Treatment method of spent hydrogenation catalyst, treated hydrogenation catalyst and application thereof

Abstract

The present invention relates to the field of waste hydrogenation catalyst treatment, and discloses a method for treating a waste hydrogenation catalyst, a treated hydrogenation catalyst, and an application thereof. The method comprises: 1) charring and pore enlarging the waste hydrogenation catalyst under an oxygen-containing atmosphere; 2) mixing a first leaching agent with a solid product obtained in step 1) for a first leaching, wherein the first leaching agent comprises a polyol; 3) mixing the solid product obtained in the first leaching with a second leaching agent for a second leaching, to obtain a leached product, wherein the second leaching agent is water and / or ethanol; and 4) subjecting the leached product to a low-temperature heat treatment and a high-temperature heat treatment under an oxygen-containing atmosphere, wherein the low-temperature heat treatment is performed at a temperature of 70-200° C. for 2-10 hours and the high-temperature heat treatment is performed at a temperature of 310-550° C. for 1-10 hours. The treated catalyst has a larger pore volume and higher activity stability, and has good desulfurization performance in heavy oil or residual oil hydroprocessing.

Description

Technical Field

[0001] The present invention relates to the field of hydrogenation catalyst treatment, and in particular to a method for treating a spent hydrogenation catalyst, the treated hydrogenation catalyst and applications thereof. 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] CN1921942A discloses a method for regenerating a deactivated hydroprocessing catalyst. The method comprises the following steps: first, the hydroprocessing catalyst deactivated due to carbon deposition is subjected to carbonization treatment under certain conditions to obtain an intermediate catalyst having a carbon content of 0.5-2.5 wt%. The carbonized catalyst is then contacted with a nitrogen-containing chelating agent solution and subjected to aging treatment. Finally, the regenerated catalyst is obtained by drying.

[0004] CN106669866A discloses a method for regenerating a deactivated hydrogenation catalyst. The method involves charring the deactivated hydrogenation catalyst, then impregnating the charred catalyst with a solution containing ammonium fluoroborate and 2-amino-1,3-propanediol. The impregnated hydrogenation catalyst is then regenerated after heat treatment. This method can increase the specific surface area of ​​the regenerated catalyst, promote the redispersion of active components, and achieve a high degree of sulfidation of the regenerated hydrogenation catalyst, thereby improving its reaction activity.

[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 distillate oil hydroprocessing catalysts that cannot be conventionally regenerated can be treated by special methods and applied to the heavy oil and / or residual oil hydroprocessing reaction process, replacing part of the heavy oil and / or residual oil hydrodesulfurization catalysts, thereby realizing the cascade utilization of waste distillate oil hydroprocessing catalysts, the procurement cost of existing heavy oil and / or residual oil hydroprocessing catalysts can be reduced, and at the same time, the problem of recycling and treating waste distillate oil hydroprocessing catalysts can be solved, which can create significant social and economic benefits. Summary of the Invention

[0007] The present invention aims to overcome the problem in the prior art that distillate oil hydrogenation catalysts deteriorate in performance after conventional regeneration one to two times, resulting in their inability to continue to be used. A method for treating a spent hydrogenation catalyst, the treated hydrogenation catalyst, and applications thereof are provided. The hydrogenation catalyst obtained by the method for treating the spent hydrogenation catalyst provided by the present invention has a larger pore volume and higher activity stability, and has good desulfurization performance when used in heavy oil and / or residual oil hydrogenation processes.

[0008] During the research process, the inventors of the present invention discovered that when the regenerated catalyst obtained by the existing method of recycling and treating waste distillate oil hydrogenation catalyst is reused in the distillate oil hydrogenation process, after 1-2 regeneration uses, it is difficult to meet the requirements of the distillate oil for the ultra-deep hydrogenation activity of the catalyst. For example, the activity and selectivity of the catalyst cannot fully meet the requirements. At this time, the unloaded catalyst can only be treated as hazardous waste. The high cost of waste catalyst treatment and the great pressure on environmental protection have become a difficult problem that plagues the industry. The inventors of the present invention changed their thinking and treated the waste distillate oil hydrogenation catalyst that does not meet the conventional regeneration conditions through a special method, and used it in the heavy oil and / or residual oil hydrogenation process with slightly lower catalyst requirements. Compared with distillate oil, the compounds in heavy oil and / or residual oil feedstocks have higher molecular weights and larger molecular sizes, and the reaction conditions are more stringent. Therefore, it is necessary to increase the accessibility of the catalyst active centers to the macromolecular compounds in the heavy oil and / or residual oil, improve the diffusion performance of the catalyst pores, and improve the activity stability of the catalyst under harsh reaction conditions. However, the regenerated agent obtained by the conventional regeneration method of waste distillate oil hydrogenation catalyst cannot meet the requirements of heavy oil and / or residual oil hydrogenation reaction.

