Hydrogenation catalysts and methods for their preparation and use

Abstract

The present invention discloses a hydrogenation catalyst, its preparation method, and its use. The hydrogenation catalyst is a sulfide-state hydrogenation catalyst comprising a carrier, an active component A, an active component B, and a modifying aid component. The active component A is at least one metal element selected from Group VIII, the active component B is at least one metal element selected from Group VIB, and the modifying aid component is at least one element selected from Groups IB, IIA, IIB, IIIA, and VIA. TEM-EDS analysis of the hydrogenation catalyst revealed that the content of the modifying aid component distributed within the ABS active phase region accounts for 60% to 98% of the total content of the modifying aid component. The hydrogenation catalyst of the present invention has relatively high hydrotreating capacity and stability.

Description

Detailed Description of the Invention

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of Chinese Patent Application No. 202211136689.1, filed on September 19, 2022, the contents of which are incorporated herein by reference.

[0002] [Technical Field] The present invention is in the field of hydrogenation catalysts and relates to hydrogenation catalysts and their preparation and use.

[0003] [Background technology] Currently, the active phase used in residue hydrotreating is mainly Co(Ni)-Mo(W)-S. To better meet various needs, the active phase can be modified with heteroatoms during the catalyst preparation process to improve the catalyst's performance.

[0004] CN101722039A discloses a hydrogenation catalyst and its preparation method, in which gallium and rare earth metal elements are introduced during the catalyst preparation process to modify the catalyst. In this modification method, the additives mainly modify the support, so the improvement effect is limited and the active metals are significantly migrated during the heavy oil processing process.

[0005] CN113559875A discloses a hydrogenation catalyst and its preparation method, in which phosphorus and magnesium are introduced as auxiliary agents during the support preparation process to adjust the pore structure and pore diffusion of the catalyst. This method still relies mainly on support modification, without targeting the active phase, and is therefore not suitable for the hydrotreating of unconventional, low-quality feedstocks.

[0006] CN101844081A discloses a method for preparing a selective hydrogenation catalyst, in which the hydrodesulfurization effect of the catalyst is improved by introducing a zinc auxiliary during the active metal impregnation process. However, in this modification method, it is difficult to simultaneously sulfurize zinc and nickel, and a large amount of the active phase remains unmodified by Zn. As a result, the desulfurization activity is insufficient when processing low-quality petroleum products, especially residual oils with a relatively high sulfur content.

[0007] Summary of the Invention [Problem to be solved by the invention] In order to overcome the problems of the prior art hydrogenation catalysts that need to be further improved in hydrotreating capacity, crude oil compatibility and stability, the present invention provides a hydrogenation catalyst and its preparation method and use, and the hydrogenation catalyst according to the present invention has relatively high hydrotreating capacity and stability and is suitable for treating various crude oils.

[0008] [Means for solving the problem] A first aspect of the present invention provides a hydrogenation catalyst, the hydrogenation catalyst being a sulfide-state hydrogenation catalyst comprising a carrier, an active component A, an active component B, and a modifying aid component, wherein the active component A is at least one selected from Group VIII metal elements, the active component B is at least one selected from Group VIB metal elements, and the modifying aid component is at least one selected from Group IB, Group IIA, Group IIB, Group IIIA, and Group VIA elements; The hydrogenation catalyst was characterized by the TEM-EDS method, and the content of the modifying aid component distributed in the ABS active phase region was found to account for 60% to 95%, preferably 75% to 90%, of the total content of the modifying aid components.

[0009] In the hydrogenation catalyst according to the present invention, the content of the modifying aid component distributed in the region of the ABS active phase is relatively high, so that the modifying aid component can play a better role and effectively combine with the ABS active phase.

[0010] As a result of research, the present inventors have found that most of the prior art focuses on the problem of introducing metal assistants into oxidized state hydrogenation catalysts, but the present inventors have found that this modification has problems such as no orientation, lack of specificity, low effectiveness, insufficient compatibility with petroleum products and insufficient stability.

[0011] A second aspect of the present invention provides a method for preparing a hydrogenation catalyst, the method comprising: (1) sulfiding the oxidized state hydrogenation catalyst to obtain a sulfided state hydrogenation catalyst; (2) desulfurizing the sulfided hydrogenation catalyst; and step (3) catalytically reacting the treated catalyst obtained in step (2) with a material containing a precursor of the modifying aid component, The modifying aid component is at least one selected from Group IB, Group IIA, Group IIB, Group IIIA, and Group VIA elements.

[0012] In the method for preparing the hydrogenation catalyst according to the present invention, the oxidized hydrogenation catalyst is first sulfurized and then desulfurized, so that the metal active phase to be modified reaches a specific desulfurized high activity state, and the outer edge of the active phase becomes an exposed active metal. This effectively maintains the tricoordinated sulfur atoms and stable ABS crystal structure inside the hydrogenation active phase, allowing the modification aid component to more effectively contact with the metal phase in the outer layer of the active phase. In the obtained hydrogenation catalyst, the modification aid component (represented by R) forms an A, B, and S RABS composite mixed active phase, thereby achieving the purpose of modification.

[0013] A third aspect of the present invention provides the use of a hydrogenation catalyst according to the first aspect or prepared by the method according to the second aspect in the hydrogenation of petroleum products.

[0014] The catalyst according to the present invention is applied to the hydrogenation of petroleum products and has relatively high hydrotreating capacity and stability. By selecting different modifier components, the catalyst according to the present invention can also obtain additional advantages such as selectivity.

[0015] [Mode for Carrying Out the Invention] The endpoints of the ranges and any values ​​disclosed herein should be understood not to be limited to the exact range or value, but to include values ​​close to these ranges or values. In the case of numerical ranges, the endpoints of each range, the endpoints of each range and individual dot values, and the individual dot values ​​can be combined to obtain one or more new numerical ranges, which are considered to be specifically disclosed herein.

[0016] In the present invention, all percentages and percentage contents are by weight unless otherwise specified.

[0017] A first aspect of the present invention provides a hydrogenation catalyst, the hydrogenation catalyst being a sulfide-state hydrogenation catalyst comprising a carrier, an active component A, an active component B and a modifying aid component, wherein the active component A is at least one selected from Group VIII metal elements, the active component B is at least one selected from Group VIB metal elements, and the modifying aid component is at least one selected from Group IB, Group IIA, Group IIB, Group IIIA and Group VIA elements; The hydrogenation catalyst was characterized by TEM-EDS, and the result showed that the content of the modifying aid component distributed in the ABS active phase region accounted for 60% to 98% of the total content of the modifying aid component.

[0018] According to the present invention, the ABS active phase has the conventional definition in the field of hydrogenation catalysts, and refers to the effective active center of a hydrogenation catalyst. This concept was proposed by Haldor Topsoe in 1984.

[0019] In the present invention, the ratio of the content of the modification aid component distributed in the region of the ABS active phase to the total content of the modification aid components is RABS / R 総 where R is the modifier component, RABS is the content of the modifier component distributed in the region of the ABS active phase, and R 総represents the total content of the modifying aid components in the catalyst. 総 The characteristics were characterized using TEM-EDS (transmission electron microscopy-energy dispersive X-ray spectroscopy). The instrument used was a JEOL JEM2200FS transmission electron microscope (made in Japan) equipped with a scanning transmission accessory and an EDAX X-ray energy spectrum accessory. The accelerating voltage of the electron microscope was 200 kV. In STEM mode, the condenser aperture was set to 2, and the spot size was 0.5 nm. The measurement process was as follows: the catalyst particles were crushed and the sample was prepared using the suspension method. 0.1 g of the catalyst sample was placed in a 2 mL container and ultrasonically dispersed in absolute ethanol. The supernatant was removed, and 2-3 drops were taken with a dropper and dropped into a 3 mm diameter sample net. After drying, the test sample was obtained, which was then observed and analyzed using a TEM. Next, the content distribution of the modifier components in the active phase region observed by TEM was statistically analyzed in combination with EDS, and the ratio of the content of the modifier components distributed in the ABS active phase region to the total content of the modifier components (RABS / R 総 The RABS / R of the present invention is calculated based on the corresponding peak area of ​​the modifying aid component. 総 is obtained by selecting 40 TEM images combined with data obtained from EDS analysis and taking the average value.

[0020] According to one preferred embodiment of the present invention, the content of the modifying aid component distributed within the region of the ABS active phase is 75% to 98% of the total content of the modifying aid component, for example, 75%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, and any value within a range consisting of any two of these values.

[0021] In the prior art, the modifier components are often introduced into the oxidized catalyst and then sulfurized. In the prior art, the method of combining the components and then forming the active phase is adopted, and the modifier components that truly play an effective role account for a relatively small proportion. Through research, the inventors have found that in the prior art, the ratio of the content of the modifier components distributed within the Ni-Mo-S active phase to the total content of the modifier components is generally 30% or less.

[0022] According to a preferred embodiment of the present invention, the hydrogenation catalyst is characterized by a TEM-EDS method, and the sulfur content at the edges and corners of the ABS active phase is 6.0% or less of the total sulfur content in the ABS active phase, preferably 0.5% to 4.5%, for example, 0.5%, 1%, 2%, 3%, 4%, 4.5%, or any value within a range consisting of any two of these values. By adopting this preferred embodiment, the sulfur content at the edges and corners of the active phase is appropriately reduced, which favors exposure of vacant orbitals of the active component atoms, strengthens the adsorption of organic compounds from the modification aid component by the active phase during the metal modification process, and improves the fixation of the modification aid component at the edges and corners of the active phase.

[0023] The ratio of the sulfur content at the edges and corners of the ABS active phase to the total sulfur content in the ABS active phase is S エッジ及び角部 / S 総 where S エッジ及び角部 is the sulfur content at the edges and corners of the ABS active phase, S 総 represents the total sulfur content in the ABS active phase. エッジ及び角部 / S 総is characterized by TEM-EDS (transmission electron microscope-energy dispersive X-ray spectroscopy), using the same instrument model as above. The measurement process is as follows: The catalyst particles are crushed and a sample is prepared by suspension. 0.1 g of the catalyst sample is placed in a 2 mL container and ultrasonically dispersed in absolute ethanol. The supernatant is removed, and 2-3 drops are taken with a dropper and placed on a 3 mm diameter sample net. The sample is then dried to obtain the test sample, which is then observed and analyzed by TEM. The S content distribution in the active phase region observed by TEM is then combined with EDS for statistical analysis. In this invention, the edges and corners of the active phase are defined as positions less than 1 nm from the end point of the edge of the active phase. Any active phase observed by TEM electron microscope was selected, and a statistical analysis of the sulfur content at a position less than 1 nm from the end point of the edge of the active phase and the sulfur content in the active phase was performed in combination with EDS. The ratio of the sulfur content at the edge and corner of the ABS active phase to the total sulfur content of the ABS active phase (S エッジ及び角部 / S 総 The S of the present invention was obtained. エッジ及び角部 / S 総 is obtained by selecting 40 TEM images combined with data obtained by EDS analysis and taking the average value. In the prior art modification method of Ni-Mo-S type hydrogenation active phase, the auxiliary element is introduced when the active metal is in the oxide precursor state. When the active metal is sulfurized, the auxiliary element is difficult to be supported on the active phase with high selectivity, and the direct modification effect is relatively poor. Furthermore, the sulfurized state catalysts provided by the prior art are in the form of S. エッジ及び角部 / S 総 The value of is relatively large.

[0024] According to the present invention, the content of active component A, in terms of element, based on the mass of the hydrogenation catalyst, is preferably 1 to 10%, preferably 1.5% to 6%, for example, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, and any value within a range consisting of any two of these values, and the content of active component B, in terms of element, is preferably 6% to 24%, preferably 8% to 18%, for example, 8%, 9%, 10%, 12%, 14%, 16%, 18%, and any value within a range consisting of any two of these values.

[0025] According to the present invention, the content of the modifying aid component, in terms of element, based on the mass of the hydrogenation catalyst, is preferably 0.2% to 4%, preferably 0.8% to 4%, for example, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, and any value within a range consisting of any two of these values. The present invention can effectively improve the performance of the hydrogenation catalyst with only a relatively small amount of the modifying aid component.

[0026] According to the present invention, the content of elemental sulfur, based on the mass of the hydrogenation catalyst, is preferably 3% to 20%, preferably 4% to 15%, for example, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, and any value within a range consisting of any two of these values.

[0027] In the present invention, the contents of active component A, active component B, modifying aid component, and sulfur element in the hydrogenation catalyst are measured by ICP, using an OPTIMA 7000 DV atomic emission spectrometer manufactured by PE Corp. 0.1 g of sample is dissolved in a mixed solution of 3HCl:1HNO3:0.5HF by volume, and then the mixed solution is diluted to a predetermined volume with deionized water to adjust the content of the target element in the solution to 1 to 10 ppm, and then measurement is performed.

[0028] In one particularly preferred embodiment of the present invention, the content of active component A is, in element, 1 to 10%, preferably 1.5% to 6%, based on the mass of the hydrogenation catalyst; the content of active component B is, in element, 6% to 24%, preferably 8% to 18%; the content of the modifying auxiliary component is, in element, 0.2% to 4%, preferably 0.8% to 4%; the content of elemental sulfur is, in element, 3% to 20%, preferably 4% to 15%; and the content of the carrier is, in element, 42 to 89%, preferably 57 to 85%.

[0029] The hydrogenation catalyst according to the present invention may further contain other components, but it is known that the total content of all components in the hydrogenation catalyst is 100%.

[0030] According to one preferred embodiment of the present invention, the active component A is Co and / or Ni, and the active component B is Mo and / or W.

