Treatment method of waste hydrogenation catalyst, hydrogenation catalyst, and hydrotreating method of heavy oil and / or residual oil

Abstract

The present invention relates to the technical field of waste catalyst treatment, and discloses a waste hydrogenation catalyst treatment method, a hydrogenation catalyst, and a heavy oil and / or residual oil hydrotreatment method, the method comprises: (1) in an oxygen-containing atmosphere, carrying out carbon burning treatment on the waste hydrogenation catalyst; (2) leaching part of metal in the catalyst obtained in the step (1) by adopting an acid solution to obtain a leaching solution and a leaching residual catalyst; (3) mixing the leachate with a vanadium removal agent, carrying out vanadium removal treatment, and then carrying out solid-liquid separation; (4) carrying out optional washing and drying on a solid-phase product obtained by solid-liquid separation, and then carrying out roasting treatment to obtain vanadium pentoxide of which the purity is not lower than 98%; and (5) dipping the liquid-phase product obtained by solid-liquid separation in the leaching residual catalyst obtained in the step (2), and then carrying out high-temperature activation treatment at 600-800 DEG C. The hydrogenation catalyst obtained by the treatment method has good demetallization performance and high desulfurization activity stability.

Description

Technical Field

[0001] This invention relates to the field of waste catalyst treatment technology, specifically to a method for treating waste hydrotreating catalysts, hydrotreating catalysts, and a method for hydrotreating heavy oil and / or residue oil. Background Technology

[0002] Fixed-bed residue hydrotreating is currently the most widely used residue processing technology. It provides high-quality, clean feedstock for subsequent residue conversion processes such as FCC and DCC, improving the yield and quality of light oils and chemical products. Maximizing the conversion of residue into clean light oils and chemical products is key to the efficient utilization of petroleum resources. However, during the reaction, large amounts of metallic impurities such as V and Ni in the residue gradually deposit on the catalyst surface, clogging pores and covering active sites, thus causing catalyst deactivation. On the one hand, because a large amount of impurities such as nickel and vanadium are deposited on the surface of the deactivated catalyst, it is difficult to reuse it through regeneration. Therefore, the discharged residue hydrotreating waste catalyst is usually treated as hazardous waste. High cost of waste catalyst treatment and significant environmental pressure have become a problem plaguing the industry, and the generation of hazardous catalyst waste is detrimental to the green and sustainable development of enterprises. On the other hand, the large amount of metal deposited in the deactivated catalyst is also difficult to effectively recover and utilize.

[0003] CN1921942A reports a method for regenerating a deactivated hydrotreating catalyst. First, the deactivated hydrotreating catalyst due to carbon deposition is subjected to carbonization treatment under certain conditions to obtain an intermediate catalyst with a carbon content of 0.5-2.5 wt%. Then, the carbonized catalyst is contacted and aged with a nitrogen-containing chelating agent solution. Finally, the regenerated catalyst is obtained by drying.

[0004] CN106669866A discloses a method for regenerating a deactivated hydrogenation catalyst. This method involves carbonizing the deactivated catalyst, then impregnating the carbonized catalyst with a solution containing ammonium fluoroborate and 2-amino-1,3-propanediol. The impregnated hydrogenation catalyst is then regenerated through heat treatment. This method can increase the specific surface area of ​​the regenerated catalyst, promote the redispersion of active components, and result in a high degree of sulfidation and improved reactivity of the regenerated hydrogenation catalyst.

[0005] However, the above-mentioned regeneration methods are generally only applicable to the regeneration of spent catalysts from distillate oil hydrotreating, and their applicability to spent catalysts from residue oil hydrotreating is insufficient. Therefore, how to process these spent catalysts from residue oil hydrotreating that cannot be conventionally regenerated through special methods and reuse them in the heavy oil and / or residue oil hydrotreating process to achieve the reuse of spent catalysts from residue oil hydrotreating, while extracting and recovering high-value metals such as vanadium from the waste catalysts, is a difficult problem that has plagued this industry. Summary of the Invention

[0006] The purpose of this invention is to overcome the problems of high cost, difficulty in reuse, and poor stability of waste catalysts in the treatment of residual oil hydrotreating in the prior art. This invention provides a method for treating waste hydrotreating catalysts, a hydrotreating catalyst, and a method for treating heavy oil and / or residual oil hydrotreating. The hydrotreating catalyst obtained by this method has good demetallization performance and high desulfurization activity stability when applied in the hydrotreating process of heavy oil and / or residual oil.

[0007] To achieve the above objectives, the present invention provides a method for treating waste hydrogenation catalyst, comprising: (1) The waste hydrogenation catalyst was carbonized under an oxygen-containing atmosphere; The spent hydrogenation catalyst contains deposited impurities, including vanadium, and the vanadium content, calculated as oxides, is not less than 3 wt% based on the total amount of the spent hydrogenation catalyst. (2) Part of the metal in the catalyst obtained in step (1) is leached with an acid solution to obtain a leachate and a leached catalyst residue; In this embodiment, compared with the spent hydrogenation catalyst, the vanadium leaching rate in the residual catalyst, calculated as oxides, is 60-95%; (3) The leachate is mixed with a vanadium removal agent for vanadium removal treatment, and then solid-liquid separation is performed; (4) The solid product obtained by solid-liquid separation is optionally washed and dried, and then calcined to obtain vanadium pentoxide with a purity of not less than 98%. (5) Impregnate the liquid phase product obtained from the solid-liquid separation with the catalyst obtained in step (2), and then perform high-temperature activation treatment at 600-800℃.