[0009] In order to achieve the above object, the first aspect of the present invention provides a method for treating a spent hydrogenation catalyst, the method comprising:

[0010] 1) Carburizing and pore-enlarging the spent hydrogenation catalyst in an oxygen-containing atmosphere;

[0011] 2) mixing a first soaking agent with the solid product obtained in step 1) to perform a first soaking; the first soaking agent comprises a polyol;

[0012] 3) mixing the solid product obtained by 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;

[0013] 4) heat-treating the leached product under an oxygen-containing atmosphere to obtain a hydrogenation catalyst;

[0014] The heat treatment includes low-temperature heat treatment and high-temperature heat treatment. The conditions of the low-temperature heat treatment include: temperature of 70-200°C and time of 2-10 hours. The conditions of the high-temperature heat treatment include: temperature of 310-550°C and time of 1-10 hours.

[0015] The second aspect of the present invention provides a hydrogenation catalyst obtained by the method for treating the spent hydrogenation catalyst according to the first aspect.

[0016] The third aspect of the present invention provides use of the hydrogenation catalyst described in the second aspect in the hydroprocessing of heavy oil and / or residual oil.

[0017] In the conventional regeneration process of waste distillate oil hydrogenation catalysts, the active metals are redispersed with a solvent and then usually dried only at low temperature without high-temperature calcination. For example, the heat treatment temperature of the waste catalyst in CN102463127A does not exceed 200°C. This is because the catalyst treated by the conventional regeneration method is still reused in the distillate oil hydrogenation reaction, where the reaction conditions are relatively milder, and low-temperature drying treatment is conducive to improving catalyst activity. The purpose of the present invention is to regenerate the waste distillate oil hydrogenation catalyst and apply it to the heavy oil / residue oil hydrogenation reaction, where the reaction temperature and pressure are higher and the properties of the reaction raw materials are worse, so the catalyst needs to have higher activity and stability. In their research, the inventors found that the activity and stability of the distillate oil hydrogenation catalyst under harsh reaction conditions can be improved by combining low-temperature heat treatment with high-temperature heat treatment.

[0018] Compared with the prior art, the hydrogenation catalyst obtained by the treatment method of the spent hydrogenation catalyst provided by the present invention has a larger pore volume and higher activity and stability, can be applied to the hydrogenation reaction process of heavy oil and / or residual oil, and has a good desulfurization effect.

[0019] After being treated by the treatment method provided by the present invention, the waste distillate oil hydrogenation catalyst is applied to the heavy oil and / or residual oil hydrogenation reaction process to replace part of the heavy oil and / or residual oil hydrodesulfurization catalyst, thereby realizing the cascade utilization of the waste distillate oil hydrogenation catalyst, thereby reducing the procurement cost of the existing heavy oil and / or residual oil hydrogenation catalyst, and solving the problem of recycling the waste distillate oil hydrogenation catalyst, thereby creating significant social and economic benefits. DETAILED DESCRIPTION

[0020] The endpoints of the ranges and any values ​​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 endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0021] A first aspect of the present invention provides a method for treating a spent hydrogenation catalyst, the method comprising:

[0022] 1) Carburizing and pore-enlarging the spent hydrogenation catalyst in an oxygen-containing atmosphere;

[0023] 2) mixing a first soaking agent with the solid product obtained in step 1) to perform a first soaking; the first soaking agent comprises a polyol;

[0024] 3) mixing the solid product obtained by 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;

[0025] 4) heat-treating the leached product under an oxygen-containing atmosphere to obtain a hydrogenation catalyst;

[0026] The heat treatment includes low-temperature heat treatment and high-temperature heat treatment. The conditions of the low-temperature heat treatment include: temperature of 70-200°C and time of 2-10 hours. The conditions of the high-temperature heat treatment include: temperature of 310-550°C and time of 1-10 hours.

[0027] In the present invention, a waste hydrogenation 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 hydrogenation catalysts that cannot meet the hydrogenation activity requirements after long-term recycling even after regeneration by existing means, and used hydrogenation catalysts that can continue to be used after regeneration by existing means. The waste hydrogenation catalyst can be various hydrogenation catalysts conventionally used for various oil products in the field, and the present invention has no particular limitation on this. According to a specific embodiment of the present invention, the waste hydrogenation catalyst of the present invention includes but is not limited to at least one of a waste gasoline hydrogenation catalyst, a waste diesel hydrogenation catalyst, a waste kerosene hydrogenation catalyst and a waste wax oil hydrogenation catalyst. The embodiments of the present invention are illustratively described using a waste diesel hydrogenation catalyst as an example.

[0028] According to the present invention, 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.

[0029] The present invention provides a relatively broad range of molybdenum and / or tungsten, as well as nickel and / or cobalt content. These ranges can be adjusted by those skilled in the art based on practical circumstances. More preferably, the molybdenum and / or tungsten content, calculated as oxides, is 10-40% by weight, and the nickel and / or cobalt content is 1.5-8% by weight, based on the total amount of fresh catalyst corresponding to the spent hydrogenation catalyst. Conventional ranges for 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. These ranges can be selected by those skilled in the art using conventional methods, and the present invention will not further elaborate on these ranges.

