g of basic cobalt carbonate, 21g of molybdenum oxide, 6.5g of phosphoric acid and 3.3g of citric acid and add them to 50ml of deionized water. Heat and stir to dissolve evenly. After cooling, make up the volume according to the saturated water absorption rate of the nickel and magnesium carrier B. Use this solution to impregnate the carrier B in an ultrasonic instrument with a frequency of 33kHz for 3 hours to obtain catalyst C1. Put catalyst C1 into a 200mL hydrothermal reactor and hydrothermally treat it at 120℃ for 4 hours to obtain catalyst C2. Treat catalyst C2 at 400℃ in air atmosphere for 4 hours to obtain catalyst C3 (catalyst precursor).

[0166] (3) Take 3.3g of citric acid and add it to 50ml of deionized water. Make up the volume according to the saturated water absorption rate of catalyst C3. Impregnate catalyst C3 with this solution for 2 hours, dry at 120℃ for 4 hours, and treat at 350℃ for 4 hours under normal pressure hydrogen atmosphere to obtain catalyst F6.

[0167] The evaluation conditions for the catalyst were the same as in Example 1. The relevant analytical data of the catalyst are shown in Table 3, and the evaluation data are shown in Table 4.

[0168] Comparative Example 7

[0169] (1) Take 100g of the above-mentioned industrial alumina carrier, weigh 19g of nickel nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of the alumina carrier, impregnate the carrier with this solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 550℃ for 4 hours to obtain nickel-containing carrier A. Then weigh 8.3g of magnesium nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of nickel-containing carrier A, impregnate carrier A with this solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 400℃ for 4 hours to obtain nickel and magnesium-containing carrier B (modified carrier).

[0170] (2) Weigh 2.5g of basic cobalt carbonate, 21g of molybdenum oxide, 6.5g of phosphoric acid and 3.3g of citric acid and add them to 50ml of deionized water. Heat and stir to dissolve evenly. After cooling, make up the volume according to the saturated water absorption rate of the nickel and magnesium carrier B. Use this solution to impregnate carrier B in an ultrasonic instrument with a frequency of 33kHz for 3 hours to obtain catalyst C1. Treat catalyst C1 at 400℃ in air atmosphere for 4 hours to obtain catalyst C2 (catalyst precursor).

[0171] (3) Take 3.3g of citric acid and add it to 50ml of deionized water. Make up the volume according to the saturated water absorption rate of catalyst C2. Impregnate catalyst C2 with this solution for 2 hours, dry at 120℃ for 4 hours, and treat at 350℃ for 4 hours under normal pressure hydrogen atmosphere to obtain catalyst F7.

[0172] The evaluation conditions for the catalyst were the same as in Example 1. The relevant analytical data of the catalyst are shown in Table 3, and the evaluation data are shown in Table 4.

[0173] Comparative Example 8

[0174] (1) Take 100g of the above-mentioned industrial alumina carrier, weigh 19g of nickel nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of the alumina carrier, impregnate the carrier with this solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 550℃ for 4 hours to obtain nickel-containing carrier A. Then weigh 8.3g of magnesium nitrate, add it to 50ml of deionized water, stir and dissolve evenly, make up the volume according to the saturated water absorption rate of nickel-containing carrier A, impregnate carrier A with this solution for 2 hours, dry at 120℃ for 4 hours, and calcine at 400℃ for 4 hours to obtain nickel and magnesium-containing carrier B (modified carrier).

[0175] (2) Weigh 2.5g of basic cobalt carbonate, 21g of molybdenum oxide, 6.5g of phosphoric acid and 3.3g of citric acid and add them to 50ml of deionized water. Heat and stir to dissolve evenly. After cooling, make up the volume according to the saturated water absorption rate of the nickel and magnesium carrier B. Use this solution to impregnate the carrier B in an ultrasonic instrument with a frequency of 33kHz for 3 hours to obtain catalyst C1. Put catalyst C1 into a 200mL hydrothermal reactor and hydrothermally treat it at 120℃ for 4 hours to obtain catalyst C2. Treat catalyst C2 at 400℃ in air atmosphere for 4 hours to obtain catalyst C3 (catalyst precursor).

[0176] (3) Take 3.3g of citric acid and add it to 50ml of deionized water. Make up the volume according to the saturated water absorption rate of catalyst C3. Impregnate catalyst C3 with this solution for 2 hours and dry it at 120℃ for 4 hours to obtain catalyst F8.

