Sulfide catalysts, hydrogenation catalysts, their preparation methods, and applications

Abstract

This invention relates to the field of hydrogenation catalysts, specifically to a sulfidation-type catalyst, a hydrogenation catalyst, its preparation method, and its applications. The catalyst comprises an active phase and a support, wherein the active phase contains Group VIB, lanthanide, and Group VIII metals; after sulfidation, the active phase of the catalyst exhibits a tower-like structure. The hydrogenation catalyst of this invention, after sulfidation, exhibits a tower-like structure with fully exposed active sites such as edges, corners, and sides, resulting in good hydrogenation activity (for polycyclic aromatic hydrocarbons), high desulfurization and denitrification rates, and the ability to be used under relatively mild conditions with a long service life.

Description

Technical Field

[0001] This invention relates to the field of hydrogenation catalysts, specifically to a sulfidation catalyst, a hydrogenation catalyst, a method for preparing the same, and applications of the catalyst. Background Technology

[0002] With the increasing deterioration and heavier composition of crude oil, and the rising demands for higher quality petroleum products, hydrogenation has become a crucial step in the refining industry. More than 80% of petroleum products undergo hydrogenation.

[0003] Hydrogenation catalysts mainly consist of two parts: a metal component and a support. The metal component is predominantly a Group VIB or Group VIII metal, such as W, Mo, Co, and Ni. Supports include Al₂O₃, TiO₂, zeolite, activated carbon, clay, and diatomaceous earth. The metal component is supported on a porous support in an oxidized state, promoting reactions such as hydrodenitrogenation, hydrodesulfurization, hydrodemetallization, olefin hydrogenation saturation, and hydrocracking. Theoretical research and production experience both indicate that the deterioration of feedstock leading to coking, metal deposition, and the aggregation of the active phase during preparation are the main causes of hydrogenation catalyst deactivation. The increasing deterioration of feedstock and the continuous upgrading of oil quality necessitate hydrogenation catalysts with higher activity and stability. Key technologies for improving catalyst activity and stability include optimizing support properties, impregnation solution formulations, catalyst preparation technology, and upgrading sulfidation processes to enhance catalyst activity and stability, improve catalyst diffusion performance and sol-gel capacity, while simultaneously improving the dispersion of the active phase and reducing aggregation and poisoning.

[0004] CN1175481A discloses an impregnation solution for preparing a hydrocracking catalyst, the composition of which is: 25-65g WO3 / 100ml solution, 3-20g NiO / 100ml solution, and further contains at least one organic acid or ammonium salt, the content of which is 0.5-15g / 100ml solution.

[0005] CN102836725A discloses a method for preparing a catalyst with high hydrogenation activity. The method includes firstly kneading and extruding a solid compound containing a group III metal with alumina to obtain an alumina composite with a high specific surface area containing a group III metal; then, subjecting it to a hydrothermal reaction in an autoclave with a salt solution of a group VIB metal, urea, and reaction aids; and finally, drying and calcining to obtain a hydrorefining catalyst. Compared with conventional impregnation methods, the catalyst prepared by this invention generates a novel metal active phase precursor through surface reaction on the support, which is more easily sulfided into a type II Co(Ni)-Mo(W)-S phase with higher hydrogenation activity. Simultaneously, it reduces the formation of spinel without hydrogenation activity, thus significantly improving the catalyst's hydrodesulfurization and hydronitrogenation activity, making it particularly suitable for the deep hydrorefining of low-quality, high-sulfur distillate oils. Compared with the prior art, the catalyst provided by this invention adopts a kneading and extrusion molding method and a low calcination temperature, resulting in a high proportion of micropores and macropores in the catalyst. This easily leads to uneven distribution and underutilization of active components, and therefore, a rapid decline in activity is very likely to occur in actual industrial applications.

[0006] CN102397796A discloses an impregnation solution and a method for preparing a catalyst using the impregnation solution. The impregnation solution contains a compound containing a Group VIB metal, an organic acid salt containing a Group VIII metal, an inorganic acid, and an organic acid additive. The concentration of the organic additive in the impregnation solution is 1-150 g / L. Based on oxides, the concentration of the Group VIB metal compound is 100-1100 g / L, the concentration of the organic acid salt containing a Group VIII metal is 10-800 g / L, and the concentration of the inorganic acid is 1-100 g / L. Using the provided impregnation solution to prepare a hydrogenation catalyst improves the catalyst performance, particularly significantly enhancing the hydrogenation catalytic activity for heavy aromatics.

[0007] While the above methods improve the performance of hydrogenation catalysts to some extent, it is difficult for the active components to be fully loaded onto the support when preparing catalysts with high metal loading. Even if the active components achieve a high loading, their dispersion is poor, which limits the improvement of catalyst activity. Summary of the Invention

[0008] The purpose of this invention is to overcome the problem of low activity of hydrogenation catalysts in the prior art, and to provide a sulfidation catalyst, a hydrogenation catalyst, a preparation method thereof, and the application of the catalyst. This catalyst has the characteristics of good hydrogenation activity and high desulfurization and denitrification rate.

[0009] To achieve the above objectives, the first aspect of the present invention provides a hydrogenation catalyst comprising an active phase and a support, wherein the active phase comprises Group VIB metals, lanthanides, and Group VIII metals; and the active phase of the catalyst, after sulfidation, exhibits a tower-like structure.

[0010] A second aspect of the present invention provides a sulfidation catalyst, which is obtained by sulfidation treatment of the hydrogenation catalyst described in the first aspect; the active phase of the sulfidation catalyst has a tower-shaped structure.

[0011] A third aspect of the present invention provides a method for preparing a hydrogenation catalyst, the method comprising:

[0012] (1) Prepare solution I by mixing group VIB metal precursor, lanthanide metal precursor and first auxiliary agent; prepare solution II by mixing group VIII metal precursor and optional second auxiliary agent; mix solution I and solution II, add third auxiliary agent to obtain solution III;

[0013] (2) Solution III comes into contact with the carrier, followed by conditioning, drying, and calcination;

[0014] Wherein, the first auxiliary agent is an amino compound and / or an inorganic acid; the second auxiliary agent is an organic acid-metal complexing agent; the third auxiliary agent is an alcohol and / or a ketone; the concentration of the Group VIII metal precursor in solution III is above 45 g / L, and the concentration of the Group VIB metal precursor is above 140 g / L.

[0015] The fourth aspect of the present invention provides the application of the hydrogenation catalyst described in the first aspect and / or the sulfidation catalyst described in the second aspect and / or the catalyst prepared by the preparation method described in the third aspect in the hydrogenation refining of ethylene tar, wherein the hydrogenation catalyst described in the first aspect and / or the catalyst prepared by the preparation method described in the third aspect are subjected to sulfidation treatment before hydrogenation.

[0016] Through the above technical solution, the present invention has the following advantages:

[0017] The hydrogenation catalyst of this invention has a tower-shaped structure after sulfidation, with active sites such as edges, corners and sides fully exposed. It has good hydrogenation activity (for polycyclic aromatic hydrocarbons), high desulfurization and denitrification rate, can be used under relatively mild conditions, and has a long service life.

[0018] The preparation method of this invention is as follows: ① A first auxiliary agent is used as a co-solvent to dissolve a Group VIB metal compound to obtain a high metal concentration; ② A second auxiliary agent can reduce the interaction between the active component and the support, delay the sulfidation of Group VIII metals, and increase the sulfidation temperature of Group VIII metals; ③ A third auxiliary agent reduces the viscosity of the impregnation solution, thereby preparing a hydrogenation catalyst with the characteristics of this invention; at the same time, the preferred curing time and low-temperature sulfidation time can further improve the performance of the hydrogenation catalyst of this invention.

[0019] When the hydrogenation catalyst of this invention is used for the hydrogenation refining of ethylene tar, the naphthalene conversion rate is not less than 95%, the bromine value of the hydrogenated product is less than 0.5gBr / 100g oil, the tetrahydronaphthalene selectivity is 99%, and the sulfur and nitrogen content is less than 1ppm. The resulting product can be used as a high-quality raw material for the production of BTX, realizing the upgrading of oil products to chemical products, greatly improving the added value of the product, and the catalyst has good stability. Attached Figure Description

[0020] Figure 1 This is a TEM image of the sulfidation catalyst in Example 1;

[0021] Figure 2 This is a TEM image of the sulfidation catalyst in Example 6;

[0022] Figure 3 The TEM image shows the sulfidation catalyst in Comparative Example 2.

[0023] Figure 4 This is a TEM image of the sulfidation catalyst in Comparative Example 3;

[0024] Figure 5 These are the TPR diagrams of the catalysts in Examples 1 and 5;

[0025] Figure 6 This is a TEM image of the sulfidation catalyst in Comparative Example 1;

[0026] Figure 7 This is a TEM image of the sulfidation catalyst in Example 10;

[0027] Figure 8 This is the catalyst stability curve from Example 1. Detailed Implementation

[0028] 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.

[0029] This invention provides a hydrogenation catalyst comprising an active phase and a support, wherein the active phase contains Group VIB metals, lanthanides, and Group VIII metals; and the active phase of the catalyst exhibits a tower-like structure after sulfidation.

[0030] The hydrogenation catalyst of this invention has a tower-shaped structure after sulfidation, with active sites such as edges, corners and sides fully exposed. It has good hydrogenation activity of polycyclic aromatic hydrocarbons, high desulfurization and denitrification rate, can be used under relatively mild conditions and has a long service life.

[0031] In this invention, the tower-shaped structure is a layered structure resembling a tower.

[0032] According to a preferred embodiment of the present invention, the tower-shaped structure has 3-10 stacked layers, preferably 3-5 layers. By adopting the aforementioned preferred embodiment, the activity, desulfurization and denitrification rate, and service life of the hydrogenation catalyst can be further improved.