[0030] It should be noted that, in addition to the carrier and the active metal components supported on the carrier, the spent hydrogenation catalyst also includes impurities and carbon deposited after long-term recycling. The "total amount of fresh catalyst corresponding to the spent hydrogenation catalyst is used as a benchmark" in the present invention means that the content of molybdenum and / or tungsten and the content of nickel and / or cobalt are based on the fresh catalyst, that is, the above-mentioned deposited impurities and carbon are not included. Since the spent hydroprocessing catalyst has the characteristics of high carbon deposits and / or deposited impurities (such as iron, calcium, sodium, silicon) compared to the fresh agent, the deposited impurities come from the raw oil. Therefore, the present invention uses the carbon content and / or deposited impurity content to indicate whether the catalyst is a spent hydrogenation catalyst. Generally, the carbon content and deposited impurity content of the fresh agent are basically 0, while the carbon content of the spent hydrogenation catalyst can be as high as 30% by weight, and the deposited impurity content can be as high as 20% by weight.

[0031] 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%, and the deposited impurity content is less than 20%. Preferably, the carbon content of the spent hydrogenation catalyst is less than 15%, and the deposited impurity content is less than 10%. Further preferably, the carbon content of the spent hydrogenation catalyst is 5-13%, and the deposited impurity content is 1-8%.

[0032] Preferably, based on the total weight of the fresh catalyst corresponding to the hydrogenation catalyst, the content of active metal components in the hydrogenation catalyst is not less than 18% in terms of oxides; based on the total weight of the hydrogenation catalyst, the content of deposited impurities in the hydrogenation catalyst is not more than 2% in terms of oxides.

[0033] The present invention provides a method for treating spent hydrogenation catalysts, which has excellent treatment effects on spent hydrogenation catalysts with high carbon deposits and high amounts of deposited impurities. Existing treatment methods commonly involve regenerating the catalyst by first charring it under certain conditions, followed by redispersion of the active phase using a solution containing specific compound components. For example, CN111821998A discloses impregnation of the charred catalyst with C1-C20 organic alcohols, organic acids, organic amines, and organic ammonium salts, while CN111822060A discloses a two-stage charring and pore expansion process followed by impregnation with a solution containing a phosphorus compound. Both methods aim to redisperse the active phase and improve the dispersion of active metals. However, the inventors of the present invention have discovered that while such saturated or unsaturated impregnation methods can improve the dispersion of the active phase, they cannot remove inactive deposited impurities from the spent hydrogenation catalyst. Compared with existing treatment methods, the treatment method provided by the present invention can not only effectively remove carbon deposits and deposited impurities in the spent hydrogenation catalyst, but also ensure that the prepared hydrogenation catalyst maintains a high content of active metal components. The resulting hydrodesulfurization catalyst is used in residual oil hydroprocessing and has a high desulfurization rate.

[0034] The term "the total weight of the fresh catalyst corresponding to the hydrogenation catalyst is taken as the basis" in the present invention means that the active metal component content is based on the fresh catalyst, that is, the deposited impurities and carbon in the catalyst are not included in the total amount.

[0035] In the present invention, unless otherwise specified, the carbon content of the spent hydrogenation catalyst is determined by extracting the catalyst with toluene using a carbon-sulfur analyzer, and the deposited impurity content is determined by calcining the catalyst at 600° C. in air for 3 hours using X-ray fluorescence spectrometry.

[0036] According to a preferred embodiment of the present invention, the specific surface area of ​​the spent hydrogenation catalyst is 30-300m 2 / g, pore volume is 0.05-0.3mL / g, and the most probable pore diameter is greater than 1nm; further preferably, the specific surface area of ​​the spent hydrogenation catalyst is 50-200m 2 / g, the pore volume is 0.05-0.2mL / g, and the most probable pore diameter is 1.5-4nm.

[0037] In the present invention, unless otherwise specified, the specific surface area, pore volume and most probable pore diameter of the spent hydrogenation catalyst are measured by a low-temperature nitrogen adsorption method.

[0038] The inventors of the present invention have found that, preferably, a hydrogenation catalyst obtained by treating a spent hydrogenation catalyst meeting the above-mentioned physicochemical characteristics and used in heavy oil and / or residual oil hydroprocessing has higher desulfurization performance.

[0039] The inventors of the present invention have also discovered that using spent hydrogenation 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 resulting hydrogenation catalyst. Prior to use, the spent hydrogenation catalyst can be sieved to obtain a spent hydrogenation catalyst meeting the aforementioned preferred particle size requirements. Therefore, the method provided herein preferably further includes sieving the spent hydrogenation catalyst prior to step 1).

[0040] In the present invention, the first and second leaching are carried out in sequence, which can effectively remove impurities deposited on the spent hydrogenation catalyst during the reaction and some aggregated low-activity metal components, thereby achieving the purpose of unblocking the pores and increasing the pore volume of the catalyst.

[0041] According to the present invention, the first impregnating agent includes a polyol, and the second impregnating agent is water and / or ethanol. The use of a combination of the above impregnating agents for synergistic impregnation is more conducive to improving the desulfurization performance of the obtained hydrogenation catalyst.

[0042] In order to further improve the immersion effect, preferably, the general formula of the polyol is C n H 2n+2-x (OH) x , wherein n=2-5, x=2-3, preferably, the polyol is ethylene glycol and / or glycerol.

[0043] Preferably, the first impregnating agent also contains water, and the concentration of the first impregnating agent is 0.01-4 mol / L, preferably 0.01-2 mol / L. Within the above preferred concentration range, it is helpful to selectively remove impurities deposited on the catalyst during the reaction and aggregated low-activity metal components. If the concentration of the first impregnating agent is too high, it may cause excessive removal of dispersed high-activity metal components on the catalyst.

