Regeneration method of inactivated hydrogenation catalyst

Abstract

The invention discloses a regeneration method of an inactivated hydrogenation catalyst, which comprises the following steps: (1) impregnating the inactivated hydrogenation catalyst by using an organic solution containing an organic phosphide A as an impregnation liquid, and then carrying out drying and high-temperature roasting treatment; the temperature of the high-temperature roasting treatment is 450 to 800 DEG C, preferably 500 to 750 DEG C; (2) soaking or washing the catalyst obtained by roasting in the step (1) by adopting an ionic liquid solution containing an organic phosphide B, preferably soaking; and washing and drying to obtain the final regenerated hydrogenation catalyst. The regeneration method can effectively remove alkali metal impurities and alkaline earth metal impurities adsorbed on acid sites on the surface of the catalyst, so that the activity of the catalyst is recovered.

Description

Technical Field

[0001] The invention belongs to the technical field of catalyst regeneration and relates to a regeneration method for a deactivated hydrogenation catalyst. Background Art

[0002] Hydrogenation catalysts are crucial for producing clean fuel oil and other chemical feedstocks. During the hydrogenation process, catalysts can become deactivated due to a variety of factors, primarily carbon deposition and metallic impurity deposition. Simply landfilling deactivated catalysts not only pollutes the environment but also wastes resources. Therefore, the regeneration of deactivated hydrogenation catalysts has attracted considerable attention.

[0003] CN114130409A provides a method for regenerating a hydrogenation catalyst. The method comprises: (1) mixing deactivated hydrogenation catalysts A1 and A2, immersing the mixture in a solvent, and ultrasonically treating the mixture to obtain a mixture of catalyst B and black powder; (2) recovering catalyst B and filtering the mixture of the black powder to obtain powder C; (3) grinding catalyst B into powder, sieving to obtain catalyst powder D, and then forming, drying, and calcining to obtain a regenerated carrier; (4) dissolving powder C in diesel, impregnating the regenerated carrier, and drying to obtain a regenerated hydrogenation catalyst.

[0004] CN109926105A provides a method for regenerating a hydrogenation catalyst, which comprises the following steps: (1) contacting the hydrogenation catalyst to be regenerated with an oxygen-containing gas for charring to obtain catalyst A; (2) contacting catalyst A with an organic compound solution and performing a heat treatment to obtain catalyst B; and (3) introducing hydrazine hydrate into catalyst B, followed by a heat treatment to obtain a regenerated catalyst.

[0005] The catalyst regeneration method involved in the above patent is for conventional catalysts that have been deactivated due to carbon deposition, transition metal deposition, and the like. This deactivation can often be adjusted during the reaction process by increasing the reaction temperature. Generally, when the reaction cycle is about to end and cannot be adjusted by increasing the reaction temperature, it is necessary to use the regeneration method in the prior art to regenerate the catalyst. In actual operation, there is also a phenomenon of sudden deactivation of the catalyst during the normal operation cycle due to improper operating conditions and fluctuations in the reaction raw materials. Regarding how to regenerate this abnormally deactivated hydrogenation catalyst and whether it can be regenerated, the prior art does not provide relevant solutions. It is necessary to make a specific analysis of the cause of deactivation and provide relevant solutions. Summary of the Invention

[0006] The inventors encountered abnormal deactivation of hydrogenation catalysts during the operation of industrial equipment. Shortly after the hydroprocessing catalyst was put into operation, it showed severe deactivation. Even with the temperature increase, the activity of the catalyst could not be restored, forcing the refinery to shut down. Through in-depth research, the inventors found that the cause of catalyst deactivation was not carbon deposits and transition metal deposition, but a significant increase in the alkali metal and alkaline earth metal content in the catalyst. This was caused by improper raw material control during the industrial production process, resulting in the inclusion of not only alkali metal impurities but also alkaline earth metal impurities in the raw materials. Further research found that alkali metal / alkaline earth metal impurities would occupy acidic sites on the catalyst surface, causing the hydrogenation catalyst to deactivate rapidly.

[0007] Based on the above research results, the present invention proposes a method for regenerating a deactivated hydrogenation catalyst, which can effectively remove alkali metal impurities and alkaline earth metal impurities adsorbed on the acidic sites on the catalyst surface, thereby restoring the catalyst activity.

