Residue hydroprocessing reaction process

Abstract

The present application relates to the field of residual oil hydroprocessing, and discloses a residual oil hydroprocessing method, which comprises: under hydroprocessing conditions, sequentially contacting residual oil raw material with a hydroprocessing guard catalyst, a hydrodemetallization catalyst and a hydrodesulfurization catalyst; wherein the hydrodesulfurization catalyst is obtained by regenerating a spent hydroprocessing catalyst, and when the hydrodesulfurization catalyst is measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbance at 630 nm and 500 nm is F 630 and F 500 , and the ratio Q = F 630 / F 500 of the two is 1.3-3. The method can improve the utilization rate of the spent distillate hydroprocessing catalyst, reduce the cost of the existing residual oil hydroprocessing catalyst, and greatly improve the stability of the residual oil hydroprocessing reaction.

Description

Technical Field

[0001] This invention relates to the field of residual oil hydrotreating, and more specifically to a method for residual oil hydrotreating reaction. Background Technology

[0002] Currently, domestic refineries unload a large amount of deactivated distillate oil hydrogenation catalysts from shut-down 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 perform coking treatment on the catalyst under certain conditions, and then use a solution containing specific compound components to redisperse the active phase of the coked catalyst.

[0003] CN105944735A discloses a method for activating a type II hydrogenation catalyst that has been deactivated by carbon deposition. The method involves first regenerating the deactivated catalyst by coking to obtain a hydrogenation catalyst with a carbon content of 0.3%-1.0%. Then, the catalyst with the 0.3%-1.0% carbon content is saturated with an activation solution for 40-60 minutes, followed by curing at 60-70℃ for 8-24 hours. Finally, it is dried at 60-150℃ for 6-8 hours to obtain the activated hydrogenation catalyst. This activation method has advantages such as good activation effect and simple operation.

[0004] CN101992131A discloses a method for regenerating a hydrogenation catalyst, the regenerated hydrogenation catalyst, and its application. First, under the reaction conditions of charring during the regeneration of 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; finally, the catalyst treated in the above manner is dried to obtain a regenerated catalyst. The activity of the regenerated catalyst is significantly improved and enhanced.

[0005] After deactivated distillate oil hydrotreating catalysts are reactivated using the conventional regeneration methods described above, they are generally loaded back into the reactor for industrial application. However, after one or two regenerations, the catalyst is unlikely to meet the requirements of distillate oil for ultra-deep hydrogenation activity, at which point the discharged catalyst must be treated as hazardous waste. The high cost and significant environmental impact of spent catalyst disposal have become a major problem plaguing the industry. The path to carbon reduction and green development for domestic refining and chemical enterprises will be even more arduous, as the generation of hazardous catalyst waste is detrimental to their green and sustainable development.

[0006] If these non-regenerable waste distillate hydrotreating catalysts can be treated using special methods and applied to the hydrotreating process of heavy oil and / or residue oil, replacing part of the heavy oil and / or residue oil hydrodesulfurization catalysts, and realizing the cascade utilization of waste distillate hydrotreating catalysts, the procurement cost of existing heavy oil and / or residue oil hydrotreating catalysts can be reduced, while solving the problem of recycling and treating waste distillate hydrotreating catalysts, thus creating significant social and economic benefits. Summary of the Invention

[0007] The purpose of this invention is to overcome the problem of poor stability in the hydrogenation reaction of residual oil in the prior art, and to provide a hydrogenation reaction method for residual oil that can effectively utilize the regenerated waste hydrogenation catalyst for hydrogenation of residual oil, and has high reaction stability.

[0008] During their research, the inventors of this invention discovered that when regenerated catalysts obtained using existing methods for recovering and treating waste distillate oil hydrogenation catalysts are reused in distillate oil hydrogenation processes, they often fail to meet the requirements for ultra-deep hydrogenation activity after 1-2 regeneration cycles. For example, the catalyst's activity and selectivity may not fully meet the requirements, at which point the discharged catalyst must be treated as hazardous waste. The high cost and significant environmental impact of waste catalyst treatment have become a major problem plaguing the industry. The inventors of this invention have adopted a different approach, treating waste distillate oil hydrogenation catalysts that lack conventional regeneration conditions using a special method, and then using them in the hydrogenation processes of heavy oil and / or residue oil where the catalyst requirements are slightly lower. Compared to distillate oils, heavy oil and / or residue feedstocks contain compounds with higher molecular weights and larger molecular sizes, and the reaction conditions are more demanding. Therefore, it is necessary to increase the accessibility of catalyst active centers to large molecular compounds in heavy oil and / or residue, improve the diffusion performance of catalyst channels, and enhance the activity stability of catalysts under harsh reaction conditions. However, the regenerators obtained by conventional waste distillate oil hydrogenation catalyst regeneration methods cannot meet the requirements of heavy oil and / or residue hydrogenation reactions.

[0009] The inventors of this invention combine a hydrodesulfurization catalyst obtained by treating waste hydrotreating catalyst with a hydroprotection catalyst and a hydrodemetallization catalyst for use in the hydrotreating process of residual oil. This not only effectively utilizes the waste hydrotreating catalyst, but also achieves high desulfurization rate and good stability.

[0010] To achieve the above objectives, the present invention provides a method for hydrogenation of residual oil, the method comprising:

[0011] Under hydrotreating conditions, the residue feedstock is sequentially contacted with a hydroprotection catalyst, a hydrodemetallization catalyst, and a hydrodesulfurization catalyst.

[0012] The hydrodesulfurization catalyst is obtained by regenerating spent hydrodesulfurization catalyst. When measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbance of this hydrodesulfurization catalyst at 630 nm and 500 nm are respectively F0. 630 and F 500 And the ratio of the two is Q = F 630 / F 500 It is 1.3-3.