[0008] The second aspect of the present invention provides a hydrogenation catalyst obtained by the above-mentioned method for treating waste hydrogenation catalyst; Preferably, when the hydrogenation catalyst is measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbance at 630 nm and 500 nm are respectively F 630 and F 500 And the ratio of the two is Q=F 630 / F 500 The value is 1.3-3, preferably 1.4-2.8.

[0009] A third aspect of the present invention provides a method for hydrotreating heavy oil and / or residual oil, comprising: contacting heavy oil and / or residual oil with a hydrotreating catalyst under hydrotreating reaction conditions; wherein the hydrotreating catalyst is the hydrotreating catalyst described in the second aspect.

[0010] The present invention provides a method for treating spent hydrotreating catalysts, specifically for spent hydrotreating catalysts of residual oil with a large amount of vanadium impurities deposited on their surface. The method involves first carbonizing the catalyst, followed by acid leaching and vanadium removal. The leaching solution is used as an impregnation solution to impregnate the remaining catalyst, enabling the reuse of active metals. A high-temperature activation treatment at 600-800℃ is then performed. This process ensures the complete recovery and reuse of all effective metal components from the spent hydrotreating catalyst. The resulting hydrotreating catalyst, when applied to the hydrotreating of heavy oil and / or residual oil, exhibits good demetallization performance and high desulfurization activity stability. Furthermore, the method provides the production of solid vanadium pentoxide with a purity of not less than 98%, which can be used in steelmaking and other fields, thereby increasing the added economic benefits of spent catalyst treatment.

[0011] In this invention, by controlling the degree of acid leaching, vanadium impurities deposited in waste hydrogenation catalysts can be appropriately removed without damaging the catalyst framework structure. The inventors of this invention discovered in their research that controlling the leaching rate of vanadium in the residual catalyst, calculated as oxides, within the range of 60-95% ensures that at least some vanadium remains in the catalyst. This not only improves the hydrogenation demetallization activity of the treated catalyst but also guarantees the vanadium recovery rate. If the vanadium extraction rate is too low, the vanadium residue will cause pore blockage in the catalyst, affecting the diffusion of reactant molecules; if the vanadium extraction rate is too high, it will damage the alumina framework structure of the catalyst, thereby affecting the strength of the catalyst. Detailed Implementation

[0012] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0013] The first aspect of this invention provides a method for treating waste hydrogenation catalyst, comprising: (1) The waste hydrogenation catalyst was carbonized under an oxygen-containing atmosphere; The spent hydrogenation catalyst contains deposited impurities, including vanadium, and the vanadium content, calculated as oxides, is not less than 3 wt% based on the total amount of the spent hydrogenation catalyst. (2) Part of the metal in the catalyst obtained in step (1) is leached with an acid solution to obtain a leachate and a leached catalyst residue; In this embodiment, compared with the spent hydrogenation catalyst, the vanadium leaching rate in the residual catalyst, calculated as oxides, is 60-95%; (3) The leachate is mixed with a vanadium removal agent for vanadium removal treatment, and then solid-liquid separation is performed; (4) The solid product obtained by solid-liquid separation is optionally washed and dried, and then calcined to obtain vanadium pentoxide with a purity of not less than 98%. (5) Impregnate the liquid phase product obtained from the solid-liquid separation with the catalyst obtained in step (2), and then perform high-temperature activation treatment at 600-800℃.

[0014] In this invention, the above-mentioned treatment method can fully recover and utilize the effective metal components in the waste hydrogenation catalyst. The resulting hydrogenation catalyst, when applied to the hydrogenation process of heavy oil and / or residual oil, has good demetallization performance and high desulfurization activity stability. It can also produce solid vanadium pentoxide with a purity of not less than 98% as a byproduct, which can be used in steelmaking and other fields, thereby improving the additional economic benefits of waste catalyst treatment.

[0015] In this invention, spent hydrotreating catalyst refers to a catalyst whose performance (including at least one of activity, selectivity, and stability) deteriorates after use. This includes both spent hydrotreating catalysts that, even after long-term recycling and regeneration using existing methods, cannot achieve the required hydrotreating activity, and used hydrotreating catalysts that can still be used after regeneration using existing methods. The spent hydrotreating catalyst can be any type of hydrotreating catalyst conventionally used for various oil products in this field, and this invention does not impose any particular limitation on it. According to a specific embodiment of this invention, the spent hydrotreating catalyst includes, but is not limited to, spent residue oil hydrotreating catalysts and / or spent heavy oil hydrotreating catalysts.

[0016] According to the present invention, preferably, the spent hydrogenation catalyst includes a support and an active metal component supported on the support, as well as deposited impurities deposited on the surface of the spent hydrogenation catalyst, wherein the active metal component includes molybdenum and / or tungsten and nickel and / or cobalt; and the deposited impurities include carbon and vanadium.

