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; wherein compared with the waste hydrogenation catalyst, the leaching rate of vanadium in the leaching residual catalyst in terms of oxide is 62-94%; (3) carrying out extraction treatment on the leaching solution to obtain an extraction solution containing V < 4 + > and a raffinate; and (4) dipping the leaching residual catalyst obtained in the step (2) by adopting the raffinate, and then carrying out high-temperature activation treatment at 600-800 DEG C. The hydrogenation catalyst obtained by the treatment method is applied to the hydrotreating process of heavy oil and / or residual oil, and has relatively good demetallization performance and relatively high desulfurization activity stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of waste hydrogenation catalyst treatment, in particular to a waste hydrogenation catalyst treatment method, a hydrogenation catalyst and a heavy oil and / or residual oil hydroprocessing method. BACKGROUND

[0002] The fixed-bed residual oil hydrogenation process is the most widely used residual oil processing process at present, which can provide high-quality clean feedstock for subsequent residual oil FCC, DCC and other conversion processes, improve the yield and quality of light oil and chemical products, and is the key to efficient utilization of petroleum resources. However, in the reaction process, a large amount of V, Ni and other metal impurities contained in the residual oil will gradually deposit on the surface of the catalyst, block the pore and cover the active center, thereby causing catalyst deactivation. On the one hand, due to the deposition of a large amount of nickel and vanadium impurities on the surface of the deactivated catalyst, it is difficult to reuse by regeneration treatment, so the unloaded residual oil hydrogenation waste catalyst can only be treated as hazardous waste. The high cost of waste catalyst treatment and the great environmental pressure have become a difficult problem for the industry, and the generation of catalyst hazardous waste is not conducive to the green and sustainable development of enterprises; on the other hand, a large amount of metal deposited in the deactivated catalyst is also difficult to effectively recover and utilize.

[0003] CN1921942A reports a method for regenerating deactivated hydroprocessing catalyst, which first carries out carbon burning treatment on the deactivated hydroprocessing catalyst due to carbon deposition under certain conditions to obtain an intermediate catalyst with a carbon content of 0.5-2.5wt%, then contacts the carbon-burned catalyst with a solution containing a nitrogen-containing chelating agent and ages the catalyst, and finally obtains the regenerated catalyst through drying treatment.

[0004] CN106669866A discloses a method for regenerating deactivated hydrogenation catalyst, which carries out carbon burning treatment on the deactivated hydrogenation catalyst, then impregnates the carbon-burned catalyst with a solution containing ammonium fluoroborate and 2-amino-1,3-propanediol, and obtains the regenerated hydrogenation catalyst after heat treatment of the impregnated hydrogenation catalyst. This method can improve the specific surface area of the regenerated catalyst, promote the redispersion of the active components, and improve the reaction activity of the regenerated hydrogenation catalyst with high sulfidation degree.

[0005] However, the above-mentioned regeneration methods are generally only suitable for the regeneration treatment of distillate oil hydrogenation waste catalysts, and have insufficient applicability to residual oil hydrogenation waste catalysts. Therefore, how to treat these residual oil hydrogenation waste catalysts which cannot be conventionally regenerated by special methods and then apply them to the heavy oil and / or residual oil hydrogenation reaction process to realize the reuse of residual oil hydrogenation waste catalysts and extract and recover high-value vanadium and other metals from the waste catalysts is a difficult problem plaguing the industry. SUMMARY

[0006] The present application aims to overcome the problems of high cost, difficult reuse and poor stability of the existing technology, and provide a treatment method of waste hydrogenation catalyst, a hydrogenation catalyst, and a method of heavy oil and / or residual oil hydroprocessing, the hydrogenation catalyst obtained by the treatment method has good gold removal ability and high desulfurization activity stability.

