Residual oil hydrogenation reaction method

Abstract

The present invention relates to the field of residual oil hydrotreatment, and discloses a residual oil hydrogenation reaction method, which comprises: sequentially contacting a residual oil raw material with a hydrogenation protection catalyst, a hydrodemetallization catalyst and a hydrodesulfurization catalyst under a hydrotreatment condition, wherein the hydrodesulfurization catalyst is obtained by regenerating a waste hydrogenation catalyst, when the hydrodesulfurization catalyst is measured by diffuse reflection ultraviolet-visible spectrum, the absorbance at 630 nm and the absorbance at 500 nm are F630 and F500 respectively, and the ratio Q of the absorbance at 630 nm and the absorbance at 500 nm is equal to F630 / F500 and is 1.3-3. The method can improve the utilization rate of the waste distillate oil hydrogenation catalyst, reduce the cost of the existing residual oil hydrogenation catalyst, and greatly improve the stability of the residual oil hydrogenation reaction.

Description

Technical Field

[0001] The present invention relates to the field of residual oil hydroprocessing, and in particular to a residual oil hydrogenation reaction method. Background Art

[0002] At present, domestic refineries unload a large amount of distillate oil hydrogenation catalysts that have been deactivated after the reaction from idle units every year. The main reasons for the deactivation of distillate oil hydrogenation catalysts are coke deposition and metal sintering. For this type of deactivated catalyst, the commonly used regeneration method is to first char the catalyst under certain conditions, and then use a solution containing specific compound components to redisperse the active phase of the charred catalyst.

[0003] CN105944735A discloses a method for activating a Type II hydrogenation catalyst deactivated by carbon deposition. The method includes first charring the deactivated Type II hydrogenation catalyst to obtain a hydrogenation catalyst with a carbon content of 0.3%-1.0%. The hydrogenation catalyst with a carbon content of 0.3%-1.0% is then saturated with an activation solution for 40-60 minutes, then cured at a temperature of 60-70°C for 8-24 hours. Finally, the catalyst is dried at a temperature of 60-150°C for 6-8 hours to obtain an activated hydrogenation catalyst. This activation method has the advantages of good activation effect and simple operation.

[0004] CN101992131A discloses a method for regenerating a hydrogenation catalyst, a regenerated hydrogenation catalyst, and applications thereof. The method comprises the following steps: first, under reaction conditions of regenerating and charring the hydrogenation catalyst, the catalyst to be regenerated is contacted with an oxygen-containing gas; then, the charred catalyst is contacted with a solution containing a phosphorus-containing compound; and finally, the treated catalyst is dried to obtain a regenerated catalyst, wherein the activity of the regenerated catalyst is significantly improved and enhanced.

[0005] After deactivated distillate hydrogenation catalysts are restored through conventional regeneration methods, they are typically loaded back into the reactor for further industrial use. After one or two regenerations, the catalysts no longer meet the distillate's ultra-deep hydrogenation activity requirements, forcing them to be disposed of as hazardous waste. The high cost and environmental pressure of waste catalyst disposal have become a major challenge for the industry. Domestic refining and petrochemical companies face a long and arduous journey in achieving carbon emission reduction and green development, and the generation of hazardous catalyst waste is detrimental to their sustainable, green development.

[0006] If these waste hydrofining catalysts that cannot be regenerated conventionally can be treated by special methods and then applied to the heavy oil and / or residue oil hydrofining reaction process to replace part of the heavy oil and / or residue oil hydrodesulfurization catalysts, realizing the cascade utilization of waste hydrofining catalysts, the procurement cost of existing heavy oil and / or residue oil hydrofining catalysts can be reduced. At the same time, the problem of recycling and treating waste hydrofining catalysts can be solved, creating obvious social and economic benefits. Summary of the Invention

[0007] The object of the present invention is to overcome the problem of poor stability in the residue oil hydrofining reaction existing in the prior art, and provide a residue oil hydrofining reaction method. This reaction method can effectively utilize the waste hydrofining catalyst after regeneration treatment for residue oil hydrofining, and has high reaction stability.

[0008] The inventors of the present invention found during the research process that when the regenerated catalyst obtained by using the existing recycling and treating method of waste hydrofining catalysts is reused in the hydrofining process of distillate oil, after 1-2 times of regeneration and use, it is difficult to meet the requirements of the distillate oil for the ultra-deep hydrofining activity of the catalyst. For example, the activity and selectivity of the catalyst cannot fully meet the requirements. At this time, the discharged catalyst can only be treated as hazardous waste. The high cost of waste catalyst treatment and the great environmental protection pressure have become problems that plague the industry. The inventors of the present invention changed their thinking and treated the waste hydrofining catalysts that do not have conventional regeneration conditions by special methods and then used them in the heavy oil and / or residue oil hydrofining process where the requirements for the catalyst are slightly lower. Compared with distillate oil, the molecular weight of compounds in heavy oil and / or residue oil raw materials is higher, the molecular size is larger, and the reaction conditions are more severe. Therefore, it is necessary to increase the accessibility of the catalyst active center to the macromolecular compounds in heavy oil and / or residue oil, improve the diffusion performance of the catalyst pores, and improve the activity stability of the catalyst under severe reaction conditions. However, the regenerated agent obtained by the conventional regeneration method of waste hydrofining catalysts cannot meet the requirements of heavy oil and / or residue oil hydrofining reactions. [[ID= (10)]]

[0009] The inventors of the present invention used the hydrodesulfurization catalyst obtained by treating waste hydrofining catalysts in combination with a hydroprotection catalyst and a hydrodemetallization catalyst in the hydrotreating process of residue oil, not only effectively utilized the waste hydrofining catalyst, but also had a high desulfurization rate and good stability.

[0010] To achieve the above object, the present invention provides a residue oil hydrofining reaction method, which includes:

[0011] Under hydrotreating conditions, contacting the residue oil raw material with a hydroprotection catalyst, a hydrodemetallization catalyst, and a hydrodesulfurization catalyst in sequence;

[0012] Among them, the hydrodesulfurization catalyst is obtained by regenerating a waste hydrocatalyst. When the hydrodesulfurization catalyst is measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbances at 630 nm and 500 nm are F 630 and F 500 , and the ratio Q of the two is Q = F 630 / F 500 is 1.3 - 3.

[0013] In the prior art, it is generally considered that the spinel structure formed in the catalyst will affect the initial activity of the catalyst. However, the inventors of the present invention have found that forming an appropriate amount of spinel structure will not only not have too much impact on the total activity of the catalyst, but also in the residue oil hydrogenation reaction, as the hydrodesulfurization catalyst participates in the reaction process, the formed spinel structure will gradually release the reaction activity, greatly improving the service life of the hydrodesulfurization catalyst and making the stability of the residue oil hydrogenation reaction better.

