Treatment method of waste hydrogenation catalyst, treated hydrogenation catalyst and application of treated hydrogenation catalyst

Abstract

The invention relates to the field of hydrogenation catalyst treatment, and discloses a treatment method of a waste hydrogenation catalyst, the treated hydrogenation catalyst and application thereof, the method comprises the following steps: 1) in an oxygen-containing atmosphere, performing charking treatment on the waste hydrogenation catalyst; the most probable pore size of the waste hydrogenation catalyst is greater than 4nm; (2) mixing a first immersion cleaning agent with the solid product obtained in the step (1), and carrying out first immersion cleaning; the first immersion cleaning agent comprises polyhydric alcohol; 3) mixing the solid product obtained by the first immersion cleaning with a second immersion cleaning agent, and carrying out second immersion cleaning to obtain an immersion cleaning product; the second immersion cleaning agent is water and / or ethanol; and (4) under the oxygen-containing atmosphere, the immersion cleaning product is subjected to low-temperature heat treatment and high-temperature heat treatment, the low-temperature heat treatment temperature ranges from 50 DEG C to 180 DEG C, the time ranges from 2 h to 10 h, the high-temperature heat treatment temperature ranges from 320 DEG C to 580 DEG C, and the time ranges from 1 h to 10 h. The obtained hydrogenation catalyst is used in a heavy oil and / or residual oil hydrotreatment process, and has good desulfurization performance.

Description

Technical Field

[0001] The present invention relates to the field of hydrotreating catalyst treatment, and particularly relates to a method for treating waste hydrotreating catalysts, the treated hydrotreating catalysts and their applications. Background Art

[0002] At present, refineries in China unload a large amount of deactivated fractionated oil hydrotreating catalysts after reaction from shutdown units every year. The main reasons for the deactivation of fractionated oil hydrotreating catalysts are coke deposition and metal sintering. For such deactivated catalysts, the common regeneration method is to first carry out carbon burning treatment on the catalyst under certain conditions, and then use a solution containing specific compound components to carry out active phase redispersion treatment on the carbon-burned catalyst.

[0003] CN105944735A discloses an activation method for carbon-deposited and deactivated type II hydrotreating catalysts. First, the carbon-deposited and deactivated type II hydrotreating catalysts are subjected to carbon burning regeneration treatment to obtain hydrotreating catalysts with a carbon content of 0.3%-1.0%; then the hydrotreating catalysts with a carbon content of 0.3%-1.0% are saturatedly impregnated with an activation solution for 40-60 minutes, and then cured at a temperature of 60-70°C for 8-24 hours; finally, drying treatment is carried out at a temperature of 60-150°C for 6-8 hours to obtain activated hydrotreating catalysts. This activation method has the advantages of good activation effect and simple operation.

[0004] CN101992131A discloses a regeneration method for hydrotreating catalysts, the regenerated hydrotreating catalysts and their applications. First, under the reaction conditions of hydrotreating catalyst regeneration carbon burning, the catalyst to be regenerated is contacted with an oxygen-containing gas; then the carbon-burned catalyst is contacted with a solution containing a phosphorus-containing compound; finally, the above-treated catalyst is dried to obtain a regenerated catalyst. The activity of the regenerated catalyst after being treated by this method is significantly improved.

[0005] After the deactivated fractionated oil hydrotreating catalysts are restored to activity by the above conventional regeneration methods, they are generally refilled into the reaction device for industrial application again; when the catalysts are regenerated and used 1-2 times, it is difficult to meet the requirements of the fractionated oil for the ultra-deep hydrotreating activity of the catalysts. At this time, the unloaded catalysts can only be treated as hazardous wastes. The treatment cost of waste catalysts is high and the environmental protection pressure is great, which has become a difficult problem plaguing the industry. The road to carbon emission reduction and green development for domestic refining and chemical enterprises will be even more arduous. The generation of catalyst hazardous wastes is not conducive to the green and sustainable development of enterprises.

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

[0007] The object of the present invention is to overcome the problem that the performance of the hydrofining catalyst for distillate oil with a relatively large pore volume and pore diameter deteriorates after 1-2 conventional regenerations and cannot be used continuously. A method for treating spent hydrocatalysts, the hydrocatalyst after treatment, and its application are provided. The hydrocatalyst obtained by the method for treating spent hydrocatalysts provided by the present invention has higher activity and stability and has good desulfurization performance when used in the heavy oil and / or residue hydrotreating process.

[0008] In the research process, the inventors of the present invention found that the regenerated catalyst obtained by using the existing recovery and treatment method of spent hydrofining catalysts for distillate oil is reused in the distillate oil hydrotreating process. After 1-2 regenerations, it is difficult to meet the requirements of the distillate oil for the ultra-deep hydrotreating 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 treating waste catalysts and the great environmental protection pressure have become problems that plague the industry. The inventors of the present invention changed their thinking and treated the spent hydrofining catalysts that do not have the conditions for conventional regeneration by special methods and used them in the heavy oil and / or residue hydrotreating process where the requirements for the catalyst are slightly reduced. Compared with distillate oil, the molecular weight of compounds in heavy oil and / or residue raw materials is higher, the molecular size is larger, and the reaction conditions are more severe. Therefore, it is necessary to increase the accessibility of the catalyst active center to the macromolecular compounds in heavy oil and / or residue, improve the diffusion performance of the catalyst pores, and improve the activity stability of the catalyst under severe reaction conditions. However, the regenerated agent obtained by the conventional regeneration method of spent hydrofining catalysts cannot meet the requirements of the heavy oil and / or residue hydrotreating reaction.