[0013] 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 this invention have discovered that the formation of an appropriate amount of spinel structure will not only not have a significant impact on the total activity of the catalyst, but also, in the hydrotreating reaction of residue oil, as the hydrodesulfurization catalyst participates in the reaction process, the formed spinel structure will gradually release its reactivity, greatly improving the service life of the hydrodesulfurization catalyst and making the hydrotreating reaction of residue oil more stable.

[0014] Compared with the prior art, the residue hydrotreating method provided by the present invention can improve the utilization rate of waste distillate hydrotreating catalysts, especially providing a way to reuse distillate hydrotreating catalysts with high carbon deposits and high sediment impurities. On the other hand, it can effectively reduce the cost of existing residue hydrotreating catalysts and greatly improve the stability of residue hydrotreating reactions. Therefore, the method provided by the present invention has higher economic benefits. Detailed Implementation

[0015] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0016] This invention provides a method for hydrogenating residual oil, the method comprising:

[0017] Under hydrotreating conditions, the residue feedstock is sequentially contacted with a hydroprotection catalyst, a hydrodemetallization catalyst, and a hydrodesulfurization catalyst.

[0018] The hydrodesulfurization catalyst is obtained by regenerating spent hydrodesulfurization catalyst. When measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbance of this hydrodesulfurization catalyst at 630 nm and 500 nm are respectively F0. 630 and F 500 And the ratio of the two is Q = F 630 / F 500 It 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 this invention have discovered that the formation of an appropriate amount of spinel structure will not only not have a significant impact on the total activity of the catalyst, but also, in the hydrotreating reaction of residue oil, as the hydrodesulfurization catalyst participates in the reaction process, the formed spinel structure will gradually release its reactivity, greatly improving the service life of the hydrodesulfurization catalyst and making the hydrotreating reaction of residue oil more stable.

[0020] In this invention, the hydrodesulfurization catalyst is obtained by treating spent hydrodesulfurization catalyst, further improving the overall economic efficiency of the process. In the conventional regeneration process of spent distillate oil hydrodesulfurization catalysts, the active metal is redispersed using a solvent, and drying is typically carried out only at low temperatures, without high-temperature calcination. For example, in CN102463127A, the heat treatment temperature does not exceed 200°C. This is because the catalyst treated by conventional regeneration methods is still reused in the distillate oil hydrodesulfurization reaction, where the reaction conditions are relatively milder, and low-temperature drying is beneficial for improving catalyst activity. The purpose of this invention is to apply the regenerated spent distillate oil hydrodesulfurization catalyst to the hydrodesulfurization reaction of heavy oil / residue oil, where the reaction temperature and pressure are higher, and the reactant properties are worse, thus requiring the catalyst to possess higher activity and stability. The inventors discovered in their research that a heat treatment method combining low-temperature and high-temperature heat treatment can improve the activity and stability of the prepared hydrodesulfurization catalyst under harsh reaction conditions. When used in conjunction with a hydroprotection catalyst and a hydrodemetallization catalyst in the hydrodesulfurization process of residue oil, it not only effectively utilizes the spent hydrodesulfurization catalyst but also achieves a high desulfurization rate.

[0021] In this invention, "residue oil" refers to the components remaining at the bottom of the distillation column during crude oil distillation, including atmospheric residue oil and vacuum residue oil. The method provided by this invention is applicable to the hydrotreating of various residue oils. Preferably, the density of the residue oil is 920-1050 kg / m³. 3 The residual carbon content is less than 15% by weight; the sulfur content is less than 5% by weight.

[0022] In this invention, the formation of spinel structures in the catalyst is determined by ultraviolet-visible spectroscopy (DRUVS). The instrument used is an Agilent Cary 300 UV-Vis analyzer with a wavelength range of 190 nm–1100 nm, wavelength accuracy of ±0.1 nm, wavelength reproducibility of ±0.1 nm, baseline stability of 0.0003 / h, stray light of less than 0.02%, and 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 absorbance at 630 nm and 500 nm are F0 and F1, respectively. 630 and F 500 And the ratio of the two is Q = F630 / F 500 The value is 1.4-2.8. Under this preferred embodiment, it is more beneficial to improve the catalytic activity of the hydrodesulfurization catalyst and further improve the stability of the residue hydrotreating reaction. When the Q value is less than 1, the improvement in activity stability is not significant; 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 of the two is Q = F. 630 / F 500 For specific ratios or ranges between two points, 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, etc., more preferably, Q = F. 630 / F 500 The value is 1.7-2.2. Under the above-mentioned preferred conditions, it is more beneficial to improve the hydrodesulfurization performance and stability in the hydrotreating reaction of residue oil.

[0024] According to the present invention, preferably, based on the total weight of the fresh catalyst corresponding to the hydrogenation catalyst, the active metal content in the hydrogenation catalyst, calculated as oxides, is not less than 18 wt%; based on the total weight of the hydrogenation catalyst, the content of deposited impurities in the hydrogenation catalyst, calculated as oxides, is not more than 2 wt%. The phrase "based on the total weight of the fresh catalyst corresponding to the hydrogenation catalyst" in the present invention refers to the active metal component content being calculated based on the fresh catalyst, i.e., deposited impurities and carbon in the catalyst are not included in the total amount. Under the above preferred conditions, it is more advantageous to improve 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 m². 2 / g, with a pore volume of 0.3-1.5mL / g and a most probable pore size of 6-16nm; preferably, the specific surface area of ​​the hydrodesulfurization catalyst is 80-250m². 2 The catalyst has a pore volume of 0.21-1.2 mL / g and a most probable pore size of 8-15 nm. Under the above-mentioned preferred conditions, it is beneficial to further improve the activity and stability of the catalyst for the hydrogenation reaction of residue oil.