[0014] Compared with the prior art, the residue oil hydrotreating method provided by the present invention can, on the one hand, improve the utilization rate of the waste distillate oil hydrocatalyst, especially provide a way to reuse the distillate oil hydrocatalyst with a high carbon deposition amount and high deposited impurities, and on the other hand, can effectively reduce the cost of the existing residue oil hydrocatalyst and greatly improve the stability of the residue oil hydrogenation reaction. Therefore, the method provided by the present invention has higher economic benefits. Detailed Embodiments

[0015] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0016] The present invention provides a residue oil hydrogenation reaction method, which includes:

[0017] Under hydrotreating conditions, contacting a residue oil feedstock with a hydroprotection catalyst, a hydrodemetallation catalyst, and a hydrodesulfurization catalyst in sequence;

[0018] Among them, the hydrodesulfurization catalyst is obtained by regenerating a waste hydrocatalyst. When the hydrodesulfurization catalyst is measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbances at 630 nm and 500 nm are F 630 and F 500 , and the ratio Q of the two is Q = F 630 / F 500 is 1.3 - 3.

[0019] In the prior art, it is generally believed that the spinel structure formed in the catalyst will affect the initial activity of the catalyst. However, the inventors of the present invention have found that forming an appropriate amount of spinel structure will not only not have too much impact on the total activity of the catalyst, but also in the residue hydrotreating reaction, as the hydrodesulfurization catalyst participates in the reaction process, the formed spinel structure will gradually release the reaction activity, greatly improving the service life of the hydrodesulfurization catalyst and making the stability of the residue hydrotreating reaction better.

[0020] In the present invention, the hydrodesulfurization catalyst is obtained by treating waste hydrocatalysts, further improving the economy of the overall process. During the regeneration of conventional waste distillate oil hydrocatalysts, after the active metals are redispersed with a solvent, they are usually dried only at low temperature without high-temperature calcination. For example, in CN102463127A, the heat treatment temperature does not exceed 200 °C. This is because the catalyst treated by the conventional regeneration method is still reused in the distillate oil hydrotreating reaction, and its reaction conditions are relatively milder. Low-temperature drying treatment is beneficial to improving the catalyst activity. However, the purpose of the present invention is to apply the regenerated waste distillate oil hydrocatalyst to the heavy oil / residue hydrotreating reaction, where the reaction temperature and pressure are higher and the properties of the reaction raw materials are worse. Therefore, the catalyst is required to have higher activity and stability. The inventors have found in the research that by combining low-temperature heat treatment and high-temperature heat treatment, the activity and stability of the prepared hydrodesulfurization catalyst under harsh reaction conditions can be improved. When used in combination with a hydroprotection catalyst and a hydrodemetallization catalyst in the hydrotreating process of residue, not only the waste hydrocatalyst is effectively utilized, but also a high desulfurization rate is achieved.

[0021] In the present invention, "residue" refers to the components remaining at the bottom of the distillation tower during crude oil distillation, including atmospheric residue and vacuum residue. The method provided by the present invention is applicable to the hydrotreating of various residues. Preferably, the density of the residue is 920 - 1050 kg / m 3 ; the carbon residue content is below 15 wt%; and the sulfur content is below 5 wt%.

[0022] In the present invention, the formation of the spinel structure in the catalyst is determined by ultraviolet-visible spectroscopy (DRUVS). The instrument used is the Cary300 ultraviolet-visible analyzer of Agilent Technologies, with a wavelength range of 190 nm - 1100 nm, a wavelength accuracy of ±0.1 nm, a wavelength reproducibility of ±0.1 nm, a baseline stability of 0.0003 / h, stray light of below 0.02%, and a photometer accuracy of ±0.003.

[0023] According to the present invention, preferably, when the hydrodesulfurization catalyst is measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbances at 630 nm and 500 nm are F 630 and F 500 , and the ratio Q of the two is Q = F630 / F 500 is 1.4 - 2.8. Under this preferred embodiment, it is more conducive to improving the catalytic activity of the hydrodesulfurization catalyst and further enhancing the stability of the residue hydrotreating reaction. When the Q value is lower than 1, the improvement of activity stability is not obvious; when the Q value is greater than 3, the initial activity is too low, affecting the normal use of the catalyst. For example, the ratio Q = F 630 / F 500 is specific ratios such as 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8 or the range between two points. More preferably, Q = F 630 / F 500 is 1.7 - 2.2. In the above - mentioned preferred case, it is more conducive to improving the hydrodesulfurization performance and stability in the residue hydrotreating reaction.

[0024] According to the present invention, preferably, based on the total weight of the fresh catalyst corresponding to the hydrotreating catalyst, calculated as oxides, the active metal content in the hydrotreating catalyst is not less than 18 wt%; based on the total weight of the hydrotreating catalyst, calculated as oxides, the content of deposited impurities in the hydrotreating catalyst is not more than 2 wt%. The "based on the total weight of the fresh catalyst corresponding to the hydrotreating catalyst" mentioned in the present invention means that the content of the active metal component is calculated based on the fresh catalyst, that is, the deposited impurities and carbon in the catalyst are not included in the total amount. In the above - mentioned preferred case, it is more conducive to improving the hydrodesulfurization performance and stability in the residue hydrotreating reaction.

[0025] According to the present invention, preferably, the specific surface area of the hydrodesulfurization catalyst is 50 - 280 m 2 / g, the pore volume is 0.3 - 1.5 mL / g, and the most probable pore diameter is 6 - 16 nm; preferably, the specific surface area of the hydrodesulfurization catalyst is 80 - 250 m 2 / g, the pore volume is 0.21 - 1.2 mL / g, and the most probable pore diameter is 8 - 15 nm. In the above - mentioned preferred case, it is beneficial to further improve the activity and stability of the catalyst for residue hydrotreating reaction.

[0026] According to a specific embodiment of the present invention, the method for regenerating the spent hydrodesulfurization catalyst includes:

[0027] 1) Under an oxygen - containing atmosphere, subject the spent hydrodesulfurization catalyst to carbon burning treatment;

[0028] 2) Mix the first leaching agent with the solid product obtained in step 1) and conduct the first leaching; the first leaching agent includes polyols;

[0029] 3) Mix the solid product obtained from the first leaching with a second leaching agent for second leaching to obtain a leached product; the second leaching agent is water and / or ethanol;

[0030] 4) Under an oxygen-containing atmosphere, subject the leached product to high-temperature activation at a temperature of 600-800 °C for 1-10 hours.