[0007] To achieve the above-mentioned purpose, the present application provides a treatment method of waste hydrogenation catalyst, comprising: (1) under an oxygen-containing atmosphere, the waste hydrogenation catalyst is subjected to carbon burning treatment; The waste hydrogenation catalyst contains deposited impurities, and the deposited impurities include vanadium, and the content of vanadium in the waste hydrogenation catalyst is not less than 3wt% in terms of oxide based on the total amount of the waste hydrogenation catalyst. (2) using an acid solution to leach part of the metals in the catalyst obtained in step (1), to obtain a leaching solution and a leaching residue catalyst; Compared with the waste hydrogenation catalyst, the leaching residue catalyst has a vanadium leaching rate of 62-94% in terms of oxide. (3) the leaching solution is subjected to extraction treatment to obtain a V 4+ -containing extraction solution and a raffinate; (4) the raffinate is used to impregnate the leaching residue catalyst obtained in step (2), and then high-temperature activation treatment is carried out at 600-800℃.

[0008] The present application provides a hydrogenation catalyst obtained by the treatment method of the waste hydrogenation catalyst.

[0009] Preferably, when the hydrogenation catalyst is measured by diffuse reflectance ultraviolet-visible spectroscopy, the absorbance at 630nm and 500nm is F 630 and F 500 , and the ratio Q=F 630 / F 500 is 1.3-3, preferably 1.4-2.8.

[0010] The present application provides a method of heavy oil and / or residual oil hydroprocessing, 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 of the second aspect.

[0011] Residual oil is the heaviest component in crude oil, which contains a large amount of metal impurities such as V and Ni, and these metal impurities gradually deposit on the surface of the catalyst during the reaction process. The treatment method of the waste hydrogenation catalyst provided by the application can appropriately remove the deposited vanadium impurities in the waste hydrogenation catalyst while keeping the catalyst skeleton structure from being damaged by controlling the degree of acid leaching, and then the vanadium is extracted by using a multi-stage extraction method, so that the purity of the obtained vanadium-containing solution is greater than 99.8%, which can be used as a raw material of the electrolyte of the all-vanadium redox flow battery; the raffinate is reused in the residual catalyst and then subjected to high-temperature activation treatment at 600-800 DEG C, which can recover and utilize all the effective metal components in the raffinate, which is beneficial to reducing the catalyst cost and reducing the environmental protection pressure of hazardous waste discharge, and the obtained hydrogenation catalyst has good metal removal ability and high desulfurization activity stability when applied in the heavy oil and / or residual oil hydrogenation treatment process. DETAILED DESCRIPTION

[0012] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and any values are understood to be approximate values. The endpoints of the ranges of values and the values of individual points are not to be construed as limiting the maximum or minimum values which can be obtained. The range of values should be understood to encompass values which are near to or approximately the same as the values stated. For ranges of numerical values, the endpoints of each range, the endpoints of each range and individual point values, and individual point values can be combined with each other to form one or more new ranges of values, which are to be considered as specifically disclosed herein.

[0013] The first aspect of the application provides a treatment method of waste hydrogenation catalyst, comprising: (1) performing carbon burning treatment on the waste hydrogenation catalyst under an oxygen-containing atmosphere; The waste hydrogenation catalyst contains deposited impurities, and the deposited impurities include vanadium, and the content of vanadium in the form of oxide is not less than 3wt% based on the total amount of the waste hydrogenation catalyst; (2) leaching part of the metals in the catalyst obtained in step (1) by using an acid solution to obtain a leaching solution and a residual catalyst; Compared with the waste hydrogenation catalyst, the leaching rate of vanadium in the form of oxide in the residual catalyst is 62-94%; (3) performing extraction treatment on the leaching solution to obtain a V 4+ containing extraction solution and a raffinate; (4) impregnating the residual catalyst obtained in step (2) with the raffinate, and then performing high-temperature activation treatment at 600-800 DEG C.

[0014] In the present application, the waste hydrogenation catalyst refers to a catalyst whose performance (at least one of activity, selectivity and stability) is deteriorated after use, which includes not only the discarded hydrogenation catalyst which cannot meet the hydrogenation activity requirement even after long-term cyclic use and regeneration treatment by existing means, but also the used hydrogenation catalyst which can still be used after regeneration by existing means. The waste hydrogenation catalyst can be various hydrogenation catalysts commonly used in the field of various oil products, and the present application does not have a particular limitation thereon. According to one specific embodiment of the present application, the waste hydrogenation catalyst includes but is not limited to waste residual oil hydrogenation catalyst and / or waste heavy oil hydrogenation catalyst.

