Process for the regeneration of a deactivated hydrogenation catalyst

Abstract

The application discloses a regeneration method of inactivated hydrogenation catalyst, which comprises the following steps: firstly, mixing the inactivated hydrogenation catalyst with a first auxiliary agent, and then carrying out roasting treatment to obtain material A after separation; and then fully mixing the material A obtained after separation, a second auxiliary agent, a third auxiliary agent and an alcohol solvent, and carrying out roasting treatment to obtain a regenerated hydrogenation catalyst. Meanwhile, the application also provides a regenerated hydrogenation catalyst obtained by using the above regeneration method. The overall regeneration method does not need to use a sulfuration agent for resulfuration, and the sulfuration process is omitted, so that the technical economy is good.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of petroleum chemical catalysis, and relates to a regeneration method of a catalytic material, in particular to a regeneration method of a hydrogenation catalyst. BACKGROUND

[0002] The activity of a catalyst will gradually decrease during use, i.e. the catalyst is deactivated, and the speed of deactivation is closely related to the properties of raw materials, operating conditions, product requirements and the characteristics of the catalyst itself. Hydrogenation catalyst regeneration is to prolong the service life of the catalyst and reduce production costs. The essence of ex-situ regeneration technology is to remove the surface carbon by contacting the deactivated catalyst with an oxygen-containing gas, i.e. to regenerate the catalyst by carbon burning. Since high-temperature carbon burning is required for treatment, most of the active metals in the catalyst exist in an oxidized state, and the activity of the catalyst needs to be restored by sulfurization again when it is used again, which causes waste of sulfurizing agent and complicated steps and poor economic efficiency. Compared with fresh catalyst, the high temperature during high-temperature carbon burning treatment causes the metals to easily aggregate, the number of active centers of the catalyst after carbon burning is reduced, the hydrogenation activity is decreased, and the recycling of the catalyst is affected.

[0003] CN200810012213.0 discloses a regeneration method of a hydrogenation deactivated catalyst, which first removes the carbon on the surface of the catalyst by sulfur burning and carbon burning treatment of the deactivated catalyst, then treats it with a sulfur compound such as mercaptan and / or sulfide, and finally obtains a regenerated catalyst by calcination. This method can effectively reduce the interaction between the carrier and the metal, and obtain a regenerated catalyst with good activity recovery. However, the active metals are very easy to aggregate during high-temperature carbon burning, the number of active centers of the catalyst after carbon burning is reduced, the hydrogenation activity is decreased, and the active metals exist in an oxidized state after carbon burning, so the catalyst needs to be re-sulfurized to restore its activity, which also causes waste of sulfurizing agent. CN114425460A discloses a regeneration method of a deactivated hydrogenation catalyst, which first mixes the deactivated hydrogenation catalyst with an organic acid and / or organic acid salt solution for heat treatment, then mixes the heat-treated sample with a complexing agent for heat treatment again to obtain a regenerated catalyst. This method does not need high-temperature carbon burning, the obtained regenerated catalyst is in a sulfidized state, does not need to be re-sulfurized, saves the amount of sulfurizing agent, and the process is simple, but this method cannot remove the carbon on the catalyst, so the carbon content of the deactivated catalyst cannot be greater than 4.0wt%, and the regeneration effect of this method is very poor for a deactivated catalyst with a carbon content greater than 4.0wt%. SUMMARY

[0004] In view of the problems and deficiencies in the prior art, the present application provides a regeneration method of deactivated hydrogenation catalyst. First, the deactivated hydrogenation catalyst is mixed with a first additive, then a first heat treatment is performed under anaerobic conditions, the catalyst after heat treatment is mixed with a second additive and a third additive, and then a second heat treatment is performed to obtain a regenerated catalyst. The overall regeneration process does not need to use sulfidation agent for re-sulfidation, and the sulfidation process is omitted, which is good in technical and economic efficiency. Due to the presence of the first additive, the carbon content of the deactivated catalyst can be higher, solving the problem that the deactivated catalyst with high carbon content can only be treated by carbon burning. Due to the re-dispersion of the second additive on the active metal and the hydrogen bonding and steric hindrance of the bulky group of the third additive, the interaction between the active component and the carrier of the hydrogenation catalyst is weakened, the active component is re-dispersed, and the growth and agglomeration of the active component are effectively inhibited, greatly improving the hydrogenation activity of the regenerated catalyst.