[0031] The inventors of the present invention found that by first subjecting the spent hydrotreating catalyst to carbon burning treatment, then successively performing the first leaching and the second leaching, and then subjecting the second leached product to high-temperature activation, the carbon deposits and deposited impurities in the spent hydrotreating catalyst can be effectively removed. At the same time, a relatively high content of active metal components can be maintained in the prepared hydrodesulfurization catalyst, forming a hydrodesulfurization catalyst with a specific spinel structure. The hydrodesulfurization catalyst obtained thereby has a high desulfurization rate and stability when applied to residue hydrotreating. If the activation temperature is too low or the activation time is too short, the content of spinel in the treated catalyst is too low, and the improvement effect of the hydrogenation activity and stability of the active components in the treated hydrodesulfurization catalyst is not obvious; if the activation temperature is too high or the activation time is too long, the content of spinel in the treated hydrodesulfurization catalyst is too high, which affects the initial hydrogenation activity of the catalyst.

[0032] In the present invention, the spent hydrotreating catalyst refers to a catalyst whose performance (which may include at least one of activity, selectivity, and stability) deteriorates after use. It includes both discarded hydrotreating catalysts that cannot meet the hydrotreating activity requirements even after being regenerated by existing means after long-term cyclic use, and used hydrotreating catalysts that can still be used after being regenerated by existing means. The spent hydrotreating catalyst can be various hydrotreating catalysts commonly used for various oil products in the art, and the present invention has no particular limitation thereto. According to a specific embodiment of the present invention, the spent hydrotreating catalyst of the present invention includes, but is not limited to, at least one of spent gasoline hydrotreating catalysts, spent diesel hydrotreating catalysts, spent kerosene hydrotreating catalysts, and spent wax oil hydrotreating catalysts. The examples of the present invention are illustratively described by taking the spent diesel hydrotreating catalyst as an example.

[0033] According to the present invention, preferably, the spent hydrotreating catalyst includes a carrier and active metal components supported on the carrier, and the active metal components include molybdenum and / or tungsten and nickel and / or cobalt.

[0034] The present invention selects a relatively wide range of the contents of molybdenum and / or tungsten and nickel and / or cobalt, and those skilled in the art can make appropriate adjustments according to the actual situation. Further preferably, based on the total amount of the fresh catalyst corresponding to the waste hydrogenation catalyst, calculated as oxides, the content of molybdenum and / or tungsten is 10-40% by weight, and the content of nickel and / or cobalt is 1.5-8% by weight. The conventional selection ranges of the active metal components molybdenum and / or tungsten and nickel and / or cobalt in waste gasoline hydrogenation catalysts, waste diesel hydrogenation catalysts, waste kerosene hydrogenation catalysts, and waste wax oil hydrogenation catalysts may vary, and those skilled in the art can make selections by conventional means, which will not be elaborated herein one by one.

[0035] The composition of the waste hydrogenation catalyst is determined by X-ray fluorescence spectrometry (XRF). For the specific method, see Petrochemical Analysis Method RIPP133-90.

[0036] It should be noted that in addition to the carrier and the active metal components supported on the carrier, the waste hydrogenation catalyst also includes impurities and carbon deposited through long-term cyclic use. The "based on the total amount of the fresh catalyst corresponding to the waste hydrogenation catalyst" mentioned in the present invention means that the contents of molybdenum and / or tungsten and nickel and / or cobalt are calculated based on the fresh catalyst, that is, the above-mentioned deposited impurities and carbon are not included. Since the waste hydrogenation treatment catalyst has characteristics such as high carbon deposition and / or high content of deposited impurities (such as iron, calcium, sodium, silicon) compared with the fresh catalyst, and the deposited impurities come from the feedstock oil. Therefore, the present invention uses the carbon content and / or the content of deposited impurities to indicate whether the catalyst is a waste hydrogenation catalyst. Generally, the carbon content and the content of deposited impurities of the fresh catalyst are basically 0, while the carbon content of the waste hydrogenation catalyst can be as high as 30% by weight, and the content of deposited impurities can be as high as 20% by weight.

[0037] According to a preferred embodiment of the present invention, based on the total weight of the waste hydrogenation catalyst, the carbon content of the waste hydrogenation catalyst is less than 30 wt%, and the content of deposited impurities is less than 20 wt%. Preferably, the carbon content of the waste hydrogenation catalyst is less than 15 wt%, and the content of deposited impurities is less than 10 wt%. Further preferably, the carbon content of the waste hydrogenation catalyst is 5-13 wt%, and the content of deposited impurities is 1-8 wt%.

[0038] In the present invention, unless otherwise specified, the carbon content of the waste hydrogenation catalyst is determined by a carbon-sulfur analyzer after the catalyst is extracted with toluene, and the content of deposited impurities is determined by X-ray fluorescence spectrometry after the catalyst is calcined in air at 600 °C for 3 hours.

[0039] Using the above-preferred method for regenerating spent hydrotreating catalysts has excellent treatment effects on spent hydrotreating catalysts with high carbon deposition and high impurity deposition. Among the existing regeneration methods, the commonly used regeneration method is to first perform carbon burning treatment on the catalyst under certain conditions, and then use a solution containing specific compound components to perform active phase redispersion treatment on the carbon-burned catalyst. For example, CN111821998A discloses impregnating the carbon-burned catalyst with organic alcohols, organic acids, organic amines, and organic ammonium salts having 1 to 20 carbon atoms, and CN111822060A discloses performing two-stage carbon burning and pore expansion, and then impregnating with a solution containing a phosphorus compound. The purpose is to perform active phase redispersion to improve the dispersion degree of active metals. However, the inventors of the present invention have found that although this saturated or unsaturated impregnation method can improve the dispersion degree of the active phase, it cannot remove the inactive deposited impurities in the spent hydrotreating catalyst. Compared with the existing treatment methods, the regeneration method provided by the present invention can not only effectively remove the carbon deposition and deposited impurities in the spent hydrotreating catalyst, but also ensure that the prepared hydrodesulfurization catalyst maintains a high content of active metal components. The hydrodesulfurization catalyst obtained thereby has a high desulfurization rate when applied to residue hydrotreating.

[0040] According to the method for regenerating a spent hydrotreating catalyst of the present invention, this method is particularly suitable for spent hydrotreating catalysts having a small pore volume and pore diameter, because in addition to improving the activity stability of the catalyst, the high-temperature activation step of this method also has the effect of pore expansion. Preferably, the specific surface area of the spent hydrotreating catalyst is 30-300 m 2 / g, the pore volume is 0.05-0.3 mL / g, and the most probable pore diameter is greater than 1 nm; more preferably, the specific surface area of the spent hydrotreating catalyst is 50-200 m 2 / g, the pore volume is 0.05-0.2 mL / g, and the most probable pore diameter is 1.5-4 nm.