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

[0027] 1) The spent hydrogenation catalyst is carbonized under an oxygen-containing atmosphere;

[0028] 2) Mix the first washing agent with the solid product obtained in step 1) and perform a first washing; the first washing agent includes a polyol;

[0029] 3) The solid product obtained from the first immersion washing is mixed with the second immersion washing agent, and a second immersion washing is performed to obtain the immersion product; the second immersion washing agent is water and / or ethanol;

[0030] 4) The immersion product is activated at high temperature in an oxygen-containing atmosphere. The activation temperature is 600-800℃ and the activation time is 1-10 hours.

[0031] The inventors of this invention discovered that by first carbonizing the spent hydrotreating catalyst, followed by a first and second immersion wash, and then activating the second immersion product at high temperature, carbon deposits and impurities in the spent hydrotreating catalyst can be effectively removed. Simultaneously, this ensures a high content of active metal components in the resulting hydrodesulfurization catalyst, forming a hydrodesulfurization catalyst with a specific spinel structure. The hydrodesulfurization catalyst obtained in this way exhibits high desulfurization rates and stability when applied to residual oil hydrotreating. If the activation temperature is too low or the activation time is too short, the spinel content in the treated catalyst will be too low, resulting in insufficient improvement in the hydrogenation activity and stability of the active components in the treated hydrodesulfurization catalyst. Conversely, if the activation temperature is too high or the activation time is too long, the spinel content in the treated hydrodesulfurization catalyst will be too high, affecting the initial hydrogenation activity of the catalyst.

[0032] In this invention, "waste hydrotreating catalyst" refers to a catalyst whose performance (including at least one of activity, selectivity, and stability) deteriorates after use. This includes both spent hydrotreating catalysts that, even after long-term recycling and regeneration using existing methods, cannot achieve the required hydrotreating activity, and used hydrotreating catalysts that can still be used after regeneration using existing methods. The waste hydrotreating catalyst can be any type of hydrotreating catalyst conventionally used for various oil products in this field, and this invention does not have any particular limitation. According to a specific embodiment of this invention, the waste hydrotreating catalyst includes, but is not limited to, at least one of waste gasoline hydrotreating catalysts, waste diesel hydrotreating catalysts, waste kerosene hydrotreating catalysts, and waste wax oil hydrotreating catalysts. This invention uses a waste diesel hydrotreating catalyst as an example for illustrative purposes.

[0033] According to the present invention, preferably, the waste hydrogenation catalyst comprises a support and an active metal component supported on the support, the active metal component comprising molybdenum and / or tungsten and nickel and / or cobalt.

[0034] This invention offers a wide range of choices for the content of molybdenum and / or tungsten, as well as nickel and / or cobalt. Those skilled in the art can make appropriate adjustments based on actual conditions. More preferably, based on the total amount of fresh catalyst corresponding to the waste hydrogenation catalyst, the content of molybdenum and / or tungsten, calculated as oxides, is 10-40% by weight, and the content of nickel and / or cobalt is 1.5-8% by weight. The conventional selection ranges for the active metal components molybdenum and / or tungsten, as well as nickel and / or cobalt, in waste gasoline hydrogenation catalysts, waste diesel hydrogenation catalysts, waste kerosene hydrogenation catalysts, and waste wax oil hydrogenation catalysts may differ. Those skilled in the art can select them using conventional methods, and this invention will not elaborate further on these differences here.

[0035] The composition of the spent hydrogenation catalyst was determined by X-ray fluorescence spectrometry (XRF), and the specific method is described in Petrochemical Analytical Methods RIPP 133-90.

[0036] It should be noted that, in addition to the support and the active metal components loaded on the support, spent hydrotreating catalysts also include impurities and carbon deposited after long-term recycling. The phrase "based on the total amount of fresh catalyst corresponding to the spent hydrotreating catalyst" in this invention refers to the content of molybdenum and / or tungsten, and the content of nickel and / or cobalt, calculated based on the fresh catalyst, excluding the aforementioned deposited impurities and carbon. Because spent hydrotreating catalysts have higher levels of coke and / or deposited impurities (such as iron, calcium, sodium, and silicon) compared to fresh catalysts, with these deposited impurities originating from the feedstock oil, this invention uses carbon content and / or deposited impurity content to indicate whether a catalyst is a spent hydrotreating catalyst. Generally, the carbon content and deposited impurity content of fresh catalysts are essentially zero, while the carbon content of spent hydrotreating catalysts can be as high as 30% by weight, and the deposited impurity content 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 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%. More preferably, the carbon content of the spent hydrogenation catalyst is 5-13 wt% and the content of deposited impurities is 1-8 wt%.

[0038] In this invention, unless otherwise specified, the carbon content of the spent hydrogenation catalyst is determined by extracting the catalyst with toluene and then measuring it using a carbon-sulfur analyzer, and the content of deposited impurities is determined by calcining the catalyst in air at 600°C for 3 hours and then measuring it using X-ray fluorescence spectroscopy.

[0039] The preferred method for regenerating spent hydrogenation catalysts described above exhibits excellent treatment effects for spent hydrogenation catalysts with high carbon deposition and high levels of deposited impurities. Existing regeneration methods commonly involve first carbonizing the catalyst under certain conditions, and then redispersing the active phase of the carbonized catalyst using a solution containing specific compounds. For example, CN111821998A discloses impregnating the carbonized catalyst with C1-C20 organic alcohols, organic acids, organic amines, and organic ammonium salts. CN111822060A discloses a two-stage carbonization and pore-expansion process followed by impregnation with a phosphorus-containing compound solution. Both methods aim to redisperse the active phase and improve the dispersion of active metals. However, the inventors of this invention have discovered that while this saturated or unsaturated impregnation method can improve the dispersion of the active phase, it cannot remove inactive deposited impurities from the spent hydrogenation catalyst. Compared to existing treatment methods, the regeneration method provided by this invention can effectively remove carbon deposits and sedimentary impurities from waste hydrotreating catalysts, while ensuring that the obtained hydrodesulfurization catalyst maintains a high content of active metal components. The hydrodesulfurization catalyst obtained in this way has a high desulfurization rate when applied to the hydrotreating of residual oil.