[0044] According to the present invention, during actual operation, the immersion conditions can be adjusted according to the physical and chemical properties of the catalyst after carbonization and pore expansion. The principle is to remove as many impurities as possible that are deposited on the catalyst during the reaction, as well as the metal components with low activity in the aggregated state, while retaining as many metal components with high activity in the dispersed state as possible on the catalyst.

[0045] According to the present invention, preferably, in step 2), the volume ratio of the first soaking agent to the solid product obtained in step 1) is 1-5:1, preferably 3-5:1.

[0046] The first and second leaching can be performed in conventional manners, such as soaking the solid product in a leaching agent and then performing solid-liquid separation. The solid-liquid separation can be performed using conventional operations in the art, and the present invention is not particularly limited thereto.

[0047] Preferably, the first soaking time is 0.5-10 hours, preferably 1-5 hours. It can be understood that the first soaking time refers to the soaking time of the solid product in the first soaking agent.

[0048] According to the present invention, preferably, the first immersion is carried out under stirring conditions. Preferably, the stirring rate is 30-600 rpm, preferably 50-300 rpm. The adoption of the above preferred embodiment is conducive to improving the effect of the first immersion and improving the catalytic activity of the treated hydrogenation catalyst.

[0049] According to the present invention, preferably, the volume ratio of the second soaking agent to the solid product obtained by the first soaking is 1-6:1, preferably 2-5:1.

[0050] Preferably, the second immersion time is 0.1-2 hours, preferably 0.5-2 hours. It is understood that the second immersion time refers to the immersion time of the solid product obtained from the first immersion in the second immersion agent.

[0051] In the present invention, the specific method of the charring and pore-enlarging treatment in step 1) is not particularly limited and can be carried out in a conventional manner in the art, which is well known to those skilled in the art. Preferably, in order to further improve the catalytic activity of the hydrogenation catalyst, the charring and pore-enlarging treatment includes optional stages (1) and (2), wherein the conditions of stage (1) include: a temperature of 200-500° C. and a time of 1-10 hours, and the conditions of stage (2) include: a temperature of 500-850° C. and a time of 1-10 hours.

[0052] Preferably, the conditions of stage (1) include: temperature of 230-450°C, and time of 1-8 hours. Preferably, the conditions of stage (2) include: temperature of 600-800°C, preferably 600-750°C, and time of 1-8 hours, preferably 1-4 hours.

[0053] In the present invention, preferably, the conditions of stage (1) include: treating at a temperature of 230-280°C for 1-3 hours, and then treating at 350-450°C for 1-4 hours; adopting the above preferred embodiment, in conjunction with subsequent immersion and heat treatment, is conducive to further improving the pore volume and most probable pore diameter of the hydrogenation catalyst. The hydrogenation catalyst obtained under such preferred carbonization and pore expansion treatment conditions increases the accessibility of the catalyst active center to macromolecular compounds in heavy oil and / or residual oil, and at the same time improves the diffusion performance of the catalyst pores. When the obtained hydrogenation catalyst is used in the heavy oil and / or residual oil hydrogenation process, better desulfurization and residual carbon removal effects can be obtained.

[0054] The charcoal burning and pore enlargement treatment of the present invention can be carried out in conventional equipment, as long as step 1) can be carried out in an oxygen-containing atmosphere under the optional conditions of stage (1) and stage (2). For example, the charcoal burning and pore enlargement treatment can be carried out in a muffle furnace.

[0055] According to the present invention, in step 1), the oxygen-containing atmosphere provides oxygen for the charcoal burning treatment of the spent hydrogenation catalyst. The present invention has a wide range of selection for the content of oxygen 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 by different methods according to different requirements of the volume content of oxygen. For example, the oxygen-containing atmosphere can be provided by air. When the oxygen content of the oxygen-containing atmosphere is required to be high, the oxygen-containing atmosphere can be provided by air and oxygen. When the oxygen content of the oxygen-containing atmosphere is required to be low, the oxygen-containing atmosphere can be provided by air and an inert atmosphere (for example, nitrogen). In the embodiment of the present invention, the use of air to provide the oxygen-containing atmosphere is used as an example for illustrative description. Using air to provide the oxygen-containing atmosphere is more conducive to cost saving, but the present invention is not limited to this.

[0056] In the present invention, the heat treatment includes low-temperature heat treatment and high-temperature heat treatment. In the conventional regeneration process of waste distillate oil hydrogenation catalysts, the active metals are redispersed with a solvent and then usually dried only at low temperature without high-temperature calcination. This is because the catalyst treated by the conventional regeneration method is still reused in the distillate oil hydrogenation reaction, and its reaction conditions are relatively milder. Low-temperature drying treatment is conducive to improving catalyst activity. The purpose of the present invention is to apply the regenerated waste distillate oil hydrogenation catalyst to heavy oil / residue oil hydrogenation reaction, which has higher reaction temperature and pressure and worse reaction raw material properties. Therefore, the catalyst needs to have higher activity and stability. The inventors found in their research that the activity and stability of distillate oil hydrogenation catalysts under harsh reaction conditions can be improved by combining low-temperature heat treatment and high-temperature heat treatment.