[0008] The present invention provides a method for regenerating a deactivated hydrogenation catalyst, comprising the following steps:

[0009] (1) impregnating the deactivated hydrogenation catalyst with an organic solution containing an organic phosphide A as an impregnation liquid, followed by drying and high-temperature calcination; the high-temperature calcination temperature is 450 to 800° C., preferably 500 to 750° C.;

[0010] (2) soaking or washing the catalyst obtained by calcining in step (1) with an ionic liquid solution containing organic phosphide B, preferably soaking; after washing and drying, the final regenerated hydrogenation catalyst is obtained.

[0011] In the method of the present invention, the deactivated hydrogenation catalyst in step (1) refers to a catalyst that is partially deactivated or fails to meet the reaction requirements due to the deposition of alkali metals and / or alkaline earth metals during the hydrogenation process. The catalyst includes a carrier and an active metal component. The carrier is generally at least one of alumina, amorphous silica-alumina and molecular sieves. 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. Based on the mass of the deactivated hydrogenation catalyst after removing sulfur and carbon, the alkali metal content in the deactivated hydrogenation catalyst is 0.2wt% to 8.0wt%, preferably 0.3wt% to 5.0wt%, more preferably 0.5wt% to 3.0wt%, and even more preferably 1.0wt% to 2.0wt%; the alkaline earth metal content is 0.2wt% to 6.0wt%, preferably 0.3wt% to 4.0wt%, more preferably 0.5wt% to 2.0wt%, and even more preferably 0.8wt% to 1.5wt%; the alkali metal is one or more of lithium, sodium and potassium, and the alkaline earth metal is one or more of magnesium, calcium, strontium and barium.

[0012] In the method of the present invention, the deactivated hydrogenation catalyst in step (1) may be first subjected to a deoiling treatment; the deoiling treatment may adopt any of the means available in the art that can achieve catalyst deoiling, such as one or more of hot hydrogen circulation and solvent extraction.

[0013] In the method of the present invention, the organic phosphide A in step (1) contains an ester group and / or an aromatic group, such as one or more of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, tricresyl phosphate, triphenyl phosphite, triphenylphosphine oxide, triphenyl phosphate and dibutyl phosphite; and the concentration of the organic phosphide A in the organic solution containing the organic phosphide A is 0.01 to 1.0 g / mL.

[0014] In the method of the present invention, the organic solvent in step (1) 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.

[0015] In the method of the present invention, the molar ratio of the organic phosphide A (calculated as elemental phosphorus) contained in the organic solution containing the organic phosphide A in step (1) to the active metal component (calculated as elemental metal) contained in the deactivated hydrogenation catalyst is 0.03 to 0.6, preferably 0.05 to 0.4; the active metal component is a Group VIB metal and a Group VIII metal.

[0016] In the method of the present invention, the impregnation in step (1) can be saturated impregnation or supersaturated impregnation, preferably supersaturated impregnation, and more preferably in supersaturated impregnation, the supersaturation degree is not less than 1.05, preferably 1.08 to 3.0.

[0017] In the method of the present invention, after the supersaturated impregnation in step (1), the impregnation liquid may be removed before drying, or the impregnation liquid may not be removed and the drying may be directly performed.

[0018] In the method of the present invention, the drying treatment in step (1) is also well known to those skilled in the art, and can be carried out by drying at normal pressure or vacuum drying, preferably vacuum drying; the drying temperature is 60-140° C., and the drying time is 2-6 h.

[0019] In the method of the present invention, the time of the high-temperature calcination treatment in step (1) is 1 to 3 hours; the high-temperature calcination treatment is carried out in an oxygen-containing atmosphere, the oxygen content of the oxygen-containing atmosphere is 15% to 100% by volume, and the remainder is a mixed gas of nitrogen and an inert gas, and the inert gas includes one or more of helium, neon, argon, krypton, xenon and radon; the oxygen-containing atmosphere is preferably an air atmosphere.