[0033] According to a preferred embodiment of the present invention, the stacking layer spacing of the tower-shaped structure is 0.2-2 nm. By adopting the aforementioned preferred scheme, the activity, desulfurization and denitrification rate, and service life of the hydrogenation catalyst can be further improved.

[0034] According to a preferred embodiment of the present invention, the stacking length of the tower-shaped structure is 3-12 nm, preferably 3-6 nm. By adopting the aforementioned preferred embodiment, the activity, desulfurization and denitrification rate, and service life of the hydrogenation catalyst can be further improved.

[0035] In this invention, the sulfidation of Group VIB metal elements yields a tower-shaped structure with this characteristic, which can provide sufficient edge, side, and corner positions. The sulfidation of Group VIII metal elements can be uniformly dispersed in these edge, side, and corner positions, thereby improving catalytic performance.

[0036] In this invention, there are no particular requirements for the mass content of the active phase and the support in the catalyst. According to a preferred embodiment of the invention, the mass content of the active phase in the catalyst is 15%-60%, preferably 18%-55%; and the mass content of the support is 40%-85%, preferably 45%-82%. By adopting the aforementioned preferred scheme, the activity, desulfurization and denitrification rate, and service life of the hydrogenation catalyst can be further improved.

[0037] In this invention, there is no particular limitation on the mass ratio of Group VIB metals to Group VIII metals in the active phase. According to a preferred embodiment of the invention, the mass ratio of Group VIB metals to Group VIII metals in the active phase, calculated as oxides, is 0.1-15, preferably 0.8-12. By adopting the aforementioned preferred embodiment, the activity, desulfurization and denitrification rate, and service life of the hydrogenation catalyst can be further improved.

[0038] According to a preferred embodiment of the present invention, the content of lanthanide metal elements in the active phase, calculated as oxides, is 0.1-0.5 wt%.

[0039] In this invention, the Group VIB metal element can be a conventional choice in the art. According to a preferred embodiment of the invention, the Group VIB metal element is selected from Mo, W, and Cr, preferably Mo and / or W. By adopting the aforementioned preferred scheme, the activity, desulfurization and denitrification rate, and service life of the hydrogenation catalyst can be further improved.

[0040] In this invention, the Group VIII metal element can be a conventional choice in the art. According to a preferred embodiment of the invention, the Group VIII metal element is selected from Fe, Co, Ni, Pt, and Pd, preferably Ni and / or Co. By adopting the aforementioned preferred scheme, the activity, desulfurization and denitrification rate, and service life of the hydrogenation catalyst can be further improved.

[0041] According to a preferred embodiment of the present invention, the lanthanide metal element is La and / or Ce.

[0042] In this invention, the support can be a conventional choice in the art. According to a preferred embodiment of the invention, the support is selected from at least one of Al2O3, Al2O3-TiO2, Al2O3-TiO2-SiO2, and Al2O3-SiO2, preferably from at least one of Al2O3, Al2O3-TiO2, and Al2O3-TiO2-SiO2. By adopting the aforementioned preferred solution, the activity, desulfurization and denitrification rate, and service life of the hydrogenation catalyst can be further improved.

[0043] The present invention provides a sulfidation catalyst, which is obtained by sulfidation treatment of the hydrogenation catalyst; the active phase of the sulfidation catalyst has a tower-shaped structure.

[0044] The number of stacking layers in the tower structure is 3-10, preferably 3-5; and / or the stacking layer spacing is 0.2-2 nm; and / or the stacking length is 3-12 nm, preferably 3-6 nm.

[0045] The sulfidation catalyst of this invention has good hydrogenation activity, high desulfurization and denitrification rate, can be used under relatively mild conditions, and has a long service life.

[0046] This invention provides a method for preparing a hydrogenation catalyst, the method comprising:

[0047] (1) Prepare solution I by mixing group VIB metal precursor, lanthanide metal precursor and first auxiliary agent; prepare solution II by mixing group VIII metal precursor and optional second auxiliary agent; mix solution I and solution II, add third auxiliary agent to obtain solution III;

[0048] (2) Solution III comes into contact with the carrier, and is then cured, dried, and calcined;

[0049] Wherein, the first auxiliary agent is an amino compound and / or an inorganic acid; the second auxiliary agent is an organic acid-metal complexing agent; and the third auxiliary agent is an alcohol and / or a ketone.

[0050] The concentration of Group VIII metal precursor in solution III is above 45 g / L, and the concentration of Group VIB metal precursor is above 140 g / L.

[0051] The hydrogenation catalyst prepared by the method of this invention includes the following steps: ① using a first auxiliary agent as a co-solvent to dissolve Group VIB metal compounds to obtain a high metal concentration; ② using a second auxiliary agent to reduce the interaction between the active component and the support, delaying the sulfidation of Group VIII metals, and increasing the sulfidation temperature of Group VIII metals; ③ using a third auxiliary agent to reduce the viscosity of the impregnation solution, thereby preparing a hydrogenation catalyst with the characteristics of this invention. After sulfidation, it exhibits a tower-shaped structure with fully exposed active sites such as edges, corners, and sides, good hydrogenation activity of polycyclic aromatic hydrocarbons, high desulfurization and denitrification rates, and can be used under relatively mild conditions with a long service life. Furthermore, the use of optimized curing time and low-temperature sulfidation time can further improve the performance of the hydrogenation catalyst of this invention.

[0052] According to a preferred embodiment of the present invention, stirring is used when preparing solutions I, II and III, with a preferred stirring temperature of 10-100°C, more preferably 25-60°C, and a stirring speed of 10-200 rpm, more preferably 50-160 rpm.

[0053] According to a preferred embodiment of the present invention, the concentration of the Group VIII metal precursor in solution III is 50-500 g / L, and the concentration of the Group VIB metal precursor is 150-850 g / L. For example, the concentration of the Group VIII metal precursor in solution III can be 50 g / L, 100 g / L, 150 g / L, 200 g / L, 250 g / L, 300 g / L, 350 g / L, 400 g / L, 450 g / L, or 500 g / L; and the concentration of the Group VIB metal precursor in solution III can be 150 g / L, 300 g / L, 450 g / L, 600 g / L, 750 g / L, or 850 g / L. By adopting the aforementioned preferred embodiment, the activity, desulfurization and denitrification rate, and service life of the hydrogenation catalyst can be further improved.

[0054] According to a preferred embodiment of the present invention, the ratio of the concentration of the Group VIII metal precursor to the concentration of the Group VIB metal precursor in solution III is 0.1-1.2, more preferably 0.35-1.0. By adopting the aforementioned preferred embodiment, the activity, desulfurization and denitrification rate, and service life of the hydrogenation catalyst can be further improved.

[0055] In this invention, the metal precursor is a soluble salt of the corresponding metal element. For example, lanthanide metal salts are selected from at least one of lanthanum nitrate, lanthanum acetate, lanthanum oxalate, cerium nitrate, and cerium acetate.

[0056] In this invention, the first auxiliary agent is at least one of an amino compound and an inorganic acid. According to a preferred embodiment of the invention, the first auxiliary agent is selected from at least one of urea, acetamide, ethylenediamine, ethanolamine, diethanolamine, triethanolamine, phosphoric acid, nitric acid, and sulfuric acid. The lanthanide metal is selected from at least one of lanthanum nitrate, lanthanum acetate, lanthanum oxalate, cerium nitrate, and cerium acetate. By adopting the aforementioned preferred embodiment, the activity, desulfurization and denitrification rate, and service life of the hydrogenation catalyst can be further improved.

[0057] In this invention, the second auxiliary agent is an organic acid. According to a preferred embodiment of the invention, the second auxiliary agent is selected from at least one of 1,2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid, ethylenediaminetetraacetic acid, salicylic acid, and aminotriacetic acid. By adopting the aforementioned preferred embodiment, the activity, desulfurization and denitrification rate, and service life of the hydrogenation catalyst can be further improved.

[0058] In this invention, the third auxiliary agent is an alcohol and / or a ketone. According to a preferred embodiment of the invention, the third auxiliary agent is a mixture of alcohol and ketone, preferably with a mass ratio of 0.05-2, more preferably 0.5-1.5; more preferably, the third auxiliary agent is selected from a mixture of ethylene glycol and / or ethanol with acetone and / or 2-butanone. By adopting the aforementioned preferred embodiments, the activity, desulfurization and denitrification rate, and service life of the hydrogenation catalyst can be further improved.

[0059] In this invention, as long as the objective of the invention can be achieved, there is no particular limitation on the atomic molar ratio of the first auxiliary agent to the Group VIB metal. According to a preferred embodiment of the invention, the atomic molar ratio of the first auxiliary agent to the Group VIB metal is 0.1-1.2, for example, it can be 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, or 1.20; preferably 0.25-1.0. By adopting the aforementioned preferred scheme, the activity, desulfurization and denitrification rate, and service life of the hydrogenation catalyst can be further improved.

[0060] In this invention, as long as the objective of the invention can be achieved, there is no particular limitation on the atomic molar ratio of the second additive to the Group VIII metal. According to a preferred embodiment of the invention, the atomic molar ratio of the second additive to the Group VIII metal is 0.05-1.2, for example, it can be 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, or 1.20; preferably 0.14-0.8. By adopting the aforementioned preferred embodiment, the activity, desulfurization and denitrification rate, and service life of the hydrogenation catalyst can be further improved.

[0061] In this invention, there is no particular limitation on the mass ratio of solution III to the carrier in step (2). According to a preferred embodiment of this invention, in step (2), solution III and the carrier are in contact at a mass ratio of 0.5-2.5; preferably 1.0-2.0.

[0062] According to a preferred embodiment of the present invention, the carrier is selected from at least one of Al2O3, Al2O3-TiO2, Al2O3-TiO2-SiO2, and Al2O3-SiO2, and is preferably selected from at least one of Al2O3, Al2O3-TiO2, and Al2O3-TiO2-SiO2.