[0057] In the present invention, the selection range of the oxygen-containing atmosphere in step 4) is the same as that in step 1), and will not be repeated here.

[0058] Preferably, the low-temperature heat treatment conditions include: a temperature of 80-150° C. and a time of 3-6 hours.

[0059] Preferably, the conditions of the high temperature heat treatment include: a temperature of 351-520° C. and a time of 2-8 hours. The above preferred embodiment is advantageous in further improving the activity of the hydrogenation catalyst after treatment.

[0060] A second aspect of the present invention provides a hydrogenation catalyst obtained by the above-mentioned method for treating a spent hydrogenation catalyst.

[0061] Preferably, based on the total weight of the fresh catalyst corresponding to the hydrogenation catalyst, the content of active metal components in the hydrogenation catalyst is not less than 18% in terms of oxides; based on the total weight of the hydrogenation catalyst, the content of the deposited impurities is not higher than 2% in terms of oxides.

[0062] The hydrogenation catalyst obtained by the treatment method of the present invention is used in the heavy oil and / or residual oil hydrogenation treatment process and has high desulfurization performance.

[0063] According to the present invention, preferably, the specific surface area of ​​the hydrogenation catalyst is 80-300m 2 / g, pore volume is 0.2-1.3mL / g, and the most probable pore diameter is 5-14nm. Further preferably, the specific surface area of ​​the hydrogenation catalyst is 90-280m 2 / g, pore volume of 0.25-1.1 mL / g, and the most probable pore diameter of 7-14 nm. In the above preferred case, the activity and stability of the catalyst for heavy oil / residue hydrogenation reaction are further improved.

[0064] A third aspect of the present invention provides use of the above-mentioned hydrogenation catalyst in the hydroprocessing of heavy oil and / or residual oil.

[0065] The hydrogenation catalyst provided by the present invention is suitable for the treatment of various heavy oils and residual oils. In the present invention, "residue oil" refers to the components remaining at the bottom of the distillation tower when crude oil is distilled, including atmospheric residue oil and vacuum residue oil. "Heavy oil" refers to heavy raw oil blended from components such as residual oil and coking wax oil. Among them, the crude oil refers to natural petroleum mined from the ground, which is a liquid mineral product with hydrocarbons as the main components. The sulfur content and residual carbon content in heavy oil and / or residual oil are relatively high. For example, the sulfur content in heavy oil and / or residual oil is at least 1 weight%, and the residual carbon content is at least 8 weight%.

[0066] Compared with distillate oil, the compounds in heavy oil and / or residual oil raw materials have higher molecular weights and larger molecular sizes, and the reaction conditions are more stringent. The active centers of the hydrogenation catalyst obtained by the treatment method provided by the present invention have high accessibility to the macromolecular compounds in heavy oil and / or residual oil, and the catalyst has high activity stability under harsh reaction conditions. Therefore, the waste distillate oil hydrogenation catalyst can be directly used in the heavy oil and / or residual oil hydrogenation reaction after regeneration.

[0067] The present invention has no particular limitation on the conditions for the hydrotreating of heavy oil and / or residual oil. Preferably, the conditions for the hydrotreating of heavy oil and / or residual oil include: a temperature of 330-430°C, a hydrogen partial pressure of 10-20 MPa, a liquid hourly volume space velocity of 0.1-1 h -1 , the hydrogen-to-oil volume ratio is 500-1200.

[0068] Further preferably, the heavy oil and / or residual oil hydrotreating conditions include: temperature of 350-400°C, hydrogen partial pressure of 12-17 MPa, liquid hourly volume space velocity of 0.2-0.8 h -1 , the hydrogen-to-oil volume ratio is 500-1000.

[0069] The present invention will be described in detail below through examples.

[0070] In the following examples, the specific surface area, pore volume and most probable pore diameter were measured using a low-temperature nitrogen adsorption method.

[0071] The composition of the catalyst was determined by X-ray fluorescence spectrometry (XRF). The specific method is shown in the petrochemical analysis method RIPP133-90.

[0072] Example 1

[0073] 1) An industrial deactivated diesel hydrogenation catalyst (carbon content 10.26 wt%, iron, sodium, vanadium and other deposited impurities content 7.5 wt%, the catalyst being NiMo / Al2O3, with Ni content of 4.6 wt% and Mo content of 27.8 wt% calculated as oxides based on the total amount of fresh catalyst corresponding to the spent hydrogenation catalyst) is taken, referred to as deactivator A, and sieved to obtain a 16-20 mesh deactivator A, which is placed in a muffle furnace and subjected to a programmed temperature heating process for charring and pore expansion in an air atmosphere, comprising: stage (1) maintaining the temperature at 250°C for 1 hour, maintaining the temperature at 350°C for 2 hours, and then performing stage (2) maintaining the temperature at 650°C for 2 hours, to obtain catalyst B;

[0074] 2) At room temperature, with a stirring rate of 120 rpm, the catalyst B obtained in step 1) was first soaked with a 1.5 mol / L glycerol aqueous solution, wherein the volume of the glycerol aqueous solution used was 3 times the volume of the catalyst, and the soaking time was 2 hours, followed by solid-liquid separation;

[0075] 3) performing a second immersion of the solid product obtained in step 2) with deionized water at room temperature, wherein the volume of the deionized water used is 4 times the volume of the solid, and the immersion time is 1 hour, followed by solid-liquid separation to obtain a washed product;

[0076] 4) The washed product was heat treated, first at 120°C for 3 hours in an air atmosphere, which was designated as Catalyst C; and then Catalyst C was heat treated at 410°C for 5 hours in an air atmosphere to obtain Catalyst D.