[0017] This invention offers a wide range of choices for the content of molybdenum and / or tungsten, as well as nickel and / or cobalt. Those skilled in the art can make appropriate adjustments based on actual conditions. More preferably, based on the total amount of fresh catalyst corresponding to the waste hydrogenation catalyst, the content of molybdenum and / or tungsten, calculated as oxides, is 5-25% by weight, and the content of nickel and / or cobalt is 0.1-6% by weight. The conventional selection ranges for the active metal components molybdenum and / or tungsten, as well as nickel and / or cobalt, in waste residue oil hydrogenation catalysts or waste heavy oil hydrogenation catalysts may differ. Those skilled in the art can select them using conventional methods, and this invention will not elaborate further on these selections.

[0018] The phrase "based on the total amount of fresh catalyst corresponding to the waste hydrogenation catalyst" in this invention refers to the content of molybdenum and / or tungsten and the content of nickel and / or cobalt being calculated based on fresh catalyst, i.e., excluding the content of the aforementioned deposited impurities.

[0019] The processing method provided by this invention is particularly suitable for spent hydrogenation catalysts with high levels of deposited vanadium impurities, which is beneficial for recovering vanadium metal for use in steelmaking and other fields, thereby increasing the added economic benefits of spent catalyst treatment. Preferably, based on the total amount of the spent hydrogenation catalyst, the carbon content of the spent hydrogenation catalyst is less than 20% by weight, preferably less than 15% by weight; the vanadium content, calculated as oxides, is 3-60% by weight, preferably 30-60% by weight.

[0020] In this invention, unless otherwise specified, the carbon content of the spent hydrogenation catalyst is determined by extracting the catalyst with toluene and then measuring it using a carbon-sulfur analyzer, and the vanadium content is determined by calcining the catalyst in air at 600°C for 3 hours and then measuring it using X-ray fluorescence spectroscopy.

[0021] Preferably, the specific surface area of ​​the spent hydrogenation catalyst is 4-300 m². 2 / g, pore volume is 0.05-0.7mL / g, and most probable pore size is greater than 1nm.

[0022] In a preferred embodiment, the method provided by the present invention further includes sieving the waste hydrogenation catalyst before step (1) to make the particle size of the waste hydrogenation catalyst 10-30 mesh, preferably 14-20 mesh, and more preferably 16-20 mesh.

[0023] Preferably, the conditions for the charcoal burning process are: a temperature of 200-500℃ and a time of 2-8 hours.

[0024] In a further preferred embodiment, the charcoal burning process includes three optional stages: Stage I, Stage II, and Stage III, performed sequentially. Stage I is characterized by a temperature of 200-300°C and a time of 1-3 hours; Stage II is characterized by a temperature of 300-380°C and a time of 1-3 hours; and Stage III is characterized by a temperature of 380-500°C and a time of 1-4 hours. This gradient heating method of charcoal burning not only facilitates more thorough removal of carbon deposits on the catalyst but also prevents temperature runaway during the charcoal burning process.

[0025] According to some preferred embodiments of the present invention, the oxygen-containing atmosphere provides oxygen for the carbonization treatment of waste hydrogenation catalysts. The present invention allows for a wide range of oxygen content selection in the oxygen-containing atmosphere; for example, the volume content of oxygen in the oxygen-containing atmosphere can be 5-30%, preferably 10-25%. The oxygen-containing atmosphere of the present invention can be provided using different methods depending on the required oxygen volume content. For example, the oxygen-containing atmosphere can be provided using air. When a higher oxygen content is required, air and oxygen can be used together to provide the oxygen-containing atmosphere. When a lower oxygen content is required, air and an inert atmosphere (e.g., nitrogen) can be used together to provide the oxygen-containing atmosphere. This embodiment of the present invention uses air as an example for illustration, as using air to provide the oxygen-containing atmosphere is more cost-effective, but the present invention is not limited thereto.

[0026] In this invention, no additional pore-expansion treatment is required. Through the synergistic effect of charring and acid leaching in step (2), the treated catalyst can have a suitable pore structure.

[0027] According to the present invention, the catalyst after carbonization treatment in step (1) is contacted with an acid solution to leach out some of the metal in the catalyst. In the present invention, by controlling the degree of acid leaching, it is possible to remove an appropriate amount of vanadium impurities deposited in the waste hydrogenation catalyst while keeping the catalyst skeleton structure intact, so that at least some vanadium is retained in the catalyst, thus avoiding excessive leaching of the active metal components.

[0028] In this invention, the leaching rate (%) of vanadium in the residual catalyst, calculated as oxides, is calculated as: (weight of vanadium pentoxide in the spent catalyst - weight of vanadium pentoxide in the residual catalyst) / weight of vanadium pentoxide in the spent catalyst × 100%. The carbon content is not included in the total mass of the spent catalyst or residual catalyst. The inventors of this invention discovered that controlling the leaching rate of vanadium in the residual catalyst, calculated as oxides, within the range of 60-95% can both improve the hydrodemetallization activity of the treated catalyst and ensure the vanadium recovery rate. The reason for this is speculated to be that the appropriate amount of vanadium residue in the catalyst can play a certain role in plugging pores, which is beneficial to the dispersion of active metal components on the catalyst surface.

[0029] According to some preferred embodiments of the present invention, the vanadium leaching rate in the residual catalyst, calculated as oxides, is 75-90% compared to the spent hydrogenation catalyst. In the above preferred embodiments, it is advantageous to further improve the hydrogenation demetallization activity of the obtained hydrogenation catalyst.