[0041] In the present invention, unless otherwise specified, the specific surface area, pore volume, and most probable pore diameter of the spent hydrotreating catalyst are measured by the low-temperature nitrogen adsorption method.

[0042] The inventors of the present invention have found that, preferably, the hydrodesulfurization catalyst obtained by treating the spent hydrotreating catalyst conforming to the above physical and chemical characteristics has higher desulfurization performance and stability when used in residue hydrotreating reactions.

[0043] The inventors of the present invention also found that using waste hydrotreating catalysts with a particle size of 10 - 30 mesh, preferably 14 - 20 mesh, and more preferably 16 - 20 mesh can further improve the desulfurization performance of the obtained hydrodesulfurization catalyst. The waste hydrotreating catalyst can be sieved before use to obtain a waste hydrotreating catalyst that meets the above preferred particle size requirements. Therefore, preferably, before step 1) of the method provided by the present invention, a sieving treatment of the waste hydrotreating catalyst is further included.

[0044] In the prior art, for waste hydrotreating catalysts with a smaller pore volume and pore diameter, on the basis of conventional carbon burning treatment, high-temperature pore expansion treatment is also required to further increase the pore volume and pore diameter of the catalyst, thereby improving the performance of the regenerated catalyst. However, the inventors of the present invention found in their research that in addition to improving the activity stability of the catalyst, the high-temperature activation step of the present method also has the effect of pore expansion. Therefore, in the present invention, the step 1) does not include pore expansion treatment, which is more conducive to weakening the interaction between the metal and the carrier on the catalyst, and thus improving the subsequent leaching effect to a certain extent. In this case, by performing carbon burning treatment, leaching, and high-temperature activation on the waste hydrotreating catalyst, the hydrogenation activity and stability of the regenerated hydrodesulfurization catalyst can be improved. No additional pore expansion treatment is required in this regeneration method, which simplifies the treatment process while ensuring the performance of the treated hydrodesulfurization catalyst.

[0045] In the present invention, there is no particular limitation on the specific manner of the carbon burning treatment in step 1), as long as it can remove the carbon deposits on the waste hydrotreating catalyst, and it can be carried out in a conventional manner in the art, which is well-known to those skilled in the art. To further improve the catalytic activity of the regenerated hydrogenation catalyst, preferably, in step 1), the conditions of the carbon burning treatment include: the temperature is 200 - 550 °C, preferably 220 - 450 °C; the time is 1 - 10 hours, preferably 2 - 7 hours.

[0046] According to a preferred embodiment of the present invention, the carbon burning treatment includes: first treating at a temperature of 220 - 260 °C for 1 - 3 hours, then treating at 290 - 340 °C for 1 - 2 hours, and finally treating at 350 - 450 °C for 1 - 4 hours. By adopting the above preferred embodiment, on the one hand, it is beneficial to more fully burn off the carbon deposits on the catalyst, and on the other hand, it can avoid the phenomenon of temperature runaway during the carbon burning process.

[0047] According to the present invention, in step 1), the oxygen-containing atmosphere provides oxygen for the carbon burning treatment of the spent hydrogenation catalyst. The present invention has a relatively wide selection range for the oxygen content in the oxygen-containing atmosphere. For example, in the oxygen-containing atmosphere, the volume content of oxygen can be 8-30%, preferably 10-25%. The oxygen-containing atmosphere of the present invention can be provided by different methods according to different requirements of the oxygen volume content. For example, the oxygen-containing atmosphere can be provided by air. When a higher oxygen content in the oxygen-containing atmosphere is required, the oxygen-containing atmosphere can be provided by a combination of air and oxygen. When a lower oxygen content in the oxygen-containing atmosphere is required, the oxygen-containing atmosphere can be provided by a combination of air and an inert atmosphere (such as nitrogen). In the embodiments of the present invention, the example of providing the oxygen-containing atmosphere by air is used for illustrative purposes. Providing the oxygen-containing atmosphere by air is more conducive to cost savings, but the present invention is not limited thereto.

[0048] In the present invention, the first leaching and the second leaching are sequentially performed after the carbon burning treatment, which can effectively remove the impurities deposited on the catalyst and some aggregated low-activity metal components during the reaction of the spent hydrogenation catalyst, and further achieve the purpose of unclogging the pores and increasing the pore volume of the catalyst, which helps to further improve the desulfurization performance of the regenerated hydrodesulfurization catalyst.

[0049] According to the present invention, the first leaching agent includes polyhydric alcohol, and the second leaching agent is water and / or ethanol. The combined synergistic leaching with the above leaching agents is more conducive to improving the desulfurization performance of the obtained hydrodesulfurization catalyst.

[0050] To further improve the leaching effect, preferably, the general formula of the polyhydric alcohol is C n H 2n+2-x (OH) x , where n = 2-5 and x = 2-3. For example, the polyhydric alcohol is at least one of ethylene glycol, glycerol, and 1,3-propanediol.

[0051] According to a preferred embodiment of the present invention, the polyhydric alcohol is 1,3-propanediol. The inventors of the present invention found in the research that in the spent hydrogenation catalyst without high-temperature pore expansion, the interaction force between the metal and the carrier is relatively weak. For the spent hydrogenation catalyst without pore expansion treatment, using the first leaching agent containing 1,3-propanediol for the first leaching can further improve the catalytic activity of the treated hydrodesulfurization catalyst.

[0052] Preferably, the first leaching agent further contains water, and the concentration of the first leaching agent is 0.01 - 3 mol / L, preferably 0.01 - 1.5 mol / L. Within the above preferred concentration range, it helps to selectively remove the impurities deposited on the catalyst and the aggregated low-activity metal components during the reaction process. If the concentration of the first leaching agent is too high, the highly active metal components in the dispersed state on the catalyst may be overly removed.

[0053] According to the present invention, during the actual operation process, the leaching conditions can be adjusted according to the physical and chemical properties of the catalyst after carbon burning. The principle is to remove as many impurities deposited on the catalyst and the aggregated low-activity metal components as possible during the reaction process, while retaining the highly active metal components in the dispersed state on the catalyst as much as possible.

[0054] According to the present invention, preferably, in step 2), the volume ratio of the amount of the first leaching agent to the solid product obtained in step 1) is 1 - 6:1, preferably 3 - 6:1.

