Regeneration method of waste hydrogenation catalyst, hydrogenation catalyst obtained through regeneration and application of hydrogenation catalyst

Abstract

The invention relates to the field of hydrogenation catalysts, and discloses a regeneration method of a waste hydrogenation catalyst, the hydrogenation catalyst obtained through regeneration and application of the hydrogenation catalyst, and the method comprises the following steps: 1) in an oxygen-containing atmosphere, carrying out charking treatment on the waste hydrogenation catalyst; (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) in an oxygen-containing atmosphere, the immersion cleaning product is subjected to high-temperature activation, the high-temperature activation temperature ranges from 600 DEG C to 800 DEG C, and the time ranges from 1 h to 10 h. The method can effectively remove deposited carbon and deposited impurities in the waste hydrogenation catalyst, ensures high active metal component content, forms the hydrogenation catalyst with a specific spinel structure, is applied to residual oil hydrotreatment, and has high desulfurization rate and stability.

Description

Technical Field

[0001] The present invention relates to hydrogenation catalyst treatment, and in particular to a method for regenerating a spent hydrogenation catalyst, the regenerated 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] CN105944735A discloses a method for activating a Type II hydrogenation catalyst deactivated by carbon deposition. The method includes first charring the deactivated Type II hydrogenation catalyst to obtain a hydrogenation catalyst with a carbon content of 0.3%-1.0%. The hydrogenation catalyst with a carbon content of 0.3%-1.0% is then saturated with an activation solution for 40-60 minutes, then cured at a temperature of 60-70°C for 8-24 hours. Finally, the catalyst is dried at a temperature of 60-150°C for 6-8 hours to obtain an activated hydrogenation catalyst. This activation method has the advantages of good activation effect and simple operation.

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

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

[0006] If these waste fractionated oil hydrogenation catalysts that cannot be regenerated conventionally can be treated by special methods and then applied to the heavy oil and / or residue oil hydrogenation reaction process to replace part of the heavy oil and / or residue oil hydrodesulfurization catalysts, realizing the cascade utilization of waste fractionated oil hydrogenation catalysts, the procurement cost of existing heavy oil and / or residue oil hydrogenation catalysts can be reduced. At the same time, the problem of recycling and treating waste fractionated oil hydrogenation 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 problems of insufficient catalytic activity and poor stability in the application of the regenerated fractionated oil hydrogenation catalyst in the residue oil hydrodesulfurization reaction in the prior art, and to provide a regeneration method for waste hydrogenation catalysts, the hydrogenation catalyst obtained by regeneration and its application. The hydrogenation catalyst obtained by this regeneration method has higher activity and stability.

[0008] In the research process, the inventors of the present invention found that when the regenerated catalyst obtained by using the existing recovery and treatment method of waste fractionated oil hydrogenation catalyst is reused in the fractionated oil hydrogenation treatment process, after 1-2 times of regeneration and use, it is difficult to meet the requirements of the fractionated 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 discharged catalyst can only be treated as hazardous waste. The high cost of waste catalyst treatment and the great environmental protection pressure have become problems that plague the industry. The inventors of the present invention changed their thinking and treated the waste fractionated oil hydrogenation catalyst that does not have conventional regeneration conditions by special methods and used it in the heavy oil and / or residue oil hydrogenation process where the requirements for the catalyst are slightly lower. Compared with fractionated oil, the molecular weight of compounds in heavy oil and / or residue oil raw materials is higher, the molecular size is larger, and the reaction conditions are more severe. Therefore, it is necessary to increase the accessibility of the catalyst active center to the macromolecular compounds in heavy oil and / or residue oil, improve the diffusion performance of the catalyst pores, and improve the activity and stability of the catalyst under severe reaction conditions. However, the regenerated agent obtained by the conventional regeneration method of waste fractionated oil hydrogenation catalyst cannot meet the requirements of heavy oil and / or residue oil hydrogenation reaction.

[0009] To achieve the above object, on the one hand, the present invention provides a regeneration method for waste hydrogenation catalysts, which includes:

[0010] 1) Under an oxygen-containing atmosphere, the waste hydrogenation catalyst is subjected to carbon burning treatment;

[0011] 2) Mix the first leaching agent with the solid product obtained in step 1) and perform the first leaching; the first leaching agent includes polyols;

[0012] 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;

[0013] 4) Under an oxygen-containing atmosphere, subject the leached product to high-temperature activation, where the temperature of the high-temperature activation is 600 - 800 °C and the time is 1 - 10 hours.

[0014] The second aspect of the present invention provides a hydrogenation catalyst regenerated by the regeneration method of the above-mentioned waste hydrogenation catalyst.