[0030] In this invention, the leachate may contain other metal components from hydrogenation catalysts besides vanadium, such as molybdenum and nickel. This invention does not have any particular limitations on this.

[0031] According to the present invention, the leaching method in step (2) includes: immersing the catalyst obtained in step (1) in an acid solution, and then performing solid-liquid separation. The present invention does not particularly limit the method of solid-liquid separation, and it can be conventional operating methods such as centrifugation or filtration.

[0032] The present invention does not particularly limit the type of acid solution, and can use conventional inorganic or organic acids in the art. Preferably, the acid solution is an aqueous solution of at least one of hydrochloric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid and citric acid.

[0033] The present invention does not impose a particular limitation on the amount of acid solution used, as long as the leaching rate of vanadium (calculated as oxide) in the residual catalyst is 60-95%. Those skilled in the art can select the appropriate amount based on actual needs. Preferably, the volume ratio of the acid solution to the catalyst is 1-20:1, more preferably 5-15:1.

[0034] The present invention does not impose any particular limitation on the concentration of the acid solution. Preferably, the concentration of the acid solution is 0.1-4 mol / L, more preferably 0.1-2 mol / L, and even more preferably 0.5-1 mol / L.

[0035] Preferably, the leaching temperature is 20-90℃, more preferably 20-25℃, for example, it can be carried out at room temperature, and the leaching time is 0.5-10h, more preferably 0.5-1h.

[0036] According to the present invention, step (2) further includes optionally washing, drying, and calcining the solid product obtained from solid-liquid separation to obtain the leaching catalyst. The present invention does not particularly limit the operating conditions for washing and drying, and can employ conventional methods in the art. Preferably, water can be used as the washing agent, and the washing is performed 1-3 times, with the volume ratio of water to solid catalyst in each wash being 1-6:1; the drying conditions include a temperature of 80-200°C and a time of 3-6 hours.

[0037] Preferably, the roasting temperature is 300-550℃, more preferably 400-500℃, and the roasting time is 1-5h, more preferably 2-3h.

[0038] In this invention, there is no particular limitation on the vanadium removal agent; any additives capable of precipitating vanadium that are conventional in the art can be used. Preferably, the vanadium removal agent is selected from ammonium sulfate and / or ammonium halides, and the ammonium halide is preferably ammonium chloride and / or ammonium bromide. Using the above-mentioned preferred vanadium removal agent is beneficial for improving the precipitation and removal efficiency of vanadium, while avoiding the introduction of impurities into the leachate, which is conducive to the reuse of the leachate.

[0039] Preferably, the molar ratio of the amount of vanadium removal agent to the vanadium element in the leachate is (1.5-2.5):1, more preferably (1.5-2):1.

[0040] The present invention does not impose any particular limitations on the conditions for the vanadium removal treatment, which can be carried out at room temperature.

[0041] According to the present invention, after simple washing, drying and calcination of the solid product obtained by solid-liquid separation, vanadium pentoxide with a purity of not less than 98% can be obtained, which can be directly applied to steelmaking and other fields without the need for additional purification steps.

[0042] The present invention does not impose any particular limitation on the operating conditions for washing and drying, and can be carried out in accordance with conventional methods in the art. Preferably, water can be used as the detergent for washing, and the number of washing cycles is 1-3, with the volume ratio of water used to solid product in each washing cycle being 1-6:1; the drying conditions include a temperature of 80-200°C and a time of 3-6 hours.

[0043] According to some preferred embodiments of the present invention, in step (4), the calcination temperature is 400-600℃, preferably 500-600℃, and the time is 2-10h, preferably 3-5h.

[0044] In this invention, it is understood that the liquid phase product obtained after solid-liquid separation after vanadium removal treatment still contains some active metal components. Step (5) can reuse the active metal components in the catalyst as much as possible, which is beneficial to reduce the cost of the catalyst and reduce the environmental pressure of hazardous waste discharge.

[0045] In this invention, the liquid phase product obtained after vanadium removal treatment and solid-liquid separation can be directly used as the leaching residue catalyst obtained in the leaching step (2) using the leaching solution. Alternatively, an active metal precursor can be optionally introduced into the liquid phase product obtained after solid-liquid separation, and then used as the leaching residue catalyst obtained in the leaching step (2) using the leaching solution. The active metal precursor can be an organic salt, inorganic salt, or oxide containing an active metal, as long as the corresponding active metal can be provided, which is a conventional choice in the art.

[0046] According to some preferred embodiments of the present invention, step (5) further includes: optionally introducing an active metal precursor into the liquid phase product obtained by solid-liquid separation, so that the total concentration of active metal ions is 0.1-1 mol / L, and then using it to impregnate the residual catalyst obtained in step (2).

[0047] In this invention, the impregnation can be either equal-volume saturated impregnation or unsaturated impregnation. In the catalyst obtained after impregnation, the content of the active metal, calculated as oxides and based on the catalyst, is not less than that of the fresh catalyst. Preferably, the amount of the impregnation solution is such that, based on the total amount of the treated catalyst, the content of molybdenum and / or tungsten, calculated as oxides, is 5-25% by weight, the content of nickel and / or cobalt is 0.1-6% by weight, the content of vanadium is 0.1-5% by weight, and the content of the support is 64-95%.

[0048] According to the present invention, step (5) further includes optionally drying the impregnated catalyst at a temperature of 80-220°C for 2-8 hours.