[0031] According to the present invention, preferably, the active component A is Ni, and the active component B is Mo. The use of the catalyst of this preferred embodiment is further advantageous in the hydrotreating of heavy oil.

[0032] In the present invention, the specific types of the modified auxiliary components can be selected from a wide range, and all of the above types can achieve the purpose of improving the hydrotreating ability and stability of the hydrogenation catalyst of the present invention. In addition, by selecting a specific type of modified auxiliary component, the hydrogenation catalyst can have additional advantages and be suitable for processing specific petroleum products.

[0033] Preferably, the modifying aid component is at least one selected from Cu, Ag, Au, Mg, Ca, Zn, Cd, Ga, and Se, more preferably at least one of Ag, Mg, Zn, Ga, and Se.

[0034] As a result of research, the inventors have found that when Ag is selected as the modification aid component, the catalyst has relatively good stability even in a low sulfur environment, is particularly suitable for long-term processing of low-sulfur or sulfur-free feedstocks (including, but not limited to, at least one of biodiesel, Fischer-Tropsch synthetic oil, low-temperature coal tar, etc.), and the catalyst has relatively good hydrogenation saturation selectivity for aromatics, etc.

[0035] As a result of research, the present inventors have found that when Mg is selected as the modification aid component, the catalyst has relatively good olefin hydrogenation selectivity and is particularly suitable for processing crude oils containing relatively large amounts of olefins, such as at least one of coal-based synthetic oil, coal tar, hydrogenated tail oil of ebullated bed residue, and ethylene tar.

[0036] As a result of their research, the present inventors have discovered that when Zn is selected as the modification aid component, the hydrodesulfurization selectivity of the catalyst is relatively good, and the catalyst is particularly suitable for the hydrodesulfurization treatment of heavy oils such as deasphalted oil.

[0037] As a result of their research, the inventors have discovered that when Ga is selected as the modification aid component, the catalyst has relatively good hydrodenitrification selectivity and is particularly suitable for the hydrodenitrification treatment of heavy oils such as deasphalted oil.

[0038] As a result of research, the present inventors have found that when Se is selected as the modification aid component, the catalyst has relatively good selectivity for hydrogenation carbon residue removal, and is particularly suitable for treating heavy crude oils with relatively high residual carbon contents, such as low-quality heavy oils and residual oils.

[0039] In the present invention, the support is not particularly limited, and may be any of various supports conventionally used in the art, commercially available products, or supports produced by any conventional method, such as inorganic refractory oxides. Preferably, the support is at least one selected from alumina, silicon oxide, and amorphous silicon aluminum.

[0040] In the present invention, the range of selection of the specific surface area and pore volume of the carrier is relatively wide, and preferably, the specific surface area of ​​the carrier is 200 to 500 m 2 / g, preferably 250 to 400m 2 / g, and the pore volume is 0.4 to 1.0 cm 3 / g, preferably 0.6 to 0.8 cm 3 / g.

[0041] In the present invention, the support may further contain a doping element, and the doping element may be, for example, one or more of phosphorus, silicon, boron, fluorine, sodium, etc. The amount of the doping element added may be a conventional amount, preferably 0.5% to 6% of the mass of the support.

[0042] A second aspect of the present invention provides a method for preparing a hydrogenation catalyst, the method comprising: (1) sulfiding the oxidized state hydrogenation catalyst to obtain a sulfided state hydrogenation catalyst; (2) desulfurizing the sulfided hydrogenation catalyst; and step (3) catalytically reacting the treated catalyst obtained in step (2) with a material containing a precursor of the modifying aid component, The modifying aid component is at least one selected from Group IB, Group IIA, Group IIB, Group IIIA, and Group VIA elements.

[0043] In the preparation method according to the present invention, the oxidized state hydrogenation catalyst may be any of various oxidized state hydrogenation catalysts conventionally used in the art, and is not particularly limited. The catalyst may be prepared by a conventional method in the art or purchased as a commercially available catalyst. Preferably, the oxidized state hydrogenation catalyst is an oxidized state hydrogenation catalyst having a heavy oil hydrogenation function.

[0044] According to one preferred embodiment of the present invention, the oxidized state hydrogenation catalyst comprises a support, an active component A, and an active component B, wherein the active component A is at least one selected from metal elements of Group VIII, and the active component B is at least one selected from metal elements of Group VIB. The selection ranges of the support, active component A, and active component B may be the same as those described in the first aspect above, and therefore will not be described in detail here.

[0045] Preferably, based on the weight of the oxidized state hydrogenation catalyst, the content of the carrier is 50% to 90%, the content of active component B in terms of oxide is 10% to 35%, and the content of active component A in terms of oxide is 2% to 8%.

[0046] In the present invention, the sulfurization described in step (1) is not particularly limited and can be carried out by a conventional method in the art. Preferably, the sulfurization described in step (1) is complete sulfurization, i.e., the active metal in the oxidized state hydrogenation catalyst is completely sulfurized. Any known sulfurization method can be used, and preferably, the sulfurization includes dry sulfurization and / or wet sulfurization. Dry vulcanization and wet vulcanization described in the present invention have the conventional definitions in the art.

[0047] Preferably, the sulfurization conditions are a sulfurization temperature of 240 to 400°C, a sulfurization time of 2 to 10 hours, a hydrogen gas pressure of 2 to 12 MPa, and a hydrogen gas flow rate of 2 to 25 mL min -1 ·g -1 Oxidized state hydrogenation catalyst, more preferably, sulfurization temperature 280 to 380°C, sulfurization time 3 to 8 h, hydrogen gas pressure 3 to 10 MPa, hydrogen gas flow rate 3 to 20 mL min -1 ·g -1 Contains an oxidized state hydrogenation catalyst.

[0048] According to a preferred embodiment of the present invention, the sulfurizing liquid used in the wet sulfurization contains a sulfur-containing compound and an organic solvent. Preferably, the sulfur-containing compound is at least one selected from dimethyl disulfide, carbon disulfide, diethyl sulfide, ethyl mercaptan, n-butyl mercaptan, di-tert-nonyl polysulfide, and dimethyl sulfoxide. Preferably, the organic solvent is at least one selected from cyclohexane, n-heptane, aviation kerosene, and diesel.

[0049] The mass fraction of the sulfur-containing compound in the sulfurizing solution can be selected from a wide range, preferably 2% to 7%, more preferably 4% to 6%. The flow rate of the sulfurizing solution is preferably 0.5 to 5 mL h -1 ·g -1 Oxidized state hydrogenation catalyst, preferably 1-4 mL h -1 ·g -1 It is an oxidized state hydrogenation catalyst.

[0050] According to a preferred embodiment of the present invention, the sulfurization gas used in the dry sulfurization contains hydrogen sulfide and hydrogen gas, and preferably, the volume content of hydrogen sulfide in the sulfurization gas is 1 to 10%.

[0051] According to a preferred embodiment of the present invention, the desulfurization treatment is a mild desulfurization treatment, which refers to removing low-coordinated sulfur atoms at the edges and corners of the active phase after sulfurization and preserving the triple-coordinated sulfur atoms in the bulk phase of the active phase.

[0052] The oxidation state hydrogenation catalyst of the present invention undergoes primary sulfurization and desulfurization treatments in sequence, so that the metal active phase to be modified reaches a specific desulfurization high activity state, and the outer edge of the active phase becomes an exposed active metal. In addition, the three-coordinated sulfur atoms and stable ABS crystal structure inside the hydrogenation active phase can be effectively maintained, which makes it easier for the subsequent modification aid component to come into contact with the metal phase in the outer layer of the active phase more effectively. In the obtained hydrogenation catalyst, the modification aid component (represented by R) forms an ABS composite mixed active phase with active component A, active component B, and S, thereby achieving the purpose of improving the performance of the hydrogenation catalyst.

[0053] Preferably, the temperature of the desulfurization treatment in step (2) is lower than the temperature of the sulfurization, and preferably the temperature of the desulfurization treatment is 50 to 100° C. lower than the temperature of the sulfurization.

[0054] Preferably, the conditions for the desulfurization treatment include a temperature of 180 to 370°C, preferably 200 to 300°C, a treatment time of 4 to 24 hours, preferably 6 to 16 hours, and a total pressure of 2 to 18 MPa, preferably 4 to 15 MPa.

[0055] According to the present invention, in step (2), the desulfurization treatment is preferably carried out in the presence of hydrogen sulfide, preferably (a) a method of desulfurizing the sulfurized hydrogenation catalyst using hydrogen gas containing hydrogen sulfide; and This is a mild desulfurization treatment carried out by employing at least one of the methods (b) for desulfurizing the sulfurized hydrogenation catalyst using a sulfurization liquid in the presence of hydrogen gas.

[0056] According to the present invention, preferably, in method (a), the volume ratio of hydrogen sulfide to hydrogen gas is 200:1 to 800:1, preferably 300:1 to 600:1, and the total gas flow rate is 5 to 30 mL min -1 ·g -1 Oxidized state hydrogenation catalyst, preferably 10-20 mL min -1 ·g -1 It is an oxidized state hydrogenation catalyst.

[0057] According to the present invention, preferably, in method (b), the sulfurizing liquid comprises a sulfur-containing compound and an organic solvent, the sulfur-containing compound being at least one selected from dimethyl disulfide, carbon disulfide, diethyl sulfide, ethyl mercaptan, n-butyl mercaptan, di-tert-nonyl polysulfide, and dimethyl sulfoxide, and the organic solvent being at least one selected from cyclohexane, n-heptane, aviation kerosene, and diesel.

[0058] Preferably, in method (b), the mass fraction of the sulfur-containing compound in the sulfurizing solution is 0.1% to 0.6%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, and any value within a range consisting of any two of these values.

[0059] Preferably, in the desulfurization process, the flow rate of the sulfurizing solution is 0.5 to 4.5 mL h -1 ·g -1 Oxidized state hydrogenation catalyst, preferably 1-4 mL h -1 ·g -1 It is an oxidized state hydrogenation catalyst.

[0060] Preferably, in the desulfurization process, the hydrogen gas flow rate is 5 to 30 mL min -1 ·g -1 Oxidized state hydrogenation catalyst, preferably 10-20 mL min -1 ·g -1 It is an oxidized state hydrogenation catalyst.

[0061] The range of selection of the type of modification aid component described in step (3) of the present invention can be the same as the range of selection of the type of modification aid component described in the first embodiment above, and therefore will not be described in detail here.

[0062] In the present invention, the type of the modifying aid component precursor can be selected from a relatively wide range, and is preferably an organic substance and / or a hydride containing the modifying aid component, as long as the modifying aid component can be obtained by the catalytic reaction in step (3). Preferably, the modifying aid component precursor is at least one selected from gallium acetylacetonate, triethylgallium, silver stearate, silver acetylacetonate, silver cyclohexanebutyrate, magnesium stearate, dibutylmagnesium, magnesium pyruvate, magnesium L-aspartate, magnesium tetraphenylporphyrin, zinc naphthenate, zinc glycerol, diethylselenium, and hydrogen selenide.

[0063] In the present invention, the phase of the material containing the modifying aid component precursor is not particularly limited, and it may be a liquid solution or a gaseous gas.

[0064] According to one preferred embodiment of the present invention, the material containing the modifying auxiliary component precursor is an organic solution containing the modifying auxiliary component precursor.

[0065] In such a preferred embodiment, the mass content of the modifying aid component precursor in the organic solution containing the modifying aid component precursor is preferably 0.5% to 5%, for example, 0.5%, 1%, 2%, 3%, 4%, 4.5%, 5%, and any value within a range consisting of any two of these values.

[0066] The solvent for the organic solution containing the modifying aid component precursor may be selected from a relatively wide range of solvents as long as it has good compatibility with the modifying aid component precursor. Preferably, in the organic solution containing the modifying aid component precursor, the solvent is one or more selected from toluene, cyclohexane, decalin, tetralin, and n-heptane.

[0067] To further improve the properties of the prepared hydrogenation catalyst, the organic solution containing the modifying aid component precursor preferably further contains a stabilizer selected from organic basic nitrides. The stabilizer, also called a spacer, is selected from organic basic nitrides with specific basicity. These organic basic nitrides are adsorbed to the acidic centers of the support and the active component, preventing the modifying aid component from adsorbing to the support. A portion of the organic basic nitride adsorbed to the active component is converted into hydrocarbons and ammonia gas by hydrogenation and can be desorbed from the active phase, while the modifying aid component can be attached to the metal active phase.

[0068] Preferably, the stabilizer is at least one selected from triethanolamine, diethanolamine, monoethanolamine, pyridine, quinoline, and aniline.

[0069] Preferably, in the organic solution containing the modifying auxiliary component precursor, the mass content of the stabilizer is 2% to 8%, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8%, and any value within a range consisting of any two of these values.

[0070] According to one preferred embodiment of the present invention, the conditions for the contact reaction in step (3) are a temperature of 80 to 220°C, preferably 100 to 200°C, a pressure of 0.2 to 8 MPa, preferably 0.5 to 6 MPa, a reaction time of 2 to 24 hours, preferably 4 to 20 hours, and a hydrogen gas flow rate of 2 to 20 mL min -1 ·g -1 Oxidized state hydrogenation catalyst, preferably 5-15 mL min -1 ·g -1 The flow rate of the material containing the modified auxiliary component precursor is 2 to 10 mL h -1 ·g -1 Oxidized state hydrogenation catalyst, preferably 3-8 mL h -1 ·g -1 It includes being an oxidized state hydrogenation catalyst.

[0071] Some preferred embodiments in which the material containing the modifying aid component precursor is an organic solution containing the modifying aid component precursor have been described in detail above. This form is preferably used when the modifying aid component is at least one of Ag, Mg, Zn, and Ga.