[0040] The method for regenerating spent hydrogenation catalysts according to the present invention is particularly suitable for spent hydrogenation catalysts with small pore volume and pore size, because the high-temperature activation step of this method not only improves the activity and stability of the catalyst, but also expands the pores. Preferably, the specific surface area of ​​the spent hydrogenation catalyst is 30-300 m². 2 / g, with a pore volume of 0.05-0.3 mL / g and a most probable pore size greater than 1 nm; more preferably, the specific surface area of ​​the spent hydrogenation catalyst is 50-200 m² / g. 2 / g, pore volume is 0.05-0.2mL / g, and most probable pore size is 1.5-4nm.

[0041] In this invention, unless otherwise specified, the specific surface area, pore volume, and most probable pore size of the waste hydrogenation catalyst are determined by low-temperature nitrogen adsorption method.

[0042] The inventors of this invention have discovered that, in a preferred embodiment, a hydrodesulfurization catalyst obtained by treating a waste hydrotreating catalyst that meets the above-mentioned physicochemical characteristics has higher desulfurization performance and stability when used in the hydrotreating reaction of residual oil.

[0043] The inventors of this invention have also discovered that using a spent hydrotreating catalyst 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 spent hydrotreating catalyst can be sieved before use to obtain a spent hydrotreating catalyst that meets the above-mentioned preferred particle size requirements. Therefore, in a preferred embodiment, the method provided by this invention further includes sieving the spent hydrotreating catalyst before step 1).

[0044] In existing technologies, for spent hydrogenation catalysts with small pore volumes and sizes, in addition to conventional carbonization treatment, high-temperature pore-expansion treatment is required to further increase the pore volume and size of the catalyst, thereby improving the performance of the regenerated catalyst. However, the inventors of this invention discovered that the high-temperature activation step in this method not only improves the activity and stability of the catalyst but also expands the pores. Therefore, in this invention, step 1) does not include pore-expansion treatment, which is more conducive to weakening the interaction forces between the metal and the support on the catalyst, thereby improving the subsequent leaching effect to a certain extent. In this case, carbonization, leaching, and high-temperature activation of the spent hydrogenation catalyst can improve the hydrogenation activity and stability of the regenerated hydrodesulfurization catalyst. This regeneration method does not require additional pore-expansion treatment, further simplifying the process while ensuring the performance of the treated hydrodesulfurization catalyst.

[0045] In this invention, there is no particular limitation on the specific method of carbonization treatment in step 1), as long as it can remove the carbon deposits from the waste hydrogenation catalyst. Conventional methods known to those skilled in the art can be used. To further improve the catalytic activity of the regenerated hydrogenation catalyst, preferably, in step 1), the carbonization treatment conditions include: a temperature of 200-550℃, preferably 220-450℃; and a time of 1-10 hours, preferably 2-7 hours.

[0046] According to a preferred embodiment of the present invention, the charcoal burning process 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. This preferred embodiment facilitates more thorough burning off of carbon deposits on the catalyst and avoids temperature runaway during the charcoal burning process.

[0047] According to the present invention, in step 1), the oxygen-containing atmosphere provides oxygen for the carbonization treatment of the waste hydrogenation catalyst. The present invention allows for a wide range of oxygen content selection in the oxygen-containing atmosphere; for example, the volume content of oxygen in the oxygen-containing atmosphere can be 8-30%, preferably 10-25%. The oxygen-containing atmosphere of the present invention can be provided using different methods depending on the required oxygen volume content. For example, the oxygen-containing atmosphere can be provided using air. When a higher oxygen content is required, air and oxygen can be used together to provide the oxygen-containing atmosphere. When a lower oxygen content is required, air and an inert atmosphere (e.g., nitrogen) can be used together to provide the oxygen-containing atmosphere. This embodiment of the present invention uses air as an example for illustration, as using air to provide the oxygen-containing atmosphere is more cost-effective, but the present invention is not limited thereto.

[0048] In this invention, the first and second immersion washing are performed sequentially after the carbonization treatment, which can effectively remove impurities deposited on the catalyst during the reaction process and some aggregated low-activity metal components, thereby achieving the purpose of unblocking 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 impregnating agent comprises a polyol, and the second impregnating agent is water and / or ethanol. The synergistic impregnation using the combination of the above-mentioned impregnating agents is more conducive to improving the desulfurization performance of the obtained hydrodesulfurization catalyst.

[0050] To further improve the immersion effect, preferably, the polyol has the general formula C0. n H 2n+2-x (OH) x Where n = 2-5 and x = 2-3. For example, the polyol is at least one of ethylene glycol, glycerol, and 1,3-propanediol.

[0051] According to a preferred embodiment of the present invention, the polyol is 1,3-propanediol. The inventors of the present invention discovered in their research that the interaction force between the metal and the support is relatively weak in spent hydrogenation catalysts that have not undergone high-temperature pore-expansion treatment. For spent hydrogenation catalysts that have not undergone pore-expansion treatment, using a first washing agent containing 1,3-propanediol for the first washing can further improve the catalytic activity of the treated hydrodesulfurization catalyst.