[0049] According to the present invention, preferably, the high-temperature activation temperature is 610-780℃, more preferably 630-750℃, and even more preferably 650-730℃; the time is 2-8 hours. Under the above-mentioned preferred high-temperature activation conditions, a suitable amount of spinel structure can be formed in the catalyst, which is beneficial to further improve the catalytic stability of the spent hydrogenation catalyst.

[0050] In this invention, the high-temperature activation can be achieved by raising the temperature from ambient temperature to the activation temperature, or by directly raising the temperature from the drying temperature to the activation temperature; there is no particular limitation on this. This invention allows for a wide range of selection for the heating rate during high-temperature activation. Preferably, the heating rate is 50-600℃ / hour, and more preferably 100-550℃ / hour.

[0051] The second aspect of the present invention provides a hydrogenation catalyst obtained by the above-mentioned method for treating waste hydrogenation catalyst.

[0052] Preferably, the hydrogenation catalyst comprises a support and an active metal component and vanadium supported on the support, wherein the active metal component comprises molybdenum and / or tungsten and nickel and / or cobalt.

[0053] Preferably, based on the total weight of the hydrogenation catalyst, the content of molybdenum and / or tungsten, calculated as oxides, is 5-25% by weight, the content of nickel and / or cobalt is 0.1-6% by weight, the content of vanadium is 0.1-5% by weight, and the content of the support is 64-95%.

[0054] In this invention, the hydrogenation catalyst may also contain a very small amount of carbon, preferably not more than 1% by weight, more preferably not more than 0.1% by weight.

[0055] According to the present invention, when the catalyst is measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbance at 630 nm and 500 nm are respectively F 630 and F 500 And the ratio of the two is Q=F 630 / F 500 The ratio is 1.3-3, preferably 1.4-2.8. This preferred embodiment is more conducive to improving the hydrodesulfurization performance and stability of the hydrogenation catalyst. When the Q value is less than 1, the improvement in activity stability is not significant; when the Q value is greater than 3, the initial activity is too low, affecting the normal use of the catalyst. For example, the ratio of the two is Q=F. 630 / F 500 For specific ratios or ranges between two points, such as 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, etc., more preferably, Q=F 630 / F 500 The value is 1.7-2.2. Under the above preferred conditions, it is more advantageous to improve the hydrodesulfurization performance and stability of the hydrotreating catalyst in the hydrotreating of heavy oil and / or residue oil.

[0056] Preferably, the specific surface area of ​​the hydrogenation catalyst is 80-300 m². 2 / g, pore volume is 0.2-1.3mL / g, and most probable pore size is 5-20nm.

[0057] In this invention, the specific surface area, pore volume, and most accessible pore size of the catalyst are obtained by mercury porosimetry according to the national standard GB / T 21650.1-2008 / ISO 15901-1:2005.

[0058] A third aspect of the present invention provides a method for hydrotreating heavy oil and / or residual oil, comprising: contacting heavy oil and / or residual oil with a hydrotreating catalyst under hydrotreating reaction conditions; wherein the hydrotreating catalyst is the hydrotreating catalyst described in the second aspect.

[0059] The hydrogenation catalyst provided by this invention is applicable to the processing of various heavy oils and residues. In this invention, "residue" refers to the components remaining at the bottom of the distillation tower during crude oil distillation, including atmospheric residue and vacuum residue. "Heavy oil" refers to a heavy feedstock oil blended from residue and coking wax oil, among other components. Crude oil refers to natural petroleum extracted from the ground; it is a liquid mineral product primarily composed of hydrocarbons. Heavy oils and / or residues have high sulfur and carbon residue content; for example, the sulfur content is at least 1% by weight and the carbon residue content is at least 8% by weight.

[0060] The present invention provides a wide range of selection for the hydrogenation reaction conditions. Preferably, the hydrogenation reaction conditions include: a temperature of 330-430℃, more preferably 350-400℃; a hydrogen partial pressure of 10-20 MPa, more preferably 12-17 MPa; and a liquid hourly space velocity of 0.1-1 h⁻¹. -1 Preferably, it is 0.2-0.8h. -1 The hydrogen-to-oil volume ratio is 500-1200, preferably 500-1000.

[0061] The present invention will be described in detail below through embodiments.

