Regeneration method of inactivated hydrogenation catalyst

Abstract

The invention discloses a regeneration method of an inactivated hydrogenation catalyst, which comprises the following steps: mixing the inactivated hydrogenation catalyst with a first auxiliary agent, roasting, and separating to obtain a material A; and fully and uniformly mixing the separated material A, a second auxiliary agent, a third auxiliary agent and an alcohol solvent, and carrying out roasting treatment to obtain the regenerated hydrogenation catalyst. The invention also provides the regenerated hydrogenation catalyst obtained by the regeneration method. The integral regeneration method provided by the invention does not need to use a vulcanizing agent for secondary vulcanization, so that the vulcanization process is omitted, and the technical economy is good.

Description

Technical Field

[0001] The invention belongs to the field of petrochemical catalysis and relates to a method for regenerating a catalytic material, in particular to a method for regenerating a hydrogenation catalyst. Background Art

[0002] The activity of the catalyst will gradually decrease during use, that is, the catalyst is deactivated. The speed of deactivation is closely related to the nature of the raw materials, operating conditions, product requirements and the characteristics of the catalyst itself. The regeneration of the hydrogenation catalyst is to extend the service life of the catalyst and reduce production costs. The essence of the off-site regeneration technology is to remove the carbon deposits on the surface by contacting the deactivated catalyst with an oxygen-containing gas, that is, to regenerate the catalyst by charring. Since high-temperature charring is required for treatment, most of the active metals in the catalyst exist in an oxidized state. When it is reused, the catalyst needs to be sulfurized again to restore the activity of the catalyst, which will cause a waste of the sulfiding agent. At the same time, the steps are cumbersome and the economy is poor. Compared with fresh catalysts, the higher temperature during high-temperature charring treatment makes it easy for metals to aggregate during the charring process, which reduces the number of active centers of the catalyst after charring, reduces the hydrogenation activity, and affects the recycling of the catalyst.

[0003] CN200810012213.0 discloses a regeneration method for a hydrogenation deactivated catalyst, firstly, the carbon deposit on the catalyst surface is removed by burning sulfur and charcoal treatment to the deactivated catalyst, then it is treated with sulfur-containing compound mercaptan and / or thioether, and finally roasted to obtain a regenerated catalyst. This method can effectively reduce the interaction between the carrier and the metal, and obtain a regenerated catalyst with better activity recovery. However, the active metal is very easy to gather during the high-temperature charcoal burning process, so that the number of active centers of the catalyst after charcoal burning is reduced, and the hydrogenation activity decreases. At the same time, the active metal exists in an oxidized state after charcoal burning, and it is necessary to re-carry out sulfurization treatment to restore the activity of the catalyst, which also causes the waste of the vulcanizing agent at the same time. CN114425460A discloses a regeneration method for a deactivated hydrogenation catalyst, firstly, the deactivated hydrogenation catalyst is mixed with an organic acid and / or an organic acid salt solution for heat treatment, and then the heat-treated sample is mixed with a complexing agent for heat treatment again to obtain a regenerated catalyst. This method does not require high-temperature carbonization, and the resulting regenerated catalyst is in a sulfurized state and does not require resulfurization, which saves the amount of sulfurizing agent and simplifies the process. However, this method cannot remove carbon deposits on the catalyst, so the carbon content of the deactivated catalyst cannot be greater than 4.0wt%. For deactivated catalysts with carbon deposits greater than 4.0wt%, the regeneration effect of this method is very poor. Summary of the invention

[0004] In view of the problems and deficiencies in the prior art, the main technical solution of the present invention is to provide a method for regenerating a deactivated hydrogenation catalyst. First, the deactivated hydrogenation catalyst is mixed with a first auxiliary agent, and then a first heat treatment is performed under anaerobic conditions. The heat-treated catalyst is mixed with a second auxiliary agent and a third auxiliary agent, and then a second heat treatment is performed to obtain a regenerated catalyst. The overall regeneration process does not require the use of a sulfiding agent for re-sulfurization, thereby eliminating the sulfurization process and having good technical and economic performance. Due to the presence of the first auxiliary agent, the carbon deposit content of the deactivated catalyst can be relatively high, which solves the problem that the high carbon deposit content of the deactivated catalyst can only be treated by the charcoal burning method. Due to the redispersion of the active metal by the second auxiliary agent, the hydrogen bonding effect of the third auxiliary agent, and the steric hindrance of the large-volume group, the interaction between the active components of the hydrogenation catalyst and the carrier is weakened, and the growth and agglomeration of the active components are effectively suppressed while the active components are redispersed, thereby greatly improving the hydrogenation activity of the regenerated catalyst.