[0009] To achieve the above object, a first aspect of the present invention provides a method for treating spent hydrocatalysts, the method comprising:

[0010] 1) Carbon burning treatment of the spent hydrocatalyst in an oxygen-containing atmosphere;

[0011] The most probable pore diameter of the spent hydrocatalyst is greater than 4 nm;

[0012] 2) Mixing the first leaching agent with the solid product obtained in step 1) and performing the first leaching; the first leaching agent includes polyhydric alcohol;

[0013] 3) Mix the solid product obtained from the first leaching with a second leaching agent for second leaching to obtain a leached product; the second leaching agent is water and / or ethanol;

[0014] 4) Under an oxygen-containing atmosphere, perform low-temperature heat treatment and high-temperature heat treatment on the leached product. The conditions for the low-temperature heat treatment include: temperature of 50-180°C and time of 2-10 hours, and the conditions for the high-temperature heat treatment include: temperature of 320-580°C and time of 1-10 hours.

[0015] The second aspect of the present invention provides a hydrogenation catalyst obtained by the treatment method of the spent hydrogenation catalyst described in the first aspect.

[0016] The third aspect of the present invention provides the application of the hydrogenation catalyst described in the second aspect above in the hydrotreating of heavy oil and / or residue oil.

[0017] In the prior art, for spent hydrogenation catalysts with smaller pore volume and pore diameter, on the basis of conventional carbon burning treatment, high-temperature pore expansion treatment is also required to further increase the pore volume and pore diameter of the catalyst, thereby improving the performance of the regenerated catalyst. However, the inventors of the present invention found in their research that for spent hydrogenation catalysts with relatively large pore diameter, the high-temperature pore expansion treatment step will enhance the interaction force between the metal and the carrier on the catalyst, thereby weakening the subsequent leaching effect to a certain extent and affecting the regeneration effect. Through further experimental research, it was found that for macroporous spent hydrogenation catalysts with the most probable pore diameter greater than 4 nm, after conventional carbon burning treatment, directly performing two-step leaching and heat treatment steps can achieve good regeneration effects.

[0018] During the conventional regeneration process of spent distillate oil hydrogenation catalysts, after redispersing the active metal with a solvent, drying is usually only carried out at low temperature without high-temperature calcination. For example, the heat treatment temperature of the spent 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, and its reaction conditions are relatively milder. Low-temperature drying treatment is beneficial to improving the catalyst activity. The purpose of the present invention is to apply the regenerated spent distillate oil hydrogenation catalyst 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. Therefore, the catalyst needs to have higher activity stability. The inventors found in their research that through a heat treatment method combining low-temperature heat treatment and high-temperature heat treatment, the activity and stability of the distillate oil hydrogenation catalyst under harsh reaction conditions can be improved.

[0019] 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, higher activity and stability, can be applied to the heavy oil and / or residue oil hydrogenation reaction process, and has a good desulfurization effect.

[0020] After the waste hydrofining catalyst is treated by the treatment method provided by the present invention and applied to the heavy oil and / or residue hydrofining reaction process to replace part of the heavy oil and / or residue hydrodesulfurization catalyst, the cascade utilization of the waste hydrofining catalyst can be realized, the procurement cost of the existing heavy oil and / or residue hydrofining catalyst can be reduced, and at the same time, the problem of the recovery and treatment of the waste hydrofining catalyst can be solved, creating obvious social and economic benefits. Detailed implementation mode

[0021] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0022] The first aspect of the present invention provides a treatment method for a waste hydrofining catalyst, and the method includes:

[0023] 1) Under an oxygen-containing atmosphere, subject the waste hydrofining catalyst to carbon burning treatment;

[0024] The most probable pore diameter of the waste hydrofining catalyst is greater than 4 nm;

[0025] 2) Mix the first leaching agent with the solid product obtained in step 1) and perform the first leaching; the first leaching agent includes polyol;

[0026] 3) Mix the solid product obtained by the first leaching with the second leaching agent and perform the second leaching to obtain a leached product; the second leaching agent is water and / or ethanol;

[0027] 4) Under an oxygen-containing atmosphere, perform low-temperature heat treatment and high-temperature heat treatment on the leached product. The conditions for the low-temperature heat treatment include: the temperature is 50-180 °C and the time is 2-10 hours. The conditions for the high-temperature heat treatment include: the temperature is 320-580 °C and the time is 1-10 hours.

[0028] In the prior art, for spent hydrotreating catalysts with small pore volume and pore diameter, on the basis of conventional carbon burning treatment, high-temperature pore expansion treatment is also required to further increase the pore volume and pore diameter of the catalyst, thereby improving the performance of the regenerated catalyst. However, the inventors of the present invention found in their research that for spent hydrotreating catalysts with large pore volume and pore diameter, the high-temperature pore expansion treatment step will enhance the interaction between the metal and the support on the catalyst, thereby weakening the subsequent leaching effect to a certain extent and affecting the regeneration effect. Through further experimental research, it was found that for macroporous spent hydrotreating catalysts with a most probable pore diameter greater than 4 nm, after conventional carbon burning treatment, directly performing two-step leaching and heat treatment steps can achieve good regeneration effects. Therefore, in the present invention, preferably, the pore expansion treatment is not included in step 1).