[0005] The first aspect of the present application provides a regeneration method of deactivated hydrogenation catalyst, comprising the following steps:

[0006] (1) mixing the deactivated hydrogenation catalyst with a first additive, then performing a calcination treatment under anaerobic conditions, and separating to obtain material A;

[0007] (2) mixing the material A obtained after separation in step (1), a second additive, a third additive, and an alcohol solvent uniformly, then performing a calcination treatment to obtain a regenerated hydrogenation catalyst.

[0008] Further, in the above-mentioned regeneration method of deactivated hydrogenation catalyst, the deactivated hydrogenation catalyst in step (1) contains sulfur and carbon, and the sulfur exists in the form of sulfide with the active metal; the carbon content is 2.0wt%-15.0wt%, preferably 8.0wt%-12.0wt%, based on the weight of the deactivated hydrogenation catalyst.

[0009] Further, in the above-mentioned regeneration method of deactivated hydrogenation catalyst, the deactivated hydrogenation catalyst in step (1) can be various types of hydrogenation catalysts used in petroleum chemical production processes, such as one or more of hydrogenation desulfurization catalyst, hydrogenation denitrification catalyst, hydrogenation demetallization catalyst, hydrogenation refining catalyst, hydrogenation cracking catalyst, hydrogenation dearomatic catalyst, and catalytic reforming catalyst.

[0010] Further, in the above-mentioned regeneration method of deactivated hydrogenation catalyst, the first additive in step (1) can be selected from one or more of tetrahydro naphthalene, tetrahydroanthracene, tetrahydrophenanthrene, tetrahydroquinoline, dihydroanthracene, dihydrophenanthrene, indane, and tetrahydro naphthalene, preferably tetrahydro naphthalene.

[0011] Further, in the regeneration method of the deactivated hydrogenation catalyst mentioned above, the content of carbon in the deactivated hydrogenation catalyst in step (1) is 1:4 to 1:15, preferably 1:8 to 1:12, by weight ratio of the first additive.

[0012] Further, in the regeneration method of the deactivated hydrogenation catalyst mentioned above, the anaerobic condition in step (1) is carried out in the presence of an inert atmosphere, which can be one or more of nitrogen, neon, helium, krypton, argon, xenon, and is preferably nitrogen.

[0013] Further, in the regeneration method of the deactivated hydrogenation catalyst mentioned above, the calcination temperature in step (1) is 320°C to 420°C, preferably 360°C to 400°C, and the calcination time is 0.5 h to 3 h, preferably 0.5 h to 2 h.

[0014] Further, in the regeneration method of the deactivated hydrogenation catalyst mentioned above, the separation after the calcination in step (1) is carried out after the material is cooled to 20 to 40°C, and the separation can be carried out by filtration, centrifugal separation, gravity sedimentation, or the like.

[0015] Further, in the regeneration method of the deactivated hydrogenation catalyst mentioned above, the second additive in step (2) is an organic acid salt, and further, the organic acid salt is selected from one or more of ammonium formate, sodium acetate, ammonium acetate, ammonium propionate, ammonium butyrate, sodium sulfonate, ammonium sulfonate, sodium benzenesulfinate, ammonium sulfamate, and ammonium thioacetate, and is preferably ammonium acetate.

[0016] Further, in the regeneration method of the deactivated hydrogenation catalyst mentioned above, the content of the second additive is 2 wt% to 8 wt%, preferably 2 wt% to 6 wt%, based on the weight of the deactivated hydrogenation catalyst.

[0017] Further, in the regeneration method of the deactivated hydrogenation catalyst mentioned above, the third additive in step (2) is selected from one or more of urea, thiourea, tert-butyl thiourea, N-tert-butyl urea, and squaric acid amide, and is preferably squaric acid amide. The content of the third additive is 2 wt% to 10 wt%, preferably 3 wt% to 5 wt%, based on the weight of the deactivated hydrogenation catalyst.

[0018] Further, in the regeneration method of the deactivated hydrogenation catalyst mentioned above, the alcohol solvent in step (2) is one or more of alcohol compounds having 1 to 4 carbon atoms, and the alcohol compound can be one or more of ethanol, methanol, ethylene glycol, n-propanol, isopropanol, and tert-butyl alcohol, and is preferably ethanol.

[0019] Further, in the above-mentioned regeneration method of the deactivated hydrogenation catalyst, the weight ratio of the third additive to the alcohol solvent in step (2) is 1:5 to 1:15, preferably 1:8 to 1:12.