[0063] According to a preferred embodiment of the present invention, the group VIB metal element is selected from Mo, W, and Cr, preferably Mo and / or W.

[0064] According to a preferred embodiment of the present invention, the Group VIII metal element is selected from Fe, Co, Ni, Pt, and Pd, preferably Ni and / or Co.

[0065] According to a preferred embodiment of the present invention, the lanthanide metal element is La and / or Ce.

[0066] According to a preferred embodiment of the present invention, the contact conditions include: a contact temperature of 0-60°C, preferably 20-40°C.

[0067] According to a preferred embodiment of the present invention, the contact conditions include a contact time of 5-60 minutes, preferably 8-40 minutes.

[0068] According to a preferred embodiment of the present invention, the conditions for health preservation include: a health preservation temperature of 0-60℃, preferably 20-40℃; and / or

[0069] According to a preferred embodiment of the present invention, the conditions for health preservation include: the health preservation time is 2-96 hours, preferably 6-48 hours.

[0070] According to a preferred embodiment of the present invention, the drying conditions include a drying temperature of 50-130°C, preferably 60-120°C.

[0071] According to a preferred embodiment of the present invention, the drying conditions include a drying time of 3-46 hours, preferably 6-36 hours.

[0072] According to a preferred embodiment of the present invention, the drying conditions include an air volume hourly space velocity (VHSV) of 2-250 h⁻¹. -1 Preferably 20-150h -1 .

[0073] According to a preferred embodiment of the present invention, the calcination conditions include: a calcination temperature of 150-520°C, preferably 280-500°C.

[0074] According to a preferred embodiment of the present invention, the roasting conditions include: a roasting time of 2-24 hours, preferably 3-12 hours.

[0075] According to a preferred embodiment of the present invention, the calcination conditions include: an air volume space velocity of 2-250 h⁻¹. -1 Preferably 25-150h -1 .

[0076] This invention provides the application of the hydrogenation catalyst and / or the sulfidated catalyst and / or the catalyst prepared by the preparation method described above in the hydrogenation of feedstock oil, wherein the hydrogenation catalyst and / or the catalyst prepared by the preparation method are subjected to sulfidation treatment before hydrogenation.

[0077] According to a preferred embodiment of the present invention, the hydrogenation conditions include: an inlet temperature of 200-270°C, a reaction pressure of 2.3-6.0 MPa, a hydrogen-to-oil volume ratio (hydrogen to feedstock oil volume ratio) of 400-1500, and a liquid hourly space velocity of 0.2-1.8 h⁻¹. -1 .

[0078] According to a preferred embodiment of the present invention, the vulcanization conditions include: a sulfur content of 0.05-2 wt% in the vulcanizing agent; and / or a vulcanization temperature of 120-380°C; and / or a vulcanization time of 8-72 h; and / or a vulcanizing agent volume hourly space velocity of 0.3-3 h⁻¹. -1 ; and / or hydrogen-to-oil volume ratio (hydrogen to vulcanizing agent volume ratio) 300-2000; and / or vulcanization pressure 0.5-10.0 MPa;

[0079] According to a preferred embodiment of the present invention, the vulcanization temperature is 150-360°C; and / or the vulcanization time is 8-56 hours; and / or the vulcanizing agent volume hourly space velocity is 0.5-1.5 h⁻¹. -1 ; and / or hydrogen-to-oil volume ratio (volume ratio of hydrogen to vulcanizing agent) 500-1500; and / or vulcanization pressure 1.0-6.0 MPa.

[0080] According to a preferred embodiment of the present invention, vulcanization is carried out by programmed temperature rise, including: an initial temperature of 25-150°C, a heating rate of 5-15°C / min, a step temperature interval of 50-80°C, a step temperature holding time of 4-10h, a final temperature of 320-360°C, and a final temperature treatment time of 27-35h.

[0081] According to a preferred embodiment of the present invention, the feedstock oil is selected from the product of ethylene tar after deweighting and primary hydrogenation to olefins.

[0082] The present invention will be described in detail below through embodiments. The following embodiments:

[0083] The structural characteristics of the catalyst and the size of the metal nanoparticles were determined using a G2F30 transmission electron microscope (TEM) from FEI Corporation, USA. The elemental composition of the catalyst was determined using a Rigaku ZSX-100e 4580 X-ray fluorescence spectrometer, Japan.

[0084] Nitrogen and sulfur tests were performed on an Antek 900 sulfur-nitrogen analyzer. The nitrogen content test method followed standard SH / T0657-2007 (chemiluminescence method); the sulfur content test method followed standard SH / T0689-2000 (ultraviolet fluorescence method).

[0085] The naphthalene conversion rate and tetrahydronaphthalene selectivity in the product are calculated using the following formula:

[0086]

[0087]

[0088] All raw materials are commercially available.

[0089] Example 1

[0090] 1. Weigh 720 g of ammonium metatungstate, 130 g of ammonium molybdate, and 15 g of lanthanum nitrate, dissolve them in 500 g of deionized water, add 57 g of phosphoric acid, and stir at room temperature for 30 minutes to obtain aqueous solution I. Weigh 250 g of nickel nitrate and 42.5 g of 1,2-cyclohexanediaminetetraacetic acid, dissolve them in 200 g of deionized water, and stir at room temperature for 30 minutes to obtain aqueous solution II. Mix aqueous solutions I and II, add 54 g of ethylene glycol and 27 g of 2-butanone, and dilute to 1 L with deionized water. Continue stirring at room temperature for 30 minutes to obtain solution III. The concentration of the Group VIB metal precursor in solution III is 850 g / L, the concentration of the Group VIII metal precursor is 250 g / L, the atomic molar ratio of the first auxiliary agent to the Group VIB metal is 1.0, and the atomic molar ratio of the second auxiliary agent to the Group VIII metal is 0.14. The mass ratio of ethylene glycol to 2-butanone in the third auxiliary agent is 2.

[0091] 2. Catalyst Preparation

[0092] Take 1000g of Al2O3-TiO2-SiO2 support (Al2O3, 97%, TiO2, 1.5%, SiO2, 1.5%) into a rotary pot, slowly add the solution III prepared in step 1, rotate the pot at 58 rpm, and soak for 10 minutes.

[0093] For health preservation, the soaked carrier is kept at 30℃ for 48 hours.

[0094] Dry, airy atmosphere, starting at 25°C, increasing to 70°C at 10°C / hour, holding at that temperature for 8 hours, then increasing to 110°C at 10°C / hour, holding at that temperature for 4 hours.

[0095] Firing: In air atmosphere, start at 25°C, increase to 445°C at 140°C / hour, and hold at that temperature for 3 hours.

[0096] The catalyst composition is shown in Table 1.

[0097] 3. Catalyst sulfidation and evaluation

[0098] The catalyst prepared in step 2 was loaded into a fixed-bed reactor, and sulfidation began after the gas tightness was verified. The system pressure was 5.5 MPa, and the hydrogen volume hourly space velocity was 800 h⁻¹. -1 Hydrogen gas was introduced, and the temperature was increased from room temperature to 150°C at a rate of 30°C / h, with a volume hourly space velocity (VHSV) of 1 h⁻¹. -1 A sulfurizing agent containing 0.5 wt% sulfur was introduced, and the temperature was increased to 180°C at a rate of 5°C / h for 6 hours, held at this temperature for 5 hours, then increased to 230°C at a rate of 5°C / h for 10 hours, held at this temperature for 4 hours, then increased to 280°C at a rate of 10°C / h for 5 hours, held at this temperature for 4 hours, then increased to 320°C at a rate of 10°C / h for 4 hours, and held at this temperature for 2 hours. The catalytic sulfidation was then completed. The TEM image of the sulfided catalyst was obtained using a G2F30 transmission electron microscope (TEM) from FEI Corporation, USA. Figure 1As can be seen from the figure, the active phase of the sulfidation catalyst has a tower-shaped structure with 3-5 stacked layers; the stacking layer spacing is 0.2-2 nm; and the stacking length is 3-6 nm.

[0099] The temperature was lowered to 240℃ and the pressure reduced to 3.0 MPa. The first-stage hydrogenation product, after deweighting and diene removal, was then introduced. The H2 / Oil molar ratio was 1000, and the liquid hourly space velocity (LHSV) of the feedstock was 0.8 h⁻¹. -1 .

[0100] The evaluation results of the catalyst are listed in Table 2, and the catalyst stability curves are shown below. Figure 8 As shown.

[0101] Example 2

[0102] 1. Weigh 320 g of ammonium metatungstate, 105 g of ammonium molybdate, and 15 g of lanthanum nitrate, dissolve them in 400 g of deionized water, add 23.6 g of phosphoric acid, and stir at room temperature for 30 minutes to obtain aqueous solution I. Weigh 400 g of nickel nitrate and 190 g of 1,2-cyclohexanediaminetetraacetic acid, dissolve them in 400 g of deionized water, and stir at room temperature for 30 minutes to obtain aqueous solution II. Mix aqueous solutions I and II, add 27 g of ethylene glycol and 27 g of 2-butanone, and dilute to 1 L with deionized water. Continue stirring at room temperature for 30 minutes to obtain solution III. The concentration of the Group VIB metal precursor in solution III is 425 g / L, the concentration of the Group VIII metal precursor is 400 g / L, the atomic molar ratio of the first auxiliary agent to the Group VIB metal is 0.6, and the atomic molar ratio of the second auxiliary agent to the Group VIII metal is 0.4. The mass ratio of ethylene glycol to 2-butanone in the third auxiliary agent is 1.

[0103] 2. Catalyst Preparation

[0104] Take 1000g of Al2O3-TiO2-SiO2 support (Al2O3, 97%, TiO2, 1.5%, SiO2, 1.5%) into a rotary pot, slowly add the solution III prepared in step 1, rotate the pot at 58 rpm, and soak for 10 minutes.