[0015] According to the present application, preferably, the waste hydrogenation catalyst comprises a carrier and an active metal component supported on the carrier, and a deposited impurity deposited on the surface of the waste hydrogenation catalyst, the active metal component comprising molybdenum and / or tungsten and nickel and / or cobalt; and the deposited impurity comprising carbon and vanadium.

[0016] The content range of molybdenum and / or tungsten and nickel and / or cobalt is selected relatively widely in the present application, and those skilled in the art can make appropriate adjustments according to the actual situation. Further preferably, based on the total amount of fresh catalyst corresponding to the waste hydrogenation catalyst, the content of molybdenum and / or tungsten is 5-25% by weight, and the content of nickel and / or cobalt is 0.1-6% by weight. The conventional selection range of the active metal components molybdenum and / or tungsten and nickel and / or cobalt in the waste residual oil hydrogenation catalyst or waste heavy oil hydrogenation catalyst can be different, and those skilled in the art can select according to conventional means, which will not be repeated herein.

[0017] In the present application, "based on the total amount of fresh catalyst corresponding to the waste hydrogenation catalyst" means that the content of molybdenum and / or tungsten and the content of nickel and / or cobalt are calculated based on fresh catalyst, i.e. without taking the content of the above-mentioned deposited impurity into account.

[0018] The treatment method provided by the present application is particularly suitable for waste hydrogenation catalysts with high content of deposited impurity vanadium, which is beneficial to the recovery of vanadium metal for the electrolyte of all-vanadium redox flow battery, and improves the additional economic benefits of waste catalyst treatment. Preferably, based on the total amount of the waste hydrogenation catalyst, the carbon content of the waste hydrogenation catalyst is less than 20% by weight, preferably less than 15% by weight; and the vanadium content is 3-60% by weight, preferably 30-60% by weight.

[0019] In the present application, unless otherwise specified, the carbon content of the waste hydrogenation catalyst is determined by carbon-sulfur analyzer after toluene extraction of the catalyst, and the vanadium content is determined by X-ray fluorescence spectrometry after calcination of the catalyst in air at 600°C for 3 hours.

[0020] 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.

[0021] Preferably, the method provided by the present invention further includes sieving the waste hydrogenation catalyst before step (1) so that the particle size of the waste hydrogenation catalyst is 10-30 mesh, preferably 14-20 mesh, and more preferably 16-20 mesh.

[0022] In this invention, there is no particular limitation on the specific method of carbon burning treatment in step (1). As long as it can remove the carbon deposits of the waste hydrogenation catalyst, it can be carried out in a conventional manner in the art, which is well known to those skilled in the art.

[0023] 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.

[0024] Preferably, the conditions for the charcoal burning process are: a temperature of 200-500℃ and a time of 2-8 hours.

[0025] 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.

[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 some of the metal in the catalyst. According to the present invention, by controlling the degree of acid leaching, vanadium impurities deposited in the spent hydrogenation catalyst can be appropriately removed while maintaining the catalyst framework structure, and excessive leaching of active metal components can be avoided. The inventors of the present invention have found that controlling the leaching rate of vanadium in the residual catalyst, calculated as oxides, within the range of 62-94% can both improve the hydrogenation demetallization activity of the treated catalyst and ensure the vanadium recovery rate. The reason for this is speculated to be that the appropriate 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. Preferably, compared with the spent hydrogenation catalyst, the leaching rate of vanadium in the residual catalyst, calculated as oxides, is 75-90%. Under the above preferred conditions, it is beneficial to further improve the hydrogenation demetallization activity of the treated hydrogenation catalyst.

[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.

[0029] 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.

[0030] 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.

[0031] The present invention does not impose particular limitations on the concentration and amount of the acid solution, as long as the leaching rate of vanadium (calculated as oxide) in the leaching catalyst is 62-94%. Those skilled in the art can make selections according to actual needs.

[0032] 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.

[0033] Preferably, the volume ratio of the acid solution to the catalyst is 1-20:1, more preferably 5-15:1.

[0034] 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.

[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] According to the present invention, preferably, the calcination temperature is 300-550℃, more preferably 400-500℃, and the calcination time is 1-5h, more preferably 2-3h.

