Regeneration method of inactivated hydrogenation catalyst

Abstract

The invention provides a regeneration method of an inactivated hydrogenation catalyst, which comprises the following steps: step 1, roasting the inactivated hydrogenation catalyst under an alkaline condition, and then grinding and immersing in water; step 2, carrying out solid-liquid separation on the hydrogenation catalyst subjected to water immersion deactivation to obtain a solid phase and a liquid phase, adding chlorate into the liquid phase, and then adding acid liquor to obtain a metal-containing solution; and step 3, dipping the solid phase obtained in the step 2 into the metal-containing solution to obtain the regenerated hydrogenation catalyst. The catalyst obtained by the regeneration method has high activity.

Description

Technical Field

[0001] The invention relates to the field of catalyst regeneration, and in particular to a method for regenerating a deactivated hydrogenation catalyst. Background Art

[0002] Hydrogenation is an important method for converting crude oil into high-value products, and its core is the hydroprocessing catalyst. Before the catalyst is used, it is generally necessary to sulfide the oxidized catalyst. The sulfided catalyst has high hydrogenation activity and can convert inferior oil products into qualified target products.

[0003] The activity of hydrogenation catalysts will gradually decrease during use, that is, the catalyst is deactivated. The main reasons for the deactivation of industrial hydrogenation catalysts are coke formation and metal blockage, migration or aggregation of active metal components, changes in phase composition, reduction in the number of active centers, sintering of carriers, collapse and breakdown of zeolite structures, etc. At present, the activity of deactivated catalysts caused by carbon deposition can be restored by regeneration methods, but there is no suitable regeneration method for deactivated catalysts caused by metal deposition pollution and metal aggregation, and they can only be discarded.

[0004] At present, the essence of catalyst regeneration technology is to contact the deactivated catalyst with oxygen-containing gas and remove the carbon deposits on the surface by burning carbon to achieve catalyst regeneration. Since the catalyst undergoes high-temperature carbon burning during the regeneration process, most of the metals in the catalyst exist in an oxidized state. When it is used again, it needs to be sulfurized again to restore the activity of the catalyst. Compared with the fresh catalyst, the pore volume, specific surface area and hydrogenation activity of the regenerated catalyst have decreased to a certain extent.

[0005] Patent CN114425460A discloses a method for regenerating a deactivated hydrogenation catalyst, in which the deactivated hydrogenation catalyst and an organic compound solution are subjected to a first heat treatment and a second heat treatment respectively to obtain a regenerated catalyst. However, this regeneration method will result in the inability to completely remove carbon deposits on the catalyst, thus affecting the catalytic activity.

[0006] Patent CN114797967A discloses a deactivated catalyst regeneration method and a regenerated catalyst and its application. 2 Under supercritical conditions, the deactivated catalyst is treated by contacting it with carbon dioxide and ether, and then heat-treated to restore the activity of the catalyst. This method is suitable for treating titanium silicon molecular sieve catalysts, but is less effective for treating alumina-based hydrogenation catalysts.

[0007] Patent CN110201694A discloses a method for preparing a catalyst, which firstly heat treats the deactivated catalyst under anaerobic conditions, then mixes the heat-treated catalyst with an organic compound solution for heat treatment, and obtains the catalyst after the treatment. In this regeneration method, the carbon deposition of the catalyst is not completely treated, and the catalyst activity recovery is poor.

[0008] Patent CN109529880B discloses a catalyst regeneration method, which first dissolves the deactivated catalyst with an acidic aqueous solution, then adds a metal powder reducing agent to react, then dissolves it with an alkaline aqueous solution, and finally adds a reducing agent aqueous solution to treat it to obtain a regenerated catalyst. This process easily causes permanent loss of some hydrogenation active sites.

[0009] Therefore, there is a need in the art to study the regeneration of deactivated hydrogenation catalysts. Summary of the invention

[0010] The main purpose of the present invention is to provide a method for regenerating a deactivated hydrogenation catalyst, so as to overcome the defects of the prior art such as incomplete treatment of catalyst carbon deposition during the regeneration process and low catalyst activity after regeneration.