[0029] According to a preferred embodiment of the present invention, the specific surface area of the spent hydrotreating catalyst is 20 - 180 m 2 / g, the pore volume is 0.1 - 0.7 mL / g, and the most probable pore diameter is 4.1 - 8 nm; further preferably, the specific surface area of the spent hydrotreating catalyst is 30 - 150 m 2 / g, the pore volume is 0.21 - 0.5 mL / g, and the most probable pore diameter is 4.1 - 6 nm. The inventors of the present invention found that, preferably, using spent hydrotreating catalysts conforming to the above physical and chemical characteristics, after conventional carbon burning treatment, directly performing two-step leaching and heat treatment steps, the hydrotreating catalysts obtained by treatment have higher desulfurization performance when used in heavy oil and / or residue hydrotreating.

[0030] In the present invention, unless otherwise specified, the specific surface area, pore volume, and most probable pore diameter of the spent hydrotreating catalyst are measured by the low-temperature nitrogen adsorption method.

[0031] In the present invention, the spent hydrotreating catalyst refers to a catalyst whose performance (which may include at least one of activity, selectivity, and stability) deteriorates after use. It includes both discarded hydrotreating catalysts that cannot meet the hydrotreating activity requirements even after being regenerated by existing means after long-term cyclic use, and used hydrotreating catalysts that can still be used after being regenerated by existing means. The spent hydrotreating catalyst can be various hydrotreating catalysts commonly used in various oil products in the art, and the present invention has no special limitation on this. According to a specific embodiment of the present invention, the spent hydrotreating catalyst of the present invention includes but is not limited to at least one of spent gasoline hydrotreating catalysts, spent diesel hydrotreating catalysts, spent kerosene hydrotreating catalysts, and spent wax oil hydrotreating catalysts. The examples of the present invention are exemplarily described using a spent diesel hydrotreating catalyst as an example.

[0032] According to the present invention, preferably, the spent hydrotreating catalyst includes a support and an active metal component supported on the support, and the active metal component includes molybdenum and / or tungsten and nickel and / or cobalt.

[0033] The present invention selects a relatively wide range of the contents of molybdenum and / or tungsten, and nickel and / or cobalt. Those skilled in the art can make appropriate adjustments according to the actual situation. Further preferably, based on the total amount of the fresh catalyst corresponding to the waste hydrogenation catalyst, calculated as oxides, the content of molybdenum and / or tungsten is 10-40% by weight, and the content of nickel and / or cobalt is 1.5-8% by weight. The conventional selection ranges of the active metal components molybdenum and / or tungsten, and nickel and / or cobalt in waste gasoline hydrogenation catalysts, waste diesel hydrogenation catalysts, waste kerosene hydrogenation catalysts, and waste wax oil hydrogenation catalysts may vary. Those skilled in the art can make selections by conventional means, and the present invention will not elaborate on them one by one here.

[0034] It should be noted that in addition to the carrier and the active metal components supported on the carrier, the waste hydrogenation catalyst also includes impurities and carbon deposited through long-term recycling. The "based on the total amount of the fresh catalyst corresponding to the waste hydrogenation catalyst" mentioned in the present invention means that the contents of molybdenum and / or tungsten, and nickel and / or cobalt are calculated based on the fresh catalyst, that is, the above-mentioned deposited impurities and carbon are not included. Since the waste hydrogenation treatment catalyst has characteristics such as high carbon deposition and / or high content of deposited impurities (such as iron, calcium, sodium, silicon) compared with the fresh catalyst, and the deposited impurities come from the feedstock oil. Therefore, the present invention uses the carbon content and / or the content of deposited impurities to indicate whether the catalyst is a waste hydrogenation catalyst. Generally, the carbon content and the content of deposited impurities of the fresh catalyst are basically 0, while the carbon content of the waste hydrogenation catalyst can be as high as 20% by weight, and the content of deposited impurities can be as high as 15% by weight.

[0035] According to a preferred embodiment of the present invention, based on the total weight of the waste hydrogenation catalyst, the carbon content of the waste hydrogenation catalyst is less than 20 wt%, and the content of deposited impurities is less than 15 wt%. Preferably, the carbon content of the waste hydrogenation catalyst is less than 12 wt%, and the content of deposited impurities is less than 8 wt%. Further preferably, the carbon content of the waste hydrogenation catalyst is 4-10 wt%, and the content of deposited impurities is 0.8-7 wt%.

