A method for regenerating a hydrogenation catalyst

Abstract

The application discloses a regeneration method of a hydrogenation catalyst, and comprises the following steps: (1) impregnating an alkali metal poisoned hydrogenation catalyst with an organic phosphide solution, and then performing drying (preferably vacuum drying) treatment; (2) performing high-temperature calcination treatment on the catalyst obtained in the step (1); and (3) performing washing and drying treatment on the catalyst obtained in the step (2) with a buffer solution to obtain a regenerated hydrogenation catalyst. The regeneration method can effectively remove the alkali metal impurities contained in the catalyst and restore the activity of the catalyst.

Description

Technical Field

[0001] This invention belongs to the field of catalyst regeneration technology, and relates to a method for regenerating hydrogenation catalysts, particularly a method for regenerating abnormally deactivated hydrogenation catalysts. Background Technology

[0002] Hydrogenation catalysts are crucial for the production of clean fuel oils and other chemical feedstocks. During hydrogenation, catalysts can deactivate for various reasons, primarily carbon buildup and the deposition of metallic impurities. Simply landfilling deactivated catalysts not only pollutes the environment but also wastes resources; therefore, the regeneration of deactivated hydrogenation catalysts has become a significant concern.

[0003] CN202111272120.3 discloses a method for recycling and reusing spent hydrogenation catalysts. The method includes the following steps: (1) calcining the spent hydrogenation catalyst in an aerobic atmosphere; mixing the calcined product with an acid solution and heating under reflux; (2) adjusting the pH of the reflux product obtained in step (1) to 3.5-4.5 using an organic amine, and separating the solid and liquid; the organic amine has a boiling point greater than or equal to 100°C under normal pressure; (3) using the liquid product filtered in step (2) as an impregnation solution to impregnate the carrier, and heat-treating it to obtain a regenerated hydrogenation catalyst.

[0004] CN201911361889.5 discloses a method for hydrotreating heavy oil. The heavy oil feedstock is contacted with hydrogen in a hydrotreating reactor to complete the hydrotreating process. The hydrotreating reactor is filled with a regenerator obtained by regenerating a deactivated hydrotreating catalyst. The regeneration process of the regenerator is as follows: the deactivated hydrotreating catalyst is carbonized and desulfurized, then impregnated with an acidic solution containing a complexing agent, and then impregnated with an alkaline solution and treated under an ammonia atmosphere to effectively remove metallic impurities such as nickel, vanadium and iron.

[0005] The catalyst regeneration method described in the aforementioned patent is for catalysts that have become deactivated due to conventional reasons such as carbon buildup and transition metal deposition. This deactivation can often be adjusted by increasing the reaction temperature during the reaction process. However, when the reaction cycle is nearing its end and further temperature increases are no longer possible, existing regeneration methods are required to regenerate the catalyst. In actual operation, there is also a phenomenon where catalysts suddenly deactivate within the normal operating cycle due to improper operating conditions or fluctuations in reactant feedstock. Current technology does not provide solutions for how to regenerate or even whether such abnormally deactivated hydrogenation catalysts can be regenerated. A detailed analysis of the causes of deactivation is needed to provide relevant solutions. Summary of the Invention

[0006] The inventors encountered a situation where a hydrogenation catalyst underwent abnormal deactivation. The catalyst experienced severe deactivation shortly after starting operation, and even increasing the temperature could not restore its activity, forcing the refining plant to shut down. Through in-depth research, the inventors discovered that the cause of catalyst deactivation was not carbon buildup or transition metal deposition, but rather a significant increase in the alkali metal content of the deactivated catalyst, stemming from improper raw material control during industrial production. Further research revealed that the rapid deactivation of the hydrogenation catalyst due to alkali metal impurities was caused by these impurities occupying acidic sites on the catalyst surface.

[0007] Based on the above research results, this invention proposes a method for regenerating hydrogenation catalysts, mainly targeting the deactivation of hydrogenation catalysts caused by unconventional alkali metal deposition. The regeneration method can effectively remove alkali metal impurities contained in the catalyst and restore catalyst activity.

[0008] The first aspect of this invention provides a method for regenerating a hydrogenation catalyst, comprising the following: (1) The alkali metal poisoned hydrogenation catalyst is impregnated with an organophosphorus solution and then dried (preferably vacuum drying); (2) The catalyst obtained in step (1) is subjected to high-temperature calcination; (3) The catalyst obtained in step (2) is washed and dried using a buffer solution to obtain a regenerated hydrogenation catalyst.