[0011] In order to achieve the above object, the present invention provides a method for regenerating a deactivated hydrogenation catalyst, comprising the following steps:

[0012] Step 1, calcining the deactivated hydrogenation catalyst under alkaline conditions, then grinding and soaking in water;

[0013] Step 2, separating the solid and liquid of the water-immersed deactivated hydrogenation catalyst to obtain a solid phase and a liquid phase, adding a chloride salt to the liquid phase, and then adding an acid solution to obtain a metal-containing solution;

[0014] Step 3, impregnating the solid phase obtained in step 2 with the metal-containing solution to obtain a regenerated hydrogenation catalyst.

[0015] The regeneration method of the deactivated hydrogenation catalyst of the present invention, wherein in step 1, the deactivated hydrogenation catalyst is calcined under alkaline conditions: the deactivated hydrogenation catalyst and an alkaline sodium compound are mixed and calcined; the calcination temperature is 600-1000° C., and the calcination time is 4-6 hours.

[0016] The method for regenerating a deactivated hydrogenation catalyst according to the present invention, wherein the alkaline sodium compound is NaCO 3 , NaOH, NaHCO 3 One or more of the following: the alkaline sodium compound accounts for 30-50% of the total mass of the deactivated hydrogenation catalyst and the alkaline sodium compound.

[0017] In the method for regenerating a deactivated hydrogenation catalyst of the present invention, in step 1, the grinding is wet grinding, and the particle size of the deactivated hydrogenation catalyst after wet grinding is 10 μm-20 μm.

[0018] The method for regenerating a deactivated hydrogenation catalyst of the present invention, wherein in step 2, the chloride salt is NaCl, MgCl 2After the chloride salt is added to the liquid phase, the concentration of the chloride salt in the liquid phase is 0.6-0.8 mol / L.

[0019] In the method for regenerating a deactivated hydrogenation catalyst of the present invention, the acid solution is a hydrochloric acid solution, and the concentration of the hydrochloric acid solution is 0.2-0.4 mol / L.

[0020] The method for regenerating a deactivated hydrogenation catalyst of the present invention further comprises mixing the regenerated hydrogenation catalyst with a fresh hydrogenation catalyst and performing a sulfurization treatment.

[0021] The regeneration method of the deactivated hydrogenation catalyst of the present invention, wherein the conditions of the sulfurization treatment are: temperature of 280-320°C, pressure of 1.5-3.0MPa, time of 12-24h, space velocity of 3.0-3.5h -1 , the hydrogen-to-oil ratio is 200-400.

[0022] The regeneration method of the deactivated hydrogenation catalyst of the present invention, wherein the deactivated hydrogenation catalyst comprises a carrier and a metal element, the metal element is loaded on the carrier in the form of a metal oxide, the metal element is at least one of Co, Mo, Ni, W, Zn, Fe, Cu, Mn, Pt, and Pd, and the carrier is at least one of alumina, zirconium oxide, silicon oxide, activated carbon, diatomaceous earth, and zeolite.

[0023] Beneficial effects of the present invention:

[0024] The regeneration method of the deactivated hydrogenation catalyst of the present invention comprises the following steps: firstly subjecting the deactivated catalyst to alkaline roasting and grinding, and then impregnating a metal-containing solution onto the roasted carrier to obtain a regenerated hydrogenation catalyst. The regeneration method of the present invention can effectively remove carbon deposits deposited during the reaction, restore the pore structure of the catalyst, and regulate the interactions between active metal components and between the active metal components and the carrier, so that the activity of the catalyst can be improved. In addition, the method of the present invention can reuse active metals, has good economic benefits, and has a simple process, which is conducive to large-scale promotion and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 are the pore size adsorption-desorption curves of the fresh catalyst, the deactivated catalyst and the regenerated catalyst of the present invention;

[0026] Figure 2 This is the TEM image of the fresh catalyst of the present invention;

[0027] Figure 3 This is the TEM image of the regenerated catalyst of the present invention. DETAILED DESCRIPTION

[0028] The technical scheme of the present invention is described in detail below. The following implementation modes are implemented on the premise of the technical scheme of the present invention, and a detailed implementation process is given. However, the protection scope of the present invention is not limited to the following implementation modes. The structures or experimental methods of specific conditions are not specified in the following implementation modes, and generally conventional conditions are followed.