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

[0006] (1) mixing the deactivated hydrogenation catalyst and the first auxiliary agent, and then calcining them under anaerobic conditions, and obtaining material A after separation;

[0007] (2) The material A, the second auxiliary agent, the third auxiliary agent and the alcohol solvent obtained after separation in step (1) are fully mixed and then calcined to obtain a regenerated hydrogenation catalyst.

[0008] Furthermore, in the above-mentioned method for regenerating a deactivated hydrogenation catalyst, the deactivated hydrogenation catalyst in step (1) contains sulfur and carbon, and the sulfur and the active metal exist in the form of sulfides; based on the weight of the deactivated hydrogenation catalyst, the carbon content is 2.0wt% to 15.0wt%, preferably 8.0wt% to 12.0wt%.

[0009] Furthermore, in the above-mentioned method for regenerating a deactivated hydrogenation catalyst, the deactivated hydrogenation catalyst in step (1) may be various types of hydrogenation catalysts used in petrochemical production processes, such as one or more of a hydrodesulfurization catalyst, a hydrodenitrogenation catalyst, a hydrodemetallization catalyst, a hydrorefining catalyst, a hydrocracking catalyst, a hydrodearomatization catalyst, and a catalytic reforming catalyst.

[0010] Furthermore, in the above-mentioned method for regenerating a deactivated hydrogenation catalyst, the first auxiliary agent in step (1) can be selected from one or more of tetrahydronaphthalene, tetrahydroanthracene, tetrahydrophenanthrene, tetrahydroquinoline, dihydroanthracene, dihydrophenanthrene, indane, and tetrahydronaphthol, preferably tetrahydronaphthalene.

[0011] Furthermore, in the above-mentioned method for regenerating a deactivated hydrogenation catalyst, the weight ratio of the carbon content in the deactivated hydrogenation catalyst to the first auxiliary agent in step (1) is 1:4 to 1:15, preferably 1:8 to 1:12.

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

[0013] Furthermore, in the above-mentioned method for regenerating a deactivated hydrogenation catalyst, the calcination treatment temperature in step (1) is 320°C to 420°C, preferably 360°C to 400°C; and the calcination treatment time is 0.5h to 3h, preferably 0.5h to 2h.

[0014] Furthermore, in the above-mentioned method for regenerating a deactivated hydrogenation catalyst, the separation after the calcination treatment in step (1) is to wait for the material to be cooled to 20-40° C. before separation, and the separation can be carried out by suction filtration, centrifugal separation, gravity sedimentation, etc.

[0015] Furthermore, in the above-mentioned method for regenerating a deactivated hydrogenation catalyst, the second auxiliary agent in step (2) is an organic acid salt. Furthermore, 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 aminosulfonate, and ammonium thioacetate, preferably ammonium acetate.

[0016] Furthermore, in the above-mentioned method for regenerating a deactivated hydrogenation catalyst, the content of the second auxiliary agent is 2 wt% to 8 wt%, preferably 2 wt% to 6 wt%, based on the weight of the deactivated hydrogenation catalyst.

[0017] Furthermore, in the above-mentioned method for regenerating a deactivated hydrogenation catalyst, the third auxiliary agent in step (2) is selected from one or more of urea, thiourea, tert-butylthiourea, N-tert-butylurea, and squaramide, preferably squaramide. Based on the weight of the deactivated hydrogenation catalyst, the content of the third auxiliary agent is 2wt% to 10wt%, preferably 3wt% to 5wt%.

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

[0019] Furthermore, in the above-mentioned method for regenerating a deactivated hydrogenation catalyst, the weight ratio of the third auxiliary agent to the alcohol solvent in step (2) is 1:5 to 1:15, preferably 1:8 to 1:12.

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

[0021] Furthermore, in the above-mentioned method for regenerating a deactivated hydrogenation catalyst, the calcination treatment in step (2) has no limitation on the atmosphere, and can be carried out under air, oxygen, nitrogen or inert atmosphere.