[0009] In the method of the present invention, the alkali metal poisoned hydrogenation catalyst mentioned in step (1) refers to a catalyst that is partially deactivated or fails to meet the reaction requirements due to alkali metal deposition during the hydrogenation process. The catalyst includes a support and an active metal component. The support is generally at least one of alumina, amorphous silica-alumina and molecular sieve. The active metal component is generally a Group VIB metal and / or a Group VIII metal, wherein the Group VIB metal is at least one of Mo and W, and the Group VIII metal is at least one of Ni and Co.

[0010] In the method of the present invention, in step (1), based on the mass of the alkali metal deposition deactivated catalyst after removing sulfur and carbon, the alkali metal content in the alkali metal poisoned hydrogenation catalyst is 0.2wt%-8.0wt%, preferably 0.3wt%-5.0wt%, further preferably 0.5wt%-3.0wt%, and even more preferably 1wt%-2.0wt%; the alkali metal includes one or more of lithium, sodium and potassium.

[0011] In the method of the present invention, before impregnating the alkali metal poisoned hydrogenation catalyst with an organophosphorus solution in step (1), the alkali metal poisoned hydrogenation catalyst can be de-oiled; the de-oiling treatment can be any of the means in the art that can remove the oil phase from the surface and pores of the deactivated catalyst, such as thermal hydrogen cycling and / or solvent extraction.

[0012] In the method of the present invention, the organophosphorus compound used in the organophosphorus solution in step (1) contains an ester group and / or an aryl group, such as one or more of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, tricresol phosphate, triphenyl phosphite, triphenylphosphine oxide, triphenyl phosphate and dibutyl phosphite; the solvent used in the organophosphorus solution is at least one of ethers, alcohols and ketones, such as one or more of diethyl ether, methanol, ethanol, propanol, butanol, ethylene glycol and acetone, preferably one or more of methanol, ethanol, propanol and acetone.

[0013] In the method of the present invention, the molar ratio of the organophosphorus compound (calculated as elemental phosphorus) in the organophosphorus compound solution to the active metal component (calculated as elemental metal) in the alkali metal poisoning hydrogenation catalyst in step (1) is 0.03~0.6, preferably 0.05~0.4; the active metal component includes Group VIB metals and / or Group VIII metals.

[0014] In the method of the present invention, the concentration of the organophosphorus solution in step (1) is 0.01~1.0 g / mL.

[0015] In the method of the present invention, the impregnation in step (1) is saturated impregnation or supersaturated impregnation, preferably supersaturated impregnation, and more preferably in supersaturated impregnation, the supersaturation degree is not less than 1.05, and preferably 1.08~3.0.

[0016] In the method of the present invention, the drying process described in step (1) is also well known to those skilled in the art. The drying process temperature is 60~140℃ and the time is 2~6h.

[0017] In the method of the present invention, the temperature of the high-temperature roasting treatment in step (2) is 700~1000℃, preferably 800~900℃, and the time is 1~3h; the high-temperature roasting treatment is carried out in an oxygen-containing atmosphere, the oxygen content of the oxygen-containing atmosphere is 15v%~100v%, preferably an air atmosphere.

[0018] In the method of the present invention, the buffer solution in step (3) is an aqueous solution containing ammonium salt, wherein the concentration of ammonium ions is 0.003~0.04 mol / 100g; the ammonium salt is one or more of ammonium carbonate, ammonium bicarbonate, triammonium phosphate, diammonium phosphate, monoammonium phosphate, ammonium acetate and ammonium formate.

[0019] In the method of the present invention, the buffer solution in step (3) is slightly acidic / neutral with a pH value of 6.0~7.0. Depending on the required pH value of the buffer solution, acetic acid and / or ammonia can be used to adjust the pH value.

[0020] In the method of the present invention, the specific operation process of washing in step (3) is as follows: spray the catalyst obtained in step (2) with a buffer solution, and repeat the above steps 1 to 10 times according to the difference in alkali metal content until the alkali metal content is less than 0.1 wt%; wherein, the volume of the buffer solution used each time is 120% to 1000% of the saturated water absorption (volume) of the catalyst obtained in step (2).

[0021] In the method of the present invention, the drying process in step (3) can be carried out under conventional conditions in the art, such as a drying temperature of 90~150℃ and a drying time of 2~6h.