[0029] The present invention provides a method for regenerating a deactivated hydrogenation catalyst, comprising the following steps:

[0030] Step 1, calcining the deactivated hydrogenation catalyst under alkaline conditions, then grinding and soaking in water;

[0031] Step 2, separating the solid and liquid of the water-immersed deactivated hydrogenation catalyst to obtain a solid phase and a liquid phase, adding a chloride salt to the liquid phase, and then adding an acid solution to obtain a metal-containing solution;

[0032] Step 3, impregnating the solid phase obtained in step 2 with the metal-containing solution to obtain a regenerated hydrogenation catalyst.

[0033] The regeneration method of the deactivated hydrogenation catalyst of the present invention comprises the following steps: firstly, the deactivated catalyst is subjected to alkaline roasting and grinding, and then a metal-containing solution is impregnated onto the roasted carrier to obtain a regenerated hydrogenation catalyst. The regeneration method of the present invention can effectively remove carbon deposits deposited during the reaction, restore the pore structure of the catalyst, and regulate the interaction between active metal components and between the active metal components and the carrier, so that the activity of the catalyst is improved.

[0034] The present invention does not particularly limit the deactivated hydrogenation catalyst. After the hydrogenation catalyst is deactivated, it can be regenerated using the regeneration method of the present invention. In one embodiment, the hydrogenation catalyst of the present invention is a gasoline hydrogenation catalyst; in another embodiment, the hydrogenation catalyst of the present invention includes a carrier and a metal element, the metal element is loaded on the carrier in the form of a metal oxide, the metal element is at least one of Co, Mo, Ni, W, Zn, Fe, Cu, Mn, Pt, and Pd, and the carrier is at least one of aluminum oxide, zirconium oxide, silicon oxide, activated carbon, diatomaceous earth, and zeolite. The present invention does not particularly limit the form of the metal oxide, such as the conventional oxides of the above-mentioned metals in the art, and more for example, the oxides that are easily generated by the above-mentioned metals after roasting.

[0035] In one embodiment, in step 1, calcining the deactivated hydrogenation catalyst under alkaline conditions comprises: mixing the deactivated hydrogenation catalyst and an alkaline sodium compound, and calcining the mixture; the calcination temperature is 600-1000° C., and the calcination time is 4-6 hours.

[0036] The alkaline sodium compound is an alkaline compound whose cation is a sodium ion, and the pH value of the alkaline sodium compound after being dissolved in water is 8.4-8.8. In one embodiment, the alkaline sodium compound is, for example, NaCO3 , NaOH, NaCl, NaHSO 4 The basic sodium compound accounts for 30-50% of the total mass of the deactivated hydrogenation catalyst and the basic sodium compound.

[0037] In one embodiment, the grinding of the present invention is wet grinding, that is, the mixture of the calcined deactivated hydrogenation catalyst and the basic sodium compound is ground into slurry with water. The present invention does not specifically limit the water content during wet grinding.

[0038] Then, water is added to the ground mixture of the hydrogenation catalyst and the basic sodium compound for impregnation. The present invention does not specifically limit the amount of water added and the impregnation time, which can be adjusted as needed.

[0039] Step 2 of the present invention is: separating the solid and liquid of the water-immersed deactivated hydrogenation catalyst to obtain a solid phase and a liquid phase, adding chloride salt to the liquid phase, and then adding acid solution to obtain a metal-containing solution.

[0040] The hydrogenation catalyst after water immersion is in the form of slurry, and the solid and liquid are separated to obtain a solid phase and a liquid phase. The present invention does not specifically limit the method of solid-liquid separation, for example, filtering. Chloride salt is added to the separated liquid phase, and the solution is filtered to remove aluminum and phosphorus; then, acid solution is added for acidification treatment to obtain a metal-containing solution.

[0041] In one embodiment, the chloride salt is NaCl, MgCl 2 One or two of the above, after the chloride salt is added to the liquid phase, the concentration of the chloride salt in the liquid phase is 0.6-0.8 mol / L.

[0042] In one embodiment, the acid solution is a hydrochloric acid solution, and the concentration of the hydrochloric acid solution is 0.2-0.4 mol / L. For example, when the deactivated hydrogenation catalyst contains the active component molybdenum, the separated liquid phase will contain metallic molybdenum, and after adding the acid solution, a molybdic acid solution is obtained.