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

[0023] Furthermore, the obtained regenerated hydrogenation catalyst is a sulfided catalyst, which can fully utilize the sulfur originally contained in the deactivated hydrogenation catalyst and can be directly used without the need for resulfurization by supplementing a sulfiding agent, which not only saves the sulfiding agent but also simplifies the regeneration process.

[0024] The third aspect of the present invention provides a process for hydrogenation treatment of hydrocarbon-containing compounds, wherein the hydrocarbon-containing compounds and hydrogen are introduced into a reactor, and the reactor is filled with the above-mentioned regenerated hydrogenation catalyst.

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

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

[0027] Compared with the existing methods, the regeneration method of the deactivated hydrogenation catalyst provided by the present invention has the following advantages:

[0028] (1) In the regeneration method of the deactivated hydrogenation catalyst provided by the present invention, by adding the first auxiliary agent and calcining under anaerobic conditions, not only the carbon deposits on the deactivated catalyst are mostly dissolved, but also the molybdenum sulfide platelet structure is destroyed, thereby improving the dispersion degree of the molybdenum sulfide platelets on the carrier surface and the catalytic activity of the deactivated hydrogenation catalyst. At the same time, it can also ensure that the catalyst after calcination is still in a sulfurized state, making full use of the sulfur in the deactivated hydrogenation catalyst itself, without the need for resulfurization, saving the amount of sulfurizing agent and simplifying the process. For a hydrogenation catalyst with a carbon content greater than 4.0wt%, it can also be heat treated under anaerobic conditions without calcining under air conditions.

[0029] (2) In the regeneration method of the deactivated hydrogenation catalyst provided by the present invention, by adding the first auxiliary agent and calcining under anaerobic conditions, not only the dispersion degree of the active metal on the carrier surface is improved, but also the second auxiliary agent and the third auxiliary agent have more contact sites with the active metal, so that the second auxiliary agent can better play the role of redispersing the active metal and the third auxiliary agent can better play the role of inhibiting the growth and agglomeration of the active components, thereby improving the hydrogenation activity of the regenerated hydrogenation catalyst.

[0030] (3) In the regeneration method of the deactivated hydrogenation catalyst provided by the present invention, since the first auxiliary agent generates hydrogen free radicals under the anaerobic heat treatment conditions, the free radicals generated by the pyrolysis of carbon deposits are stable, and the products generated by the conversion are soluble in the first auxiliary agent. At the same time, since the heat treatment temperature is within the dehydrogenation temperature range of the first auxiliary agent, the hydrogen free radicals generated by the first auxiliary agent will induce the pyrolysis of carbon deposits on the catalyst, so that the products generated by it are dissolved in the first auxiliary agent.

[0031] (4) In the regeneration method of the deactivated hydrogenation catalyst provided by the present invention, by adding the second auxiliary agent and the third auxiliary agent, the second auxiliary agent can redisperse the active metal and the NH bond contained in the third auxiliary agent has a strong proton providing ability, which can form S...HN hydrogen bonds with sulfur in the active metal sulfide and hydrogen bonds with hydroxyl groups on the surface of the carrier, so as to coat the active metal sulfide and weaken the interaction between the active components of the hydrogenation catalyst and the carrier, thereby effectively inhibiting the growth and agglomeration of the active components while redispersing the active components, and improving the hydrogenation activity of the regenerated catalyst. At the same time, the third auxiliary agent also has a large steric hindrance, which can better disperse the active metal and inhibit its growth and agglomeration. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is the HRTEM image of the catalyst prepared in Example 1 of the present invention.

[0033] Figure 2 This is the HRTEM image of the catalyst prepared in Comparative Example 1 of the present invention. DETAILED DESCRIPTION

[0034] The following further describes in detail a method for regenerating a deactivated hydrogenation catalyst involved in the present invention through examples and comparative examples to help readers better understand the present invention, but does not constitute any limitation on the scope of implementation of the present invention.

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

[0036] The test of the active phase of the present invention is analyzed by transmission electron microscopy (TEM) to obtain the microscopic appearance of the active metal active phase. The average number of stacked layers and the average lamella length of the molybdenum disulfide wafers in the 20 randomly selected TEM photos of each sample are counted by Digital Micrograph software to calculate the distribution of the active phase on the carrier surface. The calculation formulas for the average lamella length and the average number of stacked layers are as follows:

[0037] L=∑S i L i / ∑S i

[0038]

[0039] Where Si is the number of lamellae with a lamella length of Li, L is in nm; Xi is the number of lamellae with a Ni layer.