[0022] In the method of the present invention, step (3) may also introduce an active metal component into the catalyst. The specific process of introducing the active metal component is as follows: after washing and drying, the active metal component is introduced into the obtained catalyst by impregnation; the impregnation method is saturated impregnation or supersaturated impregnation, preferably saturated impregnation; the mass of the introduced active metal component is the mass of the active metal lost during the washing process.

[0023] A second aspect of the present invention provides a regenerated hydrogenation catalyst obtained by the above method.

[0024] The third aspect of this invention provides the application of the above-mentioned regenerated hydrogenation catalyst in the hydrogenation reaction of distillate oil.

[0025] In the above applications, the regenerated hydrogenation catalyst needs to be pre-sulfurized before the distillate oil hydrogenation reaction. The pre-sulfurization technology can employ methods well-known in the art, generally either dry sulfidation or wet sulfidation. Specifically, in this invention, wet sulfidation can be used, with the following specific operating conditions: sulfidation pressure 0.1~20 MPa, sulfidation temperature 230~550℃, and liquid hourly space velocity 0.5~10.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is 50~2000:1. During the pre-sulfurization process, the metal heteropolyacid salts formed during catalyst regeneration will react and be converted into metal sulfides.

[0026] In the above applications, the distillate oil is one or more of wax oil, diesel oil, kerosene, and gasoline.

[0027] In the above applications, the operating conditions for the distillate oil hydrogenation reaction are as follows: reaction temperature 150~400℃, reaction pressure 0.5~15MPa, and liquid hourly space velocity 0.3~10h⁻¹. -1 The hydrogen-to-oil volume ratio is 100-1000.

[0028] Compared with the prior art, the present invention has the following advantages: 1. This invention analyzes the phenomenon of abnormal deactivation of hydrogenation catalysts caused by alkali metal deposition and creatively proposes a regeneration method for alkali metal poisoned hydrogenation catalysts. The method first impregnates the alkali metal poisoned hydrogenation catalyst with an organophosphorus solution. During the subsequent high-temperature calcination process, the active metal components complex with the organophosphorus to form heteropolyacid salts (such as phosphomolybdate heteropolyacid salts and phosphotungsten heteropolyacid salts), reducing the concentration of oxidized active metal components on the catalyst surface. This inhibits excessive aggregation of oxidized active metal components during high-temperature calcination. Furthermore, the synergistic effect of organophosphorus solution impregnation and high-temperature calcination solidifies the active components, effectively reducing the loss of active metal components during the washing and separation of alkali metals from the catalyst using a buffer solution. Simultaneously, during the high-temperature calcination process, alkali metal impurities form water-soluble metal molybdates (such as sodium molybdate and / or sodium tungstate) with Group VIB metal components (such as molybdenum and / or tungsten). These are then washed with a buffer solution to remove the alkali metals occupying the acidic sites of the catalyst, restoring catalyst activity.

[0029] 2. In this invention, the organophosphorus compound solution uses an organic solvent. Organic solvents have better wetting properties for carbon-containing catalysts, thereby promoting uniform impregnation of the organophosphorus compounds. Furthermore, introducing the organophosphorus compound solution using a supersaturated impregnation method is even more beneficial for uniform impregnation of the organophosphorus compounds. Implementation

[0030] The following examples further illustrate the solution and effects of the present invention, but do not constitute a limitation on the present invention.

[0031] In this invention, during the supersaturated impregnation process, the supersaturation degree is the amount (mass) of the impregnation liquid / the saturated water absorption (mass) * 100%.

[0032] In this invention, the relative desulfurization activity is calculated according to the following formula: Relative desulfurization activity % = [1 / (S)] p ) 0.65 -1 / (S f ) 0.65 ] / [1 / (S pr ) 0.65 -1 / (S f ) 0.65 ]*100% Wherein: S f Sulfur content of crude oil, mg / kg; S pr The sulfur content of the reference hydrogenated oil, in mg / kg; S p The sulfur content of the oil produced by hydrogenation of fresh catalyst, in mg / kg.

[0033] In this invention, the alkali metal poisoned hydrogenation catalyst used in the examples and comparative examples is a deactivated hydrogenation catalyst obtained from a refinery using the commercial brand FHUDS-7 hydrogenation catalyst. This deactivated hydrogenation catalyst has a sulfur content of 8.8 wt% and a carbon content of 6.2 wt%. Based on the weight of the catalyst after removing sulfur and carbon, the alkali metal content (as oxides) is 1.5 wt%, the Group VIB metal Mo content (as oxides) is 19 wt%, and the Group VIII metal Ni content (as oxides) is 3 wt%.