[0077] Example 2

[0078] 1) Catalyst B was obtained according to the method of Example 1;

[0079] 2) At room temperature, at a stirring rate of 180 rpm, the catalyst B obtained in step 1) was first soaked in a 1 mol / L ethylene glycol aqueous solution, wherein the volume of the ethylene glycol aqueous solution used was 4 times the volume of the catalyst, and the soaking time was 5 hours, followed by solid-liquid separation;

[0080] 3) performing a second immersion of the solid product obtained in step 2) with ethanol at room temperature, wherein the volume of the ethanol used is 3 times the volume of the solid, and the immersion time is 1.5 hours, followed by solid-liquid separation to obtain a washed product;

[0081] 4) The washed product was heat treated, first at 100°C for 4 hours in an air atmosphere, and then at 410°C for 4 hours in an air atmosphere, to obtain Catalyst E.

[0082] Example 3

[0083] The method of Example 1 is followed, except that in step 1), the charring and pore-enlarging treatment includes: stage (1) maintaining the temperature at 350° C. for 2 hours, followed by stage (2) maintaining the temperature at 650° C. for 2 hours, to obtain catalyst F;

[0084] The first impregnation, the second impregnation and the heat treatment were carried out in the same manner as in Example 1 to obtain Catalyst G.

[0085] Example 4

[0086] 1) Catalyst B was obtained according to the method of Example 1;

[0087] 2) At room temperature, with a stirring rate of 45 rpm, the catalyst B obtained in step 1) was first soaked in a 0.2 mol / L glycerol aqueous solution, wherein the volume of the glycerol aqueous solution used was 0.8 times the volume of the catalyst, and the soaking time was 10 minutes, followed by solid-liquid separation;

[0088] 3) performing a second immersion of the solid product obtained in step 2) with deionized water at room temperature, wherein the volume of the deionized water used is 1.5 times the volume of the solid, and the immersion time is 5 minutes, followed by solid-liquid separation to obtain a washed product;

[0089] 4) The leached product was heat treated in the same manner as in Example 1 to obtain Catalyst H.

[0090] Example 5

[0091] 1) Catalyst B was obtained according to the method of Example 1;

[0092] 2) At room temperature, with a stirring rate of 350 rpm, the catalyst B obtained in step 1) was first soaked in a 5 mol / L glycerol aqueous solution, wherein the volume of the glycerol aqueous solution used was 6 times the volume of the catalyst, and the soaking time was 12 hours, followed by solid-liquid separation;

[0093] 3) performing a second immersion of the solid product obtained in step 2) with deionized water at room temperature, wherein the volume of the deionized water used is 7 times the volume of the solid, and the immersion time is 3 hours, followed by solid-liquid separation to obtain a washed product;

[0094] 4) The leached product was heat-treated in the same manner as in Example 1 to obtain Catalyst I.

[0095] Example 6

[0096] The method of Example 1 is followed, except that the charcoaling treatment in step 1) includes: maintaining the temperature at 250° C. for 1 hour and maintaining the temperature at 410° C. for 3 hours, to obtain charcoaled catalyst J;

[0097] The first impregnation, the second impregnation and the heat treatment were carried out in the same manner as in Example 1 to obtain Catalyst K.

[0098] Example 7

[0099] The method of Example 1 was followed, except that the conditions for the first immersion in step 2) did not include stirring. The second immersion and heat treatment were performed in the same manner as in Example 1 to obtain Catalyst L.

[0100] Comparative Example 1

[0101] 1) Catalyst B was obtained according to the method of Example 1;

[0102] 2) At room temperature, with a stirring rate of 120 rpm, soaking the catalyst B obtained in step 1) in a 1.5 mol / L glycerol aqueous solution, wherein the volume of the glycerol aqueous solution used is 3 times the volume of the catalyst, for 2 hours, followed by solid-liquid separation to obtain a soaked product;

[0103] 3) The leached product was heat-treated in the same manner as in Example 1 to obtain Catalyst M.

[0104] Comparative Example 2 (conventional regeneration method)

[0105] 1) Obtain charcoaled catalyst J according to the method of Example 6;

[0106] 2) An aqueous solution of glycerol was prepared and impregnated with Catalyst J by an equal volume saturation impregnation method. The mixture was sealed and placed at room temperature (25°C) for 3 hours, wherein the mass ratio of Catalyst J to glycerol was 8.7. The mixture was then dried at 120°C in an air atmosphere for 3 hours to obtain Catalyst N.