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

[0041] Example 1

[0042] Take 100g of deactivated hydrogenation catalyst A, the carbon deposit content of catalyst A is 10.72wt%, and the specific surface area is 88m 2 / g, and its active metal content is as follows: MoO3 content is 23.9wt%, NiO content is 4.1wt%. The powder in the deactivated hydrogenation catalyst is first sieved out with a sample sieve, and then it is fully mixed with 86.0g of tetralin solution, and then calcined at 380℃ under nitrogen for 1.5 hours, and then cooled to room temperature (25℃) and filtered to obtain material A, in which the carbon content is 1.51wt%, and the specific surface area is 132m 2 / g. 3g of squaramide was added to 35mL of anhydrous ethanol, and then 3g of ammonium acetate was added thereto and stirred thoroughly, and then the stirred solution was mixed thoroughly with material A, and after mixing evenly, it was calcined in air at 160°C for 2 hours to obtain regenerated hydrogenation catalyst A1.

[0043] Example 2

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

[0045] Example 3

[0046] Take 100g of deactivated hydrogenation catalyst B, the carbon deposit content of catalyst B is 11.68wt%, and the specific surface area is 79m 2 / g, and its active metal content is as follows: MoO3 content is 20.2wt%, NiO content is 4.8wt%, and CoO content is 3.1wt%. The powder in the deactivated hydrogenation catalyst is sieved out with a sample sieve, and then it is fully mixed with 70.68g of indane, and then calcined at 370℃ under nitrogen for 2.5 hours, and then cooled to room temperature and filtered to obtain material A. The carbon content in material A is 1.59wt%, and the specific surface area is 129m 2 / g. 4g of tert-butylthiourea was added to 35ml of ethylene glycol, and then 4.5g of sodium benzenesulfinate was added thereto and stirred thoroughly, and then the stirred solution was mixed thoroughly with material A, and after mixing evenly, calcined in air at 200°C for 1.5 hours to obtain regenerated hydrogenation catalyst B1.

[0047] Example 4

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

[0049] Comparative Example 1

[0050] Take 100g of deactivated hydrogenation catalyst A, the carbon deposit content of catalyst A is 10.72wt%, and the specific surface area is 88m 2 / g, and its active metal content is as follows: MoO3 content is 23.9wt%, NiO content is 4.1wt%. The powder in the deactivated hydrogenation catalyst is first sieved out with a sample sieve, and then it is calcined under nitrogen at 380°C for 1.5 hours, then cooled to room temperature and filtered to obtain material A, which has a carbon content of 10.70% and a specific surface area of ​​92m 2 / g. 3g of squaramide was added to 35mL of anhydrous ethanol, and then 3g of ammonium acetate was added thereto and stirred thoroughly, and then the stirred solution was mixed thoroughly with material A, and after mixing evenly, calcined in air at 160°C for 2 hours to obtain regenerated hydrogenation catalyst A3.

[0051] Comparative Example 2

[0052] Take 100g of deactivated hydrogenation catalyst A, the carbon deposit content of catalyst A is 10.72wt%, and the specific surface area is 88m 2 / g, and its active metal content is as follows: MoO3 content is 23.9wt%, NiO content is 4.1wt%. First, the powder in the deactivated hydrogenation catalyst is sieved out with a sample sieve, and then it is fully mixed with 86.0g of tetralin solution, and then it is roasted under nitrogen at 280°C for 1.5 hours, and then it is cooled to room temperature and filtered to obtain material A. The carbon content in material A is 8.62wt%, and the specific surface area is 98m2 / g. 3g of squaramide was added to 35mL of anhydrous ethanol, and then 3g of ammonium acetate was added thereto and stirred thoroughly. Then the stirred solution was mixed thoroughly with material A, and after mixing evenly, it was calcined in air at 160°C for 2 hours to obtain regenerated hydrogenation catalyst A4. (The first calcination temperature is relatively low)