[0055] The first leaching and the second leaching can be carried out in a conventional manner. For example, the solid product is soaked in the leaching agent, and then solid-liquid separation is performed. The solid-liquid separation can be carried out by conventional operations in the art, and the present invention has no particular limitation on this.

[0056] Preferably, the time of the first leaching is 0.5 - 8 hours, preferably 1 - 4 hours. It can be understood that the time of the first leaching refers to the soaking time of the solid product in the first leaching agent.

[0057] According to the present invention, preferably, the first leaching is carried out under stirring conditions. Preferably, the stirring rate is 50 - 500 rpm, preferably 50 - 280 rpm. By adopting the above preferred implementation manner, it is beneficial to improve the effect of the first leaching and the catalytic activity of the hydrogenation catalyst after treatment.

[0058] According to the present invention, preferably, the volume ratio of the amount of the second leaching agent to the solid product obtained by the first leaching is 1 - 5:1, preferably 2.5 - 5:1.

[0059] Preferably, the time of the second leaching is 0.1 - 3 hours, preferably 0.5 - 3 hours. It can be understood that the time of the second leaching refers to the soaking time of the solid product obtained by the first leaching in the second leaching agent.

[0060] According to some specific embodiments of the present invention, the regeneration method further includes: drying the second leaching product and then performing high-temperature activation. The present invention has no particular limitation on the specific conditions and operation methods of the drying, and conventional methods can be used as long as the residual second leaching agent in the second leaching product can be removed. For example, the drying temperature can be 70-200°C, preferably 80-150°C, and the time can be 2-10h, preferably 3-6h.

[0061] According to the present invention, preferably, the temperature of the high-temperature activation is 610-780°C, preferably 630-750°C, more preferably 650-730°C; the time is 2-8 hours. Under the above preferred high-temperature activation conditions, an appropriate amount of spinel structure can be formed in the catalyst, which is beneficial to further improving the catalytic activity of the regenerated hydrodesulfurization catalyst.

[0062] In the present invention, the high-temperature activation can be increased from the ambient temperature to the activation temperature, or directly increased from the drying temperature of the second leaching product to the activation temperature, and there is no particular limitation on this. The present invention has a wide selection range for the heating rate during the high-temperature activation. Preferably, the heating rate of the high-temperature activation is 50-600°C / hour, preferably 100-550°C / hour.

[0063] According to the present invention, in order to further improve the desulfurization rate of the residue oil hydrogenation reaction, preferably, based on the total volume of the hydrogenation protection catalyst, the hydrogenation demetallization catalyst and the hydrodesulfurization catalyst, the content of the hydrogenation protection catalyst is 5-60% by volume, preferably 10-50% by volume, more preferably 15-30% by volume, the content of the hydrogenation demetallization catalyst is 5-50% by volume, preferably 10-40% by volume, more preferably 20-40% by volume, and the content of the hydrodesulfurization catalyst is 10-60% by volume, preferably 20-55% by volume, more preferably 40-55% by volume.

[0064] The hydrogenation protection catalyst and the hydrogenation demetallization catalyst of the present invention can each independently be various hydrogenation protection catalysts and hydrogenation demetallization catalysts commonly used in the art, and the present invention has no particular limitation on this.

[0065] The hydrogenation protection catalyst of the present invention may not contain active metal components. Preferably, the hydrogenation protection catalyst and the hydrogenation demetallization catalyst each independently contain a carrier and active metal components supported on the carrier, and the active metal components are selected from at least one of Group VIB and / or Group VIII metal elements; preferably, the Group VIB metal element is molybdenum and / or tungsten, and the Group VIII metal element is nickel and / or cobalt. More preferably, the active metal components are any one or more of the combinations of nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum, and cobalt-molybdenum.

[0066] The supports in the hydrogenation protection catalyst and the hydrodemetallization catalyst according to the present invention may each independently be selected from at least one of alumina, silica, and titanium oxide. Other elements may also be added to the support for modification, such as boron, germanium, zirconium, phosphorus, chlorine, or fluorine.

[0067] According to the present invention, preferably, in the hydrogenation protection catalyst, based on the total amount of the hydrogenation protection catalyst and in terms of oxides, the content of the active metal component is 1-15% by weight; specifically, the content of molybdenum and / or tungsten is not higher than 10% by weight, and the content of nickel and / or cobalt is not higher than 5% by weight.

[0068] In the present invention, the hydrogenation protection catalyst may be an industrial agent or may be prepared by existing methods. The hydrogenation protection catalyst may, for example, be at least one of the RG series catalysts developed by the Research Institute of Petroleum Processing, SINOPEC.

[0069] According to the present invention, preferably, in the hydrodemetallization catalyst, based on the total amount of the hydrodemetallization catalyst and in terms of oxides, the content of the active metal component is 6-20% by weight; specifically, the content of molybdenum and / or tungsten is not higher than 15% by weight, and the content of nickel and / or cobalt is not higher than 6% by weight.

[0070] In the present invention, the hydrodemetallization catalyst may be an industrial agent or may be prepared by existing methods. The hydrodemetallization catalyst may, for example, be at least one of the RDM series catalysts and the RUF series catalysts developed by the Research Institute of Petroleum Processing, SINOPEC.

[0071] According to the present invention, this method is carried out under hydrotreating conditions. Preferably, the conditions of the hydrotreating include: the temperature is 320-450 °C, the hydrogen partial pressure is 8-20 MPa, the liquid hourly space velocity is 0.1-1 h -1 , and the hydrogen-oil volume ratio is 500-1500; more preferably, the conditions of the hydrotreating include: the temperature is 350-420 °C, the hydrogen partial pressure is 12-18 MPa, the liquid hourly space velocity is 0.2-0.6 h -1 , and the hydrogen-oil volume ratio is 800-1200. In the present invention, unless otherwise specified, the hydrogen partial pressure refers to the gauge pressure.

[0072] According to the present invention, preferably, before hydrotreating, the method further includes a step of sulfiding a hydroprotection catalyst, a hydrodemetallization catalyst, and a hydrodesulfurization catalyst. The sulfiding treatment can be carried out by conventional treatment methods and conditions in the art, and the present invention has no particular limitation thereon. According to some preferred embodiments of the present invention, the sulfiding treatment can be carried out by in-situ sulfiding treatment, and the sulfiding treatment includes: in the presence of hydrogen, contacting a sulfiding agent with the hydroprotection catalyst, the hydrodemetallization catalyst, and the hydrodesulfurization catalyst for sulfiding treatment. The sulfiding agent can be provided by an oil solution of the sulfiding agent. The solvent oil can be, for example, kerosene. The content of the sulfiding agent in the oil solution is preferably 1-5 wt%, more preferably 1.5-3 wt%. The sulfiding agent can be any conventional selection in the art, for example, it can be dimethyl disulfide.