[0062] Example 1 1) Take a deactivated industrial residue hydrotreating catalyst from a refinery (12.6 wt% carbon deposits, 34.1 wt% vanadium pentoxide content, the catalyst is NiMo / Al2O3, based on the total amount of fresh catalyst corresponding to the waste hydrotreating catalyst, the content of Mo is 8.63 wt% and the content of Ni is 0.37 wt% in terms of oxides), sieve it to obtain a 16-20 mesh deactivator A, put it in a muffle furnace, and perform carbonization treatment in air atmosphere using a programmed temperature rise method. The conditions are: constant temperature at 250℃ for 1 hour, then rise to 350℃ and hold for 3 hours, and then rise to 410℃ and hold for 3 hours to obtain carbonized catalyst B; 2) At room temperature, a portion of the metal in catalyst B obtained in step 1) was leached with a 0.7 mol / L phosphoric acid solution, wherein the volume of the phosphoric acid solution used was 10 times the volume of the catalyst, the leaching time was 2 hours, and then solid-liquid separation was performed. The catalyst was washed twice with deionized water, each time using 3 times the volume of the catalyst. The washed catalyst was then dried at 130°C for 4 hours in an air atmosphere and calcined at 400°C for 3 hours to obtain catalyst C. Compared with the deactivator A, the leaching rate of vanadium in the residual catalyst, calculated as oxides, was 85.5%. 3) Add an appropriate amount of ammonium sulfate solution to the solution obtained from step 2), with the molar ratio of ammonium sulfate to vanadium in the solution being 2:1. The vanadium in the solution will form ammonium vanadate precipitate, thus performing solid-liquid separation; 4) The precipitate obtained from step 3) was washed three times with deionized water, each time using five times the volume of the catalyst. The washed catalyst was then dried at 120°C in air for 3 hours, and then kept at 530°C for 4 hours to obtain vanadium pentoxide product D, whose purity was tested to be 98.4%. 5) Add appropriate amounts of basic nickel carbonate and molybdenum trioxide to the solution obtained from step 3) according to the target amount, until the metal ion concentration in the solution is 1.5 mol / L, and then impregnate catalyst C using the equal volume saturation impregnation method. 6) The catalyst obtained from step 5) was dried at 110°C for 4 hours in an air atmosphere, and then heated to 650°C at a rate of 300°C / hour and kept at 650°C for 3 hours to obtain catalyst E.

[0063] The composition of catalyst E was characterized by X-ray fluorescence spectroscopy. Based on the total amount of catalyst E, the content of Mo was 8.86 wt%, the content of Ni was 1.91 wt%, and the content of V was 1.63 wt% (based on oxides).

[0064] When the hydrogenation catalyst was measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbance at 630 nm and 500 nm were F0 and F1, respectively. 630 and F 500 And the ratio of the two is Q=F 630 / F 500 The value of 1.8 indicates that a certain amount of spinel structure has been formed in the catalyst.

[0065] Example 2 1) Catalyst B was obtained according to the method of Example 1; 2) At room temperature, a portion of the metal in catalyst B obtained in step 1) was leached with a 1 mol / L phosphoric acid solution, wherein the volume of the phosphoric acid solution used was 10 times the volume of the catalyst, the leaching time was 3 hours, and then solid-liquid separation was performed. The catalyst was washed twice with deionized water, each time using 3 times the volume of the catalyst. The washed catalyst was then dried at 130°C for 4 hours in air atmosphere and calcined at 400°C for 3 hours to obtain the residual catalyst. Compared with the deactivator A, the leaching rate of vanadium in the residual catalyst, calculated as oxides, was 88.9%. 3) Add an appropriate amount of ammonium sulfate solution to the solution obtained from step 2), with the molar ratio of ammonium sulfate to vanadium in the solution being 2:1. The vanadium in the solution will form ammonium vanadate precipitate, thus performing solid-liquid separation; 4) The precipitate obtained from step 3) was washed three times with deionized water, each time using five times the volume of the catalyst. The washed catalyst was then dried at 120°C in air for 3 hours, and then kept at 530°C for 4 hours to obtain vanadium pentoxide product, the purity of which was tested to be 98.9%. 5) Add appropriate amounts of basic nickel carbonate and molybdenum trioxide to the solution obtained from step 3) according to the target amount until the metal ion concentration in the solution is 1 mol / L. Then, impregnate the residual catalyst obtained in step 2) using the equal volume saturation impregnation method. 6) The catalyst obtained from step 5) was dried at 110°C for 4 hours in an air atmosphere, and then heated to 680°C at a rate of 400°C / hour, and kept at 680°C for 3 hours to obtain catalyst F.

[0066] The composition of catalyst F was characterized by X-ray fluorescence spectroscopy. Based on the total amount of catalyst F, the content of Mo was 9.01 wt%, the content of Ni was 1.84 wt%, and the content of V was 1.38 wt%.

[0067] When the hydrogenation catalyst was measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbance at 630 nm and 500 nm were F0 and F1, respectively. 630 and F 500 And the ratio of the two is Q=F 630 / F 500 The value of 2 indicates that a certain amount of spinel structure has been formed in the catalyst.

[0068] Example 3 The method is the same as in Example 1, except that in step 2), a portion of the metal in catalyst B obtained in step 1) is leached with a 2.5 mol / L phosphoric acid solution. The volume of the phosphoric acid solution used is 5 times the volume of the catalyst, and the leaching time is 3 hours. Then, solid-liquid separation is performed, and the catalyst is washed twice with deionized water, with the amount of deionized water each time being 3 times the volume of the catalyst. The washed catalyst is then dried at 130°C for 4 hours in an air atmosphere and calcined at 400°C for 3 hours to obtain the residual catalyst. Compared with the deactivator A, the leaching rate of vanadium in the residual catalyst, calculated as oxides, is 94.5%.

[0069] 3) Add an appropriate amount of ammonium sulfate solution to the solution obtained from step 2), with the molar ratio of ammonium sulfate to vanadium in the solution being 2:1. The vanadium in the solution will form ammonium vanadate precipitate, thus performing solid-liquid separation; 4) Add appropriate amounts of basic nickel carbonate and molybdenum trioxide to the solution obtained from step 3) according to the target amount, until the metal ion concentration in the solution is 1 mol / L, and then impregnate the residual catalyst obtained in step 2).