[0053] Comparative Example 3

[0054] Take 100g of deactivated hydrogenation catalyst A, the carbon deposit content of catalyst A is 10.72wt%, and the specific surface area is 88m 2 / g, and its active metal content is as follows: MoO3 content is 23.9wt%, NiO content is 4.1wt%. The powder in the deactivated hydrogenation catalyst is first sieved out with a sample sieve, and then it is fully mixed with 86.0g of tetralin solution, and then calcined at 500℃ under nitrogen for 1.5 hours, and then cooled to room temperature and filtered to obtain material A, in which the carbon content is 1.41wt% and the specific surface area is 118m 2 / g. 3g of squaramide was added to 35mL of anhydrous ethanol, and then 3g of ammonium acetate was added thereto and stirred thoroughly, and then the stirred solution was mixed thoroughly with material A, and after mixing evenly, calcined at 160°C in air for 2 hours to obtain regenerated hydrogenation catalyst A5.

[0055] Comparative Example 4

[0056] Take 100g of deactivated hydrogenation catalyst A, the carbon deposit content of catalyst A is 10.72wt%, and the specific surface area is 88m 2 / g, and its active metal content is as follows: MoO3 content is 23.9wt%, and NiO content is 4.1wt%. The powder in the deactivated hydrogenation catalyst is first sieved out with a sample sieve, and then it is fully mixed with 86.0g of tetralin solution, and then roasted at 380℃ under nitrogen for 1.5 hours, then cooled to room temperature and filtered to obtain material A, 3g of squaramide is added to 35mL of anhydrous ethanol and fully stirred, then the stirred solution is fully mixed with material A, and after mixing evenly, it is roasted at 160℃ in air for 2 hours to obtain regenerated hydrogenation catalyst A6.

[0057] Comparative Example 5

[0058] Take 100g of deactivated hydrogenation catalyst A, the carbon deposit content of catalyst A is 10.72wt%, and the specific surface area is 88m 2 / g, and its active metal content is as follows: MoO3 content is 23.9wt%, and NiO content is 4.1wt%. First, the powder in the deactivated hydrogenation catalyst is sieved out with a sample sieve, and then it is fully mixed with 86.0g of tetralin solution, and then roasted at 380℃ nitrogen for 1.5 hours, and then cooled to room temperature and filtered. After filtration, material A is obtained. 3g of ammonium acetate is added to 35mL of anhydrous ethanol and fully stirred, and then the stirred solution is fully mixed with material A, and after mixing evenly, roasted at 160℃ air for 2 hours to obtain regenerated hydrogenation catalyst A7.

[0059] Regeneration catalyst evaluation test:

[0060] The regenerated hydrogenation catalysts prepared in Examples 1-4 of the present invention and Comparative Examples 1-5 and the fresh hydrogenation catalysts of the same grade were evaluated in a 10 mL microreactor. The same feedstock oil and evaluation conditions were selected. The activity evaluation process conditions of the catalysts were: reaction temperature 350° C., reaction pressure 6.0 MPa, hydrogen-to-oil ratio 50, volumetric space velocity 1.5 h -1 The properties of the feedstock oil are shown in Table 1, the carbon 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 feedstock oil and process conditions, the sulfur and nitrogen contents of the feedstock of the regenerated catalyst obtained by the process of the present invention are basically the same as those of the fresh catalyst after use, indicating that the activity of the prepared regenerated hydrogenation catalyst is equivalent to that of the fresh hydrogenation catalyst, and the activity of the catalyst has been well regenerated.

[0061] Table 1 Main properties of crude oil

[0062] project Crude oil <![CDATA[Density / (20 °C) g.cm -3 > 0.9283 Distillation range (normal pressure) / ℃ Initial distillation point / 10% 194 / 223 30％ / 50％ 239 / 255 70％ / 90％ 276 / 316 95% / final distillation point 337 / 361 <![CDATA[Sulfur / μg.g -1 > 21260.2 <![CDATA[Nitrogen / μg.g -1 > 384.5

[0063] Table 2 Carbon removal rate of regenerated catalyst

[0064] Example 1 Example 2 Example 3 Example 4 Freshener Carbon 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 removal rate 0.2％ 19.6％ 86.8％ 85.9％ 85.9％

[0065] Table 3 Evaluation results of regenerated catalyst

[0066]

[0067]

[0068] The evaluated catalysts were characterized by TEM. The characterization results are shown in Figure 1-2. 20 TEM photos were randomly selected for each sample, and the average stacking layer number and average sheet length of the molybdenum disulfide wafers in the photos were statistically calculated using a mapping software. The results are shown in Table 4. As can be seen from Table 4, compared with the fresh catalyst, the active metal of the catalyst treated by the regeneration method of the present invention was redispersed on the catalyst surface, and the morphology and number of the active phase were basically the same as those of the fresh catalyst, indicating that the active phase of the regenerated catalyst was better restored, which is consistent with the evaluation results.