[0020] In the method of the present invention, the organic phosphide B in step (2) is an amino / aminophosphoric acid compound, including one or more of aminomethylene diphosphoric acid, aminoethylene diphosphoric acid, aminopropylene diphosphoric acid, aminoethyl phosphoric acid, aminopropylphosphonic acid, aminotrimethylphosphonic acid and ethylenediaminetetramethylenephosphonic acid; based on the mass of the ionic liquid solution containing the organic phosphide B, the mass concentration of the organic phosphide B is 0.1wt% to 5wt%, preferably 0.3wt% to 2wt%.

[0021] In the method of the present invention, the ionic liquid in step (2) is a neutral ionic liquid, including one or more of imidazole tetrafluoroborate, imidazole hexafluorophosphate, pyridine tetrafluoroborate and pyridine hexafluorophosphate, preferably one or more of 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF4), 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim]PF6), 1-ethyl-3-methylimidazolium tetrafluoroborate ([Emim]BF4), 1-ethyl-3-methylimidazolium hexafluorophosphate ([Emim]PF6), N-ethylpyridinium tetrafluoroborate ([EtPy]BF4) and N-butylpyridinium hexafluorophosphate ([BuPy]PF6).

[0022] In the method of the present invention, the specific operation process of the soaking in step (2) is as follows: the catalyst obtained by calcining step (1) is soaked in an ionic liquid solution containing organic phosphide B at a temperature of 35 to 80°C, and then solid-liquid separation is performed; the soaking time is 15 to 60 minutes; the volume ratio of the ionic liquid solution containing organic phosphide B to the catalyst is 1:1 to 10:1; the solid-liquid separation can be achieved by any means of solid-liquid separation in the prior art, such as any one of sedimentation, filtration and centrifugation, preferably filtration.

[0023] In the method of the present invention, the washing process in step (2) is: washing the catalyst with an ionic liquid, the number of washing times is 1 to 10 times; the volume ratio of the ionic liquid used in each washing to the catalyst is 2:1 to 10:1; the ionic liquid is a neutral ionic liquid, including one or more of imidazole tetrafluoroborate, imidazole hexafluorophosphate, pyridine tetrafluoroborate and pyridine hexafluorophosphate, preferably one or more of 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF4), 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim]PF6), 1-ethyl-3-methylimidazolium tetrafluoroborate ([Emim]BF4), 1-ethyl-3-methylimidazolium hexafluorophosphate ([Emim]PF6), N-ethylpyridinium tetrafluoroborate ([EtPy]BF4) and N-butylpyridinium hexafluorophosphate ([BuPy]PF6).

[0024] In the method of the present invention, the drying temperature in step (2) is 90 to 150° C., and the drying time is 2 to 6 hours.

[0025] In the method of the present invention, active metal components can also be introduced into the catalyst in step (2). The specific process of introducing the active metal components is as follows: after washing and drying, the active metal components are 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 components is the mass of the active metal lost during the washing process.

[0026] The present invention provides a regenerated hydrogenation catalyst obtained by the method.

[0027] Compared with the prior art, the present invention has the following advantages:

[0028] 1. In the regeneration method of a deactivated hydrogenation catalyst of the present invention, a solution of an organic phosphide A containing ester groups and / or aromatic groups is first used to impregnate the deactivated hydrogenation catalyst, followed by drying and high-temperature calcination. During this process, the active metal components will complex with the organic phosphide A to form heteropolyacid salts (such as phosphomolybdic heteropolyacid salts and phosphotungstate heteropolyacid salts), reducing the concentration of the oxidized active metal components on the catalyst surface, thereby inhibiting excessive aggregation of the oxidized active metal components during the high-temperature calcination process. At the same time, during the high-temperature calcination process, alkali metal impurities and alkaline earth metal impurities will react with Group VIB metal components (such as molybdenum and / or tungsten) to form metal molybdates (such as sodium molybdate and / or sodium tungstate). Then, the catalyst is soaked or rinsed with an ionic liquid solution containing amino / aminophosphoric acid compounds, which can remove the alkali metal and alkaline earth metal occupying the acidic sites of the catalyst and restore the catalyst activity.