[0105] For health preservation, the soaked carrier is kept at room temperature for 48 hours.

[0106] Dry, start at room temperature, in air atmosphere, heat up to 70℃ at 10℃ / hour, hold at 70℃ for 8 hours, heat up to 110℃ at 10℃ / hour, hold at 70℃ for 4 hours.

[0107] Firing: Start at room temperature, in air atmosphere, heat up to 445℃ at 140℃ / hour, and hold at that temperature for 3 hours.

[0108] The catalyst composition is shown in Table 1.

[0109] 3. Catalyst sulfidation and evaluation

[0110] The catalyst prepared in step 2 was loaded into a fixed-bed reactor, and sulfidation began after the gas tightness was verified. The system pressure was 5.5 MPa, and the hydrogen volume hourly space velocity was 800 h⁻¹. -1 Hydrogen gas was introduced, and the temperature was increased from room temperature to 150°C at a rate of 30°C / h, with a volume hourly space velocity (VHSV) of 1 h⁻¹. -1 A sulfurizing agent containing 0.5 wt% sulfur was introduced, and the temperature was increased to 180℃ at 5℃ / h for 6 hours, held for 5 hours, then increased to 230℃ at 5℃ / h for 10 hours, held for 4 hours, then increased to 280℃ at 10℃ / h for 5 hours, held for 4 hours, then increased to 320℃ at 10℃ / h for 4 hours, and held for 2 hours to complete the catalyst sulfidation. TEM images of the sulfidated catalyst were obtained using a G2F30 transmission electron microscope (TEM) from FEI Corporation, USA. Figure 1 Similarly, as can be seen from the figure, the active phase of the sulfidation catalyst has a tower-shaped structure with 3-5 stacked layers; the stacking layer spacing is 0.2-2 nm; and the stacking length is 3-6 nm.

[0111] The temperature was lowered to 240℃ and the pressure reduced to 3.0 MPa. The first-stage hydrogenation product, after deweighting and diene removal, was then introduced. The H2 / Oil molar ratio was 1000, and the liquid hourly space velocity (LHSV) of the feedstock was 0.8 h⁻¹. -1 .

[0112] The evaluation results of the catalyst are listed in Table 2.

[0113] Example 3

[0114] 1. Weigh 400g ammonium metatungstate, 100g ammonium molybdate, and 15g lanthanum nitrate, dissolve them in 400g deionized water, add 10.2g phosphoric acid, and stir at room temperature for 30 minutes to obtain aqueous solution I. Weigh 500g nickel nitrate and 475g 1,2-cyclohexanediaminetetraacetic acid, dissolve them in 400g deionized water, and stir at room temperature for 30 minutes to obtain aqueous solution II. Mix aqueous solutions I and II, add 54g ethylene glycol and 27g 2-butanone, and dilute to 1L with deionized water. Continue stirring at room temperature for 30 minutes to obtain solution III. The concentration of Group VIB metal precursor in solution III is 500g / L, the concentration of Group VIII metal precursor is 500g / L, the atomic molar ratio of the first auxiliary agent to the Group VIB metal is 0.25, and the atomic molar ratio of the second auxiliary agent to the Group VIII metal is 0.8. The mass ratio of ethylene glycol to 2-butanone in the third auxiliary agent is 2.

[0115] 2. Catalyst Preparation

[0116] Place 100g of alumina carrier in a rotary pot, slowly add solution III prepared in step 1, rotate the pot at 58 rpm, and soak for 10 minutes.

[0117] For health preservation, the soaked carrier is kept at room temperature for 48 hours.

[0118] Dry, start at room temperature, in air atmosphere, increase temperature at 10℃ / hour to 70℃, hold for 8 hours, increase temperature at 10℃ / hour to 110℃, hold for 4 hours.

[0119] Firing: Start at room temperature, in air atmosphere, heat up to 445℃ at 140℃ / hour, and hold at that temperature for 3 hours.

[0120] The catalyst composition is shown in Table 1.

[0121] 3. Catalyst sulfidation and evaluation

[0122] The catalyst prepared in step 2 was loaded into a fixed-bed reactor, and sulfidation began after the gas tightness was verified. The system pressure was 5.5 MPa, and the hydrogen volume hourly space velocity was 800 h⁻¹. -1 Hydrogen gas was introduced, and the temperature was increased from room temperature to 150°C at a rate of 30°C / h, with a volume hourly space velocity (VHSV) of 1 h⁻¹. -1 A sulfurizing agent containing 0.5 wt% sulfur was introduced, and the temperature was increased to 180℃ at 5℃ / h for 6 hours, held for 5 hours, then increased to 230℃ at 5℃ / h for 10 hours, held for 4 hours, then increased to 280℃ at 10℃ / h for 5 hours, held for 4 hours, then increased to 320℃ at 10℃ / h for 4 hours, and held for 2 hours to complete the catalyst sulfidation. TEM images of the sulfidated catalyst were obtained using a G2F30 transmission electron microscope (TEM) from FEI Corporation, USA. Figure 1 Similarly, as can be seen from the figure, the active phase of the sulfidation catalyst has a tower-shaped structure with 3-5 stacked layers; the stacking layer spacing is 0.2-2 nm; and the stacking length is 3-6 nm.

[0123] The temperature was lowered to 240℃ and the pressure reduced to 3.0 MPa. The first-stage hydrogenation product, after deweighting and diene removal, was then introduced. The H2 / Oil molar ratio was 1000, and the liquid hourly space velocity (LHSV) of the feedstock was 0.8 h⁻¹. -1 .

[0124] The evaluation results of the catalyst are listed in Table 2.

[0125] Example 4

[0126] 1. Weigh 720 g of ammonium metatungstate, 130 g of ammonium molybdate, and 15 g of lanthanum nitrate, dissolve them in 500 g of deionized water, add 18 g of urea and 28 g of phosphoric acid, and stir at room temperature for 30 minutes to obtain aqueous solution I. Weigh 250 g of nickel nitrate and 42.5 g of 1,2-cyclohexanediaminetetraacetic acid, dissolve them in 200 g of deionized water, and stir at room temperature for 30 minutes to obtain aqueous solution II. Mix aqueous solutions I and II, add 54 g of ethylene glycol and 27 g of 2-butanone, and dilute to 1 L with deionized water. Continue stirring at room temperature for 30 minutes to obtain solution III. The concentration of the Group VIB metal precursor in solution III is 850 g / L, the concentration of the Group VIII metal precursor is 250 g / L, the atomic molar ratio of the first auxiliary agent to the Group VIB metal is 1.0, and the atomic molar ratio of the second auxiliary agent to the Group VIII metal is 0.14. The mass ratio of ethylene glycol to 2-butanone in the third auxiliary agent is 2.

[0127] 2. Catalyst Preparation

[0128] Take 1000g of Al2O3-TiO2-SiO2 support (Al2O3, 97%, TiO2, 1.5%, SiO2, 1.5%) into a rotary pot, slowly add the solution III prepared in step 1, rotate the pot at 58 rpm, and soak for 10 minutes.

[0129] For health preservation, the soaked carrier is kept at 30℃ for 48 hours.

[0130] Dry, airy atmosphere, starting at 25°C, increasing to 70°C at 10°C / hour, holding at that temperature for 8 hours, then increasing to 110°C at 10°C / hour, holding at that temperature for 4 hours.

[0131] Firing: In air atmosphere, start at 25°C, increase to 445°C at 140°C / hour, and hold at that temperature for 3 hours.

[0132] The catalyst composition is shown in Table 1.

[0133] 3. Catalyst sulfidation and evaluation

[0134] The catalyst prepared in step 2 was loaded into a fixed-bed reactor, and sulfidation began after the gas tightness was verified. The system pressure was 5.5 MPa, and the hydrogen volume hourly space velocity was 800 h⁻¹. -1Hydrogen gas was introduced, and the temperature was increased from room temperature to 150°C at a rate of 30°C / h. A sulfurizing agent containing 0.5 wt% sulfur was then introduced, and the temperature was increased to 180°C at a rate of 5°C / h for 6 hours, held at this temperature for 5 hours, then increased to 230°C at a rate of 5°C / h for 10 hours, held at this temperature for 4 hours, then increased to 280°C at a rate of 10°C / h for 5 hours, held at this temperature for 4 hours, then increased to 320°C at a rate of 10°C / h for 4 hours, and held at this temperature for 2 hours, at which point the catalyst sulfidation was complete. The sulfided catalyst was tested using a G2F30 transmission electron microscope (TEM) from FEI Corporation, USA. The images show that the active phase of the sulfided catalyst exhibits a tower-like structure with 3-5 stacked layers; the interlayer spacing is 0.2-2 nm; and the stack length is 3-6 nm.

[0135] The temperature was lowered to 240℃ and the pressure reduced to 3.0 MPa. The first-stage hydrogenation product, after deweighting and diene removal, was then introduced. The H2 / Oil molar ratio was 1000, and the liquid hourly space velocity (LHSV) of the feedstock was 0.8 h⁻¹. -1 .

[0136] The evaluation results of the catalyst are listed in Table 2.

[0137] Example 5

[0138] 1. Weigh 720 g of ammonium metatungstate, 130 g of ammonium molybdate, and 15 g of lanthanum nitrate, dissolve them in 500 g of deionized water, add 57 g of phosphoric acid, and stir at room temperature for 30 minutes to obtain aqueous solution I. Weigh 250 g of nickel nitrate and 18 g of 1,2-cyclohexanediaminetetraacetic acid, dissolve them in 200 g of deionized water, and stir at room temperature for 30 minutes to obtain aqueous solution II. Mix aqueous solutions I and II, add 54 g of ethylene glycol and 27 g of 2-butanone, and dilute to 1 L with deionized water. Continue stirring at room temperature for 30 minutes to obtain solution III. The concentration of the Group VIB metal precursor in solution III is 850 g / L, the concentration of the Group VIII metal precursor is 250 g / L, the atomic molar ratio of the first auxiliary agent to the Group VIB metal is 1.0, and the atomic molar ratio of the second auxiliary agent to the Group VIII metal is 0.057. The mass ratio of ethylene glycol to 2-butanone in the third auxiliary agent is 2.