[0034] In this invention, the saturated water absorption capacity of the alkali metal poisoning hydrogenation catalyst is 30g water / 100g catalyst.

[0035] In this invention, the vacuum degree of vacuum drying is 3*10. -3 Pa.

[0036] Example 1 117.6 g of the above-mentioned alkali metal poisoned hydrogenation catalyst was taken, and 3.12 g of triethyl phosphate was diluted with ethanol to a concentration of 49.4 mL, which was then supersaturated and impregnated onto the alkali metal poisoned hydrogenation catalyst, with a supersaturation degree of 1.4. After vacuum drying at 100 °C for 3 h, it was calcined at 800 °C for 2 h in air and allowed to cool to room temperature. The catalyst was washed with 200 mL of a triammonium phosphate / acetic acid buffer solution with a pH of 6.5 and a concentration of 0.006 mol / 100 g. After three washes, the alkali metal impurity content on the catalyst was 0.04 wt%. After drying at 120 °C for 3 h, the Mo content (calculated as MoO3) of the catalyst was measured to be 18 wt%, and the water absorption rate was 50 mL / 100 g. Then, it was saturated with an aqueous solution containing 2 g of molybdenum (calculated as molybdenum oxide) and dried at 120 °C for 3 h to obtain the regenerated hydrogenation catalyst R-1.

[0037] Example 2 117.6 g of the above-mentioned alkali metal poisoned hydrogenation catalyst was taken, and 19 g of tricresyl phosphate was diluted with ethanol to a concentration of 60 mL, which was then supersaturated and impregnated onto the alkali metal poisoned hydrogenation catalyst, with a supersaturation degree of 1.7. After vacuum drying at 120 °C for 3 h, it was calcined at 900 °C for 2 h in air atmosphere and allowed to cool to room temperature. The catalyst was washed with 150 mL of ammonium bicarbonate / acetic acid buffer solution with a pH of 6.8 and a concentration of 0.01 mol / 100 g. After four washes, the alkali metal impurity content on the catalyst was 0.03 wt%. After drying at 100 °C for 3 h, the Mo content (calculated as MoO3) of the catalyst was measured to be 17.5 wt%, and the water absorption rate was 50 mL / 100 g. Then, it was saturated with an aqueous solution containing 3 g of molybdenum (calculated as molybdenum oxide) at 110 °C for 3 h to obtain the regenerated hydrogenation catalyst R-2.

[0038] Example 3 117.6 g of the above-mentioned alkali metal poisoned hydrogenation catalyst was taken. 6.8 g of dibutyl phosphite was diluted with ethanol to a concentration of 84.7 mL and supersaturatedly impregnated onto the alkali metal poisoned hydrogenation catalyst, with a supersaturation degree of 2.4. After vacuum drying at 80 °C for 3 h, it was calcined at 750 °C for 2 h in air and allowed to cool to room temperature. The catalyst was washed with 350 mL of ammonium formate / ammonia buffer solution (pH 6.2, concentration 0.02 mol / 100 g). After three washes, the alkali metal impurity content on the catalyst was 0.03 wt%. After drying at 110 °C for 3 h, the Mo content (calculated as MoO3) of the catalyst was measured to be 17.8 wt%, and the water absorption rate was 50 mL / 100 g. Then, a saturated aqueous solution with a molybdenum content (calculated as molybdenum oxide) of 2.4 g / 100 mL was impregnated, and dried at 110 °C for 3 h to obtain the regenerated hydrogenation catalyst R-3.

[0039] Example 4 117.6 g of the above-mentioned alkali metal poisoned hydrogenation catalyst was taken, and 3.6 g of trimethyl phosphate was diluted with ethanol to a concentration of 42.4 mL, which was then supersaturated and impregnated onto the alkali metal poisoned hydrogenation catalyst, with a supersaturation degree of 1.2. After vacuum drying at 100 °C for 3 h, it was calcined at 850 °C for 3 h in air and allowed to cool to room temperature. The catalyst was washed with 250 mL of a diammonium phosphate / acetic acid buffer solution with a pH of 6.7 and a concentration of 0.03 mol / 100 g. After three washes, the alkali metal impurity content on the catalyst was 0.03 wt%. After drying at 100 °C for 3 h, the Mo content (calculated as MoO3) of the catalyst was measured to be 18.2 wt%, and the water absorption rate was 50 mL / 100 g. Then, it was saturated and impregnated with an aqueous solution containing 1.6 g of molybdenum oxide (calculated as molybdenum oxide) and dried at 110 °C for 3 h to obtain the regenerated hydrogenation catalyst R-4.