[0107] Comparative Example 3

[0108] 1) An industrial deactivated diesel hydrogenation catalyst (carbon content: 10.26 wt%, content of deposited impurities such as iron, sodium, and vanadium: 7.5 wt%, NiMo / Al2O3; Ni content: 4.6 wt%, Mo content: 27.8 wt%, calculated as oxides, based on the total amount of fresh catalyst corresponding to the spent hydrogenation catalyst) was taken, referred to as deactivator A, and sieved to obtain a 16-20 mesh deactivator A. The deactivator A was first soaked in a 1.5 mol / L glycerol aqueous solution at room temperature with a stirring rate of 120 rpm, wherein the volume of the glycerol aqueous solution used was three times the volume of the catalyst, for a soaking time of 2 hours, followed by solid-liquid separation;

[0109] 2) washing the solid product obtained in step 1) with deionized water at room temperature for a second time, wherein the volume of the deionized water used is 4 times the volume of the solid product, and the soaking time is 1 hour, followed by solid-liquid separation;

[0110] 3) The solid product obtained in step 2) was heat treated, first at 120 ° C. for 3 hours in an air atmosphere, and then placed in a muffle furnace for high-temperature treatment in an air atmosphere by programmed temperature increase, with the conditions of constant temperature at 250 ° C. for 3 hours and constant temperature at 410 ° C. for 4 hours to obtain catalyst O.

[0111] Comparative Example 4

[0112] 1) Catalyst B was obtained according to the method of Example 1;

[0113] 2) At room temperature, with a stirring rate of 120 rpm, the catalyst B obtained in step 1) was first soaked with a 1.5 mol / L oxalic acid solution, wherein the volume of the oxalic acid solution used was 3 times the volume of the catalyst, and the soaking time was 2 hours, followed by solid-liquid separation;

[0114] 3) soaking the solid product obtained in step 2) in deionized water at room temperature, wherein the volume of the deionized water used is 4 times the volume of the solid, and the soaking time is 1 hour, followed by solid-liquid separation to obtain a washed product;

[0115] 4) The leached product was heat treated in the same manner as in Example 1 to obtain Catalyst P.

[0116] The physicochemical properties of the deactivator A and catalyst BP in the above examples and comparative examples are listed in Table 1.

[0117] Table 1

[0118]

[0119]

[0120] Table 1 lists the basic physicochemical properties of catalysts A and B. Deactivator A exhibits high carbon content and deposited impurities, resulting in clogged reaction pores and a relatively small pore volume and most probable pore diameter. Compared to deactivator A, catalyst B, after charring and pore expansion, exhibits reduced carbon content and significantly increased pore volume and most probable pore diameter. Furthermore, selective removal of deposited impurities and some aggregated low-activity metal components further increases the pore volume and most probable pore diameter of catalysts C, D, and E. Furthermore, if the proportion of deposited impurities removed is too low, as in catalyst H, further increases in the catalyst's pore volume and most probable pore diameter are unlikely. If the proportion of deposited impurities removed is too high, as in catalyst I, some of the active metal components in the catalyst are also removed.

[0121] Test example

[0122] This test example is used to measure the residue oil hydroprocessing performance of the above-mentioned hydrogenation catalyst. The residue oil hydrodesulfurization catalyst (NiMo / Al2O3, calculated as oxide, Ni content is 3.0w%, Mo content is 15.4w%) developed by the Petrochemical Science Research Institute of Sinopec was used as the reference agent for the evaluation test. Specifically, the atmospheric residue of crude oil imported from the Middle East (its properties are listed in Table 2) was used as the raw material, and the hydrogenation catalysts obtained in the above-mentioned embodiments and comparative examples were evaluated on a heavy oil hydrogenation fixed-bed reactor to compare the desulfurization performance of different catalysts. The filling amount of the hydrogenation catalyst was 120mL; the evaluation conditions were: reaction temperature 380°C, hydrogen partial pressure 14MPa, liquid hourly volume space velocity 0.5h -1 , hydrogen to oil volume ratio 600: 1. The results are listed in Table 3.

[0123] The specific calculation method of desulfurization rate is as follows:

[0124]

[0125] Table 2

[0126] crude oil <![CDATA[Density (20 °C), kg / m 3 > 981.1 <![CDATA[Viscosity (100 °C) mm 2 / s]]> 120.3 Metal content, ppm Ni 29.5 V 81.1 Fe 5.9 Ca 0.7 Na 0.1 Cm% 84.41 Hm% 11.00 Sm% 4.0 Nm% 0.27 Carbon residue, m% 12.6

[0127] Table 3 Catalyst evaluation results

[0128]

[0129]

[0130] The results in Table 3 show that the hydrodesulfurization activity of Catalyst N, obtained using a conventional regeneration method, in residue oil hydroprocessing reactions was significantly lower than that of the reference catalyst, while Catalysts D and E, obtained using the method provided by the present invention, exhibited higher hydrodesulfurization activities than the reference catalyst. The results in Table 3 demonstrate that even industrially deactivated distillate oil hydroprocessing catalysts with high levels of carbon deposits and deposited impurities exhibited good hydrodesulfurization effectiveness when treated using the method provided by the present invention and applied to residue oil hydroprocessing reactions.