[0139] 2. Catalyst Preparation

[0140] Take 1000g of Al2O3-TiO2-SiO2 support (Al2O3, 97%, TiO2, 1.5%, SiO2, 1.5%) into a rotary pot, slowly add the solution III prepared in step 1, rotate the pot at 58 rpm, and soak for 10 minutes.

[0141] Aging involves aging the impregnated carrier at 30°C for 48 hours.

[0142] Dry, airy atmosphere, starting at 25°C, increasing to 70°C at 10°C / hour, holding at that temperature for 8 hours, then increasing to 110°C at 10°C / hour, holding at that temperature for 4 hours.

[0143] Firing: In air atmosphere, start at 25°C, increase to 445°C at 140°C / hour, and hold at that temperature for 3 hours.

[0144] The catalyst composition is shown in Table 1.

[0145] 3. Catalyst sulfidation and evaluation

[0146] The catalyst prepared in step 2 was loaded into a fixed-bed reactor, and sulfidation began after the gas tightness was verified. The system pressure was 5.5 MPa, and the hydrogen volume hourly space velocity was 800 h⁻¹. -1 Hydrogen gas was introduced, and the temperature was increased from room temperature to 150°C at a rate of 30°C / h. A sulfurizing agent containing 0.5 wt% sulfur was then introduced, and the temperature was increased to 180°C at a rate of 5°C / h for 6 hours, held for 5 hours, then increased to 230°C at a rate of 5°C / h for 10 hours, held for 4 hours, then increased to 280°C at a rate of 10°C / h for 5 hours, held for 4 hours, then increased to 320°C at a rate of 10°C / h for 4 hours, and held for 2 hours to complete the catalyst sulfidation. The sulfidated catalyst was tested using a G2F30 transmission electron microscope (TEM) from FEI Corporation, USA. The graph shows that the active phase of the sulfidated catalyst has a partially tower-like structure with 3-7 stacked layers; the stacking distance is 0.2-2 nm; and the stack length is 3-12 nm. Only the reduction peak temperature shifts to the higher temperature region, indicating a strong interaction between the metal and the support. (See the TPR spectrum in the figure). Figure 5 )

[0147] The temperature was lowered to 240℃ and the pressure reduced to 3.0 MPa. The first-stage hydrogenation product, after deweighting and diene removal, was then introduced. The H2 / Oil molar ratio was 1000, and the liquid hourly space velocity (LHSV) of the feedstock was 0.8 h⁻¹. -1 .

[0148] The evaluation results of the catalyst are listed in Table 2.

[0149] Example 6

[0150] 1. Weigh 720 g of ammonium metatungstate, 130 g of ammonium molybdate, and 15 g of lanthanum nitrate, dissolve them in 500 g of deionized water, add 57 g of phosphoric acid, and stir at room temperature for 30 minutes to obtain aqueous solution I; weigh 250 g of nickel nitrate and 200 g of deionized water, stir at room temperature for 30 minutes to obtain aqueous solution II; mix aqueous solution I and aqueous solution II, add 54 g of ethylene glycol and 27 g of 2-butanone, and dilute to 1 L with deionized water, continue stirring at room temperature for 30 minutes to obtain solution III. In solution III, the concentration of the Group VIB metal precursor is 850 g / L, the concentration of the Group VIII metal precursor is 250 g / L, the atomic molar ratio of the first auxiliary agent to the Group VIB metal is 1.0, and the mass ratio of ethylene glycol to 2-butanone is 2.

[0151] 2. Catalyst Preparation

[0152] Take 1000g of Al2O3-TiO2-SiO2 support (Al2O3, 97%, TiO2, 1.5%, SiO2, 1.5%) into a rotary pot, slowly add the solution III prepared in step 1, rotate the pot at 58 rpm, and soak for 10 minutes.

[0153] For health preservation, the soaked carrier is preserved at 30℃ for 48 hours.

[0154] Dry, airy atmosphere, starting at 25°C, increasing to 70°C at 10°C / hour, holding at that temperature for 8 hours, then increasing to 110°C at 10°C / hour, holding at that temperature for 4 hours.

[0155] Firing: In air atmosphere, start at 25°C, increase to 445°C at 140°C / hour, and hold at that temperature for 3 hours.

[0156] The catalyst composition is shown in Table 1.

[0157] 3. Catalyst sulfidation and evaluation

[0158] The catalyst prepared in step 2 was loaded into a fixed-bed reactor, and sulfidation began after the gas tightness was verified. The system pressure was 5.5 MPa, and the hydrogen volume hourly space velocity was 800 h⁻¹. -1 Hydrogen gas was introduced, and the temperature was increased from room temperature to 150°C at a rate of 30°C / h. A sulfurizing agent containing 0.5 wt% sulfur was then introduced, and the temperature was increased to 180°C at a rate of 5°C / h for 6 hours, held at this temperature for 5 hours, then increased to 230°C at a rate of 5°C / h for 10 hours, held at this temperature for 4 hours, then increased to 280°C at a rate of 10°C / h for 5 hours, held at this temperature for 4 hours, then increased to 320°C at a rate of 10°C / h for 4 hours, and held at this temperature for 2 hours. The sulfidation of the catalyst was then completed. The TEM image of the sulfidated catalyst was obtained using a G2F30 transmission electron microscope (TEM) from FEI Corporation, USA. Figure 2 As can be seen from the figure, the active phase of the sulfide catalyst has a tower-like structure with 4-10 stacked layers; the spacing between the stacked layers is 0.2-2 nm; and the stack length is 6-12 nm. The relatively long stack is not conducive to the formation of a sufficient number of hydrogenation active centers.

[0159] The temperature was lowered to 240℃ and the pressure reduced to 3.0 MPa. The first-stage hydrogenation product, after deweighting and diene removal, was then introduced. The H2 / Oil molar ratio was 1000, and the liquid hourly space velocity (LHSV) of the feedstock was 0.8 h⁻¹. -1 .

[0160] The evaluation results of the catalyst are listed in Table 2.

[0161] Example 7

[0162] 1. Weigh 720 g of ammonium metatungstate, 130 g of ammonium molybdate, and 15 g of lanthanum nitrate, dissolve them in 500 g of deionized water, add 57 g of phosphoric acid, and stir at room temperature for 30 minutes to obtain aqueous solution I. Weigh 45 g of nickel nitrate and 8.11 g of 1,2-cyclohexanediaminetetraacetic acid, dissolve them in 200 g of deionized water, and stir at room temperature for 30 minutes to obtain aqueous solution II. Mix aqueous solutions I and II, add 54 g of ethylene glycol and 27 g of 2-butanone, and dilute to 1 L with deionized water. Continue stirring at room temperature for 30 minutes to obtain solution III. The concentration of the Group VIB metal precursor in solution III is 850 g / L, the concentration of the Group VIII metal precursor is 45 g / L, the atomic molar ratio of the first auxiliary agent to the Group VIB metal is 1.0, and the atomic molar ratio of the second auxiliary agent to the Group VIII metal is 0.14. The mass ratio of ethylene glycol to 2-butanone in the third auxiliary agent is 2.

[0163] 2. Catalyst Preparation

[0164] Take 1000g of Al2O3-TiO2-SiO2 support (Al2O3, 97%, TiO2, 1.5%, SiO2, 1.5%) into a rotary pot, slowly add the solution III prepared in step 1, rotate the pot at 58 rpm, and soak for 10 minutes.

[0165] For health preservation, the soaked carrier is preserved at 30℃ for 48 hours.

[0166] Dry, airy atmosphere, starting at 25°C, increasing to 70°C at 10°C / hour, holding at that temperature for 8 hours, then increasing to 110°C at 10°C / hour, holding at that temperature for 4 hours.

[0167] Firing: In air atmosphere, start at 25°C, increase to 445°C at 140°C / hour, and hold at that temperature for 3 hours.

[0168] The catalyst composition is shown in Table 1.

[0169] 3. Catalyst sulfidation and evaluation

[0170] The catalyst prepared in step 2 was loaded into a fixed-bed reactor, and sulfidation began after the gas tightness was verified. The system pressure was 5.5 MPa, and the hydrogen volume hourly space velocity was 800 h⁻¹. -1 Hydrogen gas was introduced, and the temperature was increased from room temperature to 150°C at a rate of 30°C / h. A sulfurizing agent containing 0.5 wt% sulfur was then introduced, and the temperature was increased to 180°C at a rate of 5°C / h for 6 hours, held at this temperature for 5 hours, then increased to 230°C at a rate of 5°C / h for 10 hours, held at this temperature for 4 hours, then increased to 280°C at a rate of 10°C / h for 5 hours, held at this temperature for 4 hours, then increased to 320°C at a rate of 10°C / h for 4 hours, and held at this temperature for 2 hours, at which point the catalyst sulfidation was complete. The sulfided catalyst was tested using a G2F30 transmission electron microscope (TEM) from FEI Corporation, USA. The images show that the active phase of the sulfided catalyst exhibits a tower-like structure with 3-5 stacked layers; the interlayer spacing is 0.2-2 nm; and the stack length is 3-6 nm.

[0171] The temperature was lowered to 240℃ and the pressure reduced to 3.0 MPa. The first-stage hydrogenation product, after deweighting and diene removal, was then introduced. The H2 / Oil molar ratio was 1000, and the liquid hourly space velocity (LHSV) of the feedstock was 0.8 h⁻¹. -1 .

[0172] The evaluation results of the catalyst are listed in Table 2.