[0038] In this invention, the extraction process in step (3) can be carried out using conventional extraction methods in the art. Those skilled in the art can perform single-stage extraction or multi-stage extraction as needed.

[0039] Preferably, the extraction process includes: mixing the leachate with an extractant and performing multi-stage extraction, preferably 2-10 stages. This invention allows for a wide range of extractants; preferably, the extractant is selected from trioctylmethylammonium chloride and / or trioctylamine. The extractant can be commercially available; for example, trioctylmethylammonium chloride can be industrial-grade trioctylmethylammonium chloride, brand name A336. The trioctylamine can be, for example, extractant N235.

[0040] This invention does not impose any particular limitation on the amount of extractant used in the extraction process; those skilled in the art can select it according to actual needs. Preferably, the amount of extractant used is 0.1-1 mL relative to 1 g of vanadium in the leachate. The amount of extractant used refers to the total amount of extractant used in the multi-stage extraction process.

[0041] According to the present invention, preferably, step (3) further includes: containing V 4+ The extract is mixed with a back-extraction agent for back-extraction. Preferably, the back-extraction agent is a sulfuric acid solution, and the concentration of the sulfuric acid solution is preferably 2-4 mol / L.

[0042] The present invention does not impose any particular limitation on the amount of the back-extraction agent. Preferably, the volume ratio of the back-extraction agent to the extractant is 0.2-1:1.

[0043] Using the preferred embodiments described above, a high-purity vanadium oxysulfate solution can be obtained through extraction and back-extraction. The purity of the vanadium oxysulfate solution is greater than 97%, preferably greater than 99%, and can be directly used as a raw material for the electrolyte of vanadium redox flow batteries. Vanadium redox flow batteries have become one of the preferred technologies in the field of large-scale energy storage, and their consumption is increasing year by year. Extracting metals from waste electrolytes can reduce electrolyte costs.

[0044] 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.

[0045] In this invention, the leaching catalyst obtained by the leaching step (2) 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 emissions.

[0046] In this invention, the raffinate can be directly used as the impregnation solution to impregnate the impregnation catalyst obtained in step (2), or an active metal precursor can be optionally introduced into the raffinate and then used as the impregnation solution to impregnate the impregnation catalyst obtained in step (2). 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.

[0047] According to some preferred embodiments of the present invention, step (4) further includes: optionally introducing an active metal precursor into the raffinate to make the total concentration of active metal ions 0.1-5 mol / L, and then using it to impregnate the leaching catalyst obtained in step (2).

[0048] 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 itself, is not less than that of the fresh catalyst. It is understood that those skilled in the art can selectively introduce an active metal precursor into the raffinate based on the content of the active metal in the liquid product and the amount of the target active metal, so that the content of the active metal in the impregnated catalyst is not less than that of the fresh catalyst. Preferably, based on the total amount of catalyst obtained by calcination in step (4), 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 64-94.8% by weight.

[0049] According to the present invention, step (4) further includes optionally drying the impregnated catalyst at a temperature of 80-220°C for 2-8 hours.

[0050] 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.

[0051] 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.

[0052] The second aspect of the present invention provides a hydrogenation catalyst obtained by the above-mentioned method for treating waste hydrogenation catalyst.

[0053] 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 500For 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.

[0054] 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.

[0055] 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 64-94.8% by weight.

[0056] In this invention, the 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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 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.

[0062] The present invention will be described in detail below through embodiments.

[0063] 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), called deactivator A, and sieve it to obtain 16-20 mesh deactivator A. Put it into a muffle furnace and perform carbonization treatment in air atmosphere 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) Part of the metal in catalyst B obtained in step 1) was leached at room temperature using a 0.7 mol / L phosphoric acid solution. The volume of the phosphoric acid solution used was 10 times the volume of the catalyst, and the leaching time was 2 hours. Then, solid-liquid separation was performed, and the catalyst was washed twice with deionized water, with the amount of deionized water each time being 3 times the volume of the catalyst. After washing, the catalyst was 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) Vanadium in the solution obtained in step 2) is separated and purified by a multi-stage extraction method. The extraction stage is 5 stages, and A336 is selected as the extractant. The amount of extractant used is 0.6 mL relative to 1 g of vanadium in the solution, resulting in an extract containing vanadium ions and a raffinate. A 3 mol / L sulfuric acid solution is selected as the back-extraction agent. The back-extraction agent is added to the extract at a volume ratio of 0.5:1 to the extractant to obtain a vanadium oxysulfate solution with a purity of 99.9%. 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 1.5 mol / L, and then impregnate catalyst C using the equal volume saturation impregnation method. 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 E.