[0015] Preferably, based on the total weight of the fresh catalyst corresponding to the hydrogenation catalyst, in terms of oxides, the content of the active metal in the hydrogenation catalyst is not less than 18%; based on the total weight of the hydrogenation catalyst, in terms of oxides, the content of the deposited impurities in the hydrogenation catalyst is not higher than 2%; when the catalyst is measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbances at 630 nm and 500 nm are F 630 and F 500 , and the ratio Q of the two is Q = F 630 / F 500 is 1.3 - 3, preferably 1.4 - 2.8.

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

[0017] During the regeneration process of conventional waste distillate oil hydrogenation catalysts, after redispersing the active metal with a solvent, drying is usually only carried out at a 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, and its reaction conditions are relatively milder. Low-temperature drying treatment is beneficial to improving the catalyst activity. However, in the present invention, by subjecting the waste hydrogenation catalyst to carbon burning and leaching treatments and carrying out high-temperature activation at a specific temperature, the prepared hydrogenation catalyst has a specific spinel structure.

[0018] In the prior art, it is generally considered that the spinel structure formed in the catalyst will affect the initial activity of the catalyst. However, the inventors of the present invention have found that forming an appropriate amount of spinel structure will not only not have too much impact on the total activity of the catalyst, but also as the catalyst participates in the reaction process, the formed spinel structure will gradually release the reaction activity, making the activity stability of the catalyst better. Thus, on the premise of meeting the basic activity requirements, the service life of the catalyst is greatly improved, and the production efficiency is increased.

[0019] The hydrogenation catalyst regenerated by the regeneration method of the waste hydrogenation catalyst provided by the present invention has better hydrogenation 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 spent fraction oil hydrogenation catalyst is treated by the regeneration method provided by the present invention and applied to the heavy oil and / or residue oil hydrogenation reaction process to replace part of the heavy oil and / or residue oil hydrodesulfurization catalyst, the cascade utilization of the spent fraction oil hydrogenation catalyst can be realized, the procurement cost of the existing heavy oil and / or residue oil hydrodesulfurization catalyst can be reduced, and at the same time, the problem of the recovery and treatment of the spent fraction oil hydrogenation catalyst can be solved, and obvious social and economic benefits can be created. Detailed Embodiments

[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 regeneration method for a spent hydrogenation catalyst, the method comprising:

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

[0024] 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;

[0025] 3) Mix the solid product obtained from the first leaching with the second leaching agent and perform the second leaching to obtain a leaching product; the second leaching agent is water and / or ethanol;

[0026] 4) Under an oxygen-containing atmosphere, subject the leaching product to high-temperature activation, the temperature of the high-temperature activation is 600 - 800 °C, and the time is 1 - 10 hours.

[0027] The inventors of the present invention have found that by first subjecting the spent hydrogenation catalyst to carbon burning treatment, then sequentially performing the first leaching and the second leaching, and then subjecting the second leaching product to high-temperature activation, the carbon deposits and deposited impurities in the spent hydrogenation catalyst can be effectively removed, and at the same time, a high content of active metal components can be maintained in the prepared hydrogenation catalyst, forming a hydrogenation catalyst with a specific spinel structure. The hydrodesulfurization catalyst obtained thereby has a high desulfurization rate and stability when applied to residue oil hydrotreating. If the activation temperature is too low or the activation time is too short, the spinel content in the treated catalyst is too low, and the improvement effect of the hydrogenation activity and stability of the active components in the treated hydrogenation catalyst is not obvious; if the activation temperature is too high or the activation time is too long, the spinel content in the treated hydrogenation catalyst is too high, which affects the initial hydrogenation activity of the catalyst.

[0028] In the prior art, it is generally believed that the spinel structure formed in the catalyst will affect the initial activity of the catalyst. However, the inventors of the present invention have found that forming an appropriate amount of spinel structure will not only not have too much impact on the total activity of the catalyst, but also as the reaction process of the catalyst extends, the formed spinel structure will gradually release the reaction activity, making the activity stability of the catalyst better. Therefore, on the premise of meeting the basic activity requirements, the service life of the catalyst is greatly improved, and the production efficiency is increased.

[0029] 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 the discarded hydrotreating catalyst that cannot meet the hydrotreating activity requirements even after being regenerated by existing means after long-term cyclic use, and the hydrotreating catalyst that has been used but 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 particular limitation thereto. According to a specific embodiment of the present invention, the spent hydrotreating catalyst of the present invention includes, but is not limited to, at least one of a spent gasoline hydrotreating catalyst, a spent diesel hydrotreating catalyst, a spent kerosene hydrotreating catalyst, and a spent wax oil hydrotreating catalyst. The embodiments of the present invention are exemplarily described by taking the spent diesel hydrotreating catalyst as an example.

[0030] According to the present invention, preferably, the spent hydrotreating catalyst includes a carrier and an active metal component supported on the carrier, and the active metal component includes molybdenum and / or tungsten and nickel and / or cobalt.