[0029] 2. In the regeneration method of the deactivated hydrogenation catalyst of the present invention, an organic solvent is used in the organic solution containing the organic phosphide A. The organic solvent has better wettability for the carbon-containing catalyst, thereby promoting uniform impregnation of the organic phosphide. Furthermore, the organic solution containing the organic phosphide A is introduced by a supersaturated impregnation method, which further facilitates uniform impregnation of the organic phosphide A. DETAILED DESCRIPTION

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

[0031] In the present invention, the saturated water absorption capacity test method is as follows: First, the sample to be tested is dried at 120°C for 24 hours. The test substance is then weighed and its initial weight is recorded. The sample is then immersed in water and allowed to fully absorb water until it no longer absorbs water. Finally, the sample is removed, its surface moisture is wiped dry, and its saturated weight is recorded. The saturated water absorption capacity of the substance can be obtained by calculating the difference between the initial weight and the saturated weight and dividing it by the density of water.

[0032] In the present invention, in the supersaturated impregnation process, the supersaturation degree is the amount (volume) of the impregnation liquid / the saturated water absorption amount (volume)*100%.

[0033] In the present invention, the relative desulfurization activity is based on the fresh agent, and the desulfurization activity of the fresh agent is set to 100%. The relative desulfurization activity is calculated according to the following formula:

[0034] Relative desulfurization activity = [1 / (S p ) 0.65 ~1 / (S f ) 0.65 ] / [1 / (S pr ) 0.65 ~1 / (S f ) 0.65]*100%

[0035] Where: S f is the sulfur content of the raw oil (percentage); S pr S is the sulfur content of the oil generated by hydrogenation of the reference agent; p It is the sulfur content of the oil produced by hydrogenation of fresh catalyst.

[0036] The deactivated hydrogenation catalyst used in the Examples and Comparative Examples of the present invention is a commercially available FHUDS-10 hydrogenation catalyst obtained from a refinery. The deactivated hydrogenation catalyst has a sulfur content of 10.5 wt% and a carbon content of 7.7 wt%. Based on the weight of the catalyst after sulfur and carbon removal, the catalyst has an alkali metal content (calculated as oxides) of 1.4 wt%, an alkaline earth metal content (calculated as oxides) of 1.2 wt%, a Group VIB metal Mo content (calculated as oxides) of 23.5 wt%, and a Group VIII metal Co content (calculated as oxides) of 3.5 wt%.

[0037] In the present invention, the saturated water absorption capacity of the deactivated hydrogenation catalyst is 30 mL of water / 100 g of catalyst.

[0038] In the present invention, the vacuum degree of vacuum drying is 3*10 ～3 Pa.

[0039] Example 1

[0040] Take 122.2g of the above-mentioned deactivated hydrogenation catalyst, dilute 15.5g of trimethyl phosphate with ethanol to 55.0mL, and supersaturate impregnate the deactivated hydrogenation catalyst, wherein the supersaturation is 1.5. After vacuum drying at 100℃ for 3h, place it in an air atmosphere and roast it at 600℃ for 2h, and let it cool to room temperature. Soak the deactivated catalyst in 500mL of aminotrimethylphosphonic acid / 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid solution (aminotrimethylphosphonic acid mass concentration is 1.5%) at 50℃ for 30min. After filtering, rinse three times with 300mL of 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid. The alkali metal impurity content on the obtained catalyst is 0.05wt% and the alkaline earth metal impurity content is 0.04wt%. After drying at 120°C for 3 hours, the catalyst's Mo content (calculated as MoO3) was measured to be 22.0 wt% and its water absorption rate was 50 mL / 100 g. The catalyst was then saturated with an aqueous solution containing 3 g / 100 mL of molybdenum (calculated as molybdenum oxide) and dried at 110°C for 3 hours to obtain regenerated hydrogenation catalyst R~1.

[0041] Example 2

[0042] Take 122.2g of the above-mentioned deactivated hydrogenation catalyst, dilute 23.2g of dibutyl phosphite with ethanol to 91.7mL, and supersaturate impregnate the deactivated hydrogenation catalyst with a supersaturation degree of 2.5. After vacuum drying at 100℃ for 3h, place it in an air atmosphere and roast it at 500℃ for 3h, and let it cool to room temperature. Soak the deactivated catalyst in 600mL of aminoethyl phosphoric acid / 1-ethyl-3-methylimidazole hexafluorophosphate ionic liquid solution (aminoethyl phosphoric acid mass concentration is 1.0%) at 65℃ for 20min. After filtering, rinse it three times with 400mL of 1-ethyl-3-methylimidazole hexafluorophosphate ionic liquid. The resulting catalyst has an alkali metal impurity content of 0.04wt% and an alkaline earth metal impurity content of 0.04wt%. After drying at 120℃ for 3h, the catalyst Mo content (as MoO3) is measured to be 22.3wt%, and the water absorption rate is 50mL / 100g. Then, the catalyst was saturated with an aqueous solution having a molybdenum content (calculated as molybdenum oxide) of 2.4 g / 100 mL and dried at 110° C. for 3 h to obtain the regenerated hydrogenation catalyst R-2.

[0043] Example 3

[0044] 122.2g of the deactivated hydrogenation catalyst was taken, and 7.7g of triethyl phosphate was diluted with ethanol to 51.3mL. The catalyst was then supersaturated and impregnated onto the deactivated hydrogenation catalyst, with a supersaturation of 1.4. After vacuum drying at 120°C for 2h, the catalyst was calcined at 700°C in air for 2h and allowed to cool to room temperature. The deactivated catalyst was then soaked in 700mL of a 0.6% aminomethylene diphosphoric acid / N-ethylpyridinium tetrafluoroborate ionic liquid solution at 65°C for 20min. After filtration, the catalyst was rinsed four times with 300mL of N-ethylpyridinium tetrafluoroborate ionic liquid. The resulting catalyst had an alkali metal impurity content of 0.04wt% and an alkaline earth metal impurity content of 0.03wt%. After drying at 120°C for 2h, the catalyst Mo content (as MoO3) was measured to be 22.5wt%, and the water absorption rate was 50mL / 100g. Then, the catalyst was saturated with an aqueous solution having a molybdenum content (calculated as molybdenum oxide) of 2.0 g / 100 mL and dried at 110° C. for 3 h to obtain the regenerated hydrogenation catalyst R-3.

[0045] Example 4

[0046] Take 122.2g of the above-mentioned deactivated hydrogenation catalyst, dilute 15.5g of trimethyl phosphate with ethanol to 55.0mL, and supersaturate impregnate the deactivated hydrogenation catalyst, wherein the supersaturation is 1.5. After vacuum drying at 100℃ for 3h, place it in an air atmosphere and roast it at 600℃ for 2h, and let it cool to room temperature. Soak the deactivated catalyst in 500mL of aminotrimethylphosphonic acid / 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid solution (aminotrimethylphosphonic acid mass concentration is 1.5%), the soaking solution temperature is 50℃, and the soaking time is 30min. After filtering, rinse with 300mL of 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid three times. The alkali metal impurity content of the obtained catalyst is 0.05wt% and the alkaline earth metal impurity content is 0.04wt%. After drying at 120℃ for 3h, regenerated hydrogenation catalyst R-4 is obtained.

[0047] Comparative Example 1

[0048] Compared with Example 1, difference is: deactivated hydrogenation catalyst does not use organophosphide A / organic solution to impregnate, and does not need drying yet, and the second is to directly carry out roasting treatment. Take 122.2g above-mentioned deactivated hydrogenation catalyst, place 600 ℃ of roastings 2h in air atmosphere, leave standstill to cool to room temperature. 500mL aminotrimethylphosphonic acid / 1-butyl-3-methylimidazole tetrafluoroborate ionic liquid solution (aminotrimethylphosphonic acid mass concentration is 1.5%) is soaked this deactivated catalyst, temperature is 50 ℃, soaking time length is 30min. After filtration, rinse 3 times with 300mL of 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid, the alkali metal impurity content on the catalyst obtained is 0.05wt%, and alkaline earth metal impurity content is 0.04wt%. After 120 ℃ of dryings 3h, recording catalyst Mo content (as MoO 3 ) is 16.7wt%, and water absorption is 50mL / 100g. Then, the catalyst was saturated with an aqueous solution having a molybdenum content (calculated as molybdenum oxide) of 13.6 g / 100 mL and dried at 110° C. for 3 h to obtain a regenerated hydrogenation catalyst D~1.

[0049] Comparative Example 2

[0050] Compared with Example 1, the difference is that only ionic liquid is used during soaking, and ammonia / amino organic phosphide is not used. Take 122.2g of the above-mentioned deactivated hydrogenation catalyst, dilute 15.5g of trimethyl phosphate with ethanol to 55.0mL, and supersaturate and impregnate on the deactivated hydrogenation catalyst, wherein the supersaturation is 1.5. After being vacuum-dried at 100℃ for 3h, it is placed in an air atmosphere and roasted at 600℃ for 2h, and left to cool to room temperature. The deactivated catalyst is soaked in 500mL of 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid solution, the temperature is 50℃, and the soaking time is 30min. After filtering, it is rinsed 3 times with 300mL of 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid. The alkali metal impurity content on the obtained catalyst is 0.33wt%, and the alkaline earth metal impurity content is 0.72wt%. After drying at 120°C for 3 h, the catalyst's Mo content (calculated as MoO3) was measured to be 22.0 wt% and its water absorption was 50 mL / 100 g. The catalyst was then saturated with an aqueous solution containing 3 g / 100 mL of molybdenum (calculated as molybdenum oxide) and dried at 110°C for 3 h to obtain regenerated hydrogenation catalyst D-2.

[0051] Example 5

[0052] The catalysts obtained in the examples and comparative examples were subjected to activity evaluation tests in a 10 mL reaction apparatus. The feedstock oil was a conventional three-line 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 sulfurizing agent was a conventional straight-run diesel oil with 1.5 v% DMDS added. The sulfurization operating conditions were: a sulfurization pressure of 6.4 MPa, a liquid hourly volume space velocity of 1.5 h ～1 The volume ratio of hydrogen to oil was 400:1. The catalyst in the reactor was completely wetted at 140°C. The temperature was then raised to 320°C at a rate of 1°C / min and held constant for 10 hours to complete the sulfidation. The reaction operating conditions were as follows: reaction pressure 6.0 MPa, reaction temperature 365°C, liquid hourly space velocity 1.5 h ～1 The hydrogen-to-oil volume ratio was 400:1. After 24 hours of initial activity stabilization, the product properties were analyzed. The catalyst desulfurization activities are listed in Table 1.

[0053] Table 1 Desulfurization activity of catalysts in Examples and Comparative Examples

[0054] R～1 R～2 R～3 R～4 D～1 D～2 Relative desulfurization activity*, % 97 98 97 89 82 65

[0055] *Based on fresh agent, its desulfurization activity is set to 100%.

Claims

1. A method for regenerating a deactivated hydrogenation catalyst, characterized in that: Includes the following: (1) impregnating the deactivated hydrogenation catalyst with an organic solution containing an organic phosphide A as an impregnation liquid, followed by drying and high-temperature calcination; the high-temperature calcination temperature is 450 to 800° C., preferably 500 to 750° C.; (2) soaking or washing the catalyst obtained by calcining in step (1) with an ionic liquid solution containing organic phosphide B, preferably soaking; after washing and drying, the final regenerated hydrogenation catalyst is obtained.

2. The method according to claim 1, wherein: Based on the mass of the deactivated hydrogenation catalyst after removing sulfur and carbon, the alkali metal content in the deactivated hydrogenation catalyst is 0.2wt% to 8.0wt%, preferably 0.3wt% to 5.0wt%, more preferably 0.5wt% to 3.0wt%, and even more preferably 1.0wt% to 2.0wt%; the alkaline earth metal content is 0.2wt% to 6.0wt%, preferably 0.3wt% to 4.0wt%, more preferably 0.5wt% to 2.0wt%, and even more preferably 0.8wt% to 1.5wt%; the alkali metal is one or more of lithium, sodium and potassium, and the alkaline earth metal is one or more of magnesium, calcium, strontium and barium.

3. The method according to claim 1, wherein: The deactivated hydrogenation catalyst in step (1) is first subjected to deoiling treatment; the deoiling treatment adopts one or more of hot hydrogen circulation and solvent extraction.