[0043] Step 3 is: impregnating the solid phase obtained in step 2 with a metal-containing solution to obtain a regenerated hydrogenation catalyst.

[0044] The present invention does not particularly limit the impregnation method, such as equal volume impregnation, excess impregnation, spraying, etc.

[0045] In one embodiment, the regenerated hydrogenation catalyst of the present invention is mixed with a fresh hydrogenation catalyst and used in a hydrogenation reaction. In another embodiment, the hydrogenation catalyst of the present invention needs to be sulfided before use. That is, the regenerated hydrogenation catalyst is mixed with a fresh hydrogenation catalyst, sulfided, and then used in a hydrogenation reaction.

[0046] The conditions for the vulcanization treatment may be: temperature 280-320°C, pressure 1.5-3.0 MPa, time 12-24 h, air velocity 3.0-3.5 h -1 , the hydrogen-to-oil ratio is 200-400.

[0047] In one embodiment, the conditions for the hydrogenation reaction are: reaction temperature of 200-300°C, pressure of 2.0-2.2 MPa, and space velocity of 3.0-3.5 h -1 , the hydrogen-to-oil ratio is 200-400.

[0048] In one specific embodiment, the regeneration method of the deactivated hydrogenation catalyst (active metal is molybdenum) of the present invention comprises the following steps:

[0049] Step 1: fully mix the deactivated gasoline hydrogenation catalyst and sodium salt (the sodium salt accounts for 30-50% of the total mass of the deactivated gasoline hydrogenation catalyst and the sodium salt), and calcine at 600-1000° C. for 4-6 hours; the calcined hydrogenation catalyst is wet-milled and water-soaked;

[0050] Step 2: Filter the mixture in step 1 to obtain a Mo-containing solution, add 0.6-0.8 mol / L chloride salt to the filtrate to remove aluminum and phosphorus in the solution; finally, treat the filtrate with 0.2-0.4 mol / L hydrochloric acid to obtain a molybdic acid solution;

[0051] Step 3: impregnating the calcined carrier with a molybdic acid solution to obtain a regenerated gasoline hydrogenation catalyst;

[0052] Step 4: The regenerated gasoline hydrogenation catalyst is loaded with fresh catalyst grade, and the temperature is 280-320°C, the pressure is 1.5-3.0 MPa, the time is 12-24 hours, and the air velocity is 3.0-3.5 h -1 , sulfidation is carried out under the condition of hydrogen-to-oil ratio of 200-400;

[0053] Step 5: The sulfided catalyst is heated at a temperature of 200-300°C, a pressure of 2.0-2.2 MPa, and a space velocity of 3.0-3.5 h -1 , the hydrodesulfurization reaction is carried out under the condition of hydrogen-to-oil ratio of 200-400.

[0054] The regenerated catalyst of the present invention adopts CS meter to characterize the removal of carbon deposits, showing that the carbon deposits are basically removed; BET is used to characterize the pore structure of the regenerated catalyst, showing that the pore structure of the regenerated catalyst is not much different from that of the corresponding fresh catalyst; TEM is used to characterize the interaction between the active metal and the carrier, showing that the number of active metal stacking layers of the catalyst after regeneration is 2-4 layers.

[0055] The invention provides a method for regenerating a deactivated hydrogenation catalyst. The regenerated catalyst can be loaded with a fresh catalyst grade, thereby improving the combined use performance.

[0056] The technical scheme of the present invention will be further described below through specific examples. The deactivated gasoline hydrodesulfurization catalysts used in Examples 1-5 and Comparative Examples 1-3 are the same, and the fresh catalysts used are the same. In the following examples, comparative examples and tests, the fresh gasoline hydrodesulfurization catalysts include 5-10wt% SiO 2 、60-80wt%Al 2 O 3 、1-5wt%Co 2 O 3 and 5-15wt%MoO 3 The deactivated gasoline hydrodesulfurization catalyst is obtained by deactivating the above fresh gasoline hydrodesulfurization catalyst, and in addition to the above components, it also carries impurities SO 3 , Fe 2 O 3 、As 2 O 3 And a small amount of WO 3 wait.

[0057] Example 1

[0058] Take 100 mL of deactivated gasoline hydrodesulfurization catalyst and mix it with 30 wt% (NaCO 3 Accounting for deactivated gasoline hydrogenation catalyst and NaCO 3 30% of the total mass, the following examples have the same meaning) of NaCO 3 The solution was calcined at 1000°C for 4 h, and then wet-milled, soaked in water and filtered to obtain a Mo-containing solution and a solid (carrier). 100 mL of 0.6 mol / L MgCl was added to the filtrate. 2 , filter to remove aluminum and phosphorus in the solution; finally, treat the filtrate with 50 mL of 0.2 mol / L hydrochloric acid to obtain a molybdic acid solution.

[0059] The molybdenum acid solution was impregnated into the calcined carrier to obtain a regenerated gasoline hydrogenation catalyst, which was named C1. Then it was graded and loaded with the same mass of fresh gasoline hydrodesulfurization catalyst at a temperature of 280°C, a pressure of 2.0 MPa, and a space velocity of 3.0 h -1 The catalyst was sulfurized at a hydrogen-to-oil ratio of 300; then the temperature was 280°C, the pressure was 2.0 MPa, and the space velocity was 3.0 h -1 The hydrodesulfurization of gasoline was evaluated under the condition of hydrogen-to-oil ratio of 300:1.

[0060] Example 2

[0061] Take 100 mL of deactivated gasoline hydrodesulfurization catalyst and mix it with 40 wt% NaCO 3 The solution was calcined at 1000°C for 4 h, and then wet-milled, soaked in water and filtered to obtain a Mo-containing solution and a solid (carrier). 0.6 mol / L MgCl was added to the filtrate. 2 , filter to remove aluminum and phosphorus in the solution; finally, treat the filtrate with 0.2 mol / L hydrochloric acid to obtain a molybdic acid solution.

[0062] The molybdenum acid solution was impregnated into the calcined carrier to obtain a regenerated gasoline hydrogenation catalyst, which was named C2. Then it was graded and loaded with the same mass of fresh gasoline hydrodesulfurization catalyst at a temperature of 280°C, a pressure of 2.0 MPa, and a space velocity of 3.0 h -1 The catalyst was sulfurized at a hydrogen-to-oil ratio of 300; then the temperature was 280°C, the pressure was 2.0 MPa, and the space velocity was 3.0 h -1 The same gasoline as in Example 1 was evaluated for hydrodesulfurization at a hydrogen-to-oil ratio of 300:1.

[0063] Example 3

[0064] Take 100 mL of deactivated gasoline hydrodesulfurization catalyst and mix it with 50 wt% NaCO 3 The solution was calcined at 1000°C for 4 h, and then wet-milled, soaked in water and filtered to obtain a Mo-containing solution and a solid (carrier). 0.6 mol / L MgCl was added to the filtrate. 2 , filter to remove aluminum and phosphorus in the solution; finally, treat the filtrate with 0.2 mol / L hydrochloric acid to obtain a molybdic acid solution.

[0065] The molybdenum acid solution was impregnated into the calcined carrier to obtain a regenerated gasoline hydrogenation catalyst, which was named C3. Then it was graded and loaded with the same mass of fresh gasoline hydrodesulfurization catalyst at a temperature of 280°C, a pressure of 2.0 MPa, and a space velocity of 3.0 h -1 The catalyst was sulfurized at a hydrogen-to-oil ratio of 300; then the temperature was 280°C, the pressure was 2.0 MPa, and the space velocity was 3.0 h -1 The same gasoline as in Example 1 was evaluated for hydrodesulfurization at a hydrogen-to-oil ratio of 300:1.

[0066] Example 4

[0067] 100 mL of deactivated gasoline hydrodesulfurization catalyst was taken and calcined with 40 wt% NaOH at 1000 °C for 4 h, then wet-milled, water-soaked and filtered to obtain a Mo-containing solution and a solid (support); 0.6 mol / L MgCl was added to the filtrate. 2, filter to remove aluminum and phosphorus in the solution; finally, treat the filtrate with 0.2 mol / L hydrochloric acid to obtain a molybdic acid solution.

[0068] The molybdenum acid solution was impregnated into the calcined carrier to obtain the regenerated gasoline hydrogenation catalyst, which was named C4. Then it was graded and loaded with the same mass of fresh gasoline hydrodesulfurization catalyst at a temperature of 280°C, a pressure of 2.0 MPa, and a space velocity of 3.0 h -1 The catalyst was sulfurized at a hydrogen-to-oil ratio of 300; then the temperature was 280°C, the pressure was 2.0 MPa, and the space velocity was 3.0 h -1 The same gasoline as in Example 1 was evaluated for hydrodesulfurization at a hydrogen-to-oil ratio of 300:1.

[0069] Example 5

[0070] Take 100 mL of deactivated gasoline hydrodesulfurization catalyst and mix it with 50 wt% NaCO 3 The solution was calcined at 1000°C for 4 h, and then wet-milled, soaked in water and filtered to obtain a Mo-containing solution and a solid (carrier). 0.6 mol / L MgCl was added to the filtrate. 2 , filter to remove aluminum and phosphorus in the solution; finally, treat the filtrate with 0.2 mol / L hydrochloric acid to obtain a molybdic acid solution.

[0071] The molybdate solution was impregnated into the calcined carrier to obtain a regenerated gasoline hydrogenation catalyst, which was named C5. The catalyst was heated to 280 °C, 2.0 MPa and 3.0 h / min at a gas velocity of 1.0 h. -1 The catalyst was sulfurized at a hydrogen-to-oil ratio of 300; then the temperature was 280°C, the pressure was 2.0 MPa, and the space velocity was 3.0 h -1 The same gasoline as in Example 1 was evaluated for hydrodesulfurization at a hydrogen-to-oil ratio of 300:1.

[0072] Comparative Example 1

[0073] The deactivated gasoline hydrodesulfurization catalyst was graded and loaded with the same mass of fresh gasoline hydrodesulfurization catalyst. The catalyst was named D1 and heated at a temperature of 280°C, a pressure of 2.0 MPa, and a space velocity of 3.0 h -1 The catalyst was sulfurized at a hydrogen-to-oil ratio of 300; then the temperature was 280°C, the pressure was 2.0 MPa, and the space velocity was 3.0 h -1 The same gasoline as in Example 1 was evaluated for hydrodesulfurization at a hydrogen-to-oil ratio of 300:1.

[0074] Comparative Example 2

[0075] The deactivated gasoline hydrodesulfurization catalyst was heated at a temperature of 280°C, a pressure of 2.0 MPa, and a space velocity of 3.0 h-1 The catalyst was sulfurized at a hydrogen-to-oil ratio of 300; then the temperature was 280°C, the pressure was 2.0 MPa, and the space velocity was 3.0 h -1 The same gasoline as in Example 1 was evaluated for hydrodesulfurization at a hydrogen-to-oil ratio of 300:1.

[0076] Comparative Example 3

[0077] The fresh catalyst was heated to 280°C, with a pressure of 2.0 MPa and a space velocity of 3.0 h -1 The catalyst was sulfurized at a hydrogen-to-oil ratio of 300; then the temperature was 280°C, the pressure was 2.0 MPa, and the space velocity was 3.0 h -1 The same gasoline as in Example 1 was evaluated for hydrodesulfurization at a hydrogen-to-oil ratio of 300:1.

[0078] The evaluation results of the hydrodesulfurization activity of the catalysts in the examples and comparative examples are listed in Table 1.

[0079] Table 1 Hydrodesulfurization evaluation results of catalysts of Examples 1 to 5 and Comparative Examples 1 to 3

[0080]

[0081]

[0082] As shown in Table 1, the regenerated catalyst obtained by the method of the present invention has high activity. The catalyst after regeneration in Example 2 has the highest activity, with a desulfurization rate of up to 85.3% and an olefin saturation rate of 43.9%.

[0083] The present invention uses a CS meter to characterize the removal of carbon deposits, and measures the carbon and sulfur contents of the fresh gasoline hydrodesulfurization catalyst, the deactivated gasoline hydrodesulfurization catalyst, and the regenerated gasoline hydrodesulfurization catalyst using the method of the present invention. The results are shown in Table 2.