[0052] Preferably, the first eluent also contains water, and the concentration of the first eluent is 0.01-3 mol / L, preferably 0.01-1.5 mol / L. Within the above-mentioned preferred concentration range, it helps to selectively remove impurities deposited on the catalyst during the reaction process and aggregated low-activity metal components. If the concentration of the first eluent is too high, it may cause the dispersed high-activity metal components on the catalyst to be over-removed.

[0053] According to the present invention, in actual operation, the leaching conditions can be adjusted according to the physicochemical properties of the catalyst after carbonization. The principle is to remove as many impurities and aggregated low-activity metal components as possible from the catalyst during the reaction process, while retaining as many dispersed high-activity metal components as possible.

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

[0055] The first and second immersion washes can be performed in a conventional manner, such as immersing the solid product in an immersion agent and then performing solid-liquid separation. The solid-liquid separation can be performed using conventional methods in the art, and the present invention does not particularly limit this process.

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

[0057] According to the present invention, preferably, the first immersion washing is carried out under stirring conditions, preferably, the stirring rate is 50-500 rpm, and more preferably 50-280 rpm. Adopting the above preferred embodiments is beneficial to improving the effect of the first immersion washing and improving the catalytic activity of the treated hydrogenation catalyst.

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

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

[0060] According to some specific embodiments of the present invention, the regeneration method further includes: drying the second washing product and then activating it at high temperature. The present invention does not particularly limit the specific conditions and operation methods for drying; conventional methods can be used, as long as the residual second washing agent in the second washing product can be removed. For example, the drying temperature can be 70-200℃, preferably 80-150℃, and the time can be 2-10 hours, preferably 3-6 hours.

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

[0062] In this invention, the high-temperature activation can be achieved by raising the ambient temperature to the activation temperature, or by directly raising the drying temperature of the second washing product to the activation temperature; there is no particular limitation on this. This invention allows for a wide range of selection for the heating rate during high-temperature activation. Preferably, the heating rate is 50-600℃ / hour, and more preferably 100-550℃ / hour.

[0063] According to the present invention, in order to further improve the desulfurization rate of the residue hydrotreating reaction, preferably, based on the total volume of the hydroprotective catalyst, the hydrodemetallization catalyst, and the hydrodesulfurization catalyst, the content of the hydroprotective catalyst is 5-60% by volume, preferably 10-50% by volume, more preferably 15-30% by volume, the content of the hydrodemetallization 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 described in this invention can each be any of the conventionally used hydrogenation protection catalysts and hydrogenation demetallization catalysts in the art, and this invention does not have any particular limitation on them.

[0065] The hydrogenation protection catalyst of the present invention may not contain an active metal component. Preferably, both the hydrogenation protection catalyst and the hydrogenation demetallization catalyst independently contain a support and an active metal component supported on the support. The active metal component is selected from at least one 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 component is any one or more combinations of nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum, and cobalt-molybdenum.

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

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

[0068] In this invention, the hydrogenation protection catalyst can be an industrial agent or can be prepared by existing methods. For example, the hydrogenation protection catalyst can be at least one of the RG series catalysts developed by the Research Institute of Petroleum Processing, China Petroleum & Chemical Corporation.

[0069] According to the present invention, preferably, the active metal component content in the hydrodemetallization catalyst is 6-20% by weight, based on the total amount of the hydrodemetallization catalyst and calculated as oxides; 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 this invention, the hydrodemetallization catalyst can be an industrial agent or can be prepared by existing methods. For example, the hydrodemetallization catalyst can be at least one of the RDM series catalysts and RUF series catalysts developed by the Research Institute of Petroleum Processing, China Petroleum & Chemical Corporation.

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

[0072] According to the present invention, preferably, prior to the hydrotreating, the method further includes a step of sulfiding the hydroprotective catalyst, the hydrodemetallization catalyst, and the hydrodesulfurization catalyst. The sulfiding treatment can be carried out using conventional methods and conditions in the art, and the present invention does not particularly limit this. According to some preferred embodiments of the present invention, the sulfiding treatment can be carried out by in-vessel sulfiding, comprising: contacting a sulfiding agent with the hydroprotective catalyst, the hydrodemetallization catalyst, and the hydrodesulfurization catalyst in the presence of hydrogen to perform sulfiding treatment. The sulfiding agent can be provided by an oil solution of a sulfiding agent, the solvent oil being, for example, kerosene, and 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 choice in the art, for example, dimethyl disulfide.

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

[0074] The method provided by this invention can be carried out in a conventional residue hydrotreating unit, and this invention does not particularly limit its application. For example, in a residue hydrotreating unit, a hydroprotection catalyst, a hydrodemetallization catalyst, and a hydrodesulfurization catalyst can be sequentially loaded along the flow direction. The residue hydrotreating unit is preferably a fixed-bed hydrotreating unit. Furthermore, the various catalysts of this invention can be loaded into the same fixed-bed hydrotreating unit, or they can be loaded into multiple different fixed-bed hydrotreating units connected in series, as long as the loading method of the catalysts conforms to the requirements of this invention; there is no particular limitation on the number of fixed-bed hydrotreating units.

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

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

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

[0078] The composition of the catalyst was determined by X-ray fluorescence spectrometry (XRF), and the specific method is described in RIPP133-90, Petrochemical Analytical Methods.

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

[0080] The following preparation examples illustrate how waste hydrogenation catalysts are processed to obtain hydrodesulfurization catalysts.

[0081] Preparation Example 1

[0082] 1) Take industrial deactivated diesel hydrotreating catalyst (carbon content 10.67 wt%, iron, sodium and other deposited impurities content 7.2 wt%, the catalyst is NiMo / Al2O3, based on the total amount of fresh catalyst corresponding to the waste hydrotreating catalyst, the content of Ni is 4.6 wt% and the content of Mo is 27.8 wt% in terms of oxides), called deactivator A, and sieve it to obtain 16-20 mesh deactivator A. Put it into a muffle furnace and perform carbonization treatment in air atmosphere by programmed temperature rise, including: constant temperature at 250℃ for 1 hour, constant temperature at 330℃ for 2 hours, and constant temperature at 410℃ for 3 hours to obtain catalyst B;

[0083] 2) At room temperature, with a stirring speed of 100 rpm, the catalyst B obtained in step 1) was first washed with a 1.2 mol / L 1,3-propanediol aqueous solution. The volume of the 1,3-propanediol aqueous solution used was 4 times the volume of the catalyst, and the soaking time was 2 hours. Then, solid-liquid separation was performed.

[0084] 3) The solid product obtained in step 2) was subjected to a second immersion in deionized water at room temperature. The volume of deionized water used was 3.5 times the volume of the solid, and the immersion time was 1.5 hours. Then, solid-liquid separation was performed, and the product was dried at 110°C for 4 hours. This product was denoted as catalyst C.

[0085] 4) Catalyst C was activated at high temperature in air atmosphere. The conditions for high temperature activation included: temperature of 650℃, time of 3 hours, and heating rate of 200℃ / h, to obtain catalyst D.

[0086] The formation of spinel structures by the metal components and aluminum in the catalyst was determined by ultraviolet-visible spectroscopy (DRUVS). The absorbance ratio at 630 nm and 500 nm, Q = F630 / F500, was 1.94, indicating that a certain amount of spinel structures were 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, with a stirring speed of 150 rpm, the catalyst B obtained in step 1) was first washed with a 0.8 mol / L 1,3-propanediol aqueous solution. The volume of the 1,3-propanediol aqueous solution used was 5 times the volume of the catalyst, and the soaking time was 3 hours. Then, solid-liquid separation was performed.

[0090] 3) The solid product obtained in step 2) was washed a second time with ethanol at room temperature, wherein the volume of ethanol used was 4 times the volume of the solid, the soaking time was 2 hours, and then solid-liquid separation was performed, and the product was dried at 100°C for 5 hours.

[0091] 4) The product obtained in step 3) is activated at high temperature in air. The conditions for high temperature activation are: temperature of 680℃, time of 4 hours, and heating rate of 230℃ / 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 washed with a 0.1 mol / L 1,3-propanediol aqueous solution, wherein the volume of the 1,3-propanediol aqueous solution used was 0.9 times the volume of the catalyst, the soaking time was 12 minutes, and then solid-liquid separation was performed.

[0095] 3) The solid product obtained in step 2) was washed a second time with deionized water at room temperature. The volume of deionized water used was twice the volume of the solid, and the soaking time was 5 minutes. Then, solid-liquid separation was performed, and the product was dried at 110°C for 4 hours.

[0096] 4) The product obtained in step 3) is activated at high temperature in air. The conditions for high temperature activation are: temperature of 650℃, time of 3 hours, and heating rate of 200℃ / 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 washed with a 4 mol / L 1,3-propanediol aqueous solution, wherein the volume of the 1,3-propanediol aqueous solution used was 7 times the volume of the catalyst, the soaking time was 9 hours, and then solid-liquid separation was performed.

[0100] 3) The solid product obtained in step 2) was washed a second time with deionized water at room temperature. The volume of deionized water used was 6 times the volume of the solid, and the soaking time was 4 hours. Then, solid-liquid separation was performed, and then the product was dried at 110°C for 4 hours.

[0101] 4) The product obtained in step 3) is activated at high temperature in air. The conditions for high temperature activation are: temperature of 650℃, time of 3 hours, and heating rate of 200℃ / h, to obtain catalyst G.

[0102] Preparation Example 5

[0103] Following the method in Preparation Example 1, except that the high-temperature activation temperature in step 4) is 630°C, the time is 3 hours, and the activation heating rate is 200°C / hour, thus obtaining catalyst H.

[0104] Preparation Example 6

[0105] Following the method in Preparation Example 1, except that the high-temperature activation temperature in step 4) is 790°C, the time is 3 hours, and the activation heating rate is 200°C / hour, thus obtaining catalyst I.

[0106] Comparative Preparation Example 1

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

[0108] 2) At room temperature, with a stirring speed of 100 rpm, the catalyst B obtained in step 1) was soaked in a 2 mol / L 1,3-propanediol aqueous solution, wherein the volume of the 1,3-propanediol aqueous solution used was 4 times the volume of the catalyst, the soaking time was 2 hours, and then solid-liquid separation was performed, and the catalyst was dried at 110℃ for 4 hours.

[0109] 3) The product obtained in step 2) is activated at high temperature in air. The conditions for high temperature activation are: temperature of 650℃, time of 3 hours, and heating rate of 200℃ / h, to obtain catalyst J.

[0110] Comparative preparation example 2 (conventional regeneration method)

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

[0112] 2) Prepare an aqueous solution of 1,3-propanediol and impregnate catalyst B using the equal volume saturated impregnation method. Place the solution in a sealed container at room temperature (25°C) for 3 hours. The mass ratio of catalyst B to 1,3-propanediol is 8.6. Then, dry the solution at 120°C in air 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 illustrate the hydrotreating method for residual oil provided by the present invention.

[0118] Example

[0119] Atmospheric residue from imported Middle Eastern crude oil (its properties are listed in Table 2, the same below) and hydrogen are introduced into a fixed-bed hydrotreating reactor, where they sequentially contact the catalyst packed within for hydrotreating. The total catalyst packing volume in the fixed-bed hydrotreating reactor is 500 mL. Along the flow direction, the fixed-bed hydrotreating reactor is packed with hydrotreating protection catalyst, hydrotreating demetallization catalyst, and hydrotreating desulfurization catalyst in the volume fractions listed in Table 3. Before hydrotreating, the catalyst needs to undergo in-reactor sulfidation treatment. The sulfidation conditions are: kerosene containing 2 wt% dimethyl disulfide as the sulfiding agent, sulfidation temperature 320℃, sulfidation time 5 h, hydrogen partial pressure 14.0 MPa, and liquid hourly space velocity 1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio was 400:1; the hydrotreating conditions included: a reaction temperature of 380℃, a hydrogen partial pressure of 14 MPa, and a liquid hourly space velocity of 0.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 600:1.

[0120] The hydrogenation protection catalyst is the RG-30B catalyst (NiMo / Al2O3, with Ni content of 1.0 wt% and Mo content of 5.0 wt% based on oxides) developed by the Research Institute of Petroleum Processing, China Petroleum & Chemical Corporation (Sinopec). The hydrogenation demetallization catalyst is the RDM-32 catalyst (NiMo / Al2O3, with Ni content of 1.5 wt% and Mo content of 8.0 wt% based on oxides) developed by the Research Institute of Petroleum Processing, China Petroleum & Chemical Corporation (Sinopec). The hydrogenation desulfurization catalysts are the hydrogenation desulfurization catalyst and reference agent prepared in the above preparation example, respectively. The reference agent is the residue hydrogenation desulfurization catalyst (NiMo / Al2O3, with Ni content of 3.0 wt% and Mo content of 15.4 wt% based on oxides) developed by the Research Institute of Petroleum Processing, China Petroleum & Chemical Corporation (Sinopec). The desulfurization performance of the different hydrogenation desulfurization catalysts is compared, and the results are listed in Table 3.

[0121] The specific calculation method for the desulfurization rate is as follows:

[0122]

[0123] Table 2

[0124] crude 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 Residual char, m% 13.3

[0125] Table 3

[0126]

[0127]

[0128] As can be seen from the results in Table 3, the residue oil hydrogenation reaction method provided by the present invention can effectively utilize the regenerated waste hydrogenation catalyst for residue oil hydrogenation by grading the hydrogenation protection catalyst, the hydrogenation demetallization catalyst and the specific hydrogenation desulfurization catalyst. The initial reaction activity is close to that of the fresh reference agent, and the reaction stability is high, indicating that the grading system has a long service life, which is conducive to further reducing process costs.

[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 inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for hydrogenating residual oil, the method comprising: Under hydrotreating conditions, the residue feedstock is sequentially contacted with a hydroprotection catalyst, a hydrodemetallization catalyst, and a hydrodesulfurization catalyst. The hydrodesulfurization catalyst is obtained by regenerating spent hydrodesulfurization catalyst. When measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbance of this hydrodesulfurization catalyst at 630 nm and 500 nm are respectively F0. 630 and F 500 And the ratio of the two is Q=F 630 / F 500 It is 1.3-3; The method for regenerating the spent hydrogenation catalyst includes: 1) The spent hydrogenation catalyst is carbonized under an oxygen-containing atmosphere; 2) Mix the first washing agent with the solid product obtained in step 1) and perform a first washing; the first washing includes immersing the solid product in the first washing agent and then performing solid-liquid separation; the first washing agent is composed of polyol and water; 3) The solid product obtained from the first immersion is mixed with the second immersion agent and subjected to a second immersion to obtain an immersion product; the second immersion includes immersing the solid product in the second immersion agent and then performing solid-liquid separation; the second immersion agent is water and / or ethanol; 4) The immersion product is activated at high temperature in an oxygen-containing atmosphere. The activation temperature is 600-800℃ and the activation time is 1-10 hours.

2. The method according to claim 1, wherein, When the absorbance of the hydrodesulfurization catalyst was measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbance at 630 nm and 500 nm were F0 and F1, respectively. 630 and F 500 And the ratio of the two is Q=F 630 / F 500 It ranges from 1.4 to 2.

8.

3. The method according to claim 2, wherein, When the absorbance of the hydrodesulfurization catalyst was measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbance at 630 nm and 500 nm were F0 and F1, respectively. 630 and F 500 And the ratio of the two is Q=F 630 / F 500 It is 1.7-2.

2.

4. The method according to any one of claims 1-3, wherein, Based on the total weight of the fresh catalyst corresponding to the hydrodesulfurization catalyst, the active metal content in the hydrodesulfurization catalyst, calculated as oxides, is not less than 18 wt%; based on the total weight of the hydrodesulfurization catalyst, the content of deposited impurities in the hydrodesulfurization catalyst, calculated as oxides, is not more than 2 wt%.

5. The method according to any one of claims 1-3, wherein, The specific surface area of ​​the hydrodesulfurization catalyst is 50-280 m². 2 / g, pore volume is 0.3-1.5mL / g, and most probable pore size is 6-16nm.

6. The method according to claim 5, wherein, The specific surface area of ​​the hydrodesulfurization catalyst is 80-250 m². 2 / g, pore volume is 0.21-1.2mL / g, and most probable pore size is 8-15nm.

7. The method according to claim 5, wherein, Step 1) does not include hole enlargement.

8. The method according to claim 5, wherein, In step 1), the conditions for the charcoal burning process include: a temperature of 200-550℃ and a time of 1-10 hours.

9. The method according to claim 8, wherein, In step 1), the conditions for the charcoal burning process include: a temperature of 220-450℃ and a time of 2-7 hours.

10. The method according to any one of claims 1-3, wherein, The charcoal burning process includes: first, treating at a temperature of 220-260℃ for 1-3 hours, then treating at 290-340℃ for 1-2 hours, and finally treating at 350-450℃ for 1-4 hours.