4. The method according to claim 1, wherein: The organic phosphide A in step (1) contains an ester group and / or an aromatic group, and the organic phosphide A is one or more of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, tricresyl phosphate, triphenyl phosphite, triphenylphosphine oxide, triphenyl phosphate and dibutyl phosphite; and the concentration of the organic phosphide A in the organic solution containing the organic phosphide A is 0.01 to 1.0 g / mL.

5. The method according to claim 1, wherein: The organic solvent in step (1) is at least one of ethers, alcohols and ketones, including one or more of diethyl ether, methanol, ethanol, propanol, butanol, ethylene glycol and acetone, preferably one or more of methanol, ethanol, propanol and acetone.

6. The method according to claim 1, wherein: The molar ratio of the organic phosphide A (calculated as elemental phosphorus) contained in the organic solution containing the organic phosphide A in step (1) to the active metal component (calculated as elemental metal) contained in the deactivated hydrogenation catalyst is 0.03 to 0.6, preferably 0.05 to 0.4; the active metal component is a Group VIB metal and a Group VIII metal.

7. The method according to claim 1, wherein: The impregnation in step (1) is performed by saturated impregnation or supersaturated impregnation, preferably supersaturated impregnation, and more preferably, in supersaturated impregnation, the supersaturation degree is not less than 1.05, preferably 1.08 to 3.

0.

8. The method according to claim 1, wherein: The drying treatment in step (1) is carried out by normal pressure drying or vacuum drying, preferably vacuum drying; the drying temperature is 60-140° C., and the drying time is 2-6 hours.

9. The method according to claim 1, wherein: The high-temperature calcination treatment in step (1) is performed for 1 to 3 hours; the high-temperature calcination treatment is performed in an oxygen-containing atmosphere, wherein the oxygen content of the oxygen-containing atmosphere is 15% to 100% by volume, and the remainder is a mixture of nitrogen and an inert gas, wherein the inert gas includes one or more of helium, neon, argon, krypton, xenon and radon; the oxygen-containing atmosphere is preferably an air atmosphere.

10. The method according to claim 1, wherein: The organic phosphide B in step (2) is an amino / aminophosphoric acid compound, including one or more of aminomethylene diphosphoric acid, aminoethylene diphosphoric acid, aminopropylene diphosphoric acid, aminoethyl phosphoric acid, aminopropylphosphonic acid, aminotrimethylphosphonic acid and ethylenediaminetetramethylenephosphonic acid; based on the mass of the ionic liquid solution containing the organic phosphide B, the mass concentration of the organic phosphide B is 0.1wt% to 5wt%, preferably 0.3wt% to 2wt%.

11. The method according to claim 1, wherein: The ionic liquid in step (2) is a neutral ionic liquid, including one or more of imidazole tetrafluoroborate, imidazole hexafluorophosphate, pyridine tetrafluoroborate and pyridine hexafluorophosphate, preferably one or more of 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF4), 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim]PF6), 1-ethyl-3-methylimidazolium tetrafluoroborate ([Emim]BF4), 1-ethyl-3-methylimidazolium hexafluorophosphate ([Emim]PF6), N-ethylpyridine tetrafluoroborate ([EtPy]BF4) and N-butylpyridine hexafluorophosphate ([BuPy]PF6).

12. The method according to claim 1, wherein: The specific operation process of the soaking in step (2) is as follows: the catalyst obtained by calcining step (1) is soaked in an ionic liquid solution containing organic phosphide B at a temperature of 35 to 80°C, and then solid-liquid separation is performed; the soaking time is 15 to 60 minutes; the volume ratio of the ionic liquid solution containing organic phosphide B to the catalyst is 1:1 to 10:

1.

13. The method according to claim 1, wherein: The washing process in step (2) is as follows: the catalyst is washed with ionic liquid for 1 to 10 times; the volume ratio of the ionic liquid to the catalyst used in each washing is 2:1 to 10:

1.

14. The method according to claim 1, wherein: The drying temperature in step (2) is 90-150° C., and the drying time is 2-6 hours.

15. The method according to claim 1, wherein: In step (2), 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, preferably saturated impregnation; the mass of the introduced active metal component is the mass of the active metal lost during the washing process.

16. A regenerated hydrogenation catalyst obtained by the method according to any one of claims 1 to 15.