[0073] According to some preferred embodiments of the present invention, the conditions of the sulfiding treatment include: the temperature is 280-350 °C, the time is 2-8 h, the hydrogen partial pressure is 10-15 MPa, and the liquid hourly space velocity is 0.8-1.5 h -1 , and the hydrogen-oil volume ratio is 200-500:1.

[0074] The method provided by the present invention can be carried out in a conventional residue hydrotreating unit, and the present invention has no particular limitation thereon. For example, in a residue hydrotreating unit, a hydroprotection catalyst, a hydrodemetallization catalyst, and a hydrodesulfurization catalyst can be loaded in sequence along the material flow direction. The residue hydrotreating unit is preferably a fixed-bed hydrotreating unit. Moreover, various catalysts of the present invention can be loaded in the same fixed-bed hydrotreating unit, or can be respectively loaded in multiple different fixed-bed hydrotreating units connected in series, as long as the catalyst loading method is in accordance with the requirements of the present invention, and there is no particular limitation on the number of fixed-bed hydrotreating units.

[0075] The present invention will be described in detail below through examples.

[0076] In the following preparation examples, the specific surface area, pore volume, and most probable pore diameter were measured by low-temperature nitrogen adsorption method.

[0077] The carbon content in the catalyst was determined by a carbon-sulfur analyzer.

[0078] The composition of the catalyst was determined by X-ray fluorescence spectrometry (XRF). The specific method is shown in Petrochemical Analysis Method RIPP133-90.

[0079] The formation of the spinel structure in the catalyst was determined by ultraviolet-visible spectroscopy (DRUVS). An Agilent Cary 300 ultraviolet-visible analyzer was used, with a wavelength range of 190 nm - 1100 nm, a wavelength accuracy of ±0.1 nm, a wavelength reproducibility of ±0.1 nm, a baseline stability of 0.0003 / h, stray light of less than 0.02%, and a photometer accuracy of ±0.003.

[0080] The following preparation examples are used to illustrate the treatment of waste hydrotreating catalysts to obtain hydrodesulfurization catalysts.

[0081] Preparation Example 1

[0082] 1) Take an industrial deactivated diesel hydrotreating catalyst (carbon content 10.67 w%, deposition impurities such as iron and sodium content 7.2 w%, this catalyst is NiMo / Al2O3, based on the total amount of the fresh catalyst corresponding to the waste hydrotreating catalyst, in terms of oxides, the content of Ni is 4.6 w% and the content of Mo is 27.8 w%), called deactivator A. Sieve it to obtain deactivator A with a mesh size of 16 - 20. Put it into a muffle furnace and conduct carbon burning treatment in an air atmosphere in a programmed heating manner, including: keeping it at 250 °C for 1 hour, at 330 °C for 2 hours, and at 410 °C for 3 hours to obtain catalyst B;

[0083] 2) At room temperature, under a stirring rate of 100 rpm, use a 1.2 mol / L 1,3 - propanediol aqueous solution to conduct the first leaching of catalyst B obtained in step 1). The volume of the 1,3 - propanediol aqueous solution used is 4 times the volume of the catalyst, and the soaking time is 2 hours. Then, perform solid - liquid separation;

[0084] 3) At room temperature, use deionized water to conduct the second leaching of the solid product obtained in step 2). The volume of the deionized water used is 3.5 times the volume of the solid, and the soaking time is 1.5 hours. Then, perform solid - liquid separation and dry at 110 °C for 4 hours, denoted as catalyst C;

[0085] 4) High - temperature activate catalyst C in an air atmosphere. The conditions for high - temperature activation include: temperature of 650 °C, time of 3 hours, and heating rate of 200 °C / h to obtain catalyst D.

[0086] The formation of the spinel structure formed by the metal components and aluminum in the catalyst was determined by ultraviolet - visible spectroscopy (DRUVS). The absorbance ratio Q = F630 / F500 at 630 nm and 500 nm was 1.94, indicating that a certain amount of spinel structure was formed in the catalyst.

[0087] Preparation Example 2

[0088] 1) Catalyst B was obtained according to the method of Preparation Example 1;

[0089] 2) At room temperature, at a stirring rate of 150 rpm, the catalyst B obtained in step 1) was first soaked with a 0.8 mol / L 1,3-propylene glycol aqueous solution, wherein the volume of the 1,3-propylene glycol aqueous solution used was 5 times the volume of the catalyst, and the soaking time was 3 hours, followed by solid-liquid separation;

[0090] 3) The solid product obtained in step 2) was subjected to a second immersion in ethanol at room temperature, wherein the volume of the ethanol used was 4 times the volume of the solid, and the immersion time was 2 hours, followed by solid-liquid separation, and drying at 100° C. for 5 hours;

[0091] 4) The product obtained in step 3) was subjected to high-temperature activation in an air atmosphere. The high-temperature activation conditions included: temperature of 680° C., time of 4 hours, and heating rate of 230° C. / h to obtain catalyst E.

[0092] Preparation Example 3

[0093] 1) Catalyst B was obtained according to the method of Preparation Example 1;

[0094] 2) At room temperature, with a stirring rate of 35 rpm, the catalyst B obtained in step 1) was first soaked with a 0.1 mol / L 1,3-propylene glycol aqueous solution, wherein the volume of the 1,3-propylene glycol aqueous solution used was 0.9 times the volume of the catalyst, and the soaking time was 12 minutes, followed by solid-liquid separation;

[0095] 3) The solid product obtained in step 2) was subjected to a second immersion in deionized water at room temperature, wherein the volume of the deionized water used was twice the volume of the solid, and the immersion time was 5 minutes, followed by solid-liquid separation, and drying at 110° C. for 4 hours;

[0096] 4) The product obtained in step 3) was subjected to high-temperature activation in an air atmosphere. The high-temperature activation conditions included: temperature of 650° C., time of 3 hours, and heating rate of 200° C. / h to obtain catalyst F.

[0097] Preparation Example 4

[0098] 1) Catalyst B was obtained according to the method of Preparation Example 1;

[0099] 2) At room temperature, with a stirring rate of 300 rpm, the catalyst B obtained in step 1) was first soaked with a 4 mol / L 1,3-propylene glycol aqueous solution, wherein the volume of the 1,3-propylene glycol aqueous solution used was 7 times the volume of the catalyst, and the soaking time was 9 hours, followed by solid-liquid separation;

[0100] 3) At room temperature, the solid product obtained in step 2) is secondarily washed with deionized water, where the volume of the deionized water used is 6 times the volume of the solid, the soaking time is 4 hours, then solid-liquid separation is carried out, and then it is dried at 110 °C for 4 h;

[0101] 4) The product obtained in step 3) is subjected to high-temperature activation in an air atmosphere. The conditions for high-temperature activation include: the temperature is 650 °C, the time is 3 hours, and the heating rate is 200 °C / h, to obtain catalyst G.