[0020] Further, in the above-mentioned regeneration method of the deactivated hydrogenation catalyst, the calcination treatment temperature in step (2) is 100 to 250°C, preferably 150 to 200°C; and the calcination treatment time is 1h to 5h, preferably 1.5h to 3.5h.

[0021] Further, in the above-mentioned regeneration method of the deactivated hydrogenation catalyst, the calcination treatment in step (2) is not limited to the atmosphere, and can be performed in air, oxygen, nitrogen or inert atmosphere.

[0022] The second aspect of the present application provides a regenerated hydrogenation catalyst obtained by the above-mentioned regeneration method.

[0023] Further, the obtained regenerated hydrogenation catalyst is in sulfided state, and the sulfur originally contained in the deactivated hydrogenation catalyst can be fully utilized, so that the regenerated hydrogenation catalyst can be directly used without re-sulfurization by supplementing a sulfiding agent, thereby saving the sulfiding agent and simplifying the regeneration process.

[0024] The third aspect of the present application provides a hydroprocessing process of a hydrocarbon-containing compound, in which the hydrocarbon-containing compound and hydrogen are introduced into a reactor, and the reactor is filled with the above-mentioned regenerated hydrogenation catalyst.

[0025] Further, in the above-mentioned hydroprocessing process of the hydrocarbon-containing compound, the hydrocarbon-containing compound can be at least one of gasoline, diesel oil and wax oil.

[0026] Further, in the above-mentioned hydroprocessing process of the hydrocarbon-containing compound, the hydrogenation reaction operating conditions are as follows: the reaction pressure is 3.0 to 10.0MPa, the reaction temperature is 300 to 420°C, the liquid hourly space velocity is 1.0 to 2.0h -1 , and the hydrogen / oil volume ratio is 300 to 800.

[0027] The regeneration method of the deactivated hydrogenation catalyst provided by the present application has the following advantages compared with the prior art:

[0028] (1) The regeneration method of the deactivated hydrogenation catalyst provided by the application, through the addition of the first additive and the calcination treatment under the absolute oxygen condition, not only makes most of the carbon deposition on the deactivated catalyst dissolved, but also destroys the sheet crystal structure of the molybdenum sulfide, thereby improving the dispersion degree of the sheet crystal of the molybdenum sulfide on the surface of the carrier and improving the catalytic activity of the deactivated hydrogenation catalyst, and at the same time, the catalyst after the calcination treatment can still be in the sulfidation state, the sulfur in the deactivated hydrogenation catalyst is fully utilized, and the amount of the sulfidation agent used is saved, the process is simple, and for the hydrogenation catalyst with a carbon content of greater than 4.0wt%, the heat treatment under the absolute oxygen condition can also be performed without the calcination under the air condition.

[0029] (2) The regeneration method of the deactivated hydrogenation catalyst provided by the application, through the addition of the first additive and the calcination treatment under the absolute oxygen condition, not only improves the dispersion degree of the active metal on the surface of the carrier, but also makes the second additive and the third additive have more contact sites with the active metal, and the second additive and the third additive better play the roles of the re-dispersion of the active metal and the inhibition of the growth and agglomeration of the active component, thereby improving the hydrogenation activity of the regenerated hydrogenation catalyst.

[0030] (3) The regeneration method of the deactivated hydrogenation catalyst provided by the application, since the first additive generates hydrogen free radicals under the absolute oxygen heat treatment condition, the free radicals generated by the pyrolysis of the carbon deposition are stable, and the generated products can be dissolved in the first additive. At the same time, since the heat treatment temperature is in the dehydrogenation temperature range of the first additive, the hydrogen free radicals generated by the first additive can induce the pyrolysis of the carbon deposition on the catalyst, and the generated products are dissolved in the first additive.

[0031] (4) The regeneration method of the deactivated hydrogenation catalyst provided by the application, through the addition of the second additive and the third additive, the re-dispersion of the active metal by the second additive and the strong proton-providing ability of the N-H bond contained in the third additive can form S…H-N hydrogen bonds with the sulfur in the active metal sulfide and hydrogen bonds with the hydroxyl groups on the surface of the carrier, and the active metal sulfide is coated, the interaction between the active component of the hydrogenation catalyst and the carrier is weakened, thereby the active component is re-dispersed and the growth and agglomeration of the active component are effectively inhibited, and the hydrogenation activity of the regenerated catalyst is improved. At the same time, the third additive also has a large steric hindrance, which can better disperse the active metal and inhibit the growth and agglomeration of the active metal. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 The HRTEM image of the catalyst prepared in Example 1 of the application.