11. The method according to any one of claims 1-3, wherein, In step 1), 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%.

12. The method according to claim 11, wherein, In step 1), the oxygen content in the oxygen-containing atmosphere is 10-25% by volume.

13. The method according to any one of claims 1-3, wherein, The general formula for polyols is C1 n H 2n+2-x (OH) x , where n=2-5, x=2-3.

14. The method according to claim 13, wherein, The polyol is 1,3-propanediol; And / or, the concentration of the first immersion agent is 0.01-3 mol / L.

15. The method according to claim 14, wherein, The polyol is 1,3-propanediol; And / or, the concentration of the first immersion agent is 0.01-1.5 mol / L.

16. The method according to any one of claims 1-3, wherein, In step 2), the volume ratio of the first washing agent to the solid product obtained in step 1) is 1-6:1; And / or, the first immersion time is 0.5-8 hours.

17. The method according to any one of claims 1-3, wherein, The first immersion is carried out under stirring conditions, the stirring rate being 50-500 rpm.

18. The method according to claim 17, wherein, The first immersion is carried out under stirring conditions, wherein the stirring rate is 50-280 rpm.

19. The method according to any one of claims 1-3, wherein, The volume ratio of the second washing agent to the solid product obtained from the first washing is 1-5:1; And / or, the second immersion time is 0.1-3 hours.

20. The method according to any one of claims 1-3, wherein, The high-temperature activation is performed at a temperature of 610-780℃ for 2-8 hours.

21. The method according to claim 20, wherein, The high-temperature activation temperature is 630-750℃.

22. The method according to claim 21, wherein, The high-temperature activation temperature is 650-730℃.

23. The method according to any one of claims 1-3, wherein, The heating rate for high-temperature activation is 50-600℃ / hour.

24. The method according to claim 23, wherein, The heating rate for high-temperature activation is 100-550℃ / hour.

25. The method according to any one of claims 1-3, wherein, The waste hydrogenation catalyst is selected from at least one of waste gasoline hydrogenation catalyst, waste diesel hydrogenation catalyst, waste kerosene hydrogenation catalyst, and waste wax oil hydrogenation catalyst.

26. The method according to claim 25, wherein, 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%.

27. The method according to claim 26, wherein, Based on the total weight of the spent hydrogenation catalyst, the carbon content of the spent hydrogenation catalyst is less than 15 wt%, and the content of deposited impurities is less than 10 wt%.

28. The method according to any one of claims 1-3, wherein, The specific surface area of ​​the spent hydrogenation catalyst is 30-300 m². 2 / g, pore volume is 0.05-0.3mL / g, and most probable pore size is greater than 1nm.

29. The method according to claim 28, wherein, The specific surface area of ​​the spent hydrogenation catalyst is 50-200 m². 2 / g, pore volume is 0.05-0.2mL / g, and most probable pore size is 1.5-4nm.

30. The method according to any one of claims 1-3, wherein, The waste hydrogenation catalyst includes a support and an active metal component supported on the support, the active metal component including molybdenum and / or tungsten and nickel and / or cobalt.

31. The method according to claim 30, wherein, Based on the total amount of fresh catalyst corresponding to the waste 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, calculated as oxides.

32. The method according to any one of claims 1-3, wherein, Based on the total volume of the hydrogenation protection catalyst, the hydrogenation demetallization catalyst, and the hydrogenation desulfurization catalyst, the content of the hydrogenation protection catalyst is 5-60% by volume, the content of the hydrogenation demetallization catalyst is 5-50% by volume, and the content of the hydrogenation desulfurization catalyst is 10-60% by volume.

33. The method according to claim 32, wherein, Based on the total volume of the hydrogenation protection catalyst, the hydrogenation demetallization catalyst, and the hydrogenation desulfurization catalyst, the content of the hydrogenation protection catalyst is 10-50% by volume, the content of the hydrogenation demetallization catalyst is 10-40% by volume, and the content of the hydrogenation desulfurization catalyst is 20-55% by volume.

34. The method according to claim 33, wherein, Based on the total volume of the hydrogenation protection catalyst, the hydrogenation demetallization catalyst, and the hydrogenation desulfurization catalyst, the content of the hydrogenation protection catalyst is 15-30% by volume, the content of the hydrogenation demetallization catalyst is 20-40% by volume, and the content of the hydrogenation desulfurization catalyst is 40-55% by volume.

35. The method according to any one of claims 1-3, wherein, The hydrogenation protection catalyst and the hydrogenation demetallization catalyst each independently contain a support and an active metal component supported on the support, wherein the active metal component is selected from at least one metal element from Group VIB and / or Group VIII.

36. The method according to claim 35, wherein, The Group VIB metal element is molybdenum and / or tungsten, and the Group VIII metal element is nickel and / or cobalt.

37. The method of claim 35, wherein, In the hydrogenation protection catalyst, based on the total amount of the hydrogenation protection catalyst, the content of the active metal component, calculated as oxide, is 1-15% by weight.

38. The method according to claim 37, wherein, In the hydrogenation demetallization catalyst, based on the total amount of the hydrogenation demetallization catalyst, the content of the active metal component, calculated as oxides, is 6-20% by weight.

39. The method according to any one of claims 1-3, wherein, The hydrogenation conditions include: a temperature of 320-450℃, a hydrogen partial pressure of 8-20 MPa, and a liquid hourly space velocity of 0.1-1 h⁻¹. -1 The hydrogen-to-oil volume ratio is 500-1500.

40. The method according to claim 39, wherein, The hydrogenation conditions include: a temperature of 350-420℃, a hydrogen partial pressure of 12-18 MPa, and a liquid hourly space velocity of 0.2-0.6 h⁻¹. -1 The hydrogen-to-oil volume ratio is 800-1200.

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