[0031] The present invention has a relatively wide selection range for the contents of molybdenum and / or tungsten and nickel and / or cobalt, and those skilled in the art can make appropriate adjustments according to the actual situation. Further preferably, based on the total amount of the fresh catalyst corresponding to the 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. The conventional selection ranges of the active metal components molybdenum and / or tungsten and nickel and / or cobalt in the spent gasoline hydrotreating catalyst, the spent diesel hydrotreating catalyst, the spent kerosene hydrotreating catalyst, and the spent wax oil hydrotreating catalyst may vary, and those skilled in the art can make selections according to conventional means, and the present invention will not elaborate herein one by one.

[0032] The composition of the spent hydrotreating catalyst is determined by X-ray fluorescence spectrometry (XRF), and the specific method is shown in the petrochemical analysis method RIPP133-90.

[0033] It should be noted that in addition to the carrier and the active metal components supported on the carrier, the spent hydrotreating catalyst also includes impurities and carbon deposited through long-term cyclic use. The phrase "based on the total amount of the fresh catalyst corresponding to the spent hydrotreating catalyst" 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 spent hydrotreating catalyst has characteristics such as high carbon deposition and / or high contents 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 spent hydrotreating catalyst. Generally, the carbon content and the content of deposited impurities of the fresh catalyst are both basically 0, while the carbon content of the spent hydrotreating catalyst can be as high as 30 wt%, and the content of deposited impurities can be as high as 20 wt%.

[0034] According to a preferred embodiment of the present invention, based on the total weight of the spent hydrotreating catalyst, the carbon content of the spent hydrotreating catalyst is less than 30 wt%, and the content of deposited impurities is less than 20 wt%. Preferably, the carbon content of the spent hydrotreating catalyst is less than 15 wt%, and the content of deposited impurities is less than 10 wt%. More preferably, the carbon content of the spent hydrotreating catalyst is 5 - 13 wt%, and the content of deposited impurities is 1 - 8 wt%.

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

[0036] The regeneration method of spent hydrotreating catalysts provided by the present invention has excellent treatment effects on spent hydrotreating catalysts with high carbon deposition and high deposited impurity content. Among the existing regeneration means, 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. For example, CN111821998A discloses impregnating the carbon-burned catalyst with organic alcohols, organic acids, organic amines and organic ammonium salts of C1-C20, and CN111822060A discloses two-stage carbon burning and pore expansion, and then impregnating with a solution containing a phosphorus compound. The purpose of both is to carry out redispersion of the active phase to improve the dispersion degree of active metals. However, the inventors of the present invention have found that although this saturated or unsaturated impregnation method can improve the dispersion degree of the active phase, it cannot remove the inactive deposited impurities in the spent hydrotreating catalyst. Compared with the existing treatment methods, the treatment method provided by the present invention can not only effectively remove carbon deposits 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] According to the regeneration method of the spent hydrotreating catalyst of the present invention, this method is particularly suitable for spent hydrotreating catalysts with small pore volume and pore diameter, because in addition to improving the activity stability of the catalyst, the high-temperature activation step of this method also has the effect of pore expansion. Preferably, the specific surface area of the spent hydrotreating catalyst is 30-300m 2 / g, the pore volume is 0.05-0.3 mL / g, and the most probable pore diameter is greater than 1 nm; further preferably, the specific surface area of the spent hydrotreating catalyst is 50-200m 2 / g, the pore volume is 0.05-0.2 mL / g, and the most probable pore diameter is 1.5-4 nm.

[0038] 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.

[0039] The inventors of the present invention have found that, preferably, the hydrotreating catalyst obtained by treating the spent hydrotreating catalyst conforming to the above physical and chemical characteristics has higher desulfurization performance when used in heavy oil and / or residue hydrotreating.

[0040] The inventors of the present invention also found that using waste hydrotreating catalysts with a particle size of 10 - 30 mesh, preferably 14 - 20 mesh, and more preferably 16 - 20 mesh can further improve the desulfurization performance of the obtained hydrotreating catalysts. The waste hydrotreating catalysts that meet the above - preferred particle size requirements can be obtained by screening the waste hydrotreating catalysts before use. Therefore, preferably, before step 1) of the method provided by the present invention, screening treatment of the waste hydrotreating catalysts is also included.

[0041] For waste hydrotreating catalysts with a smaller pore volume and pore diameter, on the basis of conventional carbon - burning treatment, high - temperature pore - expanding treatment is also required to further increase the pore volume and pore diameter of the catalyst, thereby improving the performance of the regenerated catalyst. However, the inventors of the present invention found in their research that in addition to improving the catalytic activity stability, the high - temperature activation step of this method also has the effect of pore expansion. Therefore, in the present invention, the step 1) does not include pore - expanding treatment, which is more conducive to weakening the interaction between the metal and the support on the catalyst, and thus improving the subsequent leaching effect to a certain extent. In this case, by carbon - burning treatment, leaching, and high - temperature activation of the waste hydrotreating catalyst, the hydrogenation activity and stability of the regenerated hydrotreating catalyst can be improved. There is no need for additional pore - expanding treatment in this regeneration method, which simplifies the treatment process while ensuring the performance of the treated hydrotreating catalyst.

[0042] In the present invention, there is no particular limitation on the specific manner of the carbon - burning treatment in step 1), as long as it can remove the carbon deposits on the waste hydrotreating catalyst, and it can be carried out in a conventional manner in the art, which is well - known to those skilled in the art. To further improve the catalytic activity of the regenerated hydrotreating catalyst, preferably, in step 1), the conditions of the carbon - burning treatment include: the temperature is 200 - 550 °C, preferably 220 - 450 °C; the time is 1 - 10 hours, preferably 2 - 7 hours.

[0043] 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 - 3,40 °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.

[0044] According to the present invention, in step 1), the oxygen-containing atmosphere provides oxygen for the carbon burning treatment of the spent hydrogenation catalyst. The present invention has a relatively wide selection range for the oxygen content in the oxygen-containing atmosphere. For example, in the oxygen-containing atmosphere, the volume content of oxygen can be 8-30%, preferably 10-25%. According to different requirements for the oxygen content of the oxygen-containing atmosphere, the present invention can provide the oxygen-containing atmosphere by different methods. For example, the oxygen-containing atmosphere can be provided by air. When a higher oxygen content of the oxygen-containing atmosphere is required, the oxygen-containing atmosphere can be provided by air and oxygen together. When a lower oxygen content of the oxygen-containing atmosphere is required, the oxygen-containing atmosphere can be provided by air and an inert atmosphere (such as nitrogen) together. In the examples of the present invention, the case of providing the oxygen-containing atmosphere by air is taken as an example for illustrative description. Providing the oxygen-containing atmosphere by air is more conducive to cost savings, but the present invention is not limited thereto.

[0045] In the present invention, the first leaching and the second leaching are sequentially performed after the carbon burning treatment, which can effectively remove the impurities deposited on the catalyst during the reaction process and some aggregated low-activity metal components, and further achieve the purpose of unclogging the pores and increasing the pore volume of the catalyst, which helps to further improve the desulfurization performance of the catalyst.

[0046] According to the present invention, the first leaching agent includes polyhydric alcohol, and the second leaching agent is water and / or ethanol. The combined synergistic leaching with the above leaching agents is more conducive to improving the desulfurization performance of the obtained hydrogenation catalyst.

[0047] To further improve the leaching effect, preferably, the general formula of the polyhydric alcohol is C n H 2n+2-x (OH) x , where n = 2-5 and x = 2-3. For example, the polyhydric alcohol is at least one of ethylene glycol, glycerol, and 1,3-propanediol.

[0048] According to a preferred embodiment of the present invention, the polyhydric alcohol is 1,3-propanediol. The inventors of the present invention found in the research that in the spent hydrogenation catalyst without high-temperature pore expansion, the interaction force between the metal and the carrier is relatively weak. For the spent hydrogenation catalyst without pore expansion treatment, the first leaching with the first leaching agent containing 1,3-propanediol can further improve the catalytic activity of the treated hydrogenation catalyst.

[0049] Preferably, the first leaching agent also contains water, and the concentration of the first leaching agent is 0.01-3 mol / L, preferably 0.01-1.5 mol / L. Within the above preferred concentration range, it helps to selectively remove the impurities deposited on the catalyst during the reaction process and the aggregated low-activity metal components. If the concentration of the first leaching agent is too high, the highly active metal components in the dispersed state on the catalyst may be overly removed.

[0050] According to the present invention, during the actual operation process, the leaching conditions can be adjusted according to the physical and chemical properties of the catalyst after carbon burning. The principle is to remove as many impurities and aggregated low-activity metal components deposited on the catalyst during the reaction process as possible, while retaining as many dispersed high-activity metal components on the catalyst as possible.

[0051] According to the present invention, preferably, in step 2), the volume ratio of the amount of the first leaching agent to the solid product obtained in step 1) is 1-6:1, preferably 3-6:1.

[0052] The first leaching and the second leaching can be carried out in a conventional manner. For example, the solid product is soaked in the leaching agent, and then solid-liquid separation is carried out. The solid-liquid separation can be carried out by conventional operations in the art, and the present invention has no particular limitation thereon.

[0053] Preferably, the time of the first leaching is 0.5-8 hours, preferably 1-4 hours. It can be understood that the time of the first leaching refers to the soaking time of the solid product in the first leaching agent.