[0072] Hereinafter, a detailed description will be given of the case where the material containing a modification aid component precursor is the mixed gas containing a modification aid component precursor. Preferably, the material containing a modification aid component precursor is the mixed gas containing a modification aid component precursor, and the mixed gas further contains hydrogen gas.

[0073] Preferably, in the mixed gas containing the modification aid component precursor, the volume content of the modification aid component precursor is 1% to 20%, preferably 3% to 15%, and the volume content of hydrogen gas is 80% to 99%, preferably 85% to 97%.

[0074] In such a preferred embodiment, the modifying coagent component precursor is preferably hydrogen selenide.

[0075] In such a preferred embodiment, the conditions for the contact reaction in step (3) are preferably a temperature of 120 to 250°C, preferably 150 to 220°C, a reaction time of 1 to 8 hours, preferably 2 to 6 hours, a reaction pressure of 2 to 12 MPa, preferably 4 to 8 MPa, and a flow rate of the mixed gas containing the modifying auxiliary component precursor of 5 to 40 mL min -1 ·g -1 Oxidized state hydrogenation catalyst, preferably 10-30 mL min -1 ·g -1 It includes being an oxidized state hydrogenation catalyst.

[0076] According to the present invention, the method optionally further includes a step of secondary sulfurization of the catalyst obtained in step (3). The conditions and method of secondary sulfurization are not particularly limited and may refer to the sulfurization described in step (1). Preferably, the secondary sulfurization is wet sulfurization. The sulfurization liquid used in the secondary sulfurization may contain a sulfur-containing compound and an organic solvent, and the mass fraction of the sulfur-containing compound in the sulfurization liquid is preferably 1% to 5%, preferably 1.5% to 3.5%. The sulfur compound is preferably one or more of diethyl sulfide, ethyl mercaptan, n-butyl mercaptan, di-tert-nonyl polysulfide, and dimethyl sulfoxide, and the organic solvent is preferably at least one of cyclohexane, n-heptane, aviation kerosene, and diesel.

[0077] Furthermore, in step (4), the conditions for the secondary sulfurization are a temperature of 250 to 350°C, preferably 280 to 320°C, a time of 2 to 24 hours, preferably 4 to 16 hours, a hydrogen gas pressure of 2 to 8 MPa, preferably 2 to 6 MPa, and a hydrogen gas flow rate of 2 to 15 mL min -1 ·g -1 Oxidized state hydrogenation catalyst, preferably 5-10 mL min -1 ·g -1 The sulfurization liquid is an oxidized state hydrogenation catalyst. The flow rate of the sulfurization liquid is 1 to 5 mL h -1 ·g -1 Oxidized state hydrogenation catalyst, preferably 2-4 mL h -1 ·g -1 It is an oxidized state hydrogenation catalyst.

[0078] More preferably, the temperature of the primary sulfurization is higher than the temperature of the secondary sulfurization, preferably by 20 to 100°C higher, and the temperature of the secondary sulfurization is higher than the temperature of the desulfurization treatment, preferably by 20 to 80°C higher.

[0079] A third aspect of the present invention provides the use of the hydrogenation catalyst according to the first aspect or the hydrogenation catalyst prepared by the method according to the second aspect in the hydrogenation of petroleum products. The catalyst according to the present invention is used for the hydrogenation of petroleum products and has relatively high hydrotreating capacity and stability. Depending on the selection of different modifying auxiliary components, the catalyst according to the present invention also has further advantages.

[0080] As a result of research, the inventors have discovered that when the modification aid component is Ga, the catalyst is particularly suitable for the hydrodenitrogenation of heavy petroleum products. Preferably, the modification aid component in the hydrogenation catalyst is Ga, and the catalyst is used in the hydrodenitrogenation of heavy petroleum products. Preferably, the catalyst is used to treat heavy petroleum products having a nitrogen content of 1000 μg / g or more, preferably 1500 to 3000 μg / g, and a residual carbon mass content of 10 wt% or more, preferably 12 wt% to 15 wt%.

[0081] As a result of research, the inventors have found that when the modification aid component is Zn, the catalyst is particularly suitable for the hydrodesulfurization of heavy petroleum products. Preferably, the modification aid component in the hydrogenation catalyst is Zn, and the use is in the hydrodesulfurization of heavy petroleum products. Preferably, the catalyst is used to process heavy petroleum products having a sulfur content of 2.0 wt% or more, particularly 3.0 wt% or more. Preferably, the residual carbon content of the heavy petroleum products is 8.0 wt% or more, more preferably 10 wt% to 15 wt%.

[0082] In the present invention, the range of the total content of metallic nickel and vanadium in the heavy petroleum product is relatively wide, and the total content of metallic nickel and vanadium (Ni+V) in the heavy petroleum product is preferably less than 100 μg / g, more preferably 20 to 60 μg / g. The heavy petroleum product includes, but is not limited to, deasphalted oil.

[0083] The inventors have discovered through research that when the modified auxiliary component is Ag, the catalyst is particularly suitable for processing low-sulfur petroleum products. Preferably, the modified auxiliary component in the hydrogenation catalyst is Ag, and the use is in processing low-sulfur petroleum products. In processing low-sulfur petroleum products, the Ag-modified hydrogenation catalyst is used to hydrogenate, as well as hydrodeoxygenate and hydrodecarboxylate, substances such as olefins, diolefins, and aromatic hydrocarbons in saturated petroleum products. These catalysts have high hydrogenation saturation capacity, stable hydrodeoxygenation and hydrodeacidification capacity, and high stability, making them particularly suitable for long-term operation. Preferably, the sulfur content of the low-sulfur oil is less than 200 μg / g. The low-sulfur petroleum products include, but are not limited to, at least one of biodiesel, Fischer-Tropsch synthetic oil, and low-temperature coal tar.

[0084] As a result of research, the inventors have found that when the modification aid component is Mg, the catalyst is particularly suitable for the selective hydrosaturation of olefins in petroleum products. Preferably, the modification aid component in the hydrogenation catalyst is Mg, and the catalyst is used in the selective hydrosaturation of olefins in petroleum products. Preferably, the catalyst is used to process secondary processed crude oil having an olefin mass content of 10% or more. The secondary processed crude oil may be at least one of coal-based synthetic oil, coal tar, hydrogenated tail oil of ebullated bed residue, ethylene tar, etc.

[0085] As a result of research, the inventors have found that when the modification aid component is Se, the catalyst is particularly suitable for the hydrodecarbonization reaction of heavy crude oil. Preferably, the modification aid component in the hydrodecarbonization catalyst is Se, and the use is in the hydrodecarbonization of heavy crude oil. Preferably, the heavy crude oil has a residual carbon content of 10% or more by mass, particularly 15% or more by mass. The heavy crude oil may be derived from low-quality heavy oil and / or residual oil.

[0086] The method of the present invention preferably comprises reacting the oil with the hydrogenation catalyst in the presence of hydrogen gas. Preferably, the reaction conditions are a reaction temperature of 200 to 420°C, preferably 250 to 400°C, a hydrogen gas pressure of 4 to 25 MPa, preferably 6 to 22 MPa, and a liquid hourly space velocity of 0.1 to 3 h. -1 , preferably 0.1 to 2 hours -1 and the hydrogen-to-oil volume ratio is 400:1 to 1500:1, preferably 400:1 to 1200:1.

[0087] The preparation process and product properties of the method of the present invention are further illustrated below in conjunction with examples and comparative examples, but the following examples do not limit the method of the present invention.

[0088] In the hydrogenation catalysts in the following Examples and Comparative Examples, the ratio of the content of the modifying aid component distributed within the region of the ABS active phase to the total content of the modifying aid component, and the ratio of the sulfur content at the edges and corners of the ABS active phase to the total sulfur content in the ABS active phase were expressed by TEM-EDS (Transmission Electron Microscopy-Energy Dispersive X-ray Spectroscopy). Specific methods are described in the section on specific embodiments.

[0089] The oxidized state hydrogenation catalysts used in Examples A1 to A6 and Comparative Examples A1 to A5 below were all prepared by the following method.

[0090] 1000.0 g of dried alumina sol powder was weighed, and 30.0 g of citric acid and 10.0 g of sesbania powder were added and mixed uniformly. After that, 900.0 g of an aqueous solution containing 2.0% nitric acid by mass was added, and the mixture was compacted for 30.0 minutes. The mixture was then extruded into strands using a plate with cloverleaf-shaped holes of 1.6 mm in diameter. The mixture was dried at 120°C for 6.0 hours and then roasted at 600°C for 6.0 hours. The roasted support was designated S-0 (the specific surface area of ​​the support was 304 m). 2 / g, pore volume is 0.75 cm 3120.0 g of ammonium heptamolybdate tetrahydrate, 80.0 g of nickel nitrate hexahydrate, and 120.0 g of deionized water were weighed out, thoroughly stirred at 80°C for 30 minutes, cooled to room temperature, and then made up to a constant volume of 180.0 mL with deionized water. The resulting solution was designated Q-0.

[0091] 200 g of carrier S-0 was prepared, immersed in Q-0, and dried for 24 hours. After that, it was dried at 120°C for 4 hours and then roasted at 420°C for 4.0 hours. The resulting oxidation state hydrogenation catalyst was designated CT-0 (by weight of the catalyst, the carrier content was 68.4%, the molybdenum oxide content was 26.5%, and the nickel oxide content was 5.1%).

[0092] Example A1 1000 g of cyclohexane and 50.0 g of dimethyl disulfide were prepared, and a sulfurization liquid was prepared as SQ-0. 1000 g of cyclohexane and 2.0 g of dimethyl disulfide were prepared, and a sulfurization solution was prepared as TQ-1. 1000 g of toluene, 25.0 g of gallium acetylacetonate, and 40.0 g of triethanolamine were prepared to prepare an organic solution containing gallium, designated GQ-1. 20.0 g of CT-0 was placed in a reaction tube and sulfurized using SQ-0. In the sulfurization process, the hydrogen gas pressure was 6.0 MPa, the hydrogen gas flow rate was 300.0 mL / min, the sulfurization liquid SQ-0 flow rate was 40.0 mL / h, the sulfurization temperature was 350°C, and the sulfurization time was 6 hours. The sulfurized hydrogenation catalyst obtained was named SCT-0. The temperature of the reaction tube was lowered to 260°C, the hydrogen gas pressure was adjusted to 5.0 MPa, the hydrogen gas flow rate was set to 200.0 mL / min, TQ-1 was introduced into the reaction tube at a flow rate of 30.0 mL / h, and the treatment time was set to 9 hours. The resulting catalyst was designated TCT-1. The temperature of the reaction tube was lowered to 110°C, the hydrogen gas pressure was adjusted to 0.8 MPa, the hydrogen gas flow rate was set to 120.0 mL / min, GQ-1 was introduced into the reaction tube at a flow rate of 120.0 mL / h, and the treatment time was set to 8.0 hours. The obtained catalyst was designated ECT-1.

[0093] Example A2 The preparation process of the sulfided state hydrogenation catalyst SCT-0 was the same as that of Example A1. 1000 g of cyclohexane and 3.0 g of dimethyl disulfide were prepared, and a sulfurization solution was prepared as TQ-2. 1000 g of toluene, 15.0 g of triethylgallium, and 50.0 g of triethanolamine were prepared to prepare an organic solution containing gallium, designated GQ-2. The temperature of the reaction tube was lowered to 280°C, the hydrogen gas pressure was adjusted to 6.0 MPa, the hydrogen gas flow rate was set to 300.0 mL / min, TQ-2 was introduced into the reaction tube at a flow rate of 40.0 mL / h, and the treatment time was set to 12 hours. The resulting catalyst was designated TCT-2. The temperature of the reaction tube was lowered to 130°C, the pressure was adjusted to 1.2 MPa, the hydrogen gas flow rate was set to 150.0 mL / min, GQ-2 was introduced into the reaction tube at a flow rate of 120.0 mL / h, and the treatment time was set to 8.0 hours. The obtained catalyst was named ECT-2.

[0094] Example A3 The preparation process of the sulfided state hydrogenation catalyst SCT-0 was the same as that of Example A1. 1000 g of cyclohexane and 4.0 g of dimethyl disulfide were prepared, and a sulfurization solution was prepared as TQ-3. 1000 g of toluene, 10.0 g of triethylgallium, 20.0 g of gallium acetylacetonate, and 60.0 g of triethanolamine were prepared to prepare an organic solution containing gallium, designated GQ-3. The temperature of the reaction tube was lowered to 300°C, the hydrogen gas pressure was adjusted to 10.0 MPa, the hydrogen gas flow rate was set to 400.0 mL / min, TQ-3 was introduced into the reaction tube at a flow rate of 40.0 mL / h, and the treatment time was set to 12 hours. The resulting catalyst was designated TCT-3. The temperature of the reaction tube was lowered to 150°C, the pressure was adjusted to 1.8 MPa, the hydrogen gas flow rate was set to 180.0 mL / min, GQ-3 was introduced into the reaction tube at a flow rate of 120.0 mL / h, and the treatment time was set to 8.0 hours. The obtained catalyst was designated ECT-3.