[0036] The treatment method for spent hydrotreating catalysts provided by the present invention has excellent treatment effects on large-pore spent hydrotreating catalysts with high carbon deposition amounts and high deposited impurity amounts. Among the existing treatment means, the common regeneration method is to first perform carbon burning and pore widening treatment on the catalyst under certain conditions, and then perform active phase redispersion treatment on the carbon-burned catalyst with a solution containing specific compound components. For example, CN111821998A discloses impregnating the carbon-burned catalyst with organic alcohols, organic acids, organic amines, and organic ammonium salts having 1 to 20 carbon atoms, and CN111822060A discloses two-stage carbon burning and pore widening, and then impregnating with a solution containing a phosphorus compound. The purpose of both is to perform redispersion of the active phase to improve the dispersion degree of the active metal. However, the inventors of the present invention have found that although this saturated or unsaturated impregnation method can improve the dispersion degree of the active phase, it cannot remove the inactive deposited impurities in the spent hydrotreating catalyst. Compared with the existing treatment methods, the treatment method provided by the present invention can not only effectively remove the carbon deposition and deposited impurities in the spent hydrotreating catalyst, but also ensure that the prepared hydrotreating catalyst maintains a high content of active metal components. The hydrodesulfurization catalyst obtained therefrom has a high desulfurization rate when applied to residue hydrotreating.

[0037] In the present invention, without special instructions, the carbon content of the spent hydrotreating catalyst is determined by a carbon-sulfur analyzer after the catalyst is extracted with toluene, and the deposited impurity content is determined by X-ray fluorescence spectrometry after the catalyst is calcined in air at 600 °C for 3 hours.

[0038] The inventors of the present invention have also found that using spent hydrotreating catalysts with a particle size of 10 to 30 mesh, preferably 14 to 20 mesh, and more preferably 16 to 20 mesh can further improve the desulfurization performance of the obtained hydrotreating catalyst. The spent hydrotreating catalyst can be sieved before use to obtain a spent hydrotreating catalyst that meets the above preferred particle size requirements. Therefore, preferably, before step 1) of the method provided by the present invention, a sieving treatment is also included for the spent hydrotreating catalyst.

[0039] In the present invention, there is no particular limitation on the specific manner of the carbon burning treatment in step 1), as long as it can play a role in removing the carbon deposition of the spent hydrotreating catalyst, and it can be carried out in a conventional manner in the art and is well known to those skilled in the art. The inventors of the present invention have found in their research that for spent hydrotreating catalysts with relatively large pore diameters and pore volumes, due to their large pore diameters, too high a carbon burning temperature may lead to an increase in the interaction force between the metal and the support on the catalyst, and thus weaken the subsequent leaching effect to a certain extent. In order to further improve the catalytic activity of the treated hydrotreating catalyst, preferably, in step 1), the conditions of the carbon burning treatment include: the temperature is 200 to 550 °C, preferably 220 to 450 °C; the time is 1 to 10 hours, preferably 2 to 7 hours.

[0040] According to a preferred embodiment of the present invention, the carbon burning treatment includes: first treating at a temperature of 220 - 260 °C for 1 - 3 hours, then treating at 290 - 340 °C for 1 - 2 hours, and finally treating at 350 - 450 °C for 1 - 4 hours. By adopting the above preferred embodiment, on the one hand, it is beneficial to more fully burn off the carbon deposits on the catalyst, and on the other hand, it can avoid the phenomenon of temperature runaway during the carbon burning process.

[0041] According to the present invention, in step 1), the oxygen-containing atmosphere provides oxygen for the carbon burning treatment of the waste hydrogenation catalyst. The present invention has a relatively wide selection range for the oxygen content in the oxygen-containing atmosphere. For example, in the oxygen-containing atmosphere, the volume content of oxygen can be 8 - 30%, preferably 10 - 25%. The oxygen-containing atmosphere of the present invention can be provided by different methods according to different requirements of the oxygen volume content. For example, the oxygen-containing atmosphere can be provided by air. When a higher oxygen content in the oxygen-containing atmosphere is required, the oxygen-containing atmosphere can be provided by a combination of air and oxygen. When a lower oxygen content in the oxygen-containing atmosphere is required, the oxygen-containing atmosphere can be provided by a combination of air and an inert atmosphere (such as nitrogen). In the examples of the present invention, the case of providing the oxygen-containing atmosphere by air is taken as an example for illustrative purposes. Providing the oxygen-containing atmosphere by air is more conducive to cost savings, but the present invention is not limited thereto.

[0042] In the present invention, the first washing and the second washing are sequentially carried out after the carbon burning treatment, which can effectively remove the impurities deposited on the catalyst during the reaction process of the waste hydrogenation catalyst and some aggregated low-activity metal components, and thus achieve the purpose of unclogging the pores and increasing the pore volume of the catalyst, which helps to further improve the desulfurization performance of the catalyst.

[0043] According to the present invention, the first washing agent includes polyols, and the second washing agent is water and / or ethanol. The combined synergistic washing with the above washing agents is more conducive to improving the desulfurization performance of the obtained hydrogenation catalyst.

[0044] To further improve the washing effect, preferably, the general formula of the polyol is C 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.

[0045] According to a preferred embodiment of the present invention, the polyol is 1,3-propanediol. The inventors of the present invention found in their research that in spent hydrogenation catalysts without high-temperature pore expansion, the interaction force between the metal and the support is weak. For spent hydrogenation catalysts without pore expansion treatment, first soaking with a first soaking agent containing 1,3-propanediol can further improve the catalytic activity of the treated hydrogenation catalyst.

[0046] Preferably, the first soaking agent further contains water, and the concentration of the first soaking agent is 0.01 - 3 mol / L, preferably 0.01 - 1.5 mol / L. Within the above preferred concentration range, it is helpful to selectively remove the impurities deposited on the catalyst during the reaction process and the aggregated low-activity metal components. If the concentration of the first soaking agent is too high, the dispersed high-activity metal components on the catalyst may be overly removed.

[0047] According to the present invention, during the actual operation process, the soaking conditions can be adjusted according to the physical and chemical properties of the catalyst after carbon burning. The principle is to remove as many impurities deposited on the catalyst during the reaction process and aggregated low-activity metal components as possible, while retaining as many dispersed high-activity metal components on the catalyst as possible.

[0048] According to the present invention, preferably, in step 2), the volume ratio of the amount of the first soaking agent to the solid product obtained in step 1) is 1 - 6:1, preferably 3 - 6:1.

[0049] The first soaking and the second soaking can be carried out in a conventional manner. For example, the solid product is soaked in the soaking agent, and then solid-liquid separation is performed. The solid-liquid separation can be carried out by conventional operations in the art, and the present invention has no special limitation on this.

[0050] Preferably, the time of the first soaking is 0.5 - 8 hours, preferably 1 - 4 hours. It can be understood that the time of the first soaking refers to the soaking time of the solid product in the first soaking agent.

[0051] According to the present invention, preferably, the first soaking is carried out under stirring conditions. Preferably, the stirring rate is 50 - 500 rpm, preferably 50 - 280 rpm. By adopting the above preferred embodiment, it is beneficial to improve the effect of the first soaking and the catalytic activity of the treated hydrogenation catalyst.

[0052] According to the present invention, preferably, the volume ratio of the amount of the second soaking agent to the solid product obtained after the first soaking is 1 - 5:1, preferably 2.5 - 5:1.

[0053] Preferably, the time of the second immersion is 0.1 - 3 hours, preferably 0.5 - 3 hours. It can be understood that the time of the second immersion refers to the immersion time of the solid product obtained from the first immersion in the second immersion agent.

[0054] In the present invention, the heat treatment includes low-temperature heat treatment and high-temperature heat treatment. During the regeneration process of conventional waste fraction oil hydrogenation catalysts, after redispersing the active metal with a solvent, it is usually only dried at low temperature without high-temperature calcination. This is because the catalyst treated by the conventional regeneration method is still reused in the fraction oil hydrogenation reaction, and its reaction conditions are relatively milder. Low-temperature drying treatment is beneficial to improving the catalyst activity. However, the purpose of the present invention is to apply the regenerated waste fraction oil hydrogenation catalyst to heavy oil / residue oil hydrogenation reaction, where the reaction temperature and pressure are higher and the properties of the reaction raw materials are worse. The inventors found in the research that by combining low-temperature heat treatment and high-temperature heat treatment, the activity and stability of the fraction oil hydrogenation catalyst under harsh reaction conditions can be improved.

[0055] 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 elaborated here.

[0056] Preferably, the conditions of the low-temperature heat treatment include: the temperature is 80 - 150 °C, for example, it can be 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C and other typical but non-limiting temperatures or the range between any two of them; the time is 3 - 6 hours, for example, it can be 3 h, 4 h, 5 h, 6 h, etc.

[0057] Preferably, the conditions of the high-temperature heat treatment include: the temperature is 351 - 520 °C, for example, it can be 351 °C, 355 °C, 360 °C, 380 °C, 400 °C, 420 °C, 450 °C, 480 °C, 500 °C, 520 °C and other typical but non-limiting temperatures or the range between any two of them; the time is 2 - 8 hours. Adopting the above preferred implementation mode is beneficial to further improving the activity of the treated hydrogenation catalyst.

[0058] The second aspect of the present invention provides a hydrogenation catalyst obtained by the treatment method of the above waste hydrogenation catalyst.

[0059] Preferably, based on the total weight of the fresh catalyst corresponding to the hydrogenation catalyst, calculated as oxides, the content of the active metal component in the hydrogenation catalyst is not less than 20 wt%; based on the total weight of the hydrogenation catalyst, calculated as oxides, the content of the deposited impurities is not higher than 1.8 wt%.

[0060] In the present invention, "based on the total weight of the fresh catalyst corresponding to the hydrocatalyst" means that the content of the active metal component is calculated based on the fresh catalyst, that is, the deposited impurities and carbon in the catalyst are not included in the total amount.

[0061] The hydrocatalyst obtained by the treatment method of the present invention is used in the heavy oil and / or residue oil hydrotreating process and has high desulfurization performance.

[0062] According to the present invention, preferably, the specific surface area of the hydrocatalyst is 50 - 250 m 2 / g, the pore volume is 0.25 - 1.4 mL / g, and the most probable pore diameter is 6 - 15 nm. Further preferably, the specific surface area of the hydrocatalyst is 70 - 220 m 2 / g, the pore volume is 0.3 - 1.2 mL / g, and the most probable pore diameter is 8 - 15 nm. In the above preferred cases, it is beneficial to further improve the activity and stability of the catalyst for heavy oil / residue oil hydrocracking reaction.

[0063] The third aspect of the present invention provides the application of the above-mentioned hydrocatalyst in heavy oil and / or residue oil hydrotreating.

[0064] The hydrocatalyst provided by the present invention is applicable to the treatment of various heavy oils and residue oils. In the present 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. "Heavy oil" refers to a heavy raw material oil blended from components such as residue oil and coker gas oil. Among them, the "crude oil" refers to natural petroleum extracted from underground, which is a liquid mineral product mainly composed of hydrocarbons. The sulfur content and carbon residue content in heavy oil and / or residue oil are relatively high. For example, the sulfur content in heavy oil and / or residue oil is at least 1 wt%, and the carbon residue content is at least 8 wt%.

[0065] Compared with distillate oil, the molecular weight of compounds in heavy oil and / or residue oil raw materials is higher, the molecular size is larger, and the reaction conditions are more severe. The active centers of the hydrocatalyst obtained by the treatment method provided by the present invention have high accessibility to macromolecular compounds in heavy oil and / or residue oil, and the activity stability of the catalyst under severe reaction conditions is high. Therefore, the spent distillate oil hydrocatalyst can be directly applied to the heavy oil and / or residue oil hydrocracking reaction after regeneration.

[0066] The present invention does not particularly limit the heavy oil and / or residue oil hydrotreating conditions. Preferably, the heavy oil and / or residue oil hydrotreating conditions include: the temperature is 330 - 430 °C, the hydrogen partial pressure is 10 - 20 MPa, the liquid hourly space velocity is 0.1 - 1 h -1 , and the hydrogen-oil volume ratio is 500 - 1200.

[0067] Further preferably, the heavy oil and / or residue hydrotreating conditions include: a temperature of 350 - 400 °C, a hydrogen partial pressure of 12 - 17 MPa, a liquid hourly space velocity of 0.2 - 0.8 h -1 , and a hydrogen-oil volume ratio of 500 - 1000.

[0068] According to the present invention, preferably, before performing the heavy oil and / or residue hydrotreating, it further includes a step of sulfiding the regenerated catalyst. The sulfiding treatment can be carried out by conventional treatment methods and conditions in the art, and the present invention has no particular limitation thereon.

[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 by the low-temperature nitrogen adsorption method.

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

[0072] The carbon content was measured by a carbon-sulfur analyzer after the catalyst was extracted with toluene, and the deposited impurity content was determined by X-ray fluorescence spectrometry after the catalyst was calcined in air at 600 °C for 3 hours.

[0073] Example 1

[0074] 1) Take an industrial deactivated diesel hydrotreating catalyst (carbon content 8.72 w%, iron, sodium and other deposited impurity content 6.5 w%, this catalyst is NiMo / Al2O3, based on the total amount of the fresh catalyst corresponding to the waste hydrotreating catalyst, in terms of oxides, the content of Ni is 4.1 w%, and the content of Mo is 26.3 w%), called deactivator A. Sieve it to obtain deactivator A with a particle size of 16 - 20 mesh. Put it into a muffle furnace and carry out carbon burning treatment in an air atmosphere in a programmed temperature rising manner, including: keeping it at a constant temperature of 240 °C for 1 hour, at a constant temperature of 330 °C for 2 hours, and at a constant temperature of 410 °C for 3 hours to obtain catalyst B;

[0075] 2) At room temperature, under a stirring rate of 100 rpm, use a 1.2 mol / L 1,3-propanediol aqueous solution to perform the first washing on the catalyst B obtained in step 1). The volume of the 1,3-propanediol aqueous solution used is 4 times the volume of the catalyst, and the soaking time is 2 hours, and then solid-liquid separation is carried out;

[0076] 3) At room temperature, use deionized water to perform the second washing on the solid product obtained in step 2). The volume of the deionized water used is 3.5 times the volume of the solid, and the soaking time is 1.5 hours, and then solid-liquid separation is carried out;

[0077] 4) Heat-treat the above leached product. First, perform low-temperature heat treatment at 110 °C for 4 hours in an air atmosphere, denoted as catalyst C; then heat-treat catalyst C at 400 °C for 4 hours in an air atmosphere to obtain catalyst D.

[0078] Example 2

[0079] 1) Obtain catalyst B according to the method of Example 1;

[0080] 2) At room temperature, under a stirring rate of 150 rpm, perform the first leaching of catalyst B obtained in step 1) with a 0.8 mol / L aqueous solution of 1,3-propanediol. The volume of the 1,3-propanediol aqueous solution used is 5 times the volume of the catalyst, and the soaking time is 3 hours. Then perform solid-liquid separation;

[0081] 3) At room temperature, perform the second leaching of the solid product obtained in step 2) with ethanol. The volume of ethanol used is 4 times the volume of the solid, and the soaking time is 2 hours. Then perform solid-liquid separation;

[0082] 4) Heat-treat the above leached product. First, perform low-temperature heat treatment at 100 °C for 3 hours in an air atmosphere, and then heat-treat at 410 °C for 3 hours in an air atmosphere to obtain catalyst E.

[0083] Example 3

[0084] 1) Obtain catalyst B according to the method of Example 1;

[0085] 2) At room temperature, under a stirring rate of 35 rpm, perform the first leaching of catalyst B obtained in step 1) with a 0.1 mol / L aqueous solution of 1,3-propanediol. The volume of the 1,3-propanediol aqueous solution used is 0.9 times the volume of the catalyst, and the soaking time is 12 minutes. Then perform solid-liquid separation;

[0086] 3) At room temperature, perform the second leaching of the solid product obtained in step 2) with deionized water. The volume of deionized water used is 2 times the volume of the solid, and the soaking time is 5 minutes. Then perform solid-liquid separation to obtain the leached product;

[0087] 4) Heat-treat the above leached product according to the same method as in Example 1 to obtain catalyst F.

[0088] Example 4

[0089] 1) Obtain catalyst B according to the method of Example 1;

[0090] 2) At room temperature, under the condition that the stirring rate is 300 rpm, the catalyst B obtained in step 1) is first washed with an aqueous solution of 1,3-propanediol with a concentration of 4 mol / L. The volume of the aqueous 1,3-propanediol solution used is 7 times the volume of the catalyst, and the soaking time is 9 hours. Then, solid-liquid separation is carried out;

[0091] 3) At room temperature, the solid product obtained in step 2) is secondarily washed with deionized water. The volume of the deionized water used is 6 times the volume of the solid, and the soaking time is 4 hours. Then, solid-liquid separation is carried out to obtain the washed product;

[0092] 4) The above-mentioned washed product is heat-treated in the same manner as in Example 1 to obtain catalyst G.

[0093] Example 5

[0094] Take an industrially deactivated diesel hydrogenation catalyst (carbon content 8.72 w%, deposition impurities such as iron and sodium content 6.5 w%, this catalyst is NiMo / Al2O3, based on the total amount of the fresh catalyst corresponding to the waste hydrogenation catalyst, in terms of oxides, the content of Ni is 4.1 w%, and the content of Mo is 26.3 w%), called deactivator A. It is sieved to obtain deactivator A with a mesh size of 16 - 20. It is placed in a muffle furnace and carbon burning and pore expansion treatment are carried out in an air atmosphere in a programmed temperature rise manner, including: stage (1) maintaining a constant temperature of 250 °C for 1 hour, maintaining a constant temperature of 350 °C for 2 hours, and then carrying out stage (2) maintaining a constant temperature of 650 °C for 2 hours to obtain catalyst H;

[0095] The first washing, second washing and heat treatment are carried out in the same manner as in Example 1 to obtain catalyst I.

[0096] Example 6

[0097] 1) Catalyst B is obtained according to the method of Example 1;

[0098] 2) At room temperature, under a stirring rate of 150 rpm, the catalyst B obtained in step 1) is first washed with an aqueous solution of ethylene glycol with a concentration of 0.8 mol / L. The volume of the aqueous ethylene glycol solution used is 5 times the volume of the catalyst, and the soaking time is 3 hours. Then, solid-liquid separation is carried out;

[0099] The second washing and heat treatment are carried out in the same manner as in Example 1 to obtain catalyst J.

[0100] Comparative Example 1 (conventional regeneration method)

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

[0102] 2) Prepare an aqueous solution of 1,3 - propanediol, impregnate catalyst B by the equal - volume saturation impregnation method, and place it in a closed container at room temperature (25 °C) for 3 hours. Among them, the mass ratio of catalyst B to 1,3 - propanediol is 8.6. Then, dry it in an air atmosphere at 120 °C for 4 hours to obtain catalyst K.

[0103] Comparative Example 2

[0104] 1) Obtain catalyst H according to the method of Example 5;

[0105] 2) Prepare an aqueous solution of 1,3 - propanediol, impregnate catalyst H by the equal - volume saturation impregnation method, and place it in a closed container at room temperature (25 °C) for 3 hours. Among them, the mass ratio of catalyst H to 1,3 - propanediol is 8.6. Then, dry it in an air atmosphere at 120 °C for 4 hours to obtain catalyst L.

[0106] Table 1

[0107]

[0108] Table 1 lists the basic physical and chemical properties of catalysts A - L respectively. The deactivator A has a high carbon content and a high content of deposited impurities, the reaction pores are blocked, and the pore volume and the most probable pore diameter are relatively small. It can be seen from the comparison between the examples and deactivator A that the carbon content of the catalyst treated by the method provided by the present invention decreases, and the pore volume and the most probable pore diameter increase significantly. On this basis, after selectively removing the deposited impurities and some aggregated low - activity metal components, the pore volume and the most probable pore diameter of catalysts C, D, and E further increase. In addition, if the removal ratio of the deposited impurities is too small, such as catalyst F, it is difficult to further improve the pore volume and the most probable pore diameter of the catalyst; if the removal ratio of the deposited impurities is too large, such as catalyst G, some of the active metal components in the catalyst will also be removed.

[0109] Test Example

[0110] This test example is used to measure the residue hydrotreating performance of the above - mentioned hydro - genation catalysts. The residue hydrodesulfurization catalyst (NiMo / Al2O3 developed by the Research Institute of Petroleum Processing, SINOPEC, with the content of Ni being 3.0 w% and the content of Mo being 15.4 w% in terms of oxides) is used as the reference agent for the evaluation test. Specifically, the hydro - genation catalysts obtained in the above - mentioned examples and comparative examples are subjected to in - reactor sulfidation treatment on a heavy - oil hydro - genation fixed - bed reactor, and then the atmospheric residue of imported crude oil from the Middle East (whose properties are listed in Table 2) is used as the raw material for evaluation to compare the desulfurization performance of different catalysts. The loading amount of the hydro - genation catalyst is 120 mL; sulfidation conditions: the sulfiding agent is kerosene containing 2 wt% dimethyl disulfide, the sulfidation temperature is 320 °C, the sulfidation time is 5 h, the hydrogen partial pressure is 14.0 MPa, and the liquid hourly space velocity is 1.2 h -1, a hydrogen-oil volume ratio of 400:1; evaluation conditions: reaction temperature 380 °C, hydrogen partial pressure 14 MPa, liquid hourly space velocity 0.5 h -1 , a hydrogen-oil volume ratio of 600:1. The results of the reaction for 24 h are listed in Table 3.

[0111] Among them, the specific calculation method of the desulfurization rate is as follows:

[0112]

[0113] Table 2

[0114]

[0115]

[0116] Table 3 Catalyst Evaluation Results

[0117] Catalyst number Desulfurization rate / % C 82.6 D 87.8 E 87.3 F 80.8 G 72.7 I 84.9 J 86.0 K 70.7 L 72.3 Reference agent 85.7

[0118] It can be seen from the results in Table 3 that, compared with the conventional regeneration method, the treatment method provided by the present invention for treating waste hydrotreating catalysts and applying them to residue hydrotreating reactions also has good hydrodesulfurization effects. The hydrodesulfurization activities of catalysts D and E obtained by using the method provided by the present invention are higher than those of the reference agent. By comparing catalysts D, F, and G, it can be seen that under preferred conditions, by controlling the leaching conditions, it is beneficial to further improve the activity of the treated catalyst.

[0119] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the technical concept scope of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A method for treating waste hydrogenation catalysts, the method comprising: 1) Under an oxygen-containing atmosphere, subjecting the waste hydrogenation catalyst to carbon burning treatment; The most probable pore diameter of the waste hydrogenation catalyst is greater than 4 nm; 2) Mixing a first leaching agent with the solid product obtained in step 1) for first leaching; the first leaching agent includes polyhydric alcohol; 3) Mixing the solid product obtained from the first leaching with a second leaching agent for second leaching to obtain a leached product; the second leaching agent is water and / or ethanol; 4) Under an oxygen-containing atmosphere, subjecting the leached product to low-temperature heat treatment and high-temperature heat treatment, the conditions of the low-temperature heat treatment including: temperature of 50 - 180 °C, time of 2 - 10 hours, and the conditions of the high-temperature heat treatment including: temperature of 320 - 580 °C, time of 1 - 10 hours.

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

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

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

5. The processing method according to any one of claims 1-4, wherein, The conditions of the low-temperature heat treatment include: temperature of 80 - 150 °C, time of 3 - 6 hours; And / or, the conditions of the high-temperature heat treatment include: temperature of 351 - 520 °C, time of 2 - 8 hours.

6. The processing method according to any one of claims 1-5, 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; Preferably, the specific surface area of the spent hydrogenation catalyst is 20-180 m 2 / g, the pore volume is 0.1-0.7 mL / g, and the most probable pore diameter is 4.1-8 nm; Further preferably, the specific surface area of the spent hydrogenation catalyst is 30-150 m 2 / g, the pore volume is 0.21-0.5 mL / g, and the most probable pore diameter is 4.1-6 nm.

7. The processing method according to any one of claims 1-6, wherein Based on the total weight of the waste hydrogenation catalyst, the carbon content of the waste hydrogenation catalyst is less than 20 wt%, and the deposited impurity content is less than 15 wt%. Preferably, the carbon content of the waste hydrogenation catalyst is less than 12 wt%, and the deposited impurity content is less than 8 wt%; Preferably, the spent hydrotreating catalyst comprises a carrier and an active metal component supported on the carrier, and the active metal component comprises molybdenum and / or tungsten and nickel and / or cobalt; more preferably, based on the total amount of the fresh catalyst corresponding to the spent hydrotreating catalyst, calculated as oxides, the content of molybdenum and / or tungsten is 10-40% by weight, and the content of nickel and / or cobalt is 1.5-8% by weight.

8. A hydrotreating catalyst obtained by the method for treating the spent hydrotreating catalyst according to any one of claims 1-7; Preferably, based on the total amount of the fresh catalyst corresponding to the hydrotreating catalyst, calculated as oxides, the content of the active metal component in the hydrotreating catalyst is not less than 20 wt%; based on the total weight of the hydrotreating catalyst, calculated as oxides, the content of the deposited impurities in the hydrotreating catalyst is not higher than 1.8 wt%.

9. The hydrogenation catalyst according to claim 8, wherein, The specific surface area of the catalyst is 50-250 m 2 / g, the pore volume is 0.25-1.4 mL / g, and the most probable pore diameter is 6-15 nm; Preferably, the specific surface area of the catalyst is 70 - 220 m 2 / g, the pore volume is 0.3 - 1.2 mL / g, and the most probable pore diameter is 8 - 15 nm.

10. Use of the hydrotreating catalyst according to claim 8 or 9 in the hydrotreating of heavy oil and / or residue oil.

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