[0033] Figure 2 The HRTEM image of the catalyst prepared in Comparative Example 1 of the application. DETAILED DESCRIPTION

[0034] The regeneration method of the deactivated hydrogenation catalyst according to the present application is further described in detail by way of examples and comparative examples below to help the readers better understand the present application, but does not constitute any limitation to the implementable scope of the present application.

[0035] The experimental methods in the following examples are all conventional methods in the art, unless otherwise specified. The experimental materials used in the following examples are all purchased from conventional biochemical reagent stores, unless otherwise specified.

[0036] The active phase of the present application is tested by transmission electron microscopy (TEM) to obtain the microscopic morphology of the active metal active phase. 20 TEM photos randomly selected from each sample are counted for the average stacking number and average sheet length of the molybdenum disulfide crystal sheets in the photos by Digital Micrograph software to calculate the distribution of the active phase on the surface of the carrier. The calculation formulae of the average sheet length and the average stacking number are as follows:

[0037] L =∑S i L i / ∑S i

[0038]

[0039] wherein Si is the number of sheets with sheet length Li, L is in nm; and Xi is the number of sheets with Ni layers.

[0040] In this paper, the specific surface area and pore structure data are determined by an ASAP 2400 full-automatic physical and chemical analyzer; the metals in the catalyst are analyzed by a UV-visible spectrophotometer of PE, USA; the carbon and sulfur contents in the catalyst are determined by an EMIA-820 carbon and sulfur determinator; and the high-resolution transmission electron microscopy (HR-TEM) characterization is performed by a JEM-2100 transmission electron microscope.

[0041] Example 1

[0042] Take 100 g of the deactivated hydrogenation catalyst A, the carbon deposition content of the catalyst A is 10.72 wt%, the specific surface area is 88 m 2 / g, and the active metal contents are as follows: the MoO3 content is 23.9 wt%, and the NiO content is 4.1 wt%. The powder in the deactivated hydrogenation catalyst is sieved out by a sample sieve, then it is mixed with 86.0 g of tetrahydro naphthalene solution, then it is calcined at 380℃ under nitrogen condition, the calcination treatment time is 1.5 hours, then it is cooled to room temperature (25℃) and then filtered. The carbon content in the obtained material A after filtration is 1.51 wt%, the specific surface area is 132 m 2 / g. 3 g of squaric amide was added to 35 mL of anhydrous ethanol, 3 g of ammonium acetate was then added thereto and stirred thoroughly, the stirred solution was then thoroughly mixed with the deactivated hydrogenation catalyst A, and after uniform mixing, the mixture was calcined at 160°C in air for 2 hours to obtain the regenerated hydrogenation catalyst A1.

[0043] Example 2

[0044] A 100 g of the deactivated hydrogenation catalyst A was used, the catalyst A had a coke content of 10.72 wt%, a specific surface area of 88 m 2 / g, and the active metal content was as follows: MoO3 content of 23.9 wt%, NiO content of 4.1 wt%. The powder in the deactivated hydrogenation catalyst was sieved out using a sample sieve, and then thoroughly mixed with 128.0 g of a tetrahydroquinoline solution, and then calcined at 420°C in nitrogen for 1 hour, and then after being cooled to room temperature, suction filtered to obtain the material A, which had a carbon content of 1.39 wt% and a specific surface area of 135 m 2 / g. 3.5 g of N-tert-butyl urea was added to 40 mL of isopropyl alcohol, 2.5 g of ammonium sulfonate was then added thereto and stirred thoroughly, the stirred solution was then thoroughly mixed with the material A, and after uniform mixing, the mixture was calcined at 140°C in air for 3 hours to obtain the regenerated hydrogenation catalyst A2.

[0045] Example 3

[0046] A 100 g of the deactivated hydrogenation catalyst B was used, the catalyst B had a coke content of 11.68 wt%, a specific surface area of 79 m 2 / g, and the active metal content was as follows: MoO3 content of 20.2 wt%, NiO content of 4.8 wt%, CoO content of 3.1 wt%. The powder in the deactivated hydrogenation catalyst was sieved out using a sample sieve, and then thoroughly mixed with 70.68 g of indane, and then calcined at 370°C in nitrogen for 2.5 hours, and then after being cooled to room temperature, suction filtered to obtain the material A, which had a carbon content of 1.59 wt% and a specific surface area of 129 m 2 / g. 4 g of tert-butyl thiourea was added to 35 mL of ethylene glycol, 4.5 g of sodium benzenesulfinate was then added thereto and stirred thoroughly, the stirred solution was then thoroughly mixed with the material A, and after uniform mixing, the mixture was calcined at 200°C in air for 1.5 hours to obtain the regenerated hydrogenation catalyst B1.