[0095] Example A4 The preparation processes of the carrier S-0, the solution Q-0, the oxidation state hydrogenation catalyst CT-0, the sulfurization solution SQ-0, and the sulfurization catalyst SCT-0 were the same as those in Example A1. The temperature of the reaction tube was lowered to 280°C, the reaction pressure was adjusted to 6.0 MPa, and a mixed gas of hydrogen gas and hydrogen sulfide was introduced into the reaction tube so that the volume ratio of hydrogen gas to hydrogen sulfide was 400:1 and the total flow rate of the mixed gas was 400 mL / min. The treatment time was set to 12 hours. The resulting catalyst was designated TCT-4. 1000 g of toluene, 15.0 g of triethylgallium, 15.0 g of gallium acetylacetonate, and 60.0 g of triethanolamine were prepared to prepare an organic solution containing gallium, designated GQ-4. The temperature of the reaction tube was lowered to 150°C, the pressure was adjusted to 0.6 MPa, the hydrogen gas flow rate was set to 150.0 mL / min, GQ-4 was introduced into the reaction tube at a flow rate of 120.0 mL / h, and the treatment time was set to 8.0 hours. The obtained catalyst was named ECT-4.

[0096] Example A5 The preparation processes of the carrier S-0, the solution Q-0, the oxidation state hydrogenation catalyst CT-0, the sulfurization solution SQ-0, and the sulfurization catalyst SCT-0 were the same as those in Example A1. The temperature of the reaction tube was lowered to 280°C, the reaction pressure was adjusted to 6.0 MPa, and a mixed gas of hydrogen gas and hydrogen sulfide was introduced into the reaction tube so that the volume ratio of hydrogen gas to hydrogen sulfide was 500:1 and the total flow rate of the mixed gas was 500 mL / min. The treatment time was set to 12 hours. The obtained catalyst was designated TCT-5. 1000 g of toluene, 10.0 g of triethylgallium, 20.0 g of gallium acetylacetonate, and 60.0 g of triethanolamine were prepared to prepare an organic solution containing gallium, designated GQ-5. The temperature of the reaction tube was lowered to 150°C, the pressure was adjusted to 0.6 MPa, the hydrogen gas flow rate was set to 150.0 mL / min, GQ-5 was introduced into the reaction tube at a flow rate of 120.0 mL / h, and the treatment time was set to 8.0 hours. The obtained catalyst was named ECT-5.

[0097] Example A6 The method of Example A1 was used, except that triethanolamine was not added to GQ-1. The obtained catalyst was designated as ECT-6.

[0098] Comparative Example A1 20.0 g of CT-0 was placed in a reaction tube and sulfurized using SQ-0. In the sulfurization process, the hydrogen gas pressure was 6.0 MPa, the hydrogen gas flow rate was 300.0 mL / min, the sulfurization liquid SQ-0 flow rate was 40.0 mL / h, the sulfurization temperature was 350°C, and the sulfurization time was 6 hours. The catalyst after sulfurization was named DCT-1.

[0099] Comparative example A2 The preparation process of catalyst DCT-1 was the same as that of Comparative Example A1. The reaction tube containing DCT-1 was cooled to 260°C, the hydrogen gas pressure was adjusted to 5.0 MPa, the hydrogen gas flow rate was set to 200.0 mL / min, TQ-1 was introduced into the reaction tube at a flow rate of 30.0 mL / h, and the treatment time was set to 9 hours. The resulting catalyst was designated DCT-2.

[0100] Comparative example A3 The preparation process of the sulfided state hydrogenation catalyst SCT-0 was the same as that of Example A1. The reaction tube containing SCT-0 was cooled to 110°C, the pressure was adjusted to 0.8 MPa, the hydrogen gas flow rate was set to 120.0 mL / min, GQ-1 was introduced into the reaction tube at a flow rate of 120 mL / h, and the treatment time was set to 8.0 hours. The resulting catalyst was designated DCT-3.

[0101] Comparative example A4 The preparation process of the sulfided state hydrogenation catalyst SCT-0 was the same as that of Example A1. The reaction tube containing SCT-0 was cooled to 260°C, the hydrogen gas pressure was adjusted to 5.0 MPa, the hydrogen gas flow rate was 240.0 mL / min, and the treatment time was 9 hours. The obtained catalyst was named DTCT-4. The temperature of the reaction tube was lowered to 110°C, the pressure was adjusted to 0.8 MPa, the hydrogen gas flow rate was set to 120.0 mL / min, GQ-1 was introduced into the reaction tube at a flow rate of 120 L / h, and the treatment time was set to 8.0 hours. The resulting catalyst was designated DCT-4.

[0102] Comparative Example A5 1000.0 g of dried alumina sol powder was weighed, 30.0 g of citric acid, and 10.0 g of sesbania powder were added and mixed uniformly. 900.0 g of a 2.0% nitric acid aqueous solution was added, and the mixture was compacted for 30.0 minutes. It was then extruded into strands using a plate with cloverleaf holes (1.6 mm in diameter). It was dried at 120°C for 6.0 hours and then roasted at 600°C for 6.0 hours. The roasted support was designated S-0. 120.0 g of ammonium heptamolybdate tetrahydrate, 80.0 g of nickel nitrate hexahydrate, 12.0 g of anhydrous gallium nitrate, and 120.0 g of deionized water were weighed out, thoroughly stirred at 80°C for 30 minutes, cooled to room temperature, and then made up to a constant volume of 180.0 mL with deionized water. The resulting solution was designated DQ-5. 200 g of carrier S-0 was prepared, immersed in DQ-5, dried for 24 hours, dried at 120°C for 4 hours, and then roasted at 420°C for 4.0 hours. The resulting oxidation state hydrogenation catalyst was designated DCT-0. 20.0 g of DCT-0 was placed in a reaction tube and sulfurized using SQ-0 (similar to Example A1). In the sulfurization process, the hydrogen gas pressure was 6.0 MPa, the hydrogen gas flow rate was 300.0 mL / min, the sulfurization liquid SQ-0 flow rate was 40.0 mL / h, the sulfurization temperature was 350°C, and the sulfurization time was 6 hours. The sulfurized hydrogenation catalyst obtained was named DCT-5. The physicochemical compositions of the above catalysts are shown in Table A1.

[0103] [Table 1]

[0104] The hydrogenation catalysts were characterized by TEM-EDS to obtain the percentage of the Ga content distributed within the Ni-Mo-S active phase region relative to the total Ga content, and the percentage of the sulfur content at the edges and corners of the Ni-Mo-S active phase relative to the total sulfur content in the Ni-Mo-S active phase, as shown in Table A2.

[0105] [Table 2]

[0106] Test Example A1 The activity of the catalysts obtained in each of Examples A1 to A6 was evaluated. The properties of the deasphalted oil are shown in Table A3. A fixed-bed process was employed, and a hydrogenation protection agent (FZC-100B) was packed in front of the catalyst so that the volume ratio of the hydrogenation protection agent to the hydrodenitrification catalyst obtained in the examples was 1:4. The operating conditions were a reaction temperature of 390°C, a reaction pressure of 20.0 MPa, a hydrogen-to-oil volume ratio of 1000:1, and a liquid hourly space velocity of 0.2 h -1 After 2000 hours of reaction evaluation, the residual carbon value, sulfur content, and nitrogen content of the fraction above 200°C in the hydrotreated oil were analyzed, and the results are shown in Table A4.

[0107] Comparative test example A1 The activity of the catalysts obtained in each of Comparative Examples A1 to A5 was evaluated. The properties of the deasphalted oil are shown in Table A3. A fixed-bed process was employed, and a hydrogenation protection agent (FZC-100B) was packed in front of the catalyst so that the volume ratio of the hydrogenation protection agent to the hydrodenitrification catalyst obtained in the comparative example was 1:4. The operating conditions were a reaction temperature of 390°C, a reaction pressure of 20.0 MPa, a hydrogen-to-oil volume ratio of 1000:1, and a liquid hourly space velocity of 0.2 h -1 After 2000 hours of reaction evaluation, the residual carbon value, sulfur content, and nitrogen content of the fraction above 200°C in the hydrotreated oil were analyzed, and the results are shown in Table A4.

[0108] [Table 3]

[0109] [Table 4]

[0110] As can be seen from the evaluation results in Table A4, the hydrogenation catalyst prepared in the present invention not only has a high hydrodenitrification ability, but also a high aromatic hydrocarbon saturation ability and a high hydrodesulfurization ability.

[0111] In the present invention, the oxidized state hydrogenation catalysts used in the following Examples B1 to B5 and Comparative Examples B1 to B5 were all prepared by the following method. 1000.0 g of dried alumina sol powder was weighed, 30.0 g of citric acid, and 10.0 g of sesbania powder were added and mixed uniformly. After that, 900.0 g of an aqueous solution containing 2.0% nitric acid by mass was added, and the mixture was compacted for 30.0 minutes. The mixture was then extruded into strands using a plate with cloverleaf-shaped holes of 1.6 mm in diameter. The resulting mixture was dried at 120°C for 6.0 hours and then roasted at 600°C for 6.0 hours. The roasted support was designated S-0 (the specific surface area of ​​the support was 304 m). 2 / g, pore volume is 0.75 cm 3 / g). 100.0 g of ammonium heptamolybdate tetrahydrate, 60.0 g of nickel nitrate hexahydrate, and 120.0 g of deionized water were weighed and thoroughly stirred at 80°C for 30 minutes, then cooled to room temperature. The solution was then diluted to 180.0 mL with deionized water, and the resulting solution was designated Q-0. 200 g of support S-0 was immersed in Q-0 and dried for 24 hours, then dried at 120°C for 4 hours, and then roasted at 420°C for 4.0 hours. The resulting oxidation-state hydrogenation catalyst was designated CT-0 (based on the mass of the catalyst, the support content was 70.2%, the molybdenum oxide content was 25.0%, and the nickel oxide content was 4.8%).

[0112] Example B1 1000 g of cyclohexane and 50.0 g of dimethyl disulfide were prepared, and a sulfurization liquid was prepared as SQ-0. 1000 g of cyclohexane and 2.0 g of dimethyl disulfide were prepared, and a sulfurization solution was prepared as TQ-1. 2000 g of toluene, 70.0 g of silver stearate, and 80.0 g of aniline were prepared to prepare an organic solution containing silver, designated YQ-1. 20.0 g of CT-0 was placed in a reaction tube, and primary sulfurization was carried out using SQ-0 under the following conditions: sulfurization temperature: 350°C, hydrogen gas pressure: 6.0 MPa, hydrogen gas flow rate: 300.0 mL / min, sulfurization solution SQ-0 flow rate: 40.0 mL / h, and sulfurization time: 6 hours. The sulfurized hydrogenation catalyst obtained was designated SCT-0. The temperature of the reaction tube was lowered to 260°C, the hydrogen gas pressure was adjusted to 5.0 MPa, the hydrogen gas flow rate was set to 200.0 mL / min, TQ-1 was introduced into the reaction tube at a flow rate of 30.0 mL / h, and the treatment time was set to 9 hours. The resulting catalyst was designated TCT-1. The temperature of the reaction tube was lowered to 110°C, the hydrogen gas pressure was adjusted to 1.0 MPa, the hydrogen gas flow rate was set to 120.0 mL / min, YQ-1 was introduced into the reaction tube at a flow rate of 80.0 mL / h, and the treatment time was set to 9.0 hours. The obtained catalyst was designated ECT-1.

[0113] Example B2 The preparation process of the sulfided state hydrogenation catalyst SCT-0 was the same as that of Example B1. 1000 g of cyclohexane and 3.0 g of carbon disulfide were prepared to prepare a sulfurization liquid designated as TQ-2. 2000 g of toluene, 80.0 g of silver acetylacetone, and 80.0 g of aniline were prepared to prepare an organic solution containing silver, designated YQ-2. 1000 g of cyclohexane and 30.0 g of carbon disulfide were prepared, and a sulfurization liquid was prepared as RQ-2. The temperature of the reaction tube was lowered to 280°C, the hydrogen gas pressure was adjusted to 6.0 MPa, the hydrogen gas flow rate was set to 300.0 mL / min, TQ-2 was introduced into the reaction tube at a flow rate of 40.0 mL / h, and the treatment time was set to 12 hours. The resulting catalyst was designated TCT-2. The temperature of the reaction tube was lowered to 130°C, the hydrogen gas pressure was adjusted to 1.5 MPa, the hydrogen gas flow rate was set to 150.0 mL / min, YQ-2 was introduced into the reaction tube at a flow rate of 100.0 mL / h, and the treatment time was set to 12.0 hours. The obtained catalyst was named ECT-2.

[0114] Example B3 The preparation process of the sulfided state hydrogenation catalyst SCT-0 was the same as that of Example B1. 1000 g of cyclohexane and 4.0 g of dimethyl disulfide were prepared, and a sulfurization solution was prepared as TQ-3. 2000 g of toluene, 90.0 g of silver cyclohexane butyrate, and 80.0 g of aniline were prepared to prepare an organic solution containing silver, designated YQ-3. The temperature of the reaction tube was lowered to 300°C, the hydrogen gas pressure was adjusted to 10.0 MPa, the hydrogen gas flow rate was set to 400.0 mL / min, TQ-3 was introduced into the reaction tube at a flow rate of 40.0 mL / h, and the treatment time was set to 12 hours. The resulting catalyst was designated TCT-3. The temperature of the reaction tube was lowered to 150°C, the hydrogen gas pressure was adjusted to 2.0 MPa, the hydrogen gas flow rate was set to 180.0 mL / min, YQ-3 was introduced into the reaction tube at a flow rate of 120.0 mL / h, and the treatment time was set to 15.0 hours. The obtained catalyst was designated ECT-3.

[0115] Example B4 The preparation process of the sulfided state hydrogenation catalyst SCT-0 was the same as that of Example B1. 2000 g of toluene, 100.0 g of silver stearate, and 80.0 g of aniline were prepared to prepare an organic solution containing silver, designated YQ-4. The temperature of the reaction tube was lowered to 260°C, the reaction pressure was adjusted to 4.0 MPa, and a mixed gas of hydrogen gas and hydrogen sulfide was introduced so that the partial pressure ratio of hydrogen gas to hydrogen sulfide was 300:1 and the flow rate of the mixed gas was 300.0 mL / min. The treatment time was set to 12 hours. The obtained catalyst was designated TCT-4. The temperature of the reaction tube was lowered to 140°C, the hydrogen gas pressure was adjusted to 2.5 MPa, the hydrogen gas flow rate was set to 150.0 mL / min, YQ-4 was introduced into the reaction tube at a flow rate of 100.0 mL / h, and the treatment time was set to 12.0 hours. The obtained catalyst was named ECT-4.

[0116] Example B5 The preparation process of the sulfided state hydrogenation catalyst SCT-0 was the same as that of Example B1. 2000 g of toluene, 60.0 g of silver acetylacetone, and 80.0 g of aniline were prepared to prepare an organic solution containing silver, designated YQ-5. The temperature of the reaction tube was lowered to 260°C, the reaction pressure was adjusted to 4.0 MPa, and a mixed gas of hydrogen gas and hydrogen sulfide was introduced so that the partial pressure ratio of hydrogen gas to hydrogen sulfide was 250:1 and the flow rate of the mixed gas was 350.0 mL / min, and the treatment time was set to 12 hours. The obtained catalyst was designated TCT-5. The temperature of the reaction tube was lowered to 160°C, the hydrogen gas pressure was adjusted to 3.0 MPa, the hydrogen gas flow rate was set to 160.0 mL / min, YQ-5 was introduced into the reaction tube at a flow rate of 100.0 mL / h, and the treatment time was set to 12.0 hours. The obtained catalyst was named ECT-5.

[0117] Comparative Example B1 20.0 g of CT-0 was placed in a reaction tube and sulfurized using SQ-0. In the sulfurization process, the hydrogen gas pressure was 6.0 MPa, the hydrogen gas flow rate was 300.0 mL / min, the sulfurization liquid SQ-0 flow rate was 40.0 mL / h, the sulfurization temperature was 350°C, and the sulfurization time was 6.0 hours. The catalyst after sulfurization was named DCT-1.

[0118] Comparative example B2 The preparation process of catalyst DCT-1 was the same as that of Comparative Example B1. The reaction tube containing DCT-1 was cooled to 260°C, the hydrogen gas pressure was adjusted to 5.0 MPa, the hydrogen gas flow rate was set to 200.0 mL / min, TQ-1 was introduced into the reaction tube at a flow rate of 30.0 mL / h, and the treatment time was set to 9 hours. The resulting catalyst was designated DCT-2.

[0119] Comparative Example B3 The preparation process of the sulfided state hydrogenation catalyst SCT-0 was the same as that of Example B1. 2000 g of toluene, 90.0 g of silver cyclohexane butyrate, and 80.0 g of aniline were prepared to prepare an organic solution containing silver, designated DYQ-3. The reaction tube containing SCT-0 was cooled to 150°C, the hydrogen gas pressure was adjusted to 2.0 MPa, the hydrogen gas flow rate was set to 180.0 mL / min, DYQ-3 was introduced into the reaction tube at a flow rate of 120.0 mL / h, and the treatment time was set to 15.0 hours. The resulting catalyst was designated DCT-3.

[0120] Comparative example B4 The preparation process of catalyst DCT-1 was the same as that of Comparative Example B1. 2000 g of toluene, 90.0 g of silver cyclohexane butyrate, and 80.0 g of aniline were prepared to prepare an organic solution containing silver, designated DYQ-4. The reaction tube containing DCT-1 was cooled to 300°C, the hydrogen gas pressure was adjusted to 10.0 MPa, the hydrogen gas flow rate was 400.0 mL / min, and the treatment time was 12 hours. The obtained catalyst was named DTCT-4. The temperature of the reaction tube containing DTCT-4 was lowered to 150°C, the hydrogen gas pressure was adjusted to 2.0 MPa, the hydrogen gas flow rate was set to 180.0 mL / min, DYQ-4 was introduced into the reaction tube at a flow rate of 120.0 mL / h, and the treatment time was set to 15.0 hours. The resulting catalyst was designated DCT-4.

[0121] Comparative Example B5 1000.0 g of dried alumina sol powder was weighed, 30.0 g of citric acid, and 10.0 g of sesbania powder were added and mixed uniformly. 900.0 g of a 2.0% nitric acid aqueous solution was added, and the mixture was compacted for 30.0 minutes. It was then extruded into strands using a plate with cloverleaf holes (1.6 mm in diameter). It was dried at 120°C for 6.0 hours and then roasted at 600°C for 6.0 hours. The roasted support was designated S-0. 100.0 g of ammonium heptamolybdate tetrahydrate, 60.0 g of nickel nitrate hexahydrate, 7.5 g of silver nitrate, and 120.0 g of deionized water were weighed out, thoroughly stirred at 80°C for 30 minutes, cooled to room temperature, and then made up to a constant volume of 180.0 mL with deionized water. The resulting solution was designated DQ-5. 200 g of carrier S-0 was prepared, immersed in DQ-5, dried for 24 hours, dried at 120°C for 4 hours, and then roasted at 420°C for 4.0 hours. The resulting oxidation state hydrogenation catalyst was designated DCT-0. 20.0 g of DCT-0 was placed in a reaction tube and subjected to primary sulfurization using SQ-0. In the sulfurization process, the hydrogen gas pressure was 6.0 MPa, the hydrogen gas flow rate was 300.0 mL / min, the sulfurization liquid SQ-0 flow rate was 40.0 mL / h, the sulfurization temperature was 350°C, and the sulfurization time was 6 hours. The sulfurized hydrogenation catalyst obtained was designated DCT-5. The compositions of the above catalysts are shown in Table B1.

[0122] [Table 5]

[0123] The hydrogenation catalysts obtained in each example were characterized by TEM-EDS to obtain the percentage of the Ag content distributed within the Ni-Mo-S active phase region relative to the total Ag content, and the percentage of the sulfur content at the edges and corners of the Ni-Mo-S active phase relative to the total sulfur content of the Ni-Mo-S active phase, as shown in Table B2.

[0124] [Table 6]

[0125] Test Example B1 The activity and stability of catalysts ECT-1 to ECT-5 of Examples B1 to B5 were investigated in a fixed-bed hydrogenation reactor. The evaluation conditions were a reaction pressure of 8.0 MPa, a hydrogen-to-oil volume ratio of 500:1, a temperature of 300°C, and a volumetric space velocity of 2.0 h -1 Samples were collected and analyzed at two time points, 500 and 1500 hours after the reaction. The crude oil used here was a Fischer-Tropsch synthetic oil, and its properties are shown in Table B3. The catalyst evaluation results are shown in Table B4.

[0126] Comparative test example B1 The activity and stability of the catalysts DCT-1 to DCT-5 of Comparative Examples B1 to B5 were investigated in a fixed-bed hydrogenation reactor under the same evaluation conditions as in Test Example B1.

[0127] [Table 7]

[0128] [Table 8]

[0129] As can be seen from the evaluation results in Table B4, when the hydrogenation catalyst of the present invention was used to process low-sulfur Fischer-Tropsch synthetic oil, it exhibited good hydrodeoxidation and hydrogenation saturation performance and maintained good activity stability even under long-term operating conditions.

[0130] In the present invention, the oxidized state hydrogenation catalysts used in the following Examples C1 to C5 and Comparative Examples C1 to C5 were all prepared by the following method. 1000.0 g of alumina sol dry powder was weighed, and 10.0 g of citric acid and 50.0 g of sesbania powder were added and mixed uniformly. After that, 900.0 g of an aqueous solution with an acetic acid mass fraction of 1.0% was added, and after kneading for 20.0 min, the mixture was extruded into strands using a plate with cloverleaf-shaped holes of 2.4 mm in diameter. After drying at 120°C for 6.0 h, it was roasted at 750°C for 6.0 h. The roasted support was designated S-0 (analysis showed that the specific surface area of ​​the support was 322 m). 2 / g, and the pore volume of the support is 0.9 cm 3 40.0 g of ammonium heptamolybdate tetrahydrate, 25.0 g of nickel nitrate hexahydrate, and 150.0 g of deionized water were weighed out, thoroughly stirred at 80°C for 30 minutes, cooled to room temperature, and then made up to a constant volume of 210.0 mL with deionized water. The resulting solution was designated Q-0. 200 g of carrier S-0 was prepared, immersed in Q-0, and dried for 24 hours. After that, it was dried at 120°C for 4 hours and then roasted at 420°C for 4.0 hours. The resulting oxidation state hydrogenation catalyst was designated CT-0 (by weight of the catalyst, the carrier content was 84.1%, the molybdenum oxide content was 13.2%, and the nickel oxide content was 2.7%).

[0131] Example C1 1000 g of cyclohexane and 50.0 g of dimethyl disulfide were prepared, and a sulfurization liquid was prepared as SQ-0. 1000 g of cyclohexane and 2.0 g of dimethyl disulfide were prepared, and a sulfurization solution was prepared as TQ-1. 2000 g of toluene, 35.0 g of magnesium tetraphenylporphyrin, and 50.0 g of diethanolamine were prepared, and an organic solution containing magnesium was prepared, designated MQ-1. 20.0 g of CT-0 was placed in a reaction tube and sulfurized using SQ-0. In the sulfurization process, the hydrogen gas pressure was 6.0 MPa, the hydrogen gas flow rate was 300.0 mL / min, the sulfurization liquid SQ-0 flow rate was 40.0 mL / h, the sulfurization temperature was 350°C, and the sulfurization time was 6 hours. The catalyst after sulfurization was named SCT-0. The temperature of the reaction tube was lowered to 260°C, the hydrogen gas pressure was adjusted to 5.0 MPa, the hydrogen gas flow rate was set to 200.0 mL / min, TQ-1 was introduced into the reaction tube at a flow rate of 30.0 mL / h, and the treatment time was set to 9 hours. The resulting catalyst was designated TCT-1. The temperature of the reaction tube was lowered to 110°C, the hydrogen gas pressure was adjusted to 0.4 MPa, the gas flow rate was set to 100.0 mL / min, MQ-1 was introduced into the reaction tube at a flow rate of 80.0 mL / h, and the treatment time was set to 10.0 hours. The obtained catalyst was designated ECT-1.

[0132] Example C2 The preparation processes of the carrier S-0, the solution Q-0, the oxidation state hydrogenation catalyst CT-0, the sulfurization solution SQ-0, and the sulfurization catalyst SCT-0 were the same as those in Example C1. 1000 g of cyclohexane and 3.0 g of dimethyl disulfide were prepared, and a sulfurization solution was prepared as TQ-2. 2000 g of toluene, 16.0 g of magnesium L-aspartate, and 50.0 g of diethanolamine were prepared to prepare an organic solution containing magnesium, designated MQ-2. The temperature of the reaction tube was lowered to 280°C, the hydrogen gas pressure was adjusted to 6.0 MPa, the hydrogen gas flow rate was set to 300.0 mL / min, TQ-2 was introduced into the reaction tube at a flow rate of 40.0 mL / h, and the treatment time was set to 12 hours. The resulting catalyst was designated TCT-2. The temperature of the reaction tube was lowered to 130°C, the pressure was adjusted to 0.6 MPa, the gas flow rate was set to 120.0 mL / min, MQ-2 was introduced into the reaction tube at a flow rate of 100.0 mL / h, and the treatment time was set to 12.0 hours. The obtained catalyst was named ECT-2.

[0133] Example C3 The preparation processes of the carrier S-0, the solution Q-0, the oxidation state hydrogenation catalyst CT-0, the sulfurization solution SQ-0, and the sulfurization catalyst SCT-0 were the same as those in Example C1. 1000 g of cyclohexane and 4.0 g of dimethyl disulfide were prepared, and a sulfurization solution was prepared as TQ-3. 2000 g of cyclohexane, 12.0 g of di-n-butylmagnesium, and 50.0 g of diethanolamine were prepared, and an organic solution containing magnesium was prepared, designated MQ-3. The temperature of the reaction tube was lowered to 300°C, the hydrogen gas pressure was adjusted to 8.0 MPa, the hydrogen gas flow rate was set to 400.0 mL / min, TQ-3 was introduced into the reaction tube at a flow rate of 40.0 mL / h, and the treatment time was set to 12 hours. The resulting catalyst was designated TCT-3. The temperature of the reaction tube was lowered to 150°C, the pressure was adjusted to 0.8 MPa, the gas flow rate was set to 140.0 mL / min, MQ-3 was introduced into the reaction tube at a flow rate of 120.0 mL / h, and the treatment time was set to 10.0 hours. The obtained catalyst was designated ECT-3.

[0134] Example C4 The preparation process of the sulfided catalyst SCT-0 was the same as that of Example C1. The temperature of the reaction tube was lowered to 280°C, the reaction pressure was adjusted to 6.0 MPa, and a mixed gas of hydrogen gas and hydrogen sulfide was introduced into the reaction tube so that the volume ratio of hydrogen gas to hydrogen sulfide was 350:1 and the total flow rate of the mixed gas was 350 mL / min. The treatment time was set to 12 hours. The obtained catalyst was designated TCT-4. 2000.0 g of toluene, 12.0 g of magnesium pyruvate, and 50.0 g of diethanolamine were prepared, and an organic solution containing magnesium was prepared, designated MQ-4. The temperature of the reaction tube was lowered to 140°C, the pressure was adjusted to 0.6 MPa, the gas flow rate was set to 130.0 mL / min, MQ-4 was introduced into the reaction tube at a flow rate of 120.0 mL / h, and the treatment time was set to 12.0 hours. The obtained catalyst was named ECT-4.

[0135] Example C5 The preparation process of the sulfided catalyst SCT-0 was the same as that of Example C1. The temperature of the reaction tube was lowered to 300°C, the reaction pressure was adjusted to 6.0 MPa, and a mixed gas of hydrogen gas and hydrogen sulfide was introduced into the reaction tube so that the volume ratio of hydrogen gas to hydrogen sulfide was 550:1 and the total flow rate of the mixed gas was 450 mL / min. The treatment time was set to 12 hours. The obtained catalyst was designated TCT-5. 2000.0 g of n-octane, 30.0 g of magnesium stearate, and 50.0 g of diethanolamine were prepared, and an organic solution containing magnesium was prepared and designated MQ-5. The temperature of the reaction tube was lowered to 150°C, the pressure was adjusted to 0.6 MPa, the gas flow rate was set to 130.0 mL / min, MQ-5 was introduced into the reaction tube at a flow rate of 120.0 mL / h, and the treatment time was set to 14.0 hours. The obtained catalyst was named ECT-5.

[0136] Comparative Example C1 20.0 g of CT-0 was placed in a reaction tube and sulfurized using SQ-0. In the sulfurization process, the hydrogen gas pressure was 6.0 MPa, the hydrogen gas flow rate was 300.0 mL / min, the sulfurization liquid SQ-0 flow rate was 40.0 mL / h, the sulfurization temperature was 350°C, and the sulfurization time was 6.0 hours. The catalyst after sulfurization was named DCT-1.

[0137] Comparative Example C2 The preparation process of catalyst DCT-1 was the same as that of Comparative Example C1. The reaction tube containing DCT-1 was cooled to 260°C, the hydrogen gas pressure was adjusted to 5.0 MPa, the hydrogen gas flow rate was set to 200.0 mL / min, TQ-1 was introduced into the reaction tube at a flow rate of 30.0 mL / h, and the treatment time was set to 9 hours. The resulting catalyst was designated DCT-2.

[0138] Comparative Example C3 The preparation process of the sulfided state hydrogenation catalyst SCT-0 was the same as that of Example C1. 2000 g of toluene, 35.0 g of magnesium tetraphenylporphyrin, and 50.0 g of diethanolamine were prepared, and an organic solution containing magnesium was prepared, designated DGQ-3. The reaction tube containing SCT-0 was cooled to 110°C, the pressure was adjusted to 0.4 MPa, the gas flow rate was set to 100.0 mL / min, DGQ-3 was introduced into the reaction tube at a flow rate of 80.0 mL / h, and the treatment time was set to 10.0 hours. The resulting catalyst was designated DCT-3.

[0139] Comparative example C4 The preparation process of catalyst DCT-1 was the same as that of Comparative Example C1. 2000 g of toluene, 35.0 g of magnesium tetraphenylporphyrin, and 50.0 g of diethanolamine were prepared, and an organic solution containing magnesium was prepared, designated DGQ-4. The reaction tube containing DCT-1 was cooled to 260°C, the hydrogen gas pressure was adjusted to 5.0 MPa, the hydrogen gas flow rate was 200.0 mL / min, and the treatment time was 9 hours. The obtained catalyst was named DTCT-4. The temperature of the reaction tube was lowered to 110°C, the pressure was adjusted to 0.4 MPa, the gas flow rate was set to 100.0 mL / min, DGQ-4 was introduced into the reaction tube at a flow rate of 80.0 mL / h, and the treatment time was set to 10.0 hours. The resulting catalyst was designated DCT-4.

[0140] Comparative example C5 The preparation process of carrier S-0 was the same as that of Example C1. 40.0 g of ammonium heptamolybdate tetrahydrate, 25.0 g of nickel nitrate hexahydrate, 15.0 g of anhydrous magnesium nitrate, and 150.0 g of deionized water were weighed out, thoroughly stirred at 80°C for 30 minutes, cooled to room temperature, and then made up to a volume of 210.0 mL with deionized water. The resulting solution was designated DQ-5. 200 g of carrier S-0 was prepared, immersed in DQ-5, dried for 24 hours, dried at 120°C for 4 hours, and then roasted at 420°C for 4.0 hours. The resulting oxidation state hydrogenation catalyst was designated DCT-0. 20.0 g of DCT-0 was placed in a reaction tube and sulfurized using SQ-0 (similar to Example 1). In the sulfurization process, the hydrogen gas pressure was 6.0 MPa, the hydrogen gas flow rate was 300.0 mL / min, the sulfurization liquid SQ-0 flow rate was 40.0 mL / h, the sulfurization temperature was 350°C, and the sulfurization time was 6 hours. The sulfurized hydrogenation catalyst obtained was named DCT-5. The compositions of the above catalysts are shown in Table C1.

[0141] [Table 9]

[0142] The Mg-modified hydrogenation catalyst was characterized by TEM-EDS to obtain the percentage of the Mg content distributed within the Ni-Mo-S active phase region relative to the total Mg content, and the percentage of the sulfur content at the edges and corners of the Ni-Mo-S active phase relative to the total sulfur content of the Ni-Mo-S active phase, as shown in Table C2.

[0143] [Table 10]

[0144] Test example C1 The activity of the catalysts obtained in each of Examples C1 to C5 was evaluated. The properties of the crude oil are shown in Table C3. The hydrogenation of the feedstock was evaluated. The evaluation conditions were a reaction temperature of 320°C, a reaction pressure of 8.0 MPa, and a liquid hourly space velocity of 2.5 h -1 The catalyst was evaluated for 1000 hours at a hydrogen-to-oil volume ratio of 800:1, and the evaluation results are shown in Table C4.

[0145] Comparative test example C1 The catalysts obtained in each of Comparative Examples C1 to C5 were evaluated for activity. The properties of the crude oil are shown in Table C3. The hydrogenation of the feedstock was evaluated. The evaluation conditions were a reaction temperature of 320°C, a reaction pressure of 8.0 MPa, and a liquid hourly space velocity of 2.5 h -1 The catalyst was evaluated for 1000 hours at a hydrogen-to-oil volume ratio of 800:1, and the evaluation results are shown in Table C4.

[0146] [Table 11]

[0147] [Table 12]

[0148] As can be seen from the evaluation results in Table C4, the Mg-modified hydrogenation catalyst prepared by the method of the present invention not only has good hydrogenation activity, but also good hydrogenation saturation performance for olefins and good catalytic stability.

[0149] In the present invention, the oxidized state hydrogenation catalysts used in the following Examples D1 to D5 and Comparative Examples D1 to D5 were all prepared by the following method. 1000.0 g of dried alumina sol powder was weighed, and 10.0 g of citric acid and 30.0 g of sesbania powder were added and mixed uniformly. After that, 1000.0 g of an aqueous solution with a nitric acid mass fraction of 0.5% was added, and the mixture was compacted for 10.0 min. The mixture was then extruded into strands using a plate with cloverleaf-shaped holes of 2.0 mm in diameter. The mixture was dried at 120°C for 6.0 hours and then roasted at 800°C for 6.0 hours. The roasted support was designated S-0 (analysis showed that the specific surface area of ​​the support was 271 m). 2 / g, the pore volume of the support is 0.93 cm 3 / g. 50.0 g of ammonium heptamolybdate tetrahydrate, 30.0 g of nickel nitrate hexahydrate, and 150.0 g of deionized water were weighed out, thoroughly stirred at 60°C for 30 minutes, cooled to room temperature, and then made up to a constant volume of 200.0 mL with deionized water. The resulting solution was designated Q-0. 200 g of carrier S-0 was prepared, immersed in Q-0, and dried for 24 hours. After that, it was dried at 120°C for 4 hours and then roasted at 480°C for 4.0 hours. The resulting oxidation state hydrogenation catalyst was designated CT-0 (by weight of the catalyst, the carrier content was 72.1%, the molybdenum oxide content was 24.9%, and the nickel oxide content was 3.0%).

[0150] Example D1 1000 g of cyclohexane and 50.0 g of dimethyl disulfide were prepared, and a sulfurization liquid was prepared as SQ-0. 1000 g of cyclohexane and 2.0 g of dimethyl disulfide were prepared, and a sulfurization solution was prepared as TQ-1. 1000 g of cyclohexane, 25.0 g of glycerol zinc, and 60.0 g of monoethanolamine were prepared, and an organic solution containing zinc was prepared and designated ZQ-1. 20.0 g of CT-0 was placed in a reaction tube and sulfurized using SQ-0. In the sulfurization process, the hydrogen gas pressure was 6.0 MPa, the hydrogen gas flow rate was 300.0 mL / min, the sulfurization liquid SQ-0 flow rate was 40.0 mL / h, the sulfurization temperature was 350°C, and the sulfurization time was 6 hours. The catalyst after sulfurization was named SCT-0. The temperature of the reaction tube was lowered to 260°C, the hydrogen gas pressure was adjusted to 5.0 MPa, the hydrogen gas flow rate was set to 200.0 mL / min, TQ-1 was introduced into the reaction tube at a flow rate of 30.0 mL / h, and the treatment time was set to 9 hours. The resulting catalyst was designated TCT-1. The temperature of the reaction tube was lowered to 140°C, the hydrogen gas pressure was adjusted to 3.0 MPa, the gas flow rate was set to 120.0 mL / min, ZQ-1 was introduced into the reaction tube at a flow rate of 80.0 mL / h, and the treatment time was set to 3.0 hours. The obtained catalyst was designated ECT-1.

[0151] Example D2 The preparation processes of the carrier S-0, the solution Q-0, the oxidation state hydrogenation catalyst CT-0, the sulfurization solution SQ-0, and the sulfurization catalyst SCT-0 were the same as those in Example D1. 1000 g of cyclohexane and 3.0 g of dimethyl disulfide were prepared, and a sulfurization solution was prepared as TQ-2. 1000 g of toluene, 30.0 g of glycerol zinc, and 60.0 g of monoethanolamine were prepared, and an organic solution containing zinc was prepared and designated ZQ-2. The temperature of the reaction tube was lowered to 280°C, the hydrogen gas pressure was adjusted to 6.0 MPa, the hydrogen gas flow rate was set to 300.0 mL / min, TQ-2 was introduced into the reaction tube at a flow rate of 40.0 mL / h, and the treatment time was set to 12 hours. The resulting catalyst was designated TCT-2. The temperature of the reaction tube was lowered to 160°C, the pressure was adjusted to 4.0 MPa, the gas flow rate was set to 150.0 mL / min, ZQ-2 was introduced into the reaction tube at a flow rate of 100.0 mL / h, and the treatment time was set to 4.0 hours. The obtained catalyst was named ECT-2.

[0152] Example D3 The preparation processes of the carrier S-0, the solution Q-0, the oxidation state hydrogenation catalyst CT-0, the sulfurization solution SQ-0, and the sulfurization catalyst SCT-0 were the same as those in Example D1. 1000 g of cyclohexane and 4.0 g of dimethyl disulfide were prepared, and a sulfurization solution was prepared as TQ-3. 1000 g of toluene, 40.0 g of glycerol zinc, and 60.0 g of monoethanolamine were prepared to prepare an organic solution containing zinc, designated ZQ-3. The temperature of the reaction tube was lowered to 300°C, the hydrogen gas pressure was adjusted to 10.0 MPa, the hydrogen gas flow rate was set to 400.0 mL / min, TQ-3 was introduced into the reaction tube at a flow rate of 40.0 mL / h, and the treatment time was set to 12 hours. The resulting catalyst was designated TCT-3. The temperature of the reaction tube was lowered to 190°C, the pressure was adjusted to 5.0 MPa, the gas flow rate was set to 180.0 mL / min, ZQ-3 was introduced into the reaction tube at a flow rate of 120.0 mL / h, and the treatment time was set to 5.0 hours. The obtained catalyst was designated ECT-3.

[0153] Example D4 The preparation processes of the carrier S-0, the solution Q-0, the oxidation state hydrogenation catalyst CT-0, the sulfurization solution SQ-0, and the sulfurization catalyst SCT-0 were the same as those in Example D1. The temperature of the reaction tube was lowered to 280°C, the reaction pressure was adjusted to 6.0 MPa, and a mixed gas of hydrogen gas and hydrogen sulfide was introduced into the reaction tube so that the volume ratio of hydrogen gas to hydrogen sulfide was 350:1 and the total flow rate of the mixed gas was 350 mL / min. The treatment time was set to 12 hours. The obtained catalyst was designated TCT-4. The temperature of the reaction tube was lowered to 140°C, the hydrogen gas pressure was adjusted to 3.0 MPa, the gas flow rate was set to 120.0 mL / min, ZQ-1 was introduced into the reaction tube at a flow rate of 80.0 mL / h, and the treatment time was set to 3.0 hours. The obtained catalyst was designated ECT-4.

[0154] Example D5 The preparation processes of the carrier S-0, the solution Q-0, the oxidation state hydrogenation catalyst CT-0, the sulfurization solution SQ-0, and the sulfurization catalyst SCT-0 were the same as those in Example D1. The temperature of the reaction tube was lowered to 300°C, the reaction pressure was adjusted to 6.0 MPa, and a mixed gas of hydrogen gas and hydrogen sulfide was introduced into the reaction tube so that the volume ratio of hydrogen gas to hydrogen sulfide was 450:1 and the total flow rate of the mixed gas was 450 mL / min. The treatment time was set to 12 hours. The resulting catalyst was designated TCT-5. The temperature of the reaction tube was lowered to 140°C, the hydrogen gas pressure was adjusted to 3.0 MPa, the gas flow rate was set to 120.0 mL / min, ZQ-1 was introduced into the reaction tube at a flow rate of 80.0 mL / h, and the treatment time was set to 3.0 hours. The obtained catalyst was designated ECT-5.