[0054] According to the present invention, preferably, the first leaching is carried out under stirring conditions. Preferably, the stirring rate is 50-500 rpm, preferably 50-280 rpm. By adopting the above preferred implementation manner, it is beneficial to improve the effect of the first leaching and the catalytic activity of the treated hydrogenation catalyst.

[0055] According to the present invention, preferably, the volume ratio of the amount of the second leaching agent to the solid product obtained by the first leaching is 1-5:1, preferably 2.5-5:1.

[0056] Preferably, the time of the second leaching is 0.1-3 hours, preferably 0.5-3 hours. It can be understood that the time of the second leaching refers to the soaking time of the solid product obtained by the first leaching in the second leaching agent.

[0057] According to some specific embodiments of the present invention, the regeneration method further includes: drying the second leaching product, and then performing high-temperature activation. The present invention has no particular limitation on the specific conditions and operation methods of the drying, and conventional methods can be used as long as the residual second leaching agent in the second leaching product can be removed. For example, the drying temperature can be 70-200 °C, preferably 80-150 °C, and the time is 2-10 h, preferably 3-6 h.

[0058] According to the present invention, preferably, the temperature of the high-temperature activation is 610-780 °C, preferably 630-750 °C, more preferably 650-730 °C; and the time is 2-8 hours. Under the above-preferred conditions of high-temperature activation, an appropriate amount of spinel structure can be formed in the catalyst, which is beneficial to further improving the catalytic activity of the waste hydrogenation catalyst.

[0059] In the present invention, the high-temperature activation can be increased from the ambient temperature to the activation temperature, or directly increased from the drying temperature of the second leaching product to the activation temperature, and there is no particular limitation thereto. The present invention has a relatively wide selection range for the heating rate during the high-temperature activation. Preferably, the heating rate of the high-temperature activation is 50-600 °C / hour, preferably 100-550 °C / hour.

[0060] The second aspect of the present invention provides a hydrogenation catalyst regenerated by the regeneration method of the above-mentioned waste hydrogenation catalyst.

[0061] The inventors of the present invention found that by first performing carbon burning treatment on the waste hydrogenation catalyst, then performing first leaching and second leaching in sequence, and then performing high-temperature activation on the second leaching product, the carbon deposits and deposited impurities in the waste hydrogenation catalyst can be effectively removed, and at the same time, a relatively high content of active metal components can be maintained in the prepared hydrogenation catalyst, forming a hydrogenation catalyst with a specific spinel structure. As the catalyst participates in the reaction process, the formed spinel structure will gradually release the reaction activity, making the activity stability of the catalyst better, so that under the premise of meeting the basic activity requirements, the service life of the catalyst is greatly improved.

[0062] According to the present invention, preferably, based on the total weight of the fresh catalyst corresponding to the hydrogenation catalyst, in terms of oxides, the active metal content in the hydrogenation catalyst is not less than 18%; based on the total weight of the hydrogenation catalyst, in terms of oxides, the deposited impurity content in the hydrogenation catalyst is not higher than 2%; when the catalyst is measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbances at 630 nm and 500 nm are F 630 and F 500 , and the ratio Q of the two is Q = F 630 / F 500 is 1.3-3, preferably 1.4-2.8. Under this preferred embodiment, it is more beneficial to improve the hydrodesulfurization performance and stability of the hydrogenation catalyst. When the Q value is lower than 1, the improvement of activity stability is not obvious; when the Q value is greater than 3, the initial activity is too low, affecting the normal use of the catalyst. For example, the ratio Q of the two is Q = F 630 / F 500Specific ratios such as 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, or a range between two points. More preferably, Q = F 630 / F 500 is 1.7 - 2.2. In the above - preferred case, it is more conducive to improving the hydrodesulfurization performance and stability of the hydrogenation catalyst in the hydroprocessing of heavy oil and / or residue oil.

[0063] In the present invention, "based on the total weight of the fresh catalyst corresponding to the hydrogenation catalyst" 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.

[0064] According to the present invention, preferably, the specific surface area of the hydrogenation catalyst is 50 - 280 m 2 / g, the pore volume is 0.3 - 1.5 mL / g, and the most probable pore diameter is 6 - 16 nm; more preferably, the specific surface area of the hydrogenation catalyst is 80 - 250 m 2 / g, the pore volume is 0.21 - 1.2 mL / g, and the most probable pore diameter is 8 - 15 nm. In the above - preferred case, it is beneficial to further improve the activity and stability of the catalyst for heavy oil / residue oil hydrogenation reaction.

[0065] The third aspect of the present invention provides the application of the above - mentioned hydrogenation catalyst in the hydroprocessing of heavy oil and / or residue oil.

[0066] The hydrogenation catalyst 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 tower during crude oil distillation, including atmospheric residue oil and vacuum residue oil. "Heavy oil" refers to a heavy - quality feedstock 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%.

[0067] Compared with distillate oil, the molecular weight of compounds in heavy oil and / or residue oil feedstock is higher, the molecular size is larger, and the reaction conditions are more severe. The active centers of the hydrogenation catalyst obtained by the regeneration method provided by the present invention have high accessibility to macromolecular compounds in heavy oil and / or residue oil, and the catalyst has high activity stability under severe reaction conditions. Therefore, the spent distillate oil hydrogenation catalyst can be regenerated and directly applied to the heavy oil and / or residue oil hydrogenation reaction.

[0068] The present invention has no particular limitation on the hydrotreating conditions of the heavy oil and / or residue oil. Preferably, the hydrotreating conditions of the heavy oil and / or residue oil 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-to-oil volume ratio is 500 - 1200.

[0069] More preferably, the hydrotreating conditions of the heavy oil and / or residue oil include: the temperature is 350 - 400 °C, the hydrogen partial pressure is 12 - 17 MPa, the liquid hourly space velocity is 0.2 - 0.8 h -1 , and the hydrogen-to-oil volume ratio is 500 - 1000.

[0070] According to the present invention, preferably, before carrying out the hydrotreating of the heavy oil and / or residue oil, it further includes the 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.

[0071] The present invention will be described in detail below through examples.

[0072] In the following examples, the specific surface area, pore volume and most probable pore diameter are measured by the low-temperature nitrogen adsorption method.

[0073] The composition of the catalyst is determined by X-ray fluorescence spectrometry (XRF). The specific method is shown in the petrochemical analysis method RIPP133 - 90.

[0074] The carbon content 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.

[0075] The formation of the spinel structure in the catalyst is determined by ultraviolet-visible spectroscopy (DRUVS). The instrument uses the Cary300 ultraviolet-visible analyzer of Agilent Technologies, wavelength range: 190 nm - 1100 nm, wavelength accuracy: ±0.1 nm, wavelength reproducibility: ±0.1 nm, baseline stability: 0.0003 / h, stray light: below 0.02%, and photometer accuracy: ±0.003.

[0076] Example 1

[0077] 1) Take the industrially deactivated diesel hydrogenation catalyst (carbon content 10.67 w%, deposition impurities such as iron and sodium content 7.2 w%, this catalyst is NiMo / Al2O3, based on the total amount of fresh catalyst corresponding to the waste hydrogenation catalyst, in terms of oxides, the content of Ni is 4.6 w%, and the content of Mo is 27.8 w%), called deactivator A, sieve it to obtain deactivator A with a mesh size of 16 - 20, put it into a muffle furnace, and carry out carbon burning treatment in an air atmosphere in a programmed temperature rise manner, including: keep it at a constant temperature of 240 °C for 1 hour, keep it at a constant temperature of 330 °C for 2 hours, and keep it at a constant temperature of 410 °C for 3 hours to obtain catalyst B;

[0078] 2) At room temperature, under a stirring rate of 100 rpm, use a 1.2 mol / L aqueous solution of 1,3 - propanediol to carry out the first leaching of catalyst B obtained in step 1), where the volume of the 1,3 - propanediol aqueous solution used is 4 times the volume of the catalyst, the soaking time is 2 hours, and then carry out solid - liquid separation;

[0079] 3) At room temperature, use deionized water to carry out the second leaching of the solid product obtained in step 2), where the volume of the deionized water used is 3.5 times the volume of the solid, the soaking time is 1.5 hours, and then carry out solid - liquid separation, and dry it at 110 °C for 4 hours, denoted as catalyst C;

[0080] 4) Carry out high - temperature activation of catalyst C in an air atmosphere, and the conditions for high - temperature activation include: temperature is 650 °C, time is 3 hours, and the heating rate is 200 °C / h to obtain catalyst D.

[0081] Determine the formation of the spinel structure formed by the metal components and aluminum in catalyst D by ultraviolet - visible spectroscopy (DRUVS). The absorbance ratio Q = F630 / F500 at 630 nm and 500 nm is 1.94, indicating that a certain amount of spinel structure has been formed in the catalyst.

[0082] Example 2

[0083] 1) Obtain catalyst B according to the method of Example 1;

[0084] 2) At room temperature, under a stirring rate of 150 rpm, use a 0.8 mol / L aqueous solution of 1,3 - propanediol to carry out the first leaching of catalyst B obtained in step 1), where the volume of the 1,3 - propanediol aqueous solution used is 5 times the volume of the catalyst, the soaking time is 3 hours, and then carry out solid - liquid separation;

[0085] 3) At room temperature, use ethanol to carry out the second leaching of the solid product obtained in step 2), where the volume of the ethanol used is 4 times the volume of the solid, the soaking time is 2 hours, and then carry out solid - liquid separation, and dry it at 100 °C for 5 hours;

[0086] 4) Subject the product obtained in step 3) to high-temperature activation under an air atmosphere. The conditions for high-temperature activation include: temperature of 680 °C, time of 4 hours, and heating rate of 230 °C / h to obtain catalyst E.