[0102] Preparation Example 5

[0103] According to the method in Preparation Example 1, except that the high-temperature activation temperature in step 4) is 630 °C, the time is 3 h, and the heating rate for activation is 200 °C / h, to obtain catalyst H.

[0104] Preparation Example 6

[0105] According to the method in Preparation Example 1, except that the high-temperature activation temperature in step 4) is 790 °C, the time is 3 h, and the heating rate for activation is 200 °C / h, to obtain catalyst I.

[0106] Comparative Preparation Example 1

[0107] 1) Catalyst B is obtained according to the method of Preparation Example 1;

[0108] 2) At room temperature, under a stirring rate of 100 rpm, catalyst B obtained in step 1) is soaked in a 2 mol / L aqueous solution of 1,3-propanediol, where the volume of the 1,3-propanediol aqueous solution used is 4 times the volume of the catalyst, the soaking time is 2 hours, then solid-liquid separation is carried out, and it is dried at 110 °C for 4 h;

[0109] 3) The product obtained in step 2) is subjected to high-temperature activation in an air atmosphere. The conditions for high-temperature activation include: the temperature is 650 °C, the time is 3 hours, and the heating rate is 200 °C / h, to obtain catalyst J.

[0110] Comparative Preparation Example 2 (conventional regeneration method)

[0111] 1) Catalyst B is obtained according to the method of Preparation Example 1;

[0112] 2) An aqueous solution of 1,3-propanediol is prepared, and catalyst B is impregnated by the equal-volume saturation impregnation method, and is sealed and placed at room temperature (25 °C) for 3 hours. Among them, the mass ratio of catalyst B to 1,3-propanediol is 8.6, and then it is dried in an air atmosphere at 120 °C for 4 hours to obtain catalyst K.

[0113] The physicochemical properties of the catalysts prepared in the above preparation examples and comparative preparation examples are listed in Table 1.

[0114] Table 1

[0115]

[0116]

[0117] The following examples are used to illustrate the hydrotreating method of the residue oil provided by the present invention.

[0118] Example

[0119] The atmospheric residue of the Middle East imported crude oil (the properties are listed in Table 2, the same below) and hydrogen are introduced into a fixed-bed hydrotreating reactor and successively contacted with the catalysts loaded therein for hydrotreating. The total loading volume of the catalysts in the fixed-bed hydrotreating reactor is 500 mL. Along the logistics direction, a hydrotreating protective catalyst, a hydrodemetallization catalyst, and a hydrodesulfurization catalyst are loaded in the fixed-bed hydrotreating reactor in accordance with the volume contents in Table 3. Before hydrotreating, the catalysts need to be sulfided in the reactor. The sulfiding conditions are as follows: the sulfiding agent is kerosene containing 2 wt% dimethyl disulfide, the sulfiding temperature is 320 °C, the sulfiding time is 5 h, the hydrogen partial pressure is 14.0 MPa, and the liquid hourly space velocity is 1.2 h -1 , and the hydrogen-oil volume ratio is 400:1; the hydrotreating conditions include: the reaction temperature is 380 °C, the hydrogen partial pressure is 14 MPa, and the liquid hourly space velocity is 0.5 h -1 , and the hydrogen-oil volume ratio is 600:1.

[0120] Among them, the hydrotreating protective catalyst is the RG-30B catalyst (NiMo / Al2O3, calculated as oxides, the content of Ni is 1.0 wt%, and the content of Mo is 5.0 wt%) developed by the Research Institute of Petroleum Processing, SINOPEC. The hydrodemetallization catalyst is the RDM-32 catalyst (NiMo / Al2O3, calculated as oxides, the content of Ni is 1.5 wt%, and the content of Mo is 8.0 wt%) developed by the Research Institute of Petroleum Processing, SINOPEC. The hydrodesulfurization catalysts are the hydrodesulfurization catalyst prepared in the above preparation example and the reference agent respectively. The reference agent adopts the residue oil hydrodesulfurization catalyst (NiMo / Al2O3, calculated as oxides, the content of Ni is 3.0 wt%, and the content of Mo is 15.4 wt%) developed by the Research Institute of Petroleum Processing, SINOPEC. Comparing the desulfurization performances of the above different hydrodesulfurization catalysts, the results are listed in Table 3.

[0121] Among them, the specific calculation method of the desulfurization rate is as follows:

[0122]

[0123] Table 2

[0124] Feedstock oil <![CDATA[Density (20 °C), kg / m 3 > 991.6 <![CDATA[Viscosity (100 °C) mm 2 / s]]> 153.2 Metal content, ppm Ni 26.0 V 82.9 Fe 10.0 Ca 4.1 Na 2.5 C m% 84.92 H m% 10.77 S m% 3.91 N m% 0.36 Carbon residue, m% 13.3

[0125] Table 3

[0126]

[0127]

[0128] As can be seen from the results in Table 3, for the residue hydrotreating reaction method provided by the present invention, through the grading of a hydrogenation protection catalyst, a hydrodemetallization catalyst, and a specific hydrodesulfurization catalyst, the waste hydrotreating catalyst after regeneration treatment can be effectively utilized for residue hydrotreating. The initial reaction activity is close to that of a fresh reference agent, and the reaction stability is relatively high, indicating that this grading system has a relatively long service life, which is beneficial to further reducing the process cost.

[0129] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A method for residue hydrotreating reaction, the method comprising: Under hydrotreating conditions, contacting a residue feedstock with a hydroprotection catalyst, a hydrodemetallization catalyst, and a hydrodesulfurization catalyst in sequence; Among them, the hydrodesulfurization catalyst is obtained by regenerating a waste hydrocatalyst. When the hydrodesulfurization catalyst is measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbances at 630 nm and 500 nm are F 630 and F 500 , respectively, and the ratio Q of the two is Q = F 630 / F 500 and is 1.3 - 3.

2. The method according to claim 1, wherein, When the hydrodesulfurization catalyst is measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbances at 630 nm and 500 nm are F 630 and F 500 , and the ratio Q of the two is Q = F 630 / F 500 is 1.4 - 2.8, preferably 1.7 - 2.2; Preferably, based on the total weight of the fresh catalyst corresponding to the hydrodesulfurization catalyst, calculated as oxides, the active metal content in the hydrodesulfurization catalyst is not less than 18 wt%; based on the total weight of the hydrodesulfurization catalyst, calculated as oxides, the deposited impurity content in the hydrodesulfurization catalyst is not higher than 2 wt%.