[0047] Example 4

[0048] Take 100 g of deactivated hydrogenation catalyst B, the carbon deposition content of catalyst B is 11.68 wt%, the specific surface area is 79 m 2 / g, and the active metal content is as follows: the MoO3 content is 20.2 wt%, the NiO content is 4.8 wt%, and the CoO content is 3.1 wt%. The powder in the deactivated hydrogenation catalyst is sieved out with a sample sieve, then it is mixed with 140.0 g of dihydroanthracene, then it is subjected to calcination treatment under the condition of nitrogen at 350°C for 3 hours, and then it is filtered after being cooled to room temperature, and material A is obtained after filtration, the carbon content in material A is 1.43 wt%, and the specific surface area is 133 m 2 / g. 4.5 g of tert-butyl thiourea is added to 40 ml of ethylene glycol, then 4.5 g of ammonium thioacetate is added and stirred, then the stirred solution is mixed with material A, and after uniform mixing, it is subjected to calcination treatment under the condition of air at 180°C for 2 hours, and regenerated hydrogenation catalyst B2 is obtained.

[0049] Comparative Example 1

[0050] Take 100 g of deactivated hydrogenation catalyst A, the carbon deposition content of catalyst A is 10.72 wt%, the specific surface area is 88 m 2 / g, and the active metal content is as follows: the MoO3 content is 23.9 wt%, and the NiO content is 4.1 wt%. The powder in the deactivated hydrogenation catalyst is sieved out with a sample sieve, then it is subjected to calcination treatment under the condition of nitrogen at 380°C for 1.5 hours, and then it is filtered after being cooled to room temperature, and material A is obtained after filtration, the carbon content in material A is 10.70 wt%, and the specific surface area is 92 m 2 / g. 3 g of squaric acid amide is added to 35 mL of anhydrous ethanol, then 3 g of ammonium acetate is added and stirred, then the stirred solution is mixed with material A, and after uniform mixing, it is subjected to calcination treatment under the condition of air at 160°C for 2 hours, and regenerated hydrogenation catalyst A3 is obtained.

[0051] Comparative Example 2

[0052] Take 100 g of deactivated hydrogenation catalyst A, the carbon deposition content of catalyst A is 10.72 wt%, the specific surface area is 88 m 2 / g, and the active metal content is as follows: the MoO3 content is 23.9 wt%, and the NiO content is 4.1 wt%. The powder in the deactivated hydrogenation catalyst is sieved out with a sample sieve, then it is mixed with 86.0 g of tetrahydronaphthalene solution, then it is subjected to calcination treatment under the condition of nitrogen at 280°C for 1.5 hours, and then it is filtered after being cooled to room temperature, and material A is obtained after filtration, the carbon content in material A is 8.62 wt%, and the specific surface area is 98 m2 / g. 3 g of square amide was added to 35 mL of anhydrous ethanol, then 3 g of ammonium acetate was added and stirred, then the stirred solution was mixed with material A, after mixing evenly, calcination treatment was carried out at 160°C in air, and the calcination treatment time was 2 hours, to obtain regenerated hydrogenation catalyst A4. (The first calcination treatment temperature is lower)

[0053] Comparative Example 3

[0054] Take 100 g of deactivated hydrogenation catalyst A, the carbon deposition content of catalyst A is 10.72 wt%, the specific surface area is 88 m 2 / g, and the active metal content is as follows: the content of MoO3 is 23.9 wt%, and the content of NiO is 4.1 wt%. First, the powder in the deactivated hydrogenation catalyst is sieved out with a sample sieve, then it is mixed with 86.0 g of tetrahydro naphthalene solution, then calcination treatment is carried out at 500°C in nitrogen, and the calcination treatment time is 1.5 hours, then it is cooled to room temperature and then suction filtered to obtain material A, the carbon content in material A is 1.41 wt%, and the specific surface area is 118 m 2 / g. 3 g of square amide was added to 35 mL of anhydrous ethanol, then 3 g of ammonium acetate was added and stirred, then the stirred solution was mixed with material A, after mixing evenly, calcination treatment was carried out at 160°C in air, and the calcination treatment time was 2 hours, to obtain regenerated hydrogenation catalyst A4. (The first calcination treatment temperature is lower)