[0040] Example 5 The preparation method of Example 1 was followed, but the active metal was not replenished after washing to remove alkali metal impurities. 117.6 g of the above alkali metal poisoned hydrogenation catalyst was taken. 3.12 g of triethyl phosphate was diluted with ethanol to 49.4 mL and supersaturatedly impregnated onto the alkali metal poisoned hydrogenation catalyst, wherein the supersaturation degree was 1.4. After vacuum drying at 100 °C for 3 h, it was calcined at 800 °C for 2 h in air atmosphere and allowed to cool to room temperature. 200 mL of a triammonium phosphate / acetic acid buffer solution with a pH of 6.5 and a concentration of 0.006 mol / 100 g was used to wash the catalyst. After three washes, the alkali metal impurity content on the catalyst was 0.04 wt%. After drying at 120 °C for 3 h, the regenerated hydrogenation catalyst R-5 was obtained.

[0041] Example 6 The preparation method of Example 2 was followed, but the active metal was not replenished after washing to remove alkali metal impurities. 117.6 g of the above alkali metal poisoned hydrogenation catalyst was taken, and 19 g of tricresyl phosphate was diluted with ethanol to 60 mL, and supersaturated onto the alkali metal poisoned hydrogenation catalyst, wherein the supersaturation was 1.7. After vacuum drying at 120 °C for 3 h, it was calcined at 900 °C for 2 h in air atmosphere and allowed to cool to room temperature. The catalyst was washed with 150 mL of ammonium bicarbonate / acetic acid buffer solution with a pH of 6.8 and a concentration of 0.01 mol / 100 g. After four washes, the alkali metal impurity content on the catalyst was 0.03 wt%. After drying at 120 °C for 3 h, the regenerated hydrogenation catalyst R-6 was obtained.

[0042] Comparative Example 1 The preparation method of Example 1 was followed, but instead of impregnating the alkali metal poisoned hydrogenation catalyst with organophosphorus compounds, direct calcination was used. 117.6 g of the above alkali metal poisoned hydrogenation catalyst was calcined at 800°C for 2 h in air and then allowed to cool to room temperature. The catalyst was washed with 200 mL of a triammonium phosphate / acetic acid buffer solution with a pH of 6.5 and a concentration of 0.006 mol / 100 g. After three washes, the alkali metal impurity content on the catalyst was 0.20 wt%. After drying at 120°C for 3 h, the Mo content (calculated as MoO3) of the catalyst was measured to be 14 wt%, and the water absorption rate was 50 mL / 100 g. The catalyst was then saturated with an aqueous solution containing 10 g / 100 mL of molybdenum (calculated as molybdenum oxide) and dried at 120°C for 3 h to obtain regenerated hydrogenation catalyst D-1.

[0043] Comparative Example 2 The preparation method of Example 1 was followed, but the catalyst was impregnated with organophosphorus compounds and then calcined at a low temperature. 117.6 g of the above alkali metal poisoned hydrogenation catalyst was taken. 3.12 g of triethyl phosphate was diluted with ethanol to 49.4 mL and supersaturatedly impregnated onto the alkali metal poisoned hydrogenation catalyst, wherein the supersaturation degree was 1.4. After vacuum drying at 100 °C for 3 h, it was calcined at 500 °C for 2 h in air and then allowed to cool to room temperature. 200 mL of a triammonium phosphate / acetic acid buffer solution with a pH of 6.5 and a concentration of 0.006 mol / 100 g was used to wash the catalyst. After three washes, the alkali metal impurity content on the catalyst was 0.17 wt%. After drying at 120 °C for 3 h, the Mo content (calculated as MoO3) of the catalyst was measured to be 13 wt%, and the water absorption rate was 50 mL / 100 g. The regenerated hydrogenation catalyst D-2 was obtained by saturating an aqueous solution with a molybdenum content (calculated as molybdenum oxide) of 12 g / 100 mL and drying it at 120 °C for 3 h.