[0087] Example 3

[0088] 1) Obtain catalyst B according to the method of Example 1;

[0089] 2) At room temperature, under the condition of a stirring rate of 35 rpm, perform the first leaching of the 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;

[0090] 3) At room temperature, perform the second leaching of the solid product obtained in step 2) with deionized water. The volume of the deionized water used is 2 times the volume of the solid, and the soaking time is 5 minutes. Then, perform solid-liquid separation and dry at 110 °C for 4 h;

[0091] 4) Subject the product obtained in step 3) to high-temperature activation under an air atmosphere. The conditions for high-temperature activation include: temperature of 650 °C, time of 3 hours, and heating rate of 200 °C / h to obtain catalyst F.

[0092] Example 4

[0093] 1) Obtain catalyst B according to the method of Example 1;

[0094] 2) At room temperature, under the condition of a stirring rate of 300 rpm, perform the first leaching of the catalyst B obtained in step 1) with a 4 mol / L aqueous solution of 1,3-propanediol. The volume of the 1,3-propanediol aqueous solution used is 7 times the volume of the catalyst, and the soaking time is 9 hours. Then, perform solid-liquid separation;

[0095] 3) At room temperature, perform the second leaching of the solid product obtained in step 2) 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, perform solid-liquid separation and then dry at 110 °C for 4 h;

[0096] 4) Subject the product obtained in step 3) to high-temperature activation under an air atmosphere. The conditions for high-temperature activation include: temperature of 650 °C, time of 3 hours, and heating rate of 200 °C / h to obtain catalyst G.

[0097] Example 5

[0098] According to the method in Example 1, except that the high-temperature activation temperature in step 4) is 630 °C, the time is 3 h, and the heating rate of activation is 200 °C / h, catalyst H is obtained.

[0099] Example 6

[0100] According to the method in Example 1, except that the high-temperature activation temperature in step 4) is 790 °C, the time is 3 h, and the heating rate of activation is 200 °C / h, catalyst I is obtained.

[0101] Comparative Example 1

[0102] 1) Catalyst B is obtained according to the method of Example 1;

[0103] 2) At room temperature, under a stirring rate of 100 rpm, catalyst B obtained in step 1) is soaked in a 2 mol / L aqueous solution of 1,3-propanediol, wherein the volume of the used aqueous solution of 1,3-propanediol is 4 times the volume of the catalyst, the soaking time is 2 hours, then solid-liquid separation is carried out, and drying is carried out at 110 °C for 4 h;

[0104] 3) The product obtained in step 2) is subjected to high-temperature activation in an air atmosphere. The conditions for high-temperature activation include: the temperature is 650 °C, the time is 3 hours, and the heating rate is 200 °C / h, to obtain catalyst J.

[0105] Comparative Example 2 (conventional regeneration method)

[0106] 1) Catalyst B is obtained according to the method of Example 1;

[0107] 2) An aqueous solution of 1,3-propanediol is prepared, and catalyst B is impregnated by the equal-volume saturation impregnation method, and sealed and placed at room temperature (25 °C) for 3 hours. Among them, the mass ratio of catalyst B to 1,3-propanediol is 8.6, and then after drying in an air atmosphere at 120 °C for 4 hours, catalyst K is obtained.

[0108] The physical and chemical properties of the catalysts prepared in the above examples and comparative examples are listed in Table 1.

[0109] Table 1

[0110]

[0111] Test Example

[0112] This test example is used to determine the residue hydrotreating performance of the above-mentioned hydrocatalyst. A residue hydrodesulfurization catalyst (NiMo / Al2O3, calculated as oxides, with Ni content of 3.0 w% and Mo content of 15.4 w%) developed by Research Institute of Petroleum Processing, SINOPEC is used as the reference agent for the evaluation test. Specifically, the hydrocatalysts obtained in the above-mentioned examples and comparative examples are subjected to in-situ sulfidation treatment in a fixed-bed heavy oil hydrogenation 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 hydrocatalyst 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 , and the hydrogen-oil volume ratio is 400:1; evaluation conditions: the reaction temperature is 380 °C, the hydrogen partial pressure is 14 MPa, and the liquid hourly space velocity is 0.5 h -1 , and the hydrogen-oil volume ratio is 600:1. The results are listed in Table 3.