[0177] The evaluation conditions for the catalyst were the same as in Example 1. The relevant analytical data of the catalyst are shown in Table 3, and the evaluation data are shown in Table 4.

[0178] Table 1

[0179] Component Name | Value | Thiol | Sulfur (mg / kg) | <2 | Sulfur Content (mg / L) | Density (kg / m³) | 713.3 | Colorimetric Number | >30 | Total Acid Value (mg) | KOH (g) | <0.02 | Zn (mg / kg) | <0.1 | Basic Nitrogen (mg / kg) | <1 | Nitrogen Content (mg / L) | <0.2 surface

[0180] Table 2

[0181] Component Name, Value, Thiol, Sulfur (ppm), 38, Density (20℃), kg / m³ 3 799.7 Bromine value, gBr / 100mL 41 Nitrogen, μg / g 56 Sulfur, μg / g 320 Aromatics / % 56 Diene value / (gI2 / 100g) 6.1 Distillation range / ℃ 50-190 surface

[0182] Table 3

[0183]

[0184] Note: The percentage change in n before and after the first roasting treatment = (1-n2 / n1)×100%; the percentage change in m before and after the second roasting treatment = (1-m2 / m1)×100%.

[0185] Table 4

[0186]

[0187] As can be seen from the above examples, the gasoline hydrogenation catalyst prepared by the present invention, under the same evaluation conditions, has a lower aromatic loss rate when the sulfur content in the product is less than 1 μg / g, which meets the requirements for aromatic extraction feedstock. In particular, it has a good desulfurization effect and can have better selectivity for aromatic hydrogenation. While efficiently removing sulfur impurities, it effectively retains the aromatics in the feedstock, providing high-quality feedstock for aromatic extraction.

[0188] 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, wherein, The method includes: (1) loading nickel and alkali metals and / or alkaline earth metals onto a support and then calcining them to obtain a modified support; (2) loading cobalt, molybdenum and a first organic compound onto the modified support and then performing hydrothermal treatment and a first post-treatment to obtain a catalyst precursor; (3) loading a second organic compound onto the catalyst precursor and then performing hydrogenolysis post-treatment to obtain a catalyst.

2. The method according to claim 1, wherein, In step (1), the carrier is a porous material, preferably selected from at least one of alumina, silicon oxide, alumina-silicon oxide, titanium oxide, alumina-titanium oxide, silicon oxide-zirconium oxide, silicon oxide-thorium oxide, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium oxide, titanium oxide-zirconium oxide, silicon oxide-alumina-thorium oxide, silicon oxide-alumina-titanium oxide, and silicon oxide-alumina-zirconium oxide; preferably, in step (1), the alkali metal is selected from at least one of Li, Na, and K; preferably, in step (1), the alkaline earth metal is selected from at least one of Ca, Mg, Sr, and Ba.

3. The method according to claim 1 or 2, wherein, Step (1) includes: (1-1) loading nickel onto a support using an impregnation method to obtain a nickel-containing support precursor, and then performing a first calcination to obtain a nickel-containing support; (1-2) loading alkali metals and / or alkaline earth metals onto a nickel-containing support using an impregnation method to obtain a nickel-, alkali metals and / or alkaline earth metals-containing support precursor, and then performing a second calcination to obtain a modified support.

4. The method according to claim 3, wherein, In step (1-1), the ratio of nickel to aluminum on the surface of the nickel-containing carrier, n2, changes by 10-40% compared to the ratio n1 of nickel to aluminum on the surface of the nickel-containing carrier precursor. Preferably, in step (1-1), the conditions for the first calcination include: a temperature of 500-700℃ and a time of 1-8 hours. Preferably, in step (1-1), the conditions for the first calcination include: a temperature of 550-650℃ and a time of 2-6 hours.

5. The method according to claim 3, wherein, In step (1-2), compared to the ratio m1 of alkali metal and / or alkaline earth metal to aluminum on the surface of the nickel-containing, alkali metal and / or alkaline earth metal carrier precursor, the ratio m2 of alkali metal and / or alkaline earth metal to aluminum on the surface of the modified carrier changes by 10-40%; preferably, in step (1-2), the conditions for the second calcination include: a temperature of 300-500℃ and a time of 1-8 hours; preferably, in step (1-2), the conditions for the second calcination include: a temperature of 330-450℃ and a time of 2-6 hours.