[0070] 5) The catalyst obtained from step 4) was dried at 110°C for 4 hours in an air atmosphere, and then heated to 650°C at 300°C / hour and kept at 650°C for 3 hours to obtain catalyst G.

[0071] The composition of catalyst G was characterized by X-ray fluorescence spectroscopy. Based on the total amount of catalyst G, the content of Mo was 8.75 wt%, the content of Ni was 1.89 wt%, and the content of V was 0.37 wt% (based on oxides).

[0072] Example 4 The method is the same as in Example 1, except that in step 2), a portion of the metal in catalyst B obtained in step 1) is leached with a 0.1 mol / L phosphoric acid solution. The volume of the phosphoric acid solution used is 15 times the volume of the catalyst, and the leaching time is 3 hours. Then, solid-liquid separation is performed, and the catalyst is washed twice with deionized water, with the amount of deionized water each time being 3 times the volume of the catalyst. The washed catalyst is then dried at 130°C for 4 hours in an air atmosphere and calcined at 400°C for 3 hours to obtain the residual catalyst. Compared with the deactivator A, the leaching rate of vanadium in the residual catalyst, calculated as oxides, is 73.3%.

[0073] Then, following the method of Example 1, steps 3)-5) are performed, and the resulting catalyst is denoted as H.

[0074] The composition of catalyst H was characterized by X-ray fluorescence spectroscopy. Based on the total amount of catalyst H, the content of Mo was 8.82 wt%, the content of Ni was 1.83 wt%, and the content of V was 3.32 wt% (based on oxides).

[0075] Example 5 The method is the same as in Example 1, except that in step 1), the conditions for charcoal burning are: constant temperature at 250°C for 1 hour, then heated to 400°C and constant temperature for 3 hours, and then heated to 550°C and constant temperature for 3 hours.

[0076] Then, steps 2)-5) are performed according to the method of Example 1, wherein the leaching catalyst obtained in step 2) has a vanadium leaching rate of 71.8% based on oxides compared with the deactivator A.

[0077] The treated catalyst is denoted as I.

[0078] The composition of catalyst I was characterized by X-ray fluorescence spectroscopy. Based on the total amount of catalyst I, the content of Mo was 8.86 wt%, the content of Ni was 1.85 wt%, and the content of V was 3.61 wt% (based on oxides).

[0079] The physicochemical properties of the catalysts involved in the above embodiments are listed in Table 1.

[0080] Table 1

[0081] Test case This test example was used to determine the performance of the above-mentioned hydrogenation catalyst in heavy oil hydrotreating. A hydrogenation demetallization catalyst (NiMo / Al2O3, with Ni content of 1.4 wt% and Mo content of 7.7 wt% as oxides) developed by the Research Institute of Petroleum Processing, China Petroleum & Chemical Corporation, was used as the reference for the evaluation test. Specifically, heavy oil from imported Middle Eastern crude oil (its properties are listed in Table 2) was used as feedstock. The hydrogenation catalysts obtained in the above examples and comparative examples were evaluated in a heavy oil hydrotreating fixed-bed reactor to compare the demetallization performance and desulfurization activity stability of different catalysts. The hydrogenation catalyst loading was 120 mL; evaluation conditions: reaction temperature 375℃, hydrogen partial pressure 14 MPa, liquid hourly space velocity 0.6 h⁻¹. -1 The hydrogen-to-oil volume ratio was 600:1. The results are listed in Table 3.

[0082] The specific calculation methods for demetallization rate and desulfurization rate are as follows:

[0083]

[0084] Table 2

[0085] Table 3

[0086] As can be seen from the results in Table 3, the regenerated catalyst obtained by the method provided by the present invention has hydrodemetallization activity and desulfurization activity comparable to that of the fresh catalyst, and the hydrodesulfurization activity has good stability.

[0087] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for treating spent hydrogenation catalyst, comprising: (1) performing carbon burning treatment on the spent hydrogenation catalyst in an oxygen-containing atmosphere; wherein the spent hydrogenation catalyst contains deposited impurities, and the deposited impurities include vanadium, and the content of vanadium in terms of oxide is not less than 3 wt% based on the total amount of the spent hydrogenation catalyst; (2) leaching part of metals in the catalyst obtained in step (1) by using an acid solution to obtain a leaching solution and a leaching residue catalyst; wherein the leaching rate of vanadium in terms of oxide in the leaching residue catalyst is 60-95% compared with the spent hydrogenation catalyst; (3) mixing the leaching solution with a vanadium removal agent to perform vanadium removal treatment, and then performing solid-liquid separation; (4) performing optional washing and drying on the solid phase product obtained by the solid-liquid separation, and then performing calcination treatment to obtain vanadium pentoxide with a purity of not less than 98%; (5) impregnating the leaching residue catalyst obtained in step (2) with the liquid phase product obtained by the solid-liquid separation, and then performing high-temperature activation treatment at 600-800℃.

2. The treatment method of claim 1, wherein, The spent hydrogenation catalyst includes spent residual oil hydrogenation catalyst and / or spent heavy oil hydrogenation catalyst; Preferably, the spent hydrogenation catalyst has a specific surface area of 4-300 m 2 / g, a pore volume of 0.05-0.7 mL / g, and a most probable pore diameter of greater than 1 nm. Preferably, the spent hydrogenation catalyst includes a carrier, active metals and deposited impurities, the active metals include molybdenum and / or tungsten and nickel and / or cobalt, and the deposited impurities include carbon and vanadium; Preferably, the carbon content of the spent hydrogenation catalyst is less than 20 wt% based on the total amount of the spent hydrogenation catalyst, and the vanadium content in terms of oxide is 3-60 wt%.