[0113] Among them, the specific calculation method of the desulfurization rate is as follows:

[0114]

[0115] Table 2

[0116] Feedstock oil <![CDATA[Density (20 °C), kg / m 3 > 991.6 <![CDATA[Viscosity (100 °C) mm 2 / s]]> 153.2 Metal content, ppm Ni 26.0 V 82.9 Fe 10.0 Ca 4.1 Na 2.5 C m% 84.92 H m% 10.77 S m% 3.91 N m% 0.36 Carbon residue, m% 13.3

[0117] Table 3 Catalyst Evaluation Results

[0118]

[0119]

[0120] It can be seen from the results in Table 3 that, compared with the conventional regeneration method, the hydrodesulfurization activity of the catalyst obtained by the regeneration method provided by the present invention in the residue hydrotreating reaction is close to that of the reference example, and the activity stability after operating for 1000 hours is better. The results in Table 3 show that even for an industrially deactivated fraction oil hydrocatalyst with a high coke content and a high content of deposited impurities, after being treated by the method provided by the present invention and applied to the residue hydrotreating reaction, it also has good hydrodesulfurization effect.

[0121] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A method for regenerating a spent hydrogenation catalyst, the method comprising: 1) carbonizing the spent hydrogenation catalyst in an oxygen-containing atmosphere; 2) mixing a first leaching agent with the solid product obtained in step 1) and performing a first leaching; the first leaching agent comprises a polyol; 3) mixing the solid product obtained from the first leaching with a second leaching agent and performing a second leaching to obtain a leached product; the second leaching agent is water and / or ethanol; 4) subjecting the leached product to high-temperature activation in an oxygen-containing atmosphere, the temperature of the high-temperature activation being 600 - 800 °C and the time being 1 - 10 hours.

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

3. The regeneration 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 polyol is 1,3-propanediol; Preferably, the first leaching agent further contains water, and the concentration of the first leaching agent is 0.01 - 3 mol / L, preferably 0.01 - 1.5 mol / L.

4. The regeneration 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 regeneration method according to any one of claims 1-4, wherein, The temperature of the high-temperature activation is 610 - 780 °C, preferably 630 - 750 °C, more preferably 650 - 730 °C; the time is 2 - 8 hours; And / or, the heating rate of the high-temperature activation is 50 - 600 °C / hour, preferably 100 - 550 °C / hour.

6. The regeneration method according to any one of claims 1-5, wherein, The spent hydrogenation catalyst is selected from at least one of a spent gasoline hydrogenation catalyst, a spent diesel hydrogenation catalyst, a spent kerosene hydrogenation catalyst, and a spent wax oil hydrogenation catalyst; And / or, based on the total weight of the spent hydrogenation catalyst, the carbon content of the spent hydrogenation catalyst is less than 30 wt%, and the deposited impurity content is less than 20 wt%. Further preferably, the carbon content of the spent hydrogenation catalyst is less than 15 wt%, and the deposited impurity content is less than 10 wt%; Preferably, the specific surface area of the spent hydrogenation catalyst is 30-300 m 2 / g, the pore volume is 0.05-0.3 mL / g, and the most probable pore diameter is greater than 1 nm; More preferably, the specific surface area of the spent hydrogenation catalyst is 50-200 m 2 / g, the pore volume is 0.05-0.2 mL / g, and the most probable pore diameter is 1.5-4 nm; Preferably, the spent 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, the content of molybdenum and / or tungsten is 10-40% by weight and the content of nickel and / or cobalt is 1.5-8% by weight in terms of oxides.

7. A hydrotreating catalyst regenerated by the regeneration method of the spent hydrotreating catalyst according to any one of claims 1-6.

8. The hydrogenation catalyst according to claim 7, wherein Based on the total weight of the fresh catalyst corresponding to the hydrogenation catalyst, calculated as oxides, the active metal content in the hydrogenation catalyst is not less than 18 wt%; based on the total weight of the hydrogenation catalyst, calculated as oxides, the deposited impurity content in the hydrogenation catalyst is not higher than 2 wt%; when the catalyst is measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbances at 630 nm and 500 nm are F 630 and F 500 , and the ratio Q of the two is Q = F 630 / F 500 is 1.3 - 3, preferably 1.4 - 2.

8.

9. The hydrogenation catalyst according to claim 7 or 8, wherein The specific surface area of the hydrogenation catalyst is 50-280 m 2 / g, the pore volume is 0.3-1.5 mL / g, and the most probable pore diameter is 6-16 nm; Preferably, the specific surface area of the hydrogenation catalyst is 80 - 250 m 2 / g, the pore volume is 0.21 - 1.2 mL / g, and the most probable pore diameter is 8 - 15 nm.

10. Use of the hydrotreating catalyst according to any one of claims 7-9 in the hydrotreating of heavy oil and / or residue oil.

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