[0064] 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 8.90 wt%, the content of Ni was 1.86 wt%, and the content of V was 1.62 wt% (based on oxides).

[0065] 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 2.1 indicates that a certain amount of spinel structure has been formed in the catalyst.

[0066] Example 2 1) Catalyst B was obtained according to the method of Example 1; 2) Part of the metal in catalyst B obtained in step 1) was leached at room temperature using a 1 mol / L phosphoric acid solution. The volume of the phosphoric acid solution used was 10 times the volume of the catalyst, and the leaching time was 3 hours. Then, solid-liquid separation was performed, and the catalyst was washed twice with deionized water, with the amount of deionized water each time being 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 the residual catalyst. Compared with the deactivator A, the leaching rate of vanadium in the residual catalyst, calculated as oxides, was 88.9%. 3) Vanadium in the solution obtained in step 2) is separated and purified by a multi-stage extraction method. The extraction stage is 5 stages, and A336 is selected as the extractant. The amount of extractant used is 0.5 mL relative to 1 g of vanadium in the solution, resulting in an extract containing vanadium ions and a raffinate. A 4 mol / L sulfuric acid solution is selected as the back-extraction agent. The back-extraction agent is added to the extract at a volume ratio of 0.5:1 to obtain a vanadium oxysulfate solution with a purity of 99.9%. 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 1.5 mol / L, and then impregnate the remaining catalyst using the equal volume saturation impregnation method. 5) The catalyst obtained from step 4) was dried at 110°C for 4 hours in an air atmosphere, and then heated to 680°C at 400°C / hour and kept at 680°C for 3 hours to obtain catalyst F.

[0067] 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 8.65 wt%, the content of Ni was 1.90 wt%, and the content of V was 1.40 wt% (based on oxides).

[0068] 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 2.0 indicates that a certain amount of spinel structure has been formed in the catalyst.

[0069] 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, each time using 3 times the volume of the catalyst. The washed catalyst is then dried at 130°C for 4 hours in air and calcined at 400°C for 3 hours to obtain the residual catalyst. Compared with the deactivator A, the vanadium leaching rate in the residual catalyst, calculated as oxides, is 94.5%.

[0070] 3) Vanadium in the solution obtained in step 2) is separated and purified by multi-stage extraction, wherein the number of extraction stages is 5, the extractant is A336, and the amount of extractant used is 0.6 mL relative to 1 g of vanadium in the solution, to obtain an extract containing vanadium ions and a raffinate. The stripping agent is a 3 mol / L sulfuric acid solution. The stripping agent is added to the extract at a volume ratio of 0.5:1 to the extractant for stripping. 4) Add appropriate amounts of basic nickel carbonate and molybdenum trioxide to the raffinate 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 raffinate catalyst obtained in step 2).

[0071] 5) The catalyst obtained from step 4) was dried at 110°C for 4 hours in an air atmosphere, and then kept at 410°C for 4 hours. The treated catalyst is denoted as G.

[0072] 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 8.57 wt%, the content of Ni was 1.87 wt%, and the content of V was 0.58 wt% (based on oxides).

[0073] 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, each time using three times the volume of the catalyst. The washed catalyst is then dried at 130°C for 4 hours in air and calcined at 400°C for 3 hours to obtain the residual catalyst. Compared with the deactivator A, the vanadium leaching rate in the residual catalyst, calculated as oxides, is 73.3%.

[0074] Then, following the method of Example 1, steps 3)-5) are performed, and the resulting catalyst is denoted as H.

[0075] 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 8.86 wt%, the content of Ni was 1.83 wt%, and the content of V was 3.92 wt% (based on oxides).

[0076] 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.

[0077] 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 deactivating agent A. 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 9.01 wt%, the content of Ni was 1.86 wt%, and the content of V was 3.63 wt% (based on oxides).