[0044] Comparative Example 3 The preparation method of Example 1 was followed, but the catalyst was washed with dilute nitric acid with a pH of 3 to remove alkali metal impurities. 117.6 g of the above alkali metal poisoned hydrogenation catalyst was taken. 3.12 g of triethyl phosphate was diluted with ethanol to 49.4 mL and supersaturated onto the alkali metal poisoned hydrogenation catalyst, where the supersaturation was 1.4. After vacuum drying at 100 °C for 3 h, it was calcined at 500 °C for 2 h in air and allowed to cool to room temperature. 200 mL of dilute nitric acid solution with a pH of 3 was used to wash the catalyst. After three washes, the alkali metal impurity content on the catalyst was 0.03 wt%. After drying at 120 °C for 3 h, the Mo content (calculated as MoO3) of the catalyst was measured to be 13.5 wt%, and the water absorption rate was 50 mL / 100 g. The catalyst was then saturated with an aqueous solution containing 11 g of molybdenum (calculated as molybdenum oxide) and dried at 120 °C for 3 h to obtain regenerated hydrogenation catalyst D-3.

[0045] Example 6 The catalysts obtained in the examples and comparative examples were subjected to activity evaluation tests in a 10 mL reaction apparatus. The feedstock was conventional straight-run diesel oil with a sulfur content of 1.9 wt%, a nitrogen content of 290 ng / μL, and a final boiling point of 367 °C. Before the reaction began, the catalyst needed to be pre-sulfurized. The sulfiding agent was conventional straight-run diesel oil with 1.5 vol% DMDS added. The sulfidation conditions were: sulfidation pressure 6.4 MPa, liquid hourly space velocity (LISH) 1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio was 400:1. The catalyst in the reactor was completely wetted at 140℃, then the temperature was increased to 320℃ at a rate of 1℃ / min and held at this temperature for 10 hours to complete sulfidation. The reaction operating conditions were as follows: reaction pressure 6.4 MPa, reaction temperature 360℃, and liquid hourly space velocity (LISH) 1.5 h⁻¹. -1The hydrogen-to-oil volume ratio was 400:1. After initial activity stabilization for 24 hours, the product properties were analyzed. The properties and relative desulfurization activity of the catalyst are listed in Table 1.

[0046] Table 1. Catalyst properties and desulfurization activity in the examples and comparative examples

[0047] *Based on the fresh agent, its desulfurization activity is set to 100%.

Claims

1. A method for regenerating a hydrogenation catalyst, characterized in that: Includes the following: (1) The alkali metal poisoned hydrogenation catalyst was impregnated with an organophosphorus compound solution and then dried. (2) The catalyst obtained in step (1) is subjected to high-temperature calcination; (3) The catalyst obtained in step (2) is washed and dried using a buffer solution to obtain a regenerated hydrogenation catalyst; The organophosphorus compounds used in the organophosphorus solution in step (1) are one or more of the following: trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, tricresol phosphate, triphenyl phosphite, triphenylphosphine oxide, triphenyl phosphate, and dibutyl phosphite. The high-temperature calcination treatment in step (2) is carried out at a temperature of 700~1000℃ for 1~3 hours. The buffer solution mentioned in step (3) is an aqueous solution containing ammonium salt; the ammonium salt is one or more of ammonium carbonate, ammonium bicarbonate, triammonium phosphate, diammonium phosphate, monoammonium phosphate, ammonium acetate, and ammonium formate; The buffer solution mentioned in step (3) is slightly acidic / neutral with a pH value of 6.0~7.

0.

2. The method according to claim 1, characterized in that: The drying process described in step (1) is vacuum drying.

3. The method according to claim 1, characterized in that: The alkali metal poisoned hydrogenation catalyst mentioned in step (1) refers to a catalyst that is partially deactivated or fails to meet the reaction requirements due to alkali metal deposition during the hydrogenation process.

4. The method according to claim 1, characterized in that: In step (1), the mass of the alkali metal poisoning hydrogenation catalyst after removing sulfur and carbon is used as the basis, and the alkali metal content in the alkali metal poisoning hydrogenation catalyst is 0.2wt%-8.0wt%; the alkali metal includes one or more of lithium, sodium and potassium.

5. The method according to claim 4, characterized in that: In step (1), the mass of the alkali metal poisoning hydrogenation catalyst after removing sulfur and carbon is used as the basis, and the alkali metal content in the alkali metal poisoning hydrogenation catalyst is 0.3wt%-5.0wt%.

6. The method according to claim 4, characterized in that: In step (1), the mass of the alkali metal poisoning hydrogenation catalyst after removing sulfur and carbon is used as the basis, and the alkali metal content in the alkali metal poisoning hydrogenation catalyst is 0.5wt%-3.0wt%.

7. The method according to claim 4, characterized in that: In step (1), the mass of the alkali metal poisoning hydrogenation catalyst after removing sulfur and carbon is used as the basis, and the alkali metal content in the alkali metal poisoning hydrogenation catalyst is 1wt%-2.0wt%.

8. The method according to claim 1, characterized in that: In step (1), before impregnating the alkali metal poisoned hydrogenation catalyst with an organophosphorus solution, the alkali metal poisoned hydrogenation catalyst is subjected to an oil removal treatment; the oil removal treatment is performed by either thermal hydrogen cycling or solvent extraction.

9. The method according to claim 1, characterized in that: In step (1), the solvent used in the organophosphorus solution is at least one of ethers, alcohols and ketones.

10. The method according to claim 9, characterized in that: In step (1), the solvent used for the organophosphorus solution is one or more of diethyl ether, methanol, ethanol, propanol, butanol, ethylene glycol and acetone.

11. The method according to claim 9, characterized in that: In step (1), the solvent used in the organophosphorus solution is one or more of methanol, ethanol, propanol and acetone.

12. The method according to claim 1, characterized in that: In step (1), the molar ratio of the organophosphorus compound in the organophosphorus solution to the active metal component in the alkali metal poisoning hydrogenation catalyst is 0.03 to 0.6; the active metal component includes Group VIB metals and / or Group VIII metals, wherein the organophosphorus compound is calculated as elemental phosphorus and the active metal component is calculated as elemental metal.

13. The method according to claim 12, characterized in that: In step (1), the molar ratio of the organophosphorus compounds in the organophosphorus solution to the active metal components in the alkali metal poisoning hydrogenation catalyst is 0.05 to 0.

4.

14. The method according to claim 1, characterized in that: The concentration of the organophosphorus solution in step (1) is 0.01~1.0 g / mL.

15. The method according to claim 1, characterized in that: The impregnation described in step (1) is saturated impregnation or supersaturated impregnation.

16. The method according to claim 15, characterized in that: The impregnation described in step (1) is a supersaturated impregnation.

17. The method according to claim 15, characterized in that: In step (1), the supersaturation degree in the supersaturated impregnation is not less than 1.

05.

18. The method according to claim 15, characterized in that: In step (1), the supersaturation degree in the supersaturation impregnation is 1.08~3.

0.

19. The method according to claim 1, characterized in that: The drying process in step (1) is carried out at a temperature of 60~140℃ for 2~6 hours.

20. The method according to claim 1, characterized in that: The high-temperature roasting treatment in step (2) is carried out at a temperature of 800~900℃; the high-temperature roasting treatment is carried out in an oxygen-containing atmosphere with an oxygen content of 15v%~100v.

21. The method according to claim 20, characterized in that: In step (2), the oxygen-containing atmosphere is an air atmosphere.

22. The method according to claim 1, characterized in that: In step (3), an aqueous solution containing ammonium salt is used, wherein the concentration of ammonium ions is 0.003~0.04 mol / 100g.

23. The method according to claim 1, characterized in that: The specific operation process of washing in step (3) is as follows: spray the catalyst obtained in step (2) with a buffer solution, and repeat the above steps 1 to 10 times according to the difference in alkali metal content until the alkali metal content is less than 0.1 wt%; wherein, the volume of the buffer solution used each time is 120% to 1000% of the saturated water absorption volume of the catalyst obtained in step (2).

24. The method according to claim 1, characterized in that: In step (3), the drying temperature is 90~150℃ and the drying time is 2~6h.

25. The method according to claim 1, characterized in that: In step (3), an active metal component is also introduced into the catalyst. The specific process of introducing the active metal component is as follows: after washing and drying, the active metal component is introduced into the obtained catalyst by impregnation. The impregnation method is saturated impregnation or supersaturated impregnation. The mass of the introduced active metal component is the mass of the active metal lost during the washing process.

26. The method according to claim 25, characterized in that: In step (3), the impregnation method is saturated impregnation.

27. A regenerated hydrogenation catalyst obtained by the method of any one of claims 1-26.

28. The application of the regenerated hydrogenation catalyst according to claim 27 in the hydrogenation reaction of distillate oil.

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