3. The treatment method according to claim 1 or 2, wherein, In step (5), the temperature rising rate of the high-temperature activation treatment is 50-600℃ / h, preferably 100-550℃ / h; Preferably, the temperature of the high-temperature activation treatment is 610-780℃, preferably 630-750℃, and more preferably 650-730℃; Preferably, the time of the high-temperature activation treatment is 2-8h, preferably 4-6h.

4. The treatment method according to any one of claims 1 to 3, wherein In step (1), the volume content of oxygen in the oxygen-containing atmosphere is 5-30%, preferably 10-25%; Preferably, the carbon burning treatment is performed at a temperature of 200-500℃ for 2-8h; Preferably, the carbon burning treatment includes optional stages I, II and III performed in sequence, the conditions of the stage I include a temperature of 200-300℃ and a time of 1-3h, the conditions of the stage II include a temperature of 300-380℃ and a time of 1-3h, and the conditions of the stage III include a temperature of 380-500℃ and a time of 1-4h.

5. The treatment method according to any one of claims 1 to 4, wherein, The leaching rate of vanadium in terms of oxide in the leaching residue catalyst is 75-90% compared with the spent hydrogenation catalyst; Preferably, the leaching manner in step (2) includes soaking the catalyst obtained in step (1) in an acid solution, and then performing solid-liquid separation; Preferably, the leaching temperature is 20-90℃, and the time is 0.5-10h; Preferably, the acid solution is an aqueous solution of at least one of hydrochloric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid and citric acid; Preferably, the concentration of the acid solution is 0.1-4 mol / L. Preferably, the volume ratio of the acid solution to the catalyst is 1-20:1; Preferably, step (2) further comprises: subjecting the solid-phase product obtained by the solid-liquid separation to optional washing, drying and calcination to obtain the residual catalyst; Preferably, the calcination temperature is 300-550℃.

6. The treatment method according to any one of claims 1 to 5, wherein In step (3), the molar ratio of the amount of the vanadium removal agent to the vanadium element in the leaching solution is (1.5-2.5):1; Preferably, the vanadium removal agent is selected from ammonium sulfate and / or ammonium halide, preferably ammonium chloride and / or ammonium bromide.

7. The treatment method according to any one of claims 1 to 6, wherein In step (4), the calcination temperature is 400-600℃ and the time is 2-10h.

8. The treatment method according to any one of claims 1 to 7, wherein Step (5) further comprises: optionally introducing an active metal precursor into the liquid-phase product obtained by the solid-liquid separation to make the total concentration of active metal ions 0.1-5mol / L, and then using the liquid-phase product to impregnate the residual catalyst obtained in step (2).

9. The hydrogenation catalyst obtained by the treatment method of the waste hydrogenation catalyst according to any one of claims 1-8; Preferably, the hydrogenation catalyst comprises a carrier, an active metal component and vanadium supported on the carrier, the active metal component comprising molybdenum and / or tungsten and nickel and / or cobalt; Preferably, the content of molybdenum and / or tungsten is 5-25% by weight, the content of nickel and / or cobalt is 0.1-6% by weight, the content of vanadium is 0.1-5% by weight, and the content of the carrier is 64-95% by weight, based on the total weight of the hydrogenation catalyst; Preferably, the hydrogenation catalyst has an absorbance at 630 nm and at 500 nm, respectively, of F 630 and F 500 , and the ratio Q = F 630 / F 500 is 1.3 to 3, preferably 1.4 to 2.8, when measured by diffuse reflectance UV-Vis spectroscopy. Preferably, the hydrogenation catalyst has a specific surface area of 80-300 m 2 / g, a pore volume of 0.2-1.3 mL / g and a most probable pore diameter of 5-20 nm.

10. A process for the hydroprocessing of heavy oil and / or residuum comprising: Under hydrogenation reaction conditions, heavy oil and / or residual oil is contacted with a hydrogenation catalyst; wherein the hydrogenation catalyst is the hydrogenation catalyst according to claim 9; Preferably, the hydrogenation catalyst comprises a carrier, an active metal component and vanadium supported on the carrier, the active metal component comprising molybdenum and / or tungsten and nickel and / or cobalt; Preferably, the content of molybdenum and / or tungsten is 5-25% by weight, the content of nickel and / or cobalt is 0.1-6% by weight, the content of vanadium is 0.1-5% by weight, and the content of the carrier is 64-95% by weight, based on the total weight of the hydrogenation catalyst; Under hydrogenation reaction conditions, heavy oil and / or residual oil is contacted with a hydrogenation catalyst; wherein the hydrogenation catalyst is the hydrogenation catalyst according to claim 9; Preferably, the hydrogenation reaction conditions include: temperature of 330-430°C, preferably 350-400°C, hydrogen partial pressure of 10-20 MPa, preferably 12-17 MPa, liquid hourly space velocity of 0.1-1 h -1 , preferably 0.2-0.8 h -1 , hydrogen to oil volume ratio of 500-1200, preferably 500-1000.

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