[0055] Comparative Example 4

[0056] Take 100 g of deactivated hydrogenation catalyst A, the carbon deposition content of catalyst A is 10.72 wt%, the specific surface area is 88 m 2 / g, and the active metal content is as follows: the content of MoO3 is 23.9 wt%, and the content of NiO is 4.1 wt%. First, the powder in the deactivated hydrogenation catalyst is sieved out with a sample sieve, then it is mixed with 86.0 g of tetrahydro naphthalene solution, then calcination treatment is carried out at 380°C in nitrogen, and the calcination treatment time is 1.5 hours, then it is cooled to room temperature and then suction filtered to obtain material A, 3 g of square amide is added to 35 mL of anhydrous ethanol and stirred, then the stirred solution is mixed with material A, after mixing evenly, calcination treatment is carried out at 160°C in air, and the calcination treatment time is 2 hours, to obtain regenerated hydrogenation catalyst A6.

[0057] Comparative Example 5

[0058] Take 100 g of deactivated hydrogenation catalyst A, the carbon deposition content of catalyst A is 10.72 wt%, the specific surface area is 88 m 2 / g, and the active metal content is as follows: MoO3 content is 23.9wt%, NiO content is 4.1wt%. The powder in the deactivated hydrogenation catalyst is sieved out by a sample divider, and then mixed with 86.0g of tetrahydro naphthalene solution, and then calcined at 380℃ under nitrogen for 1.5 hours, and then filtered after being cooled to room temperature. Material A is obtained after filtration. 3g of ammonium acetate is added to 35mL of anhydrous ethanol and stirred, and then the stirred solution is mixed with material A, and then calcined at 160℃ under air for 2 hours to obtain regenerated hydrogenation catalyst A7.

[0059] Evaluation test of the regenerated catalyst

[0060] The regenerated hydrogenation catalysts prepared in examples 1-4 and comparative examples 1-5 of the present application and fresh hydrogenation catalysts of the same brand are evaluated in a 10mL micro reactor device, and the same raw oil and evaluation conditions are selected, and the activity evaluation process conditions of the catalysts are as follows: reaction temperature is 350℃, reaction pressure is 6.0MPa, hydrogen to oil ratio is 50, and volume space velocity is 1.5h-1. -1 The properties of the raw oil are shown in table 1, the coke removal rate of the regenerated hydrogenation catalyst is shown in table 2, and the evaluation results are shown in table 3. From the data in table 3, it can be seen that under the same conditions of raw oil and process conditions, the sulfur and nitrogen contents of the raw oil after use of the regenerated catalyst obtained by the process of the present application are basically the same as those of the fresh catalyst, which indicates that the activity of the prepared regenerated hydrogenation catalyst is equivalent to that of the fresh hydrogenation catalyst, and the activity of the catalyst is well regenerated.

[0061] Table 1 Main properties of the raw oil

[0062] Item Feed oil Density (20°C) g.cm -3 ]] 0.9283 Distillation range (atmospheric pressure) / °C Initial boiling point / 10% 194 / 223 30％ / 50％ 239 / 255 70％ / 90％ 276 / 316 95% / final boiling point 337 / 361 S / μg.g -1 ]]> 21260.2 Nitrogen / μg.g -1 ]] 384.5

[0063] Table 2 Coke removal rate of the regenerated catalyst

[0064] Example 1 Example 2 Example 3 Example 4 Fresh agent Carbon deposit removal rate 85.9％ 87.0％ 86.4％ 87.8％ ---- Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Carbon deposit removal rate 0.2％ 19.6％ 86.8％ 85.9％ 85.9％

[0065] Table 3 Evaluation results of the regenerated catalyst

[0066]

[0067]

[0068] TEM characterization is performed on the evaluated catalyst, and the characterization results are shown in Figures 1-2The 20 TEM photos of each sample were randomly selected and used for statistical analysis of the average number of stacked layers and the average length of the MoS2 platelets by using the software. The results are shown in Table 4. As shown in Table 4, the active metals of the catalyst treated by the regeneration method of the present application are re-dispersed on the surface of the catalyst, the morphology and number of the active phase are basically the same as those of the fresh catalyst, indicating that the active phase of the regenerated catalyst is well recovered, which is consistent with the evaluation results.