[0173] Example 8

[0174] 1. Weigh 130 g of ammonium metatungstate, dissolve 10 g of ammonium molybdate, and dissolve 15 g of lanthanum nitrate in 500 g of deionized water. Add 5 g of phosphoric acid and stir at room temperature for 30 minutes to obtain aqueous solution I. Weigh 250 g of nickel nitrate and 42.5 g of 1,2-cyclohexanediaminetetraacetic acid and dissolve in 200 g of deionized water. Stir at room temperature for 30 minutes to obtain aqueous solution II. Mix aqueous solutions I and II, add 54 g of ethylene glycol and 27 g of 2-butanone, and dilute to 1 L with deionized water. Continue stirring at room temperature for 30 minutes to obtain solution III. The concentration of the Group VIB metal precursor in solution III is 140 g / L, the concentration of the Group VIII metal precursor is 250 g / L, the atomic molar ratio of the first auxiliary agent to the Group VIB metal is 1.0, and the atomic molar ratio of the second auxiliary agent to the Group VIII metal is 0.14. The mass ratio of ethylene glycol to 2-butanone in the third auxiliary agent is 2.

[0175] 2. Catalyst Preparation

[0176] Take 1000g of Al2O3-TiO2-SiO2 support (Al2O3, 97%, TiO2, 1.5%, SiO2, 1.5%) into a rotary pot, slowly add the solution III prepared in step 1, rotate the pot at 58 rpm, and soak for 10 minutes.

[0177] For health preservation, the soaked carrier is kept at 30℃ for 48 hours.

[0178] Dry, airy atmosphere, starting at 25°C, increasing to 70°C at 10°C / hour, holding at that temperature for 8 hours, then increasing to 110°C at 10°C / hour, holding at that temperature for 4 hours.

[0179] Firing: In air atmosphere, start at 25°C, increase to 445°C at 140°C / hour, and hold at that temperature for 3 hours.

[0180] The catalyst composition is shown in Table 1.

[0181] 3. Catalyst sulfidation and evaluation

[0182] The catalyst prepared in step 2 was loaded into a fixed-bed reactor, and sulfidation began after the gas tightness was verified. The system pressure was 5.5 MPa, and the hydrogen volume hourly space velocity was 800 h⁻¹. -1Hydrogen gas was introduced, and the temperature was increased from room temperature to 150°C at a rate of 30°C / h. A sulfurizing agent containing 0.5 wt% sulfur was then introduced, and the temperature was increased to 180°C at a rate of 5°C / h for 6 hours, held at this temperature for 5 hours, then increased to 230°C at a rate of 5°C / h for 10 hours, held at this temperature for 4 hours, then increased to 280°C at a rate of 10°C / h for 5 hours, held at this temperature for 4 hours, then increased to 320°C at a rate of 10°C / h for 4 hours, and held at this temperature for 2 hours, at which point the catalyst sulfidation was complete. The sulfided catalyst was tested using a G2F30 transmission electron microscope (TEM) from FEI Corporation, USA. The images show that the active phase of the sulfided catalyst exhibits a tower-like structure with 3-5 stacked layers; the interlayer spacing is 0.2-2 nm; and the stack length is 3-6 nm.

[0183] The temperature was lowered to 240℃ and the pressure reduced to 3.0 MPa. The first-stage hydrogenation product, after deweighting and diene removal, was then introduced. The H2 / Oil molar ratio was 1000, and the liquid hourly space velocity (LHSV) of the feedstock was 0.8 h⁻¹. -1 .

[0184] The evaluation results of the catalyst are listed in Table 2.

[0185] Example 9

[0186] 1. Weigh 720 g of ammonium metatungstate, 130 g of ammonium molybdate, and 15 g of lanthanum nitrate, dissolve them in 500 g of deionized water, add 80 g of phosphoric acid, and stir at room temperature for 30 minutes to obtain aqueous solution I. Weigh 250 g of nickel nitrate and 42.5 g of 1,2-cyclohexanediaminetetraacetic acid, dissolve them in 200 g of deionized water, and stir at room temperature for 30 minutes to obtain aqueous solution II. Mix aqueous solutions I and II, add 54 g of ethylene glycol and 27 g of 2-butanone, and dilute to 1 L with deionized water. Continue stirring at room temperature for 30 minutes to obtain solution III. The concentration of the Group VIB metal precursor in solution III is 850 g / L, the concentration of the Group VIII metal precursor is 250 g / L, the atomic molar ratio of the first auxiliary agent to the Group VIB metal is 1.4, and the atomic molar ratio of the second auxiliary agent to the Group VIII metal is 0.14. The mass ratio of ethylene glycol to 2-butanone in the third auxiliary agent is 2.

[0187] 2. Catalyst Preparation

[0188] Take 1000g of Al2O3-TiO2-SiO2 support (Al2O3, 97%, TiO2, 1.5%, SiO2, 1.5%) into a rotary pot, slowly add the solution III prepared in step 1, rotate the pot at 58 rpm, and soak for 10 minutes.

[0189] For health preservation, the soaked carrier is preserved at 30℃ for 48 hours.

[0190] Dry, airy atmosphere, starting at 25°C, increasing to 70°C at 10°C / hour, holding at that temperature for 8 hours, then increasing to 110°C at 10°C / hour, holding at that temperature for 4 hours.

[0191] Firing: In air atmosphere, start at 25°C, increase to 445°C at 140°C / hour, and hold at that temperature for 3 hours.

[0192] The catalyst composition is shown in Table 1.

[0193] 3. Catalyst sulfidation and evaluation

[0194] The catalyst prepared in step 2 was loaded into a fixed-bed reactor, and sulfidation began after the gas tightness was verified. The system pressure was 5.5 MPa, and the hydrogen volume hourly space velocity was 800 h⁻¹. -1 Hydrogen gas was introduced, and the temperature was increased from room temperature to 150°C at a rate of 30°C / h. A sulfurizing agent containing 0.5 wt% sulfur was then introduced, and the temperature was increased to 180°C at a rate of 5°C / h for 6 hours, held at this temperature for 5 hours, then increased to 230°C at a rate of 5°C / h for 10 hours, held at this temperature for 4 hours, then increased to 280°C at a rate of 10°C / h for 5 hours, held at this temperature for 4 hours, then increased to 320°C at a rate of 10°C / h for 4 hours, and held at this temperature for 2 hours, at which point the catalyst sulfidation was complete. The sulfided catalyst was tested using a G2F30 transmission electron microscope (TEM) from FEI Corporation, USA. The images show that the active phase of the sulfided catalyst exhibits a tower-like structure with 3-5 stacked layers; the interlayer spacing is 0.2-2 nm; and the stack length is 3-6 nm.

[0195] The temperature was lowered to 240℃ and the pressure reduced to 3.0 MPa. The first-stage hydrogenation product, after deweighting and diene removal, was then introduced. The H2 / Oil molar ratio was 1000, and the liquid hourly space velocity (LHSV) of the feedstock was 0.8 h⁻¹. -1 .

[0196] The evaluation results of the catalyst are listed in Table 2.

[0197] Example 10

[0198] 1. Weigh 720 g of ammonium metatungstate, 130 g of ammonium molybdate, and 15 g of lanthanum nitrate, dissolve them in 500 g of deionized water, add 57 g of phosphoric acid, and stir at room temperature for 30 minutes to obtain aqueous solution I. Weigh 250 g of nickel nitrate and 42.5 g of 1,2-cyclohexanediaminetetraacetic acid, dissolve them in 200 g of deionized water, and stir at room temperature for 30 minutes to obtain aqueous solution II. Mix aqueous solutions I and II, add 54 g of ethylene glycol and 27 g of 2-butanone, and dilute to 1 L with deionized water. Continue stirring at room temperature for 30 minutes to obtain solution III. The concentration of the Group VIB metal precursor in solution III is 850 g / L, the concentration of the Group VIII metal precursor is 250 g / L, the atomic molar ratio of the first auxiliary agent to the Group VIB metal is 1.0, and the atomic molar ratio of the second auxiliary agent to the Group VIII metal is 0.14. The mass ratio of ethylene glycol to 2-butanone in the third auxiliary agent is 2.

[0199] 2. Catalyst Preparation

[0200] Take 1000g of Al2O3-TiO2-SiO2 support (Al2O3, 97%, TiO2, 1.5%, SiO2, 1.5%) into a rotary pot, slowly add the solution III prepared in step 1, rotate the pot at 58 rpm, and soak for 10 minutes.

[0201] For health preservation, the soaked carrier is kept at 30℃ for 48 hours.

[0202] Dry, airy atmosphere, starting at 25°C, increasing to 70°C at 10°C / hour, holding at that temperature for 8 hours, then increasing to 110°C at 10°C / hour, holding at that temperature for 4 hours.

[0203] Firing: In air atmosphere, start at 25°C, increase to 445°C at 140°C / hour, and hold at that temperature for 3 hours.

[0204] The catalyst composition is shown in Table 1.

[0205] 3. Catalyst sulfidation and evaluation

[0206] The catalyst prepared in step 2 was loaded into a fixed-bed reactor, and sulfidation began after the gas tightness was verified. The system pressure was 5.5 MPa, and the hydrogen volume hourly space velocity was 800 h⁻¹. -1 Hydrogen gas was introduced, and the temperature was increased from room temperature to 150°C at a rate of 30°C / h. A sulfurizing agent containing 0.5 wt% sulfur was then introduced, and the temperature was increased to 180°C at a rate of 5°C / h for 6 hours. The temperature was then increased to 320°C at a rate of 10°C / h and held at this temperature for 2 hours, at which point the catalyst sulfidation was complete. The sulfidated catalyst was tested using a G2F30 transmission electron microscope (TEM) from FEI Corporation, USA. Figure 7 As can be seen from the figure, the number of active phase stacking layers of the sulfidation catalyst is 3-10; the stacking layer spacing is 0.2-2 nm; and the stacking length is 3-12 nm.