[0155] Comparative Example D1 20.0 g of CT-0 was placed in a reaction tube and sulfurized using SQ-0. In the sulfurization process, the hydrogen gas pressure was 6.0 MPa, the hydrogen gas flow rate was 300.0 mL / min, the sulfurization liquid SQ-0 flow rate was 40.0 mL / h, the sulfurization temperature was 350°C, and the sulfurization time was 6.0 hours. The catalyst after sulfurization was named DCT-1.

[0156] Comparative example D2 The preparation process of catalyst DCT-1 was the same as that of comparative example D1. The reaction tube containing DCT-1 was cooled to 260°C, the hydrogen gas pressure was adjusted to 5.0 MPa, the hydrogen gas flow rate was set to 200.0 mL / min, TQ-1 was introduced into the reaction tube at a flow rate of 30.0 mL / h, and the treatment time was set to 9 hours. The resulting catalyst was designated DCT-2.

[0157] Comparative Example D3 The preparation process of the sulfided state hydrogenation catalyst SCT-0 was the same as that of Example D1. The reaction tube containing SCT-0 was cooled to 140°C, the pressure was adjusted to 3.0 MPa, the gas flow rate was set to 120.0 mL / min, ZQ-1 was introduced into the reaction tube at a flow rate of 80.0 mL / h, and the treatment time was set to 3.0 hours. The resulting catalyst was designated DCT-3.

[0158] Comparative Example D4 The preparation process of catalyst DCT-1 was the same as that of comparative example D1. The reaction tube containing DCT-1 was cooled to 260°C, the hydrogen gas pressure was adjusted to 5.0 MPa, the hydrogen gas flow rate was 200.0 mL / min, and the treatment time was 9 hours. The obtained catalyst was named DTCT-4. The temperature of the reaction tube was lowered to 140°C, the pressure was adjusted to 3.0 MPa, the gas flow rate was set to 120.0 mL / min, ZQ-1 was introduced into the reaction tube at a flow rate of 80.0 mL / h, and the treatment time was set to 3.0 hours. The obtained catalyst was named DCT-4.

[0159] Comparative Example D5 The preparation process of carrier S-0 was the same as that of Example D1. 50.0 g of ammonium heptamolybdate tetrahydrate, 30.0 g of nickel nitrate hexahydrate, 80.0 g of anhydrous zinc nitrate, and 150.0 g of deionized water were weighed out, thoroughly stirred at 60°C for 30 minutes, cooled to room temperature, and then made up to a volume of 200.0 mL with deionized water. The resulting solution was designated DQ-5. 200 g of carrier S-0 was prepared, immersed in DQ-5, dried for 24 hours, dried at 120°C for 4 hours, and then roasted at 420°C for 4.0 hours. The resulting oxidation state hydrogenation catalyst was designated DCT-0. 20.0 g of DCT-0 was placed in a reaction tube and sulfurized using SQ-0 (similar to Example D1). In the sulfurization process, the hydrogen gas pressure was 6.0 MPa, the hydrogen gas flow rate was 300.0 mL / min, the sulfurization liquid SQ-0 flow rate was 40.0 mL / h, the sulfurization temperature was 350°C, and the sulfurization time was 6 hours. The sulfurized hydrogenation catalyst obtained was named DCT-5. The compositions of the above catalysts are shown in Table D1.

[0160] [Table 13]

[0161] The Zn-modified hydrodesulfurization catalyst was characterized by TEM-EDS to obtain the Zn content distributed within the Ni-Mo-S active phase as a percentage of the total Zn content, and the sulfur content at the edges and corners of the Ni-Mo-S active phase as a percentage of the total sulfur content in the Ni-Mo-S active phase, as shown in Table D2.

[0162] [Table 14]

[0163] Test Example D1 The activity of the catalysts obtained in each of Examples D1 to D5 was evaluated. The properties of the deasphalted oil are shown in Table D3. A fixed-bed process was employed, and a hydrogenation protection agent (FZC-100B) was packed in front of the catalyst so that the volume ratio of the hydrogenation protection agent to the hydrodesulfurization catalyst obtained in the examples was 1:4. The operating conditions were a reaction temperature of 385°C, a reaction pressure of 18.0 MPa, a hydrogen-to-oil volume ratio of 800:1, and a liquid hourly space velocity of 0.15 h. -1 After 2000 hours of reaction evaluation, the residual carbon value, sulfur content, and nitrogen content of the fraction above 200°C in the hydrotreated oil were analyzed, and the results are shown in Table D4.

[0164] Comparative test example D1 The activity of the catalysts obtained in each of Comparative Examples D1-D5 was evaluated. The properties of the deasphalted oil are shown in Table D3. A fixed-bed process was used, and a hydrogenation protection agent (FZC-100B) was packed in front of the catalyst so that the volume ratio of the hydrogenation protection agent to the hydrodesulfurization catalyst obtained in the examples was 1:4. The operating conditions were a reaction temperature of 385°C, a reaction pressure of 18.0 MPa, a hydrogen-to-oil volume ratio of 800:1, and a liquid hourly space velocity of 0.15 h. -1 After 2000 hours of reaction evaluation, the residual carbon value, sulfur content, and nitrogen content of the fraction above 200°C in the hydrotreated oil were analyzed, and the results are shown in Table D4.

[0165] [Table 15]

[0166] [Table 16]

[0167] As can be seen from the evaluation results in Table D4, the hydrodesulfurization catalyst of the present invention not only has a high hydrodesulfurization capacity, but also has a high hydrodenitrification capacity and a high hydrogenation residual carbon removal capacity.

[0168] In the present invention, the oxidized state hydrogenation catalysts used in the following Examples E1 to E5 and Comparative Examples E1 to E5 were all prepared by the following method. 1000.0 g of dried alumina sol powder was weighed, and 20.0 g of citric acid and 20.0 g of sesbania powder were added and mixed uniformly. After that, 1000.0 g of an aqueous solution with a nitric acid mass fraction of 1.0% was added, and the mixture was compacted for 20.0 min. The mixture was then extruded into strands using a plate with cloverleaf-shaped holes of 1.8 mm in diameter. The mixture was dried at 120°C for 6.0 hours and then roasted at 700°C for 6.0 hours. Analysis of the roasted support showed that its properties were as follows: specific surface area 270 m 2 / g, pore volume 0.9 cm 374.2 g of ammonium heptamolybdate tetrahydrate, 47.3 g of nickel nitrate hexahydrate, and 150.0 g of deionized water were weighed out, thoroughly stirred at 60°C for 20 minutes, cooled to room temperature, and then made up to a constant volume of 200.0 mL with deionized water. The resulting solution was designated Q-0. 200 g of carrier S-0 was prepared, immersed in Q-0, and dried for 24 hours. After that, it was dried at 120°C for 4 hours and then roasted at 450°C for 5.0 hours. The resulting oxidation state hydrogenation catalyst was designated CT-0 (by weight of the catalyst, the carrier content was 73.3%, the molybdenum oxide content was 22.2%, and the nickel oxide content was 4.5%).

[0169] Example E1 1000 g of cyclohexane and 50.0 g of dimethyl disulfide were prepared, and a sulfurization liquid was prepared as SQ-0. 1000 g of cyclohexane and 2.0 g of dimethyl disulfide were prepared, and a sulfurization solution was prepared as TQ-1. 20.0 g of CT-0 was placed in a reaction tube and sulfurized using SQ-0. In the sulfurization process, the hydrogen gas pressure was 6.0 MPa, the hydrogen gas flow rate was 300.0 mL / min, the sulfurization liquid SQ-0 flow rate was 40.0 mL / h, the sulfurization temperature was 350°C, and the sulfurization time was 6 hours. The sulfurized hydrogenation catalyst obtained was named SCT-0. The temperature of the reaction tube was lowered to 260°C, the hydrogen gas pressure was adjusted to 5.0 MPa, the hydrogen gas flow rate was set to 200.0 mL / min, TQ-1 was introduced into the reaction tube at a flow rate of 30.0 mL / h, and the treatment time was set to 9 hours. The resulting catalyst was designated TCT-1. The temperature of the reaction tube was lowered to 160°C, the pressure was adjusted to 5.0 MPa, and a mixed gas of hydrogen gas and hydrogen selenide was introduced into the reaction tube. Here, in the mixed gas, the volume fraction of hydrogen gas was 95% and the volume fraction of hydrogen selenide was 5%, the flow rate of the mixed gas was 300.0 mL / min, and the treatment time was 3.0 hours. The obtained catalyst was designated ECT-1.

[0170] Example E2 The preparation process of the sulfided state hydrogenation catalyst SCT-0 was the same as that of Example E1. 1000 g of cyclohexane and 3.0 g of carbon disulfide were prepared to prepare a sulfurization liquid designated as TQ-2. The temperature of the reaction tube containing the sulfide-state hydrogenation catalyst SCT-0 was lowered to 280°C, the hydrogen gas pressure was adjusted to 6.0 MPa, the hydrogen gas flow rate was set to 300.0 mL / min, TQ-2 was introduced into the reaction tube at a flow rate of 40.0 mL / h, and the treatment time was set to 12 hours. The resulting catalyst was designated TCT-2. The temperature of the reaction tube was lowered to 180°C, the pressure was adjusted to 8.0 MPa, and a mixed gas of hydrogen gas and hydrogen selenide was introduced into the reaction tube. Here, the volume fraction of hydrogen gas was 93%, the volume fraction of hydrogen selenide was 7%, the flow rate of the mixed gas was 400.0 mL / min, and the treatment time was 4.0 hours. The resulting catalyst was designated ECT-2.

[0171] Example E3 The preparation process of the sulfided state hydrogenation catalyst SCT-0 was the same as that of Example E1. 1000 g of cyclohexane and 4.0 g of dimethyl sulfoxide were prepared to prepare a sulfurization solution designated as TQ-3. The temperature of the reaction tube containing the sulfide-state hydrogenation catalyst SCT-0 was lowered to 300°C, the hydrogen gas pressure was adjusted to 10.0 MPa, the hydrogen gas flow rate was set to 400.0 mL / min, TQ-3 was introduced into the reaction tube at a flow rate of 40.0 mL / h, and the treatment time was set to 12 hours. The resulting catalyst was designated TCT-3. The temperature of the reaction tube was lowered to 200°C, the pressure was adjusted to 7.0 MPa, and a mixed gas of hydrogen gas and hydrogen selenide was introduced into the reaction tube. Here, the volume fraction of hydrogen gas was 90%, the volume fraction of hydrogen selenide was 10%, the flow rate of the mixed gas was 500.0 mL / min, and the treatment time was 5.0 hours. The resulting catalyst was designated ECT-3.

[0172] Example E4 The preparation process of the sulfided state hydrogenation catalyst SCT-0 was the same as that of Example E1. The temperature of the reaction tube containing the sulfide-state hydrogenation catalyst SCT-0 was lowered to 270°C, the reaction pressure was adjusted to 6.0 MPa, and a mixed gas of hydrogen gas and hydrogen sulfide was introduced so that the partial pressure ratio of hydrogen gas to hydrogen sulfide was 400:1 and the flow rate of the mixed gas was 400.0 mL / min. The treatment time was set to 12 hours. The resulting catalyst was designated TCT-4. The temperature of the reaction tube was lowered to 180°C, the pressure was adjusted to 8.0 MPa, and a mixed gas of hydrogen gas and hydrogen selenide was introduced into the reaction tube. Here, the volume fraction of hydrogen gas was 93%, the volume fraction of hydrogen selenide was 7%, the flow rate of the mixed gas was 500.0 mL / min, and the treatment time was 4.0 hours. The resulting catalyst was designated ECT-4.

[0173] Example E5 The preparation process of the sulfided state hydrogenation catalyst SCT-0 was the same as that of Example E1. The temperature of the reaction tube containing the sulfide-state hydrogenation catalyst SCT-0 was lowered to 250°C, the reaction pressure was adjusted to 6.0 MPa, and a mixed gas of hydrogen gas and hydrogen sulfide was introduced so that the partial pressure ratio of hydrogen gas to hydrogen sulfide was 400:1 and the flow rate of the mixed gas was 400.0 mL / min. The treatment time was set to 12 hours. The resulting catalyst was designated TCT-5. The temperature of the reaction tube was lowered to 210°C, the pressure was adjusted to 7.0 MPa, and a mixed gas of hydrogen gas and hydrogen selenide was introduced into the reaction tube. Here, the volume fraction of hydrogen gas was 88%, the volume fraction of hydrogen selenide was 12%, the flow rate of the mixed gas was 300.0 mL / min, and the treatment time was 5.0 hours. The obtained catalyst was designated ECT-5.

[0174] Comparative Example E1 20.0 g of CT-0 was placed in a reaction tube and sulfurized using SQ-0. In the sulfurization process, the hydrogen gas pressure was 6.0 MPa, the hydrogen gas flow rate was 300.0 mL / min, the sulfurization liquid SQ-0 flow rate was 40.0 mL / h, the sulfurization temperature was 350°C, and the sulfurization time was 6.0 hours. The catalyst after sulfurization was named DCT-1.

[0175] Comparative example E2 The preparation process of catalyst DCT-1 was the same as that of Comparative Example E1. The reaction tube containing DCT-1 was cooled to 260°C, the hydrogen gas pressure was adjusted to 5.0 MPa, the hydrogen gas flow rate was set to 200.0 mL / min, TQ-1 was introduced into the reaction tube at a flow rate of 30.0 mL / h, and the treatment time was set to 9 hours. The resulting catalyst was designated DCT-2.