6. The method according to claim 1 or 2, wherein, Step (2) further includes introducing a phosphorus-containing compound, cobalt, molybdenum and a first organic compound onto a modified support by impregnation; preferably, the phosphorus-containing compound is selected from at least one of phosphoric acid, metaphosphoric acid, hypophosphoric acid and phosphorous acid; preferably, the molar ratio of the phosphorus-containing compound to molybdenum atoms is 0.1:1-1:1, preferably 0.2:1-0.6:

1.

7. The method according to claim 1 or 2, wherein, In step (2), the first organic compound is selected from at least one of alcohols, acids, and amines; preferably, the alcohol is selected from at least one of ethylene glycol, glycerol, diethylene glycol, and butanediol; preferably, the acid 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; preferably, the amine is selected from at least one of ethylenediamine and / or EDTA and its ammonium salt; preferably, in step (2), the molar ratio of cobalt atoms to the first organic compound based on carbon is 0.1:1-2:1, preferably 0.1:1-0.8:

1.

8. The method according to claim 1 or 2, wherein, The impregnation method in step (2) is carried out under ultrasonic conditions; preferably, the ultrasonic conditions include: the frequency of the ultrasonic wave is 20-60 kHz and the ultrasonic time is 1-5 hours; more preferably, the ultrasonic conditions include: the frequency of the ultrasonic wave is 25-45 kHz and the ultrasonic time is 2-4 hours.

9. The method according to claim 1 or 2, wherein, In step (2), the conditions for hydrothermal treatment include: a temperature of 80-260℃ and a time of 1-8 hours; preferably, in step (2), the conditions for hydrothermal treatment include: a temperature of 100-200℃ and a time of 2-6 hours; preferably, in step (2), the conditions for the first post-treatment include: a temperature of 300-500℃ and a time of 1-8 hours; more preferably, in step (2), the conditions for the first post-treatment include: a temperature of 350-450℃ and a time of 2-6 hours.

10. The method according to claim 1 or 2, wherein, In step (3), the second organic compound is selected from at least one of alcohols, acids, and amines; preferably, the alcohol is selected from at least one of ethylene glycol, glycerol, diethylene glycol, and butanediol; preferably, the acid 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; preferably, the amine is selected from at least one of ethylenediamine and / or EDTA and its ammonium salt; preferably, in step (3), the molar ratio of cobalt atoms to the second organic compound based on carbon is 0.1:1-1:1, preferably 0.2:1-0.8:

1.

11. The method according to claim 1 or 2, wherein, In step (3), the carbon content in the catalyst is 0.3-0.8% by weight, preferably 0.4-0.7% by weight; preferably, in step (3), the conditions for the hydrogenolysis post-treatment include: a temperature of 300-500℃ and a time of 1-8 hours; preferably, in step (3), the conditions for the hydrogenolysis post-treatment include: a temperature of 350-450℃ and a time of 2-6 hours; preferably, in step (3), the hydrogenolysis post-treatment is carried out in a hydrogen-containing atmosphere; preferably, in the hydrogen-containing atmosphere, the hydrogen content is 40-100% by volume, preferably 60-100% by volume, based on the total amount of hydrogen in the atmosphere.

12. The method according to claim 1 or 2, wherein, The amounts of nickel, alkali metals and / or alkaline earth metals, molybdenum and cobalt are such that, based on the total weight of the catalyst, the content of nickel is 0.1-10%, the content of cobalt is 0.1-15%, the content of molybdenum is 5-30%, and the content of alkali metals and / or alkaline earth metals is 0.1-10% in terms of oxides.

13. The hydrogenation catalyst prepared by the method of any one of claims 1-12.

14. The application of the hydrogenation catalyst according to claim 13 in the hydrogenation reaction of gasoline.

15. A method for producing aromatic hydrocarbon extraction feedstock, wherein, The method includes: in the presence of a catalyst, the reactants undergo a hydrogenation reaction, wherein the catalyst is the hydrogenation catalyst of claim 13, and the reactants are gasoline feedstock.

16. The method according to claim 15, wherein, The gasoline feedstock is selected from at least one of catalytic cracking gasoline, catalytic cracking gasoline, steam cracking gasoline, coking gasoline, and reformed gasoline; preferably, the conditions for the hydrogenation reaction include: a reaction temperature of 180-360℃, a reaction pressure of 1-4 MPa, and a volume hourly space velocity of 1-4 h⁻¹. -1 The hydrogen-to-oil volume ratio is 100-600.

Images