[0207] The temperature was lowered to 240℃ and the pressure reduced to 3.0 MPa. The first-stage hydrogenation product, after deweighting and diene removal, was then introduced. The H2 / Oil molar ratio was 1000, and the liquid hourly space velocity (LHSV) of the feedstock was 0.8 h⁻¹. -1 .

[0208] The evaluation results of the catalyst are listed in Table 2.

[0209] Comparative Example 1

[0210] 1. Weigh 720 g of ammonium metatungstate, 130 g of ammonium molybdate, and 15 g of lanthanum nitrate, dissolve them in 500 g of deionized water, add 57 g of phosphoric acid, and stir at room temperature for 30 minutes to obtain aqueous solution I. Weigh 250 g of nickel nitrate and 42.5 g of 1,2-cyclohexanediaminetetraacetic acid, dissolve them in 200 g of deionized water, and stir at room temperature for 30 minutes to obtain aqueous solution II. Mix aqueous solutions I and II, add 54 g of ethylene glycol and 27 g of cyclohexanone, and dilute to 1 L with deionized water. Continue stirring at room temperature for 30 minutes to obtain solution III. The concentration of the Group VIB metal precursor in solution III is 850 g / L, the concentration of the Group VIII metal precursor is 250 g / L, the atomic molar ratio of the first auxiliary agent to the Group VIB metal is 1.0, and the atomic molar ratio of the second auxiliary agent to the Group VIII metal is 0.14. The mass ratio of ethylene glycol to cyclohexanone in the third auxiliary agent is 2.

[0211] 2. Catalyst Preparation

[0212] Take 1000g of Al2O3-TiO2-SiO2 support (Al2O3, 97%, TiO2, 1.5%, SiO2, 1.5%) into a rotary pot, slowly add the solution III prepared in step 1, rotate the pot at 58 rpm, and soak for 10 minutes.

[0213] For health preservation, the soaked carrier is kept at 30℃ for 48 hours.

[0214] Dry, airy atmosphere, starting at 25°C, increasing to 70°C at 10°C / hour, holding at that temperature for 8 hours, then increasing to 110°C at 10°C / hour, holding at that temperature for 4 hours.

[0215] Firing: In air atmosphere, start at 25°C, increase to 445°C at 140°C / hour, and hold at that temperature for 3 hours.

[0216] The catalyst composition is shown in Table 1.

[0217] 3. Catalyst sulfidation and evaluation

[0218] The catalyst prepared in step 2 was loaded into a fixed-bed reactor, and sulfidation began after the gas tightness was verified. The system pressure was 5.5 MPa, and the hydrogen volume hourly space velocity was 800 h⁻¹. -1 Hydrogen gas was introduced, and the temperature was increased from room temperature to 150°C at a rate of 30°C / h. A sulfurizing agent containing 0.5 wt% sulfur was then introduced, and the temperature was increased to 180°C at a rate of 5°C / h for 6 hours, held at this temperature for 5 hours, then increased to 230°C at a rate of 5°C / h for 10 hours, held at this temperature for 4 hours, then increased to 280°C at a rate of 10°C / h for 5 hours, held at this temperature for 4 hours, then increased to 320°C at a rate of 10°C / h for 4 hours, and held at this temperature for 2 hours, thus completing the catalyst sulfidation. The sulfidated catalyst was tested using a G2F30 transmission electron microscope (TEM) from FEI Corporation, USA. (TEM image obtained). Figure 6As can be seen from the figure, the active phase of the sulfide catalyst is unevenly distributed, with only a very small amount forming a tower-shaped structure. The large amount of black components in the image are caused by the agglomeration of the active components.

[0219] The temperature was lowered to 240℃ and the pressure reduced to 3.0 MPa. The first-stage hydrogenation product, after deweighting and diene removal, was then introduced. The H2 / Oil molar ratio was 1000, and the liquid hourly space velocity (LHSV) of the feedstock was 0.8 h⁻¹. -1 .

[0220] The evaluation results of the catalyst are listed in Table 2.

[0221] Comparative Example 2

[0222] 1. Weigh 720 g of ammonium metatungstate, 130 g of ammonium molybdate, and 15 g of lanthanum nitrate, dissolve them in 500 g of deionized water, add 57 g of phosphoric acid, and stir at room temperature for 30 minutes to obtain aqueous solution I; weigh 250 g of nickel nitrate and 42.5 g of 1,2-cyclohexanediaminetetraacetic acid, dissolve them in 200 g of deionized water, and stir at room temperature for 30 minutes to obtain aqueous solution II. Mix aqueous solution I and aqueous solution II, and dilute to 1 L with deionized water. Continue stirring at room temperature for 30 minutes to obtain solution III. The concentration of the Group VIB metal precursor in solution III is 850 g / L, the concentration of the Group VIII metal precursor is 250 g / L, the atomic molar ratio of the first auxiliary agent to the Group VIB metal is 1.0, and the atomic molar ratio of the second auxiliary agent to the Group VIII metal is 0.14.

[0223] 2. Catalyst Preparation

[0224] Take 1000g of Al2O3-TiO2-SiO2 support (Al2O3, 97%, TiO2, 1.5%, SiO2, 1.5%) into a rotary pot, slowly add the solution III prepared in step 1, rotate the pot at 58 rpm, and soak for 10 minutes.

[0225] For health preservation, the soaked carrier is kept at 30℃ for 48 hours.

[0226] Dry, airy atmosphere, starting at 25°C, increasing to 70°C at 10°C / hour, holding at that temperature for 8 hours, then increasing to 110°C at 10°C / hour, holding at that temperature for 4 hours.

[0227] Firing: In air atmosphere, start at 25°C, increase to 445°C at 140°C / hour, and hold at that temperature for 3 hours.

[0228] The catalyst composition is shown in Table 1.

[0229] 3. Catalyst sulfidation and evaluation

[0230] The catalyst prepared in step 2 was loaded into a fixed-bed reactor, and sulfidation began after the gas tightness was verified. The system pressure was 5.5 MPa, and the hydrogen volume hourly space velocity was 800 h⁻¹. -1Hydrogen gas was introduced, and the temperature was increased from room temperature to 150°C at a rate of 30°C / h. A sulfurizing agent containing 0.5 wt% sulfur was then introduced, and the temperature was increased to 180°C at a rate of 5°C / h for 6 hours, held at this temperature for 5 hours, then increased to 230°C at a rate of 5°C / h for 10 hours, held at this temperature for 4 hours, then increased to 280°C at a rate of 10°C / h for 5 hours, held at this temperature for 4 hours, then increased to 320°C at a rate of 10°C / h for 4 hours, and held at this temperature for 2 hours. The sulfidation of the catalyst was then completed. The TEM image of the sulfidated catalyst was obtained using a G2F30 transmission electron microscope (TEM) from FEI Corporation, USA. Figure 3 As can be seen from the figure, the active phase of the sulfide catalyst is extremely unevenly distributed, and no obvious tower-shaped structure is observed.

[0231] The temperature was lowered to 240℃ and the pressure reduced to 3.0 MPa. The first-stage hydrogenation product, after deweighting and diene removal, was then introduced. The H2 / Oil molar ratio was 1000, and the liquid hourly space velocity (LHSV) of the feedstock was 0.8 h⁻¹. -1 .

[0232] The evaluation results of the catalyst are listed in Table 2.

[0233] Comparative Example 3

[0234] 1. Weigh 100g of ammonium metatungstate, 60g of ammonium molybdate, and 15g of lanthanum nitrate, dissolve them in 300g of deionized water, add 5g of phosphoric acid, and stir at room temperature for 30 minutes to obtain aqueous solution I. Weigh 45g of nickel nitrate and 8.5g of 1,2-cyclohexanediaminetetraacetic acid, dissolve them in 200g of deionized water, and stir at room temperature for 30 minutes to obtain aqueous solution II. Mix aqueous solution I and aqueous solution II, add 10g of ethylene glycol and 5g of 2-butanone, and dilute to 1L with deionized water. Continue stirring at room temperature for 30 minutes to obtain solution III. The concentration of the Group VIB metal precursor in solution III is 110g / L, the concentration of the Group VIII metal precursor is 45g / L, the atomic molar ratio of the first auxiliary agent to the Group VIB metal is 0.28, and the atomic molar ratio of the second auxiliary agent to the Group VIII metal is 0.157. The mass ratio of ethylene glycol to 2-butanone in the third auxiliary agent is 2.

[0235] 2. Catalyst Preparation

[0236] Take 1000g of Al2O3-TiO2-SiO2 support (Al2O3, 97%, TiO2, 1.5%, SiO2, 1.5%) into a rotary pot, slowly add the solution III prepared in step 1, rotate the pot at 58 rpm, and soak for 10 minutes.

[0237] For health preservation, the soaked carrier is preserved at 30℃ for 48 hours.

[0238] Dry, airy atmosphere, starting at 25°C, increasing to 70°C at 10°C / hour, holding at that temperature for 8 hours, then increasing to 110°C at 10°C / hour, holding at that temperature for 4 hours.

[0239] Firing: In air atmosphere, start at 25°C, increase to 445°C at 140°C / hour, and hold at that temperature for 3 hours.

[0240] The catalyst composition is shown in Table 1.

[0241] 3. Catalyst sulfidation and evaluation

[0242] The catalyst prepared in step 2 was loaded into a fixed-bed reactor, and sulfidation began after the gas tightness was verified. The system pressure was 5.5 MPa, and the hydrogen volume hourly space velocity was 800 h⁻¹. -1 Hydrogen gas was introduced, and the temperature was increased from room temperature to 150°C at a rate of 30°C / h. A sulfurizing agent containing 0.5 wt% sulfur was then introduced, and the temperature was increased to 180°C at a rate of 5°C / h for 6 hours, held at this temperature for 5 hours, then increased to 230°C at a rate of 5°C / h for 10 hours, held at this temperature for 4 hours, then increased to 280°C at a rate of 10°C / h for 5 hours, held at this temperature for 4 hours, then increased to 320°C at a rate of 10°C / h for 4 hours, and held at this temperature for 2 hours. The sulfidation of the catalyst was then completed. The TEM image of the sulfidated catalyst was obtained using a G2F30 transmission electron microscope (TEM) from FEI Corporation, USA. Figure 4 As can be seen from the figure, the active components are scarce, and the few active components are distributed haphazardly on the crystal wafers.