[0131] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A method for treating a spent hydrogenation catalyst, the method comprising: 1) In an oxygen-containing atmosphere, the spent hydrogenation catalyst is subjected to carbonization and pore expansion treatment; 2) mixing a first soaking agent with the solid product obtained in step 1) to perform a first soaking; the first soaking agent comprises a polyol and water, and the concentration of the polyol aqueous solution is 1-4 mol / L; The first soaking comprises soaking the solid product in a first soaking agent and then performing solid-liquid separation; The volume ratio of the first soaking agent to the solid product obtained in step 1) is 1-5:1; 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; the second leaching comprises immersing the solid product in the second leaching agent, and then performing solid-liquid separation; 4) heat-treating the leached product under an oxygen-containing atmosphere to obtain a hydrogenation catalyst; The heat treatment includes low-temperature heat treatment and high-temperature heat treatment. The conditions of the low-temperature heat treatment include: temperature of 70-200°C and time of 2-10 hours. The conditions of the high-temperature heat treatment include: temperature of 310-550°C and time of 1-10 hours.

2. The processing method according to claim 1, wherein The general formula of the polyol is C n H 2n+2-x (OH) x , where n=2-5, x=2-3.

3. The processing method according to claim 2, wherein: The polyol is ethylene glycol and / or glycerol.

4. The treatment method according to any one of claims 1 to 3, wherein: The time of the first immersion is 0.5-10 hours.

5. The processing method according to any one of claims 1 to 3, wherein: The first immersion is performed under stirring conditions, and the stirring rate is 30-600 rpm.

6. The processing method according to claim 5, wherein: The first immersion is performed under stirring conditions, and the stirring rate is 50-300 rpm.

7. The processing method according to any one of claims 1 to 3, wherein: The volume ratio of the amount of the second soaking agent to the solid product obtained by the first soaking is 1-6:

1.

8. The processing method according to any one of claims 1 to 3, wherein: The second immersion time is 0.1-2 hours.

9. The processing method according to any one of claims 1 to 3, wherein: The conditions of the low-temperature heat treatment include: a temperature of 80-150° C. and a time of 3-6 hours.

10. The processing method according to any one of claims 1 to 3, wherein: The conditions of the high temperature heat treatment include: a temperature of 351-520° C. and a time of 2-8 hours.

11. The processing method according to any one of claims 1 to 3, wherein: The charcoal burning and pore expansion treatment includes stage (1) and stage (2). The conditions of stage (1) include: temperature of 200-500°C and time of 1-10 hours. The conditions of stage (2) include: temperature of 500-850°C and time of 1-10 hours.

12. The processing method according to claim 11, wherein: The conditions of the stage (1) include: temperature of 230-450°C and time of 1-8 hours.

13. The processing method according to claim 12, wherein: The conditions of the stage (1) include: treating at a temperature of 230-280°C for 1-3 hours, and then treating at 350-450°C for 1-4 hours.

14. The processing method according to claim 11, wherein: The conditions of the stage (2) include: a temperature of 600-800° C. and a time of 1-8 hours.

15. The processing method according to claim 14, wherein: The conditions of the stage (2) include: a temperature of 600-750° C.; and a time of 1-4 hours.

16. The processing method according to any one of claims 1 to 3, wherein: In step 1) and step 4), the volume content of oxygen in the oxygen-containing atmosphere is 8-30%.

17. The processing method according to claim 16, wherein: In step 1) and step 4), the volume content of oxygen in the oxygen-containing atmosphere is 10-25%.

18. The processing method according to claim 17, wherein: In step 1) and step 4), the oxygen-containing atmosphere is a mixture of oxygen and an inert gas.

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

20. The processing method according to claim 19, wherein: Based on the total weight of the spent hydrogenation catalyst, the carbon content of the spent hydrogenation catalyst is less than 30%, and the deposited impurity content is less than 20%. The deposited impurity content is determined by calcining the spent hydrogenation catalyst at 600° C. in air for 3 hours and then measuring it by X-ray fluorescence spectrometry.

21. The processing method according to claim 20, wherein: Based on the total weight of the spent hydrogenation catalyst, the carbon content of the spent hydrogenation catalyst is less than 15%, and the deposited impurity content is less than 10%. The deposited impurity content is determined by calcining the spent hydrogenation catalyst at 600° C. in air for 3 hours and then measuring it by X-ray fluorescence spectrometry.

22. The processing method according to claim 19, wherein: The specific surface area of ​​the spent hydrogenation catalyst is 30-300m 2 / g, the pore volume is 0.05-0.3mL / g, and the most probable pore diameter is greater than 1nm.

23. The processing method according to claim 22, wherein: The specific surface area of ​​the spent hydrogenation catalyst is 50-200m 2 / g, the pore volume is 0.05-0.2mL / g, and the most probable pore diameter is 1.5-4nm.

24. The processing method according to claim 19, wherein: The spent hydrogenation catalyst includes a carrier and an active metal component supported on the carrier, wherein the active metal component includes molybdenum and / or tungsten and nickel and / or cobalt.

25. The processing method according to claim 24, wherein: Based on the total amount of 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, calculated as oxides.

26. Use of the hydrogenation catalyst obtained by the method for treating a spent hydrogenation catalyst according to any one of claims 1 to 25 in heavy oil hydrogenation treatment.

27. Use of the hydrogenation catalyst obtained by the method for treating a spent hydrogenation catalyst according to any one of claims 1 to 25 in residual oil hydroprocessing.

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