[0176] Comparative example E3 The preparation process of the sulfided state hydrogenation catalyst SCT-0 was the same as that of Example E1. The reaction tube containing SCT-0 was cooled to 180°C, the hydrogen gas pressure was adjusted to 8.0 MPa, and a mixture of hydrogen gas and hydrogen selenide was introduced into the reaction tube. The volume fraction of hydrogen gas was 93%, the volume fraction of hydrogen selenide was 7%, the gas flow rate was 400.0 mL / min, and the treatment time was 4.0 hours. The resulting catalyst was designated DCT-3.

[0177] Comparative Example E4 The preparation process of catalyst DCT-1 was the same as that of Comparative Example E1. The reaction tube containing DCT-1 was cooled to 260°C, the hydrogen gas pressure was adjusted to 5.0 MPa, the hydrogen gas flow rate was 200.0 mL / min, and the treatment time was 9 hours. The obtained catalyst was named DTCT-4. The temperature of the reaction tube was lowered to 160°C, the pressure was adjusted to 5.0 MPa, and a mixed gas of hydrogen gas and hydrogen selenide was introduced into the reaction tube. Here, the volume fraction of hydrogen gas was 95%, the volume fraction of hydrogen selenide was 5%, the flow rate of the mixed gas was 300.0 mL / min, and the treatment time was 3.0 hours. The resulting catalyst was designated DCT-4.

[0178] Comparative Example E5 20.0 g of CT-0 was placed in a reaction tube, and a mixture of hydrogen gas and hydrogen selenide was introduced into the reaction tube. The volume fraction of hydrogen gas was 90%, the volume fraction of hydrogen selenide was 10%, the reaction temperature was 200°C, the reaction pressure was 7.0 MPa, the flow rate of the mixture gas was 500.0 mL / min, and the reaction time was 5.0 hours. The resulting catalyst was designated DCT-5. The compositions of the above catalysts are shown in Table E1.

[0179] [Table 17]

[0180] The hydrogenation carbon residue removal catalyst was characterized by TEM-EDS to obtain the percentage of the Se content distributed within the Ni-Mo-S active phase of the catalyst relative to the total Se content, and the percentage of the sulfur content at the edges and corners of the Ni-Mo-S active phase relative to the total sulfur content in the Ni-Mo-S active phase, as shown in Table E2.

[0181] [Table 18]

[0182] Test Example E1 The activity of the catalysts obtained in Examples E1 to E5 was evaluated. The properties of the residual oil feedstock are shown in Table E3. A fixed-bed process was used, and a hydrogenation protection agent (FZC-100B), a hydrodemetallization catalyst (FZC-204A), and a hydrodesulfurization catalyst (FZC-33B) were packed in front of the catalyst. The volumetric ratio of the protection agent, hydrodemetallization catalyst, hydrodesulfurization catalyst, and catalyst obtained in the examples was 1.5:2.0:2.0:4.5. The operating conditions were a reaction temperature of 380°C, a reaction pressure of 16.0 MPa, a hydrogen-to-oil volume ratio of 1200:1, and a liquid hourly space velocity of 0.2 h. -1 After 2000 hours of reaction evaluation, the residual carbon value, saturates, and nitrogen content in the fraction above 200°C of the hydrotreated oil were analyzed, and the results are shown in Table E4.

[0183] Comparative test example E1 The activity of the catalysts obtained in each of Comparative Examples E1 to E5 was evaluated. The properties of the residual oil feedstock are shown in Table E3. A fixed-bed process was used, and a hydrogenation protection agent (FZC-100B), a hydrodemetallization catalyst (FZC-204A), and a hydrodesulfurization catalyst (FZC-33B) were packed in front of the catalyst. The volumetric ratio of the protection agent, hydrodemetallization catalyst, hydrodesulfurization catalyst, and the catalyst obtained in the comparative examples was 1.5:2.0:2.0:4.5. The operating conditions were a reaction temperature of 380°C, a reaction pressure of 16.0 MPa, a hydrogen-to-oil volume ratio of 1200:1, and a liquid hourly space velocity of 0.2 h. -1 After 2000 hours of reaction evaluation, the residual carbon value, saturates, and nitrogen content in the fraction above 200°C of the hydrotreated oil were analyzed, and the results are shown in Table E4.

[0184] [Table 19]

[0185] [Table 20]

[0186] As can be seen from the evaluation results in Table E4, the catalyst of the present invention has high hydrogenation residual carbon removal capacity, high hydrogenation saturation capacity, and high hydrodenitrification capacity.

Claims

1. A hydrogenation catalyst comprising: The hydrogenation catalyst is a sulfide-state hydrogenation catalyst and includes a carrier, an active component A, an active component B, and a modifying auxiliary component; The active ingredient A is at least one selected from metal elements of Group VIII, The active ingredient B is at least one selected from the metal elements of Group VIB, the modifying aid component is at least one selected from Group IB, Group IIA, Group IIB, Group IIIA, and Group VIA elements; The hydrogenation catalyst is characterized by a TEM-EDS method, and the content of the modifying aid component distributed in the A-B-S active phase region is 60% to 98%, preferably 75% to 98%, of the total content of the modifying aid components.

2. 2. The hydrogenation catalyst according to claim 1, wherein the hydrogenation catalyst is characterized by a TEM-EDS method, and the sulfur content at the edges and corners of the A-B-S active phase is 6.0% or less, preferably 0.5% to 4.5%, of the total sulfur content in the A-B-S active phase.

3. Based on the mass of the hydrogenation catalyst, the content of active component A is 1 to 10%, preferably 1.5% to 6%, in elemental terms, and the content of active component B is 6 to 24%, preferably 8 to 18%, in elemental terms; Preferably, the content of the modification aid component, in element, based on the mass of the hydrogenation catalyst, is 0.2% to 4%, preferably 0.8% to 4%; The hydrogenation catalyst according to claim 1, wherein the content of elemental sulfur is preferably 3% to 20%, preferably 4% to 15%, based on the mass of the hydrogenation catalyst.

4. The active component A is Co and / or Ni, and the active component B is Mo and / or W, Preferably, the active component A is Ni and the active component B is Mo; Preferably, the modifying aid component is at least one selected from Cu, Ag, Au, Mg, Ca, Zn, Cd, Ga, and Se, more preferably at least one selected from Ag, Mg, Zn, Ga, and Se, The hydrogenation catalyst according to any one of claims 1 to 3, wherein the support is preferably at least one selected from alumina, silicon oxide, and amorphous silicon aluminum.

5. 1. A method for preparing a hydrogenation catalyst, the method comprising: (1) sulfiding the oxidized state hydrogenation catalyst to obtain a sulfided state hydrogenation catalyst; (2) desulfurizing the sulfided hydrogenation catalyst; and step (3) catalytically reacting the treated catalyst obtained in step (2) with a material containing a precursor of the modifying aid component, The preparation method, wherein the modifying aid component is at least one selected from Group IB, Group IIA, Group IIB, Group IIIA, and Group VIA elements.

6. The oxidized state hydrogenation catalyst comprises a support, an active component A, and an active component B, wherein the active component A is at least one selected from Group VIII metal elements, and the active component B is at least one selected from Group VIB metal elements; Preferably, the active component A is Co and / or Ni, and the active component B is Mo and / or W; Preferably, the active component A is Ni and the active component B is Mo; Preferably, the support is at least one selected from alumina, silicon oxide, and amorphous silicon aluminum; Preferably, based on the weight of the oxidized state hydrogenation catalyst, the content of the carrier is 50% to 90%, the content of active component B in terms of oxide is 10% to 35%, and the content of active component A in terms of oxide is 2% to 8%.

7. The sulfurization includes dry sulfurization and / or wet sulfurization, Preferably, the sulfurization conditions are a sulfurization temperature of 240 to 400°C, a sulfurization time of 2 to 10 hours, a hydrogen gas pressure of 2 to 12 MPa, and a hydrogen gas flow rate of 2 to 25 mL min. －１ ・g －１ 7. The process according to claim 5 or 6, comprising an oxidized state hydrogenation catalyst.

8. The temperature of the desulfurization treatment in step (2) is lower than the sulfurization temperature, preferably the temperature of the desulfurization treatment is 50 to 100°C lower than the sulfurization temperature; The method according to any one of claims 5 to 7, wherein the conditions of the desulfurization treatment preferably include a temperature of 180 to 370°C, preferably 200 to 300°C, a treatment time of 4 to 24 hours, preferably 6 to 16 hours, and a total pressure of 2 to 18 MPa, preferably 4 to 15 MPa.

9. In step (2), the desulfurization treatment preferably includes: A method (a) of desulfurizing the sulfurized hydrogenation catalyst using hydrogen gas containing hydrogen sulfide; and The preparation method according to any one of claims 5 to 8, wherein the mild desulfurization treatment is carried out by employing at least one of the methods (b) for desulfurizing the sulfurized hydrogenation catalyst using a sulfurizing liquid in the presence of hydrogen gas.

10. In method (a), the volume ratio of hydrogen sulfide to hydrogen gas is 200:1 to 800:1, preferably 300:1 to 600:1, and the total gas flow rate is 5 to 30 mL min －１ ・g －１ Oxidized state hydrogenation catalyst, preferably 10 to 20 mL min －１ ・g －１ an oxidized state hydrogenation catalyst, and / or, in method (b), the sulfurizing liquid comprises a sulfur-containing compound and an organic solvent, the sulfur-containing compound being at least one selected from dimethyl disulfide, carbon disulfide, diethyl sulfide, ethyl mercaptan, n-butyl mercaptan, di-tert-nonyl polysulfide, and dimethyl sulfoxide, and the organic solvent being at least one selected from cyclohexane, n-heptane, aviation kerosene, and diesel; Preferably, the mass fraction of the sulfur-containing compound in the sulfurizing liquid is 0.1% to 0.6%, Preferably, in the desulfurization treatment process, the flow rate of the sulfurizing liquid is 0.5 to 4.5 mL h －１ ・g －１ Oxidized state hydrogenation catalyst, preferably 1 to 4 mL h －１ ・g －１ an oxidized state hydrogenation catalyst, Preferably, in the desulfurization treatment process, the hydrogen gas flow rate is 5 to 30 mL min －１ ・g －１ Oxidized state hydrogenation catalyst, preferably 10 to 20 mL min －１ ・g －１ 10. The method of claim 9, wherein the catalyst is an oxidized state hydrogenation catalyst.

11. The modifying aid component is at least one selected from Cu, Ag, Au, Mg, Ca, Zn, Cd, Ga, and Se, more preferably at least one selected from Ag, Mg, Zn, Ga, and Se, The preparation method according to any one of claims 5 to 10, wherein the modifying aid component precursor is preferably at least one selected from gallium acetylacetonate, triethylgallium, silver stearate, silver acetylacetonate, silver cyclohexanebutyrate, magnesium stearate, dibutylmagnesium, magnesium pyruvate, magnesium L-aspartate, magnesium tetraphenylporphyrin, zinc naphthenate, zinc glycerol, diethylselenium, and hydrogen selenide.

12. the material containing a modifying aid component precursor is an organic solution containing a modifying aid component precursor, Preferably, in the organic solution containing the modifying aid component precursor, the mass content of the modifying aid component precursor is 0.5% to 5%; The preparation method according to any one of claims 5 to 11, wherein the solvent in the organic solution containing the modifying auxiliary component precursor is preferably one or more selected from toluene, cyclohexane, decalin, tetralin, and n-heptane.

13. The organic solution containing the modifying aid component precursor further contains a stabilizer, and the stabilizer is selected from organic basic nitrides; Preferably, the stabilizer is at least one selected from triethanolamine, diethanolamine, monoethanolamine, pyridine, quinoline, and aniline; The preparation method according to claim 12, wherein the mass content of the stabilizer in the organic solution containing the modifying auxiliary component precursor is preferably 2% to 8%.

14. The conditions for the contact reaction in step (3) are a temperature of 80 to 220°C, preferably 100 to 200°C, a pressure of 0.2 to 8 MPa, preferably 0.5 to 6 MPa, a reaction time of 2 to 24 hours, preferably 4 to 20 hours, and a hydrogen gas flow rate of 2 to 20 mL min －１ ・g －１ Oxidized state hydrogenation catalyst, preferably 5 to 15 mL min －１ ・g －１ The catalyst is an oxidized state hydrogenation catalyst, and the flow rate of the material containing the modified auxiliary component precursor is 2 to 10 mL h －１ ・g －１ Oxidized state hydrogenation catalyst, preferably 3 to 8 mL h －１ ・g －１ A process according to any one of claims 5 to 13, comprising an oxidized state hydrogenation catalyst.

15. the material containing a modification aid component precursor is a mixed gas containing a modification aid component precursor, and the mixed gas further contains hydrogen gas; Preferably, in the mixed gas containing the modification aid component precursor, the volume content of the modification aid component precursor is 1% to 20%, preferably 3% to 15%, and the volume content of hydrogen gas is 80% to 99%, preferably 85% to 97%; Preferably, the modifying aid component precursor is hydrogen selenide, Preferably, the conditions for the contact reaction in step (3) are a temperature of 120 to 250°C, preferably 150 to 220°C, a reaction time of 1 to 8 hours, preferably 2 to 6 hours, a reaction pressure of 2 to 12 MPa, preferably 4 to 8 MPa, and a flow rate of the mixed gas containing the modifying aid component precursor of 5 to 40 mL min －１ ・g －１ Oxidized state hydrogenation catalyst, preferably 10 to 30 mL min －１ ・g －１ A process according to any one of claims 5 to 11, comprising an oxidized state hydrogenation catalyst.

16. Use of the hydrogenation catalyst according to any one of claims 1 to 4 or the hydrogenation catalyst prepared by the method according to any one of claims 5 to 15 in hydrogenating petroleum products.

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