3. The method according to claim 1 or 2, wherein The specific surface area of the hydrodesulfurization catalyst is 50-280 m 2 / g, the pore volume is 0.3-1.5 mL / g, and the most probable pore diameter is 6-16 nm; Preferably, the specific surface area of the hydrodesulfurization catalyst is 80 - 250 m 2 / g, the pore volume is 0.21 - 1.2 mL / g, and the most probable pore diameter is 8 - 15 nm.

4. The method according to any one of claims 1 to 3, wherein, The method for regenerating the spent hydrocatalyst comprises: 1) Under an oxygen-containing atmosphere, subjecting the spent hydrocatalyst to carbon burning treatment; 2) Mixing a first leaching agent with the solid product obtained in step 1) and performing a first leaching; the first leaching agent comprises a polyol; 3) Mixing the solid product obtained from the first leaching with a second leaching agent and performing a second leaching to obtain a leached product; the second leaching agent is water and / or ethanol; 4) Under an oxygen-containing atmosphere, subjecting the leached product to high-temperature activation, the temperature of the high-temperature activation is 600 - 800 °C, and the time is 1 - 10 hours.

5. The method according to claim 4, wherein, The step 1) does not include pore expansion treatment; And / or, in step 1), the conditions of the carbon burning treatment include: the temperature is 200 - 550 °C, preferably 220 - 450 °C; the time is 1 - 10 hours, preferably 2 - 7 hours; Preferably, the carbon burning treatment includes: first treating at a temperature of 220 - 260 °C for 1 - 3 hours, then treating at 290 - 340 °C for 1 - 2 hours, and finally treating at 350 - 450 °C for 1 - 4 hours; And / or, the oxygen-containing atmosphere is a mixture of oxygen and an inert gas; And / or, in the oxygen-containing atmosphere, the volume content of oxygen is 8 - 30%, preferably 10 - 25%.

6. The method according to claim 4 or 5, wherein The general formula of the polyol is C n H 2n+2-x (OH) x , where n = 2 - 5 and x = 2 - 3; Preferably, the polyol is 1,3 - propanediol; Preferably, the first leaching agent further contains water, and the concentration of the first leaching agent is 0.01 - 3 mol / L, preferably 0.01 - 1.5 mol / L.

7. The method according to any one of claims 4 to 6, wherein In step 2), the volume ratio of the amount of the first leaching agent to the volume of the solid product obtained in step 1) is 1 - 6:1; And / or, the time of the first leaching is 0.5 - 8 hours; Preferably, the first leaching is carried out under stirring conditions, and the stirring rate is 50 - 500 rpm, preferably 50 - 280 rpm; And / or, the volume ratio of the amount of the second leaching agent to the volume of the solid product obtained from the first leaching is 1 - 5:1; And / or, the time of the second leaching is 0.1 - 3 hours.

8. The method according to any one of claims 4-7, wherein, The temperature of the high-temperature activation is 610 - 780 °C, preferably 630 - 750 °C, more preferably 650 - 730 °C; the time is 2 - 8 hours; And / or, the heating rate of the high-temperature activation is 50 - 600 °C / hour, preferably 100 - 550 °C / hour.

9. The method according to any one of claims 1-8, wherein, The spent hydrocatalyst is selected from at least one of a spent gasoline hydrocatalyst, a spent diesel hydrocatalyst, a spent kerosene hydrocatalyst, and a spent wax oil hydrocatalyst; And / or, based on the total weight of the spent hydrogenation catalyst, the carbon content of the spent hydrogenation catalyst is less than 30 wt%, and the content of deposited impurities is less than 20 wt%. Preferably, the carbon content of the spent hydrogenation catalyst is less than 15 wt%, and the content of deposited impurities is less than 10 wt%. Preferably, the specific surface area of the spent hydrogenation catalyst is 30 - 300 m 2 / g, the pore volume is 0.05 - 0.3 mL / g, and the most probable pore diameter is greater than 1 nm; more preferably, the specific surface area of the spent hydrogenation catalyst is 50 - 200 m 2 / g, the pore volume is 0.05 - 0.2 mL / g, and the most probable pore diameter is 1.5 - 4 nm; Preferably, the spent hydrogenation catalyst comprises a carrier and an active metal component supported on the carrier, and the active metal component comprises molybdenum and / or tungsten and nickel and / or cobalt; More preferably, based on the total amount of the fresh catalyst corresponding to the spent hydrogenation catalyst, the content of molybdenum and / or tungsten is 10-40% by weight, and the content of nickel and / or cobalt is 1.5-8% by weight in terms of oxide.

10. The method according to any one of claims 1-9, wherein, Based on the total volume of the hydrogenation protection catalyst, the hydrogenation demetallization catalyst and the hydrodesulfurization catalyst, the content of the hydrogenation protection catalyst is 5-60% by volume, preferably 10-50% by volume, more preferably 15-30% by volume; the content of the hydrogenation demetallization catalyst is 5-50% by volume, preferably 10-40% by volume, more preferably 20-40% by volume; the content of the hydrodesulfurization catalyst is 10-60% by volume, preferably 20-55% by volume, more preferably 40-55% by volume.

11. According to the method according to any one of claims 1-10, wherein, Each of the hydrogenation protection catalyst and the hydrogenation demetallization catalyst independently contains a carrier and an active metal component supported on the carrier, and the active metal component is selected from at least one of the Group VIB and / or Group VIII metal elements; Preferably, the Group VIB metal element is molybdenum and / or tungsten, and the Group VIII metal element is nickel and / or cobalt. Preferably, in the hydrogenation protection catalyst, based on the total amount of the hydrogenation protection catalyst, the content of the active metal component is 1-15% by weight in terms of oxide. Preferably, in the hydrogenation demetallization catalyst, based on the total amount of the hydrogenation demetallization catalyst, the content of the active metal component is 6-20% by weight in terms of oxide.

12. The method according to any one of claims 1-11, wherein, The hydrotreating conditions include: a temperature of 320 - 450 °C, a hydrogen partial pressure of 8 - 20 MPa, a liquid hourly space velocity of 0.1 - 1 h -1 , and a hydrogen-to-oil volume ratio of 500 - 1500; Preferably, the hydrotreating conditions include: a temperature of 350 - 420 °C, a hydrogen partial pressure of 12 - 18 MPa, a liquid hourly space velocity of 0.2 - 0.6 h -1 , and a hydrogen-to-oil volume ratio of 800 - 1200.

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