[0069] Table 4 Average number of stacking layers and average length of MoS2 flakes

[0070]

Claims

1. A method for regenerating a deactivated hydrogenation catalyst, comprising the following steps: (1) mixing the deactivated hydrogenation catalyst with a first auxiliary agent, and then calcining them under anaerobic conditions, and separating them to obtain material A; the first auxiliary agent is selected from one or more of tetrahydronaphthalene, tetrahydroanthracene, tetrahydrophenanthrene, tetrahydroquinoline, dihydroanthracene, dihydrophenanthrene, indane, and tetrahydronaphthol; (2) The material A, the second auxiliary agent, the third auxiliary agent and the alcohol solvent obtained after separation in step (1) are fully mixed and then calcined to obtain a regenerated hydrogenation catalyst; the second auxiliary agent is an organic acid salt, and the third auxiliary agent is selected from one or more of urea, thiourea, tert-butylthiourea, N-tert-butylurea and squaramide.

2. The method for regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The deactivated hydrogenation catalyst in step (1) contains sulfur and carbon, and the sulfur and the active metal exist in the form of sulfide; based on the weight of the deactivated hydrogenation catalyst, the carbon content is 2.0wt% to 15.0wt%, preferably 8.0wt% to 12.0wt%.

3. The method for regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The first auxiliary agent in step (1) is tetralin.

4. The method for regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The weight ratio of the carbon content in the deactivated hydrogenation catalyst to the first auxiliary agent in step (1) is 1:4 to 1:15, preferably 1:8 to 1:

12.

5. The method for regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The anaerobic condition in step (1) is carried out in the presence of an inert atmosphere, wherein the inert atmosphere is one or more of nitrogen, neon, helium, krypton, argon, and xenon, preferably nitrogen.

6. The method for regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The calcination treatment temperature in step (1) is 320°C to 420°C, preferably 360°C to 400°C.

7. The method for regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: 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 aminosulfonate, and ammonium thioacetate, preferably ammonium acetate.

8. The method for regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: Based on the weight of the deactivated hydrogenation catalyst, the content of the second auxiliary agent is 2 wt% to 8 wt%, preferably 2 wt% to 6 wt%.

9. The method for regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The third auxiliary agent in step (2) is squaramide.

10. The method for regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: Based on the weight of the deactivated hydrogenation catalyst, the content of the third auxiliary agent is 2 wt% to 10 wt%, preferably 3 wt% to 5 wt%.

11. The method for regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The alcohol solvent in step (2) is one or more of alcohol compounds having 1 to 4 carbon atoms, and the alcohol compound is one or more of ethanol, methanol, ethylene glycol, n-propanol, isopropanol, and tert-butanol, preferably ethanol.

12. The method for regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The weight ratio of the third auxiliary agent to the alcohol solvent in step (2) is 1:5 to 1:15, preferably 1:8 to 1:

12.

13. The method for regenerating a deactivated hydrogenation catalyst according to claim 1, characterized in that: The calcination temperature in step (2) is 100 to 250°C, preferably 150 to 200°C.

14. A regenerated hydrogenation catalyst obtained by the regeneration method according to any one of claims 1 to 13.

15. A process for hydrogenating hydrocarbon compounds, comprising introducing hydrocarbon compounds and hydrogen into a reactor, wherein the reactor is filled with the regenerated hydrogenation catalyst according to claim 14.

16. The process for hydrotreating hydrocarbon-containing compounds according to claim 15, characterized in that: The hydrocarbon-containing compound is at least one of gasoline, diesel and wax oil.

17. The process for hydrotreating hydrocarbon-containing compounds according to claim 15, characterized in that: The operating conditions of the hydrogenation reaction are as follows: reaction pressure is 3.0-10.0 MPa, reaction temperature is 300-420°C, liquid hourly volume space velocity is 1.0-2.0 h -1 , the volume ratio of hydrogen to oil is 300-800.

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