[0079] Example 6 Following the method of Example 1, except that the extractant used was trioctylamine (N235) for 5-stage extraction and back-extraction to obtain a vanadium oxysulfate solution with a purity of 97.9%.

[0080] Then, following the method of Example 1, steps 4)-5) are performed, and the resulting catalyst is denoted as J.

[0081] The composition of catalyst J was characterized by X-ray fluorescence spectroscopy. Based on the total amount of catalyst J, the content of Mo was 8.97 wt%, the content of Ni was 1.85 wt%, and the content of V was 1.63 wt% (based on oxides).

[0082] Table 1

[0083] 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.

[0084] The specific calculation methods for demetallization rate and desulfurization rate are as follows:

[0085]

[0086] Table 2

[0087] Table 3

[0088] As can be seen from the results in Table 3, the regenerated catalyst obtained by the method provided in this invention has good hydrodemetallization activity and hydrodesulfurization activity stability.

[0089] 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 leached catalyst; wherein the leaching rate of vanadium in terms of oxide in the leached catalyst is 62-94% compared with the spent hydrogenation catalyst; (3) the leaching solution is subjected to extraction treatment to obtain an extraction solution containing V 4+ and a raffinate solution; (4) impregnating the leached catalyst obtained in step (2) by using the raffinate, 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 (1), the volume content of oxygen in the oxygen-containing atmosphere is 5-30%, preferably 10-25%; Preferably, the carbon burning treatment is performed under the conditions of temperature 200-500℃ and time 2-8 hours; Preferably, the carbon burning treatment includes optional stage I, stage II and stage III performed in sequence, the conditions of the stage I include temperature 200-300℃ and time 1-3 hours, the conditions of the stage II include temperature 300-380℃ and time 1-3 hours, and the conditions of the stage III include temperature 380-500℃ and time 1-4 hours.

4. The treatment method according to any one of claims 1 to 3, wherein The leaching rate of vanadium in terms of oxide in the leached catalyst is 75-90% compared with the spent hydrogenation catalyst; Preferably, the leaching in step (2) includes soaking the catalyst obtained in step (1) in an acid solution and then performing solid-liquid separation; Preferably, the leaching is performed at a temperature of 20-90℃ for 0.5-10 hours; 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 includes optionally washing, drying and calcining the solid product obtained by solid-liquid separation to obtain the leached catalyst; Preferably, the calcination is performed at a temperature of 300-550℃.

5. The treatment method according to any one of claims 1 to 4, wherein, The extraction treatment includes mixing the leaching solution with an extractant and performing multi-stage extraction, preferably 2-10 stages of extraction; Preferably, the extractant is trioctylmethylammonium chloride and / or trioctylamine; Preferably, step (3) further comprises: mixing the extraction solution containing V 4+ with a stripping agent to perform stripping extraction; Preferably, the stripping agent is a sulfuric acid solution, and the concentration of the sulfuric acid solution is preferably 2-4 mol / L.

6. The treatment method according to any one of claims 1 to 5, wherein, Step (4) further comprises: introducing an active metal precursor into the liquid phase product obtained from the solid-liquid separation, so that the total concentration of active metal ions is 0.1-5 mol / L, and then the active metal precursor is used for impregnating the residual catalyst obtained from step (2).

7. The treatment method according to any one of claims 1 to 6, wherein The temperature increasing 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 2-8 h, preferably 4-6 h.

8. The hydrogenation catalyst obtained by the method for treating waste hydrogenation catalyst according to any one of claims 1-8; 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.

9. The hydrogenation catalyst of claim 8, wherein, The hydrogenation catalyst comprises a carrier, and an active metal component and vanadium supported on the carrier, wherein the active metal component comprises molybdenum and / or tungsten and nickel and / or cobalt; Preferably, the content of molybdenum and / or tungsten is 5-25 wt%, the content of nickel and / or cobalt is 0.1-6 wt%, the content of vanadium is 0.1-5 wt%, and the content of the carrier is 64-94.8 wt%, based on the total weight of the hydrogenation catalyst; 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: The heavy oil and / or residual oil is contacted with the hydrogenation catalyst under hydrogenation reaction conditions; wherein the hydrogenation catalyst is the hydrogenation catalyst according to claim 8 or 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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