[0084] Table 2 Comparison of CS content of fresh hydrodesulfurization catalyst, deactivated and regenerated hydrodesulfurization catalyst

[0085]

[0086] As shown in Table 2, the CS content of the deactivated gasoline hydrodesulfurization catalyst is relatively high, with a carbon content of 4.849wt% and a sulfur content of 4.829wt%. The CS content of the regenerated gasoline hydrodesulfurization catalyst is substantially the same as that of the fresh gasoline hydrodesulfurization catalyst, indicating that the method of the present invention is used to regenerate the deactivated catalyst and has a good impurity removal effect.

[0087] Figure 1 are the pore size adsorption-desorption curves of the fresh catalyst, the deactivated catalyst and the regenerated catalyst of the present invention; Figure 2This is the TEM image of the fresh catalyst of the present invention; Figure 3 This is a TEM image of the regenerated catalyst of the present invention. Figure 1-3 It can be seen that the deactivated gasoline hydrodesulfurization catalyst is regenerated by the method of the present invention, and the pore structure of the regenerated catalyst is similar to that of the fresh gasoline hydrodesulfurization catalyst.

[0088] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the scope of protection of the claims of the present invention.

Claims

1. A regeneration method for a deactivated hydrogenation catalyst, characterized in that, it comprises the following steps: Step 1, calcine the deactivated hydrogenation catalyst under alkaline conditions, then grind it and soak it in water; Step 2, separate the solid and liquid of the water-soaked deactivated hydrogenation catalyst to obtain a solid phase and a liquid phase. Add a chloride salt to the liquid phase, and then add an acid solution to obtain a metal-containing solution; Step 3, impregnate the solid phase obtained in Step 2 with the metal-containing solution to obtain a regenerated hydrogenation catalyst.

2. The regeneration method for a deactivated hydrogenation catalyst according to claim 1, characterized in that, in Step 1, calcining the deactivated hydrogenation catalyst under alkaline conditions is: mixing the deactivated hydrogenation catalyst and an alkaline sodium compound and performing calcination; the calcination temperature is 600-1000°C, and the calcination time is 4-6 h.

3. The regeneration method for a deactivated hydrogenation catalyst according to claim 2, characterized in that, The alkaline sodium compound is one or more of NaCO 3 , NaOH, and NaHCO 3 ; the alkaline sodium compound accounts for 30-50% of the total mass of the deactivated hydrogenation catalyst and the alkaline sodium compound.

4. The regeneration method for a deactivated hydrogenation catalyst according to claim 1, characterized in that, in Step 1, the grinding is wet grinding, and the particle size of the deactivated hydrogenation catalyst after wet grinding is 10 μm - 20 μm.

5. The regeneration method for a deactivated hydrogenation catalyst according to claim 1, characterized in that, In Step 2, the chloride salt is one or both of NaCl and MgCl 2 ; after the chloride salt is added to the liquid phase, the concentration of the chloride salt in the liquid phase is 0.6 - 0.8 mol / L.

6. The regeneration method for a deactivated hydrogenation catalyst according to claim 1, characterized in that, the acid solution is a hydrochloric acid solution, and the concentration of the hydrochloric acid solution is 0.2 - 0.4 mol / L.

7. The regeneration method for a deactivated hydrogenation catalyst according to claim 1, characterized in that, it further comprises mixing the regenerated hydrogenation catalyst with a fresh hydrogenation catalyst and performing a sulfidation treatment.

8. The regeneration method for a deactivated hydrogenation catalyst according to claim 8, characterized in that, The conditions for the vulcanization treatment are as follows: the temperature is 280 - 320 °C, the pressure is 1.5 - 3.0 MPa, the time is 12 - 24 h, the space velocity is 3.0 - 3.5 h -1 , and the hydrogen-to-oil ratio is 200 - 400.

9. The regeneration method for a deactivated hydrogenation catalyst according to claim 1, characterized in that, the deactivated hydrogenation catalyst comprises a carrier and a metal element, and the metal element is loaded on the carrier in the form of a metal oxide.

10. The regeneration method for a deactivated hydrogenation catalyst according to claim 9, characterized in that, the metal element is at least one of Co, Mo, Ni, W, Zn, Fe, Cu, Mn, Pt, Pd, and the carrier is at least one of alumina, zirconia, silica, activated carbon, diatomite, zeolite.

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