[0243] The temperature was lowered to 240℃ and the pressure reduced to 3.0 MPa. The first-stage hydrogenation product, after deweighting and diene removal, was then introduced. The H2 / Oil molar ratio was 1000, and the liquid hourly space velocity (LHSV) of the feedstock was 0.8 h⁻¹. -1 .

[0244] The evaluation results of the catalyst are listed in Table 2.

[0245] Table 1

[0246]

[0247]

[0248] Table 2

[0249]

[0250] 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: (1) Prepare solution I by mixing group VIB metal precursor, lanthanide metal precursor and first auxiliary agent; prepare solution II by mixing group VIII metal precursor and optional second auxiliary agent; mix solution I and solution II, add third auxiliary agent to obtain solution III; (2) Solution III comes into contact with the carrier, and is then cured, dried, and calcined; Wherein, the first auxiliary agent is an amino compound and / or an inorganic acid; the second auxiliary agent is an organic acid-metal complexing agent; and the third auxiliary agent is a mixture of water-soluble alcohols and ketones. The concentration of Group VIII metal precursor in solution III is above 45 g / L, and the concentration of Group VIB metal precursor is above 140 g / L.

2. The preparation method according to claim 1, wherein, The concentration of Group VIII metal precursor in solution III is 50-500 g / L, and the concentration of Group VIB metal precursor is 150-850 g / L.

3. The preparation method according to claim 2, wherein, The ratio of the concentration of Group VIII metal precursor to the concentration of Group VIB metal precursor in solution III is 0.1-1.

2.

4. The preparation method according to claim 2, wherein, The ratio of the concentration of Group VIII metal precursor to the concentration of Group VIB metal precursor in solution III is 0.35-1.

0.

5. The preparation method according to claim 1, wherein, The first adjuvant is selected from at least one of urea, acetamide, ethylenediamine, ethanolamine, diethanolamine, triethanolamine, phosphoric acid, nitric acid, and sulfuric acid; and / or The second adjuvant is selected from at least one of 1,2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid, ethylenediaminetetraacetic acid, salicylic acid, and aminotriacetic acid.

6. The preparation method according to claim 5, wherein, The third adjuvant is a mixture of water-soluble alcohol and ketone, wherein the mass ratio of water-soluble alcohol to ketone in the mixture is 0.05-2.

7. The preparation method according to claim 6, wherein, The third adjuvant is selected from a mixture of ethylene glycol and / or ethanol with acetone and / or 2-butanone.

8. The preparation method according to claim 1, wherein, The molar ratio of the first auxiliary agent to the Group VIB metal atoms is 0.1-1.2; and / or The molar ratio of the second additive to the Group VIII metal atoms is 0.05-1.

2.

9. The preparation method according to claim 8, wherein, The molar ratio of the first auxiliary agent to the Group VIB metal atoms is 0.25-1.0; and / or The molar ratio of the second additive to the Group VIII metal atoms is 0.14-0.

8.

10. The preparation method according to claim 1, wherein, In step (2), solution III is in contact with the carrier at a mass ratio of 0.5-2.5; and / or The support is selected from at least one of Al2O3, Al2O3-TiO2, Al2O3-TiO2-SiO2, and Al2O3-SiO2; and / or The group VIB metal elements are selected from Mo, W, Cr; and / or The group VIII metallic elements are selected from Fe, Co, Ni, Pt, and Pd; The lanthanide metal elements are La and / or Ce.

11. The preparation method according to claim 10, wherein, In step (2), solution III is contacted with the carrier at a mass ratio of 1.0-2.0; and / or The support is selected from at least one of Al2O3, Al2O3-TiO2, and Al2O3-TiO2-SiO2; and / or The group VIB metal element is Mo and / or W; and / or The Group VIII metal element is Ni and / or Co.

12. The preparation method according to any one of claims 1-11, wherein, The conditions for contact include: Contact temperature is 0-60 ℃; and / or The contact time is 5-60 minutes; and / or The conditions for maintaining health include: The optimal temperature for health maintenance is 0-60℃; and / or The duration of health maintenance is 2-96 hours. and / or The drying conditions include: The drying temperature is 50-130℃; and / or The drying time is 3-46 hours; and / or The volumetric space velocity of air is 2-250 h. -1 ; and / or The roasting conditions include: The roasting temperature is 150-520℃; and / or The roasting time is 2-24 hours; and / or The volumetric space velocity of air is 2-250 h. -1 .

13. The preparation method according to claim 12, wherein, The conditions for contact include: Contact temperature is 20-40 ℃; and / or Contact time is 8-40 minutes; and / or The conditions for maintaining health include: The optimal temperature for health maintenance is 20-40℃; and / or The recommended duration of health maintenance is 6-48 hours. and / or The drying conditions include: The drying temperature is 60-120℃; and / or The drying time is 6-36 hours; and / or The volumetric space velocity of air is 20-150 h⁻¹ -1 ; and / or The roasting conditions include: The roasting temperature is 280-500℃; and / or The roasting time is 3-12 hours; and / or The volumetric space velocity of air is 25-150 h⁻¹ -1 .

14. A hydrogenation catalyst prepared by the method according to any one of claims 1-13, characterized in that, The catalyst comprises an active phase and a support, wherein the active phase contains Group VIB metals, lanthanides, and Group VIII metals; The active phase of the catalyst, after sulfidation, has a tower-shaped structure.

15. The hydrogenation catalyst according to claim 14, wherein, The tower-shaped structure has 3-10 stacking layers; and / or The stacking layer spacing of the tower-shaped structure is 0.2-2 nm; and / or The stacking length of the tower-shaped structure is 3-6 nm; and / or The catalyst contains 15%-60% active phase by mass; 40%-85% support by mass; and / or Based on oxides, the mass ratio of Group VIB metals to Group VIII metals in the active phase is 0.1-15; and / or The content of lanthanide metal elements in the active phase is 0.1-0.5 wt% based on oxides.

16. The hydrogenation catalyst according to claim 15, wherein, The tower-shaped structure has 3-5 stacking layers; and / or The stacking length of the tower-shaped structure is 3-6 nm; and / or The catalyst contains 18%-55% active phase by mass; 45%-82% support by mass; and / or Based on oxides, the mass ratio of Group VIB metals to Group VIII metals in the active phase is 0.8-12.

17. The hydrogenation catalyst according to claim 15, wherein, The group VIB metal elements are selected from Mo, W, Cr; and / or The Group VIII metallic elements are selected from Fe, Co, Ni, Pt, Pd; and / or The lanthanide metal element is La and / or Ce; and / or The support is selected from at least one of Al2O3, Al2O3-TiO2, Al2O3-TiO2-SiO2, and Al2O3-SiO2.

18. The hydrogenation catalyst according to claim 17, wherein, The group VIB metal element is Mo and / or W; and / or The Group VIII metallic element is Ni and / or Co; and / or The support is selected from at least one of Al2O3, Al2O3-TiO2, and Al2O3-TiO2-SiO2.

19. A sulfidation catalyst, characterized in that, The sulfidated catalyst is obtained by sulfidation treatment of the hydrogenation catalyst according to any one of claims 14-18; The active phase of the sulfide-type catalyst has a tower-shaped structure.

20. The hydrogenation catalyst according to claim 19, wherein, The tower-shaped structure has 3-10 stacking layers; and / or The stacking layer spacing of the tower-shaped structure is 0.2-2 nm; and / or The stacking length of the tower-shaped structure is 3-12 nm.

21. The hydrogenation catalyst according to claim 20, wherein, The tower-shaped structure has 3-5 stacking layers; and / or The stacking length of the tower-shaped structure is 3-6 nm.

22. The application of the hydrotreating catalyst according to any one of claims 14-18 and / or the sulfidation catalyst according to any one of claims 19-21 in the hydrotreating of feedstock oil, characterized in that, The hydrogenation catalyst according to any one of claims 14-18 is subjected to sulfidation treatment before hydrogenation.

23. The application according to claim 22, wherein, The hydrogenation conditions include: an inlet temperature of 200-270℃, a reaction pressure of 2.3-6.0 MPa, a hydrogen-to-oil volume ratio of 400-1500, and a liquid hourly space velocity of 0.2-1.8 h⁻¹. -1 ; and / or The vulcanization conditions include: a sulfur content of 0.05-2 wt% in the vulcanizing agent; and / or a vulcanization temperature of 120-380℃; and / or a vulcanization time of 8-72 h; and / or a vulcanizing agent volume hourly space velocity of 0.3-3 h⁻¹. -1 ; and / or hydrogen-to-oil volume ratio of 300-2000; and / or sulfidation pressure of 0.5-10.0 MPa; and / or The feedstock oil is selected from ethylene tar after deweighting and primary hydrogenation to olefins.

24. The application according to claim 22, wherein, The vulcanization conditions include: a vulcanization temperature of 150-360℃; and / or a vulcanization time of 8-56 hours; and / or a vulcanizing agent volume hourly space velocity of 0.5-1.5 h⁻¹. -1 ; and / or hydrogen-to-oil volume ratio of 500-1500; and / or sulfidation pressure of 1.0-6.0 MPa.

25. The application according to claim 22, wherein, Vulcanization is carried out by programmed temperature rise, including: initial temperature of 25-150℃, heating rate of 5-15℃ / min, step temperature interval of 50-80℃, step temperature holding time of 4-10h, final temperature of 320-360℃, and final temperature treatment time of 27-35h.

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