[0069] Table 4 Average number of stacked layers and average length of MoS2 platelets

[0070]

Claims

1. A method for regenerating deactivated hydrogenation catalyst, comprising the following steps: (1) mixing the deactivated hydrogenation catalyst with a first additive, and then performing calcination treatment in the presence of inert atmosphere, and separating to obtain material A; the first additive is selected from one or more of tetrahydronaphthalene, tetrahydroanthracene, tetrahydrophenanthrene, tetrahydroquinoline, dihydroanthracene, dihydrophenanthrene, indane, tetrahydronaphthol; the deactivated hydrogenation catalyst contains sulfur and carbon, and the content of carbon is 2.0wt% to 15.0wt% based on the weight of the deactivated hydrogenation catalyst; the weight ratio of the content of carbon in the deactivated hydrogenation catalyst to the first additive is 1:4 to 1:15; the calcination treatment temperature is 320°C to 420°C; (2) mixing the material A obtained after separation in step (1), a second additive, a third additive, and an alcohol solvent uniformly, and then performing calcination treatment to obtain regenerated hydrogenation catalyst; the second additive is an organic acid salt, and the organic acid salt is selected from one or more of ammonium formate, sodium acetate, ammonium acetate, ammonium propionate, ammonium butyrate, sodium sulfonate, ammonium sulfonate, sodium benzenesulfinate, ammonium sulfamate, ammonium thioacetate; the third additive is selected from one or more of urea, thiourea, tert-butyl thiourea, N-tert-butyl urea, squaric amide; the alcohol solvent is one or more of alcohol compounds with carbon atom number of 1 to 4; the content of the second additive is 2wt% to 8wt% based on the weight of the deactivated hydrogenation catalyst; the content of the third additive is 2wt% to 10wt%; the weight ratio of the third additive to the alcohol solvent is 1:5 to 1:15; the calcination treatment temperature is 100°C to 250°C. The sulfur in the deactivated hydrogenation catalyst in step (1) exists in the form of sulfide; the content of carbon is 8.0wt% to 12.0wt% based on the weight of the deactivated hydrogenation catalyst. The first additive in step (1) is tetrahydronaphthalene.

2. The process for regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The weight ratio of the content of carbon in the deactivated hydrogenation catalyst to the first additive in step (1) is 1:8 to 1:

12.

3. The method for regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The inert atmosphere in step (1) is one or more of nitrogen, neon, helium, krypton, argon, xenon.

4. The method of regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The inert atmosphere in step (1) is nitrogen.

5. The method of regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The calcination treatment temperature in step (1) is 360°C to 400°C.

6. The method of regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The organic acid salt is ammonium acetate.

7. The method of regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The content of the second additive is 2wt% to 6wt% based on the weight of the deactivated hydrogenation catalyst.

8. The method of regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The third additive in step (2) is squaric amide.

9. The method of regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The content of the third additive is 3wt% to 5wt% based on the weight of the deactivated hydrogenation catalyst.

10. The process for regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The alcohol compound is one or more of ethanol, methanol, ethylene glycol, n-propanol, isopropanol, tert-butyl alcohol.

11. The process for regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The alcohol compound is ethanol.

12. The process for regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The weight ratio of the third additive to the alcohol solvent in step (2) is 1:8 to 1:

12.

13. The method of regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The calcination treatment temperature in step (2) is 150°C to 200°C.

14. The method of regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that:

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

15. The method of regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that:

17. A hydroprocessing process of hydrocarbon-containing compounds, wherein the hydrocarbon-containing compounds and hydrogen are introduced into a reactor, and the reactor is filled with the regenerated hydrogenation catalyst according to claim 16. ​ ​ 18. The hydrocarbonaceous compound hydroprocessing process according to claim 17, characterized in that: The hydrocarbon-containing compound is at least one of gasoline, diesel oil, and wax oil. The hydrocarbon-containing compound is at least one of gasoline, diesel oil, and wax oil.

19. The hydrocarbonaceous compound hydroprocessing process according to claim 17, characterized in that: The hydrogenation reaction operating conditions are as follows: the reaction pressure is 3.0-10.0 MPa, the reaction temperature is 300-420℃, the liquid hourly space velocity is 1.0-2.0 h -1 , and the hydrogen / oil volume ratio is 300-800.

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