Method for recovering activity of inactivated hydrogenation catalyst

Abstract

The invention provides a method for recovering the activity of an inactivated hydrogenation catalyst. The method comprises the following steps: introducing an organic solvent into a catalyst bed layer of a reactor to eliminate in-situ soluble carbon of the catalyst, carrying out gas stripping elution on the organic solvent, introducing hydrogen, carrying out thermal reduction, and removing catalyst coke, and introducing activated oil to perform activity recovery on the to-be-regenerated agent, wherein the activated oil comprises normal first-line oil and an active component precursor. According to the method, online recovery of the activity of the catalyst can be effectively completed, particularly, the activity of the catalyst is recovered through in-situ activation oil, deposition of active components on the catalyst can be effectively controlled, the activity recovery degree of the catalyst is controlled, and more active sites are increased while the active center is repaired.

Description

Technical Field

[0001] This invention relates to a method for in-situ activity recovery of deactivated hydrogenation catalysts, belonging to the field of catalytic hydrogenation technology. Background Technology

[0002] Hydrotreating technology is widely used in the petrochemical industry. Almost every refinery in the world has a hydrotreating unit, resulting in the use of a large amount of hydrotreating catalysts annually, along with the production of a significant amount of spent catalysts. The price of raw materials for hydrotreating catalysts also fluctuates frequently, leading to changes in catalyst costs. Considering stringent environmental regulations and economic factors, the reuse of spent catalysts is essential.

[0003] Hydrogenation catalysts are susceptible to deactivation, the most common form being coking. Coking covers the active sites of the catalyst, affecting the pore properties of the reaction and ultimately leading to the loss of catalyst activity. Currently, catalyst regeneration methods include external and internal regeneration. Internal regeneration, performed within the original unit, generally requires specialized design and is characterized by high cost and risk. External regeneration, the more widely used method, involves unloading the catalyst and regenerating and pre-treating it in a regeneration plant before reloading it back into the original reactor for activation. This process is time-consuming and labor-intensive, extending the plant's operating cycle and impacting production. Furthermore, the regenerated catalyst's activity is unlikely to reach the level of fresh catalyst, requiring more stringent reaction conditions to achieve its performance and ensure product quality. Additionally, the repeated unloading, transportation, regeneration, and loading of the catalyst can affect its strength, potentially leading to pressure drop in the unit.

[0004] CN107126976A discloses a combined steam purging-hydrogen hot stripping regeneration method for a C9 cracking hydrogenation catalyst. This method involves removing oil contaminants from the catalyst surface through hydrogen purging under heating conditions, followed by pressurized superheated steam purging to remove residual oil and low-molecular-weight polymers, then low-pressure nitrogen drying, and finally further removal of surface oligomers via hydrogen reduction, restoring the catalyst activity to over 95%. However, this process has a narrow applicability, and superheated steam purging places high demands on the catalyst, potentially leading to catalyst pulverization and breakage, resulting in pressure drop and affecting the plant's operating cycle. Furthermore, simple hydrogen reduction activation may result in incomplete activity recovery. CN107552070A discloses an in-situ activity recovery method for improving the activity of a spent hydrorefining catalyst in Mo-Ni diesel fractions. The method involves first dissolving the catalyst in an organic solution, then subjecting the impregnated catalyst to air stripping, followed by coking treatment, and finally impregnating the catalyst with a complexing restorer prepared from organic acid and solvent to restore its activity. The catalyst activity can be restored to 90-100% of that of a fresh catalyst. However, this method still relies on external activation, resulting in a long process cycle, extended operating time, and reduced enterprise profitability. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a method for in-situ activity recovery of deactivated hydrogenation catalysts. This method is highly operable, simple in process, saves time, and reduces costs. This method can ensure that the activity of the catalyst is restored to or even exceeds that of a fresh catalyst.

[0006] The technical solution of the present invention is as follows:

[0007] A method for restoring the activity of a deactivated hydrogenation catalyst includes the following steps:

[0008] (1) Organic solvent is introduced into the catalyst bed of the reactor to remove soluble carbon in situ from the catalyst, remove oil and coke precursors from the catalyst surface, and then the catalyst bed is stripped to remove the organic solvent.

[0009] (2) Hydrogen gas is introduced into the catalyst bed of the reactor for thermal reduction to remove catalyst coke;

[0010] (3) Activated oil is introduced into the catalyst bed of the reactor to restore the activity of the precursor. The activated oil includes conventional first-line oil and active component precursor.

[0011] Furthermore, the organic solvent in step (1) is selected from at least one of methanol, ethanol, isopropanol, n-butanol, isobutanol, tetrahydrofuran, ethyl acetate, butyl acetate, acetone, diethyl ether, petroleum ether, dichloromethane, chloroform, cyclohexane, and n-hexane.

[0012] Furthermore, the conditions for in-situ soluble carbon removal by introducing organic solvent in step (1) are: the pressure inside the reactor is 0.10-0.5 MPa, preferably 0.15-0.3 MPa, wherein the system pressure is provided by hydrogen or an inert atmosphere, or a mixture of hydrogen and an inert atmosphere.

[0013] Furthermore, the space velocity of the organic solvent introduced in step (1) is 0.1-3.5 h⁻¹. -1 Preferably, it is 0.5-2.5h. -1 The time for soluble carbon removal is 5-24 hours, preferably 8-16 hours; the temperature is 50-150℃, preferably 60-120℃.

[0014] Furthermore, the stripping gas used in the stripping process is hydrogen or an inert atmosphere, or a mixture of hydrogen and an inert atmosphere. The volume hourly space velocity relative to the catalyst is 1 h⁻¹. -1 The temperature of the air stripping treatment is 65-180℃, preferably 90-150℃; the air stripping time is 5-20h, preferably 8-15h.

[0015] Furthermore, in step (2), the temperature at which hydrogen is introduced for thermal reduction is 180-360℃, preferably 200-300℃; the pressure of the hydrogen is 0.15-0.8MPa, preferably 0.2-0.5MPa; the reduction time is 1-10h, preferably 3-6h; and the volume hourly space velocity of hydrogen relative to the catalyst is preferably 0.5-1.5h. -1 .

[0016] Furthermore, the active component precursor mentioned in step (3) is an oil-soluble organometallic compound containing the active metal element of the catalyst; for example, for commonly used diesel hydrotreating catalysts, the active components are mainly Group VIB metals and Group VIII metals, with Group VIB metals preferably being molybdenum and tungsten, and the corresponding active component precursor is at least one of organomolybdenum and organotungsten, specifically selected from molybdenum dialkyldithiophosphate, molybdenum dialkyldithiocarbamate, molybdenum naphthenate, molybdenum alkyl salicylate, and molybdenum alkylarylamine dithiophosphate. At least one of tungsten sulfide oxysulfide and tungsten sulfide dialkyl dithiophosphate, preferably at least one of molybdenum oxydialkyl dithiophosphate, molybdenum dialkyl dithiocarbamate and tungsten sulfide dialkyl dithiophosphate; the Group VIII metal is preferably cobalt and nickel, and the corresponding active component precursor is at least one of organonitrile and organcobalt, specifically, preferably at least one of nickel oleate, nickel bipyridine complex, nickel naphthenate, cobalt naphthenate and cobalt oleate, preferably at least one of nickel oleate, cobalt oleate, nickel naphthenate and cobalt naphthenate.

[0017] Furthermore, in step (3), the mass concentration of the Group VIB active component precursor in the activation oil is 2.5-6%, preferably 3.2-5.1%; the mass concentration of the Group VIII active component precursor in the activation oil is 0.31-0.75%, preferably 0.4-0.64%. The space velocity of the activated oil is 0.6-1.3 h⁻¹. -1 Preferably 0.7-1h -1 The activation time is 12-76 h, preferably 16-64 h; the hydrogen-to-oil volume ratio is 50-400, preferably 80-350; the activation pressure is 0.5-3.0 MPa, preferably 1.0-2.0 MPa.

[0018] Furthermore, in step (3), when the deactivated catalyst is connected in series in two reactors, a gradient activity recovery method is adopted. Specifically, the temperature of the catalyst bed in the first reactor is first controlled to be maintained at 220-360℃, and the temperature of the bed in the second reactor is maintained at 100-150℃. After the catalyst bed in the first reactor is deposited, the temperature of the first reactor is lowered to 100-150℃, and the temperature of the bed in the second reactor is raised to 220-360℃ to restore the activity of the catalyst in the second reactor. After completion, the temperature is lowered to room temperature.

[0019] Compared with the prior art, the present invention has the following advantages:

[0020] (1) The method of the present invention can effectively restore the activity of the catalyst online. The method is highly operable, does not require additional equipment, and all operations can be completed online. The deactivated catalyst is treated by organic solvent dissolution-hydrogen thermal reduction-online activity restoration. Organic solvent dissolution can effectively remove soluble coke precursors on the catalyst, and hydrogen thermal reduction can effectively reduce the coke on the catalyst, helping to restore the properties of the catalyst, including its pore properties. The in-situ activation oil can effectively control the deposition of active components on the catalyst and control the degree of catalyst activity restoration. While repairing the active center, more active sites are added.

[0021] (2) Under preferred conditions, the use of sulfur-containing organic molybdenum / tungsten active components can avoid the pre-sulfurization step of the regenerated catalyst.

[0022] (3) Compared with traditional external regeneration and regeneration technologies and activation technologies for deactivated catalysts, the online activity recovery method in this invention effectively shortens the activity recovery cycle and increases the effective operating time of the device, thereby ensuring the economic benefits of production and enterprises. At the same time, the activity recovery technology enables the catalyst activity to be restored to or even exceed that of fresh catalyst, allowing the catalyst activity to be maximized. Detailed Implementation Plan

[0023] The present invention will be described in detail below through embodiments, but the present invention is not limited to these embodiments.

[0024] Example 1

[0025] A certain deactivated hydrogenation catalyst has Mo and Ni as its main active metals. By weight, MoO3 accounts for 15.3% and NiO accounts for 2.5% of the catalyst. The hydrogenation reactor is equipped with two reactors connected in series, which are filled with the above-mentioned catalyst.

[0026] (1) First, the reactor loaded with deactivated catalyst (with a catalyst bulk density of 0.91 g / mL and a catalyst volume of 10 mL) was shut down. The temperature was lowered to 70°C, the hydrogen pressure was reduced to 0.15 MPa, the hydrogen flow rate was 6.5 L / h, and the organic solvent cyclohexane was introduced at a space velocity of 0.7 h⁻¹. -1 Solvent elution was performed for 14 hours; then, the organic solvent on the catalyst was removed by gas stripping and thermal elimination. The hydrogen gas rate was adjusted to 8 L / h, and the device was gradually heated to 100°C for 12 hours.

[0027] (2) Increase the hydrogen partial pressure of the device to 0.4 MPa, gradually raise the temperature of the device to 250°C, and carry out in-situ hydrogen thermal reduction operation for 5 hours.

[0028] (3) A primary oil containing 3.6% molybdenum dialkyl dithiocarbamate and 0.45% nickel naphthenate, the precursors of the active components, was introduced into the catalyst bed as an activation oil to reactivate and restore the catalyst. The reaction temperature was gradually increased to 320°C, and the space velocity of the activation oil was 0.8 h⁻¹. -1 The hydrogen pressure was 1.0 MPa, the hydrogen-to-oil volume ratio was 200, and the activation process lasted for 64 hours. The specific step-by-step activation procedure was as follows: The bed activation temperature of the first reactor was 320℃. After 32 hours of activation, the temperature of the first reactor was reduced to 140℃. The bed temperature of the second reactor was gradually increased to 320℃. After 32 hours of activation, the bed temperatures of both reactors were reduced to room temperature. After hydrogen purging continued for a period of time, the system pressure was reduced to 0.2 MPa to complete the active regeneration of the catalyst.

[0029] Example 2

[0030] A certain deactivated hydrogenation catalyst has Mo and Ni as its main active metals. By weight, MoO3 accounts for 15.3% and NiO accounts for 2.5% of the catalyst. The hydrogenation reactor is equipped with two reactors connected in series, which are filled with the above-mentioned catalyst.

[0031] (1) First, the reactor loaded with deactivated catalyst (where the catalyst bulk ratio is 0.91 g / mL and the catalyst volume in the device is 10 mL) was shut down. The reaction temperature was reduced to 70 °C, the hydrogen pressure in the device was reduced to 0.15 MPa, the hydrogen flow rate was 2 L / h, and the organic solvent cyclohexane was introduced at a space velocity of 0.7 h⁻¹. -1 Solvent elution was performed for 18 hours; then, the organic solvent on the catalyst was removed by gas stripping and thermal elimination. The hydrogen gas rate was adjusted to 6 L / h, and the device was gradually heated to 80°C for 18 hours.

[0032] (2) Increase the hydrogen partial pressure of the device to 0.4 MPa, gradually raise the temperature of the device to 250°C, and carry out in-situ hydrogen thermal reduction operation for 5 hours.

[0033] (3) A primary oil containing 2.6% and 0.33% by mass of the active component precursors molybdenum dialkyl dithiocarbamate and nickel naphthenate, respectively, was introduced into the catalyst bed as an activation oil to reactivate and restore the catalyst. The reaction temperature was gradually increased to 320°C, and the space velocity of the activation oil was 0.8 h⁻¹. -1 The hydrogen pressure was 1.0 MPa, the hydrogen-to-oil volume ratio was 200, and the activation process lasted for 50 hours. The bed activation temperature of the first reactor was 320℃. After 25 hours of activation, the temperature of the first reactor was reduced to 140℃. The bed temperature of the second reactor was gradually increased to 320℃. After 25 hours of activation, the bed temperatures of both reactors were reduced to room temperature. After hydrogen purging continued for a period of time, the system pressure was reduced to 0.2 MPa to complete the active regeneration of the catalyst.

[0034] Example 3

[0035] A certain deactivated hydrogenation catalyst has Mo and Ni as its main active metals. By weight, MoO3 accounts for 15.3% and NiO accounts for 2.5% of the catalyst. The hydrogenation reactor is equipped with two reactors connected in series, which are filled with the above-mentioned catalyst.

[0036] (1) First, the reactor loaded with deactivated catalyst (with a catalyst bulk ratio of 0.91 g / mL and a catalyst volume of 10 mL) was shut down. The reaction temperature was lowered to 110 °C, the hydrogen pressure in the apparatus was reduced to 0.18 MPa, the hydrogen flow rate was 6.5 L / h, and the organic solvent cyclohexane was introduced at a space velocity of 0.8 h⁻¹. -1 The catalyst was eluted for 15 hours; then the organic solvent on the catalyst was removed by gas stripping and thermal elimination. The hydrogen gas rate was adjusted to 6 L / h, and the device was gradually heated to 120°C for 10 hours.

[0037] (2) Increase the hydrogen partial pressure of the device to 0.5 MPa, gradually raise the temperature of the device to 280°C, and carry out in-situ hydrogen thermal reduction operation for 3 hours.

[0038] (3) A primary oil containing 5.0% and 0.31% by mass of the active component precursors molybdenum dialkyl dithiocarbamate and nickel naphthenate, respectively, was introduced into the catalyst bed as an activation oil to reactivate and restore the catalyst. The reaction temperature was gradually increased to 320°C, and the space velocity of the activation oil was 1.0 h⁻¹. -1 The hydrogen pressure was 1.0 MPa, the hydrogen-to-oil volume ratio was 200, the activation time was 22 h, the bed activation temperature of the first reactor was 320 °C, and after 11 h of activation, the temperature of the first reactor was reduced to 140 °C. The bed temperature of the second reactor was gradually increased to 320 °C, and after 11 h of activation, the temperature of both beds in the reactor was reduced to room temperature. After hydrogen continued to purge for a period of time, the system pressure was reduced to 0.2 MPa to complete the active regeneration of the catalyst.

[0039] Example 4

[0040] A certain deactivated hydrogenation catalyst has Mo and Ni as its main active metals. By weight, MoO3 accounts for 15.3% and NiO accounts for 2.5% of the catalyst. The hydrogenation reactor is equipped with two reactors connected in series, which are filled with the above-mentioned catalyst.

[0041] (1) First, the reactor loaded with deactivated catalyst (with a catalyst bulk ratio of 0.91 g / mL and a catalyst volume of 10 mL) was shut down. The temperature was lowered to 110°C, the hydrogen pressure was reduced to 0.15 MPa, the hydrogen flow rate was 3 L / h, and the organic solvent cyclohexane was introduced at a space velocity of 1.5 h⁻¹. -1 Solvent elution was performed for 8 hours; then, the organic solvent on the catalyst was removed by gas stripping and thermal elimination. The hydrogen gas rate was adjusted to 6 L / h, and the device was gradually cooled to 100°C for 12 hours.

[0042] (2) Increase the hydrogen partial pressure of the device to 0.3 MPa, gradually raise the temperature of the device to 300°C, and carry out in-situ hydrogen thermal reduction operation for 3 hours.

[0043] (3) A primary oil containing 3.6% molybdenum dialkyl dithiocarbamate and 0.45% nickel naphthenate, the precursors of the active components, was introduced into the catalyst bed as an activation oil to reactivate and restore the catalyst. The reaction temperature was gradually increased to 320°C, and the space velocity of the activation oil was 0.8 h⁻¹. -1The hydrogen pressure was 1.0 MPa, the hydrogen-to-oil volume ratio was 200, the activation time was 12 h, the bed activation temperature of the first reactor was 320 °C, after 6 h of activation, the temperature of the first reactor was reduced to 140 °C, the bed temperature of the second reactor was gradually increased to 320 °C, after 6 h of activation, the temperature of both beds in the reactor was reduced to room temperature, and after hydrogen continued to purge for a period of time, the system pressure was reduced to 0.2 MPa.

[0044] Example 5

[0045] A certain deactivated hydrogenation catalyst has Mo and Co as its main active metals. By weight, MoO3 accounts for 16.2% and CoO accounts for 2.7% of the catalyst. Its hydrogenation reactor is equipped with two reactors connected in series, which are filled with the above-mentioned catalyst.

[0046] (1) First, the reactor loaded with deactivated catalyst (where the catalyst bulk ratio is 0.94 g / ml and the catalyst volume in the device is 10 mL) is shut down, the temperature is reduced to 130℃, the hydrogen pressure in the device is reduced to 0.15 MPa, the hydrogen flow rate is 4 L / h, and the organic solvent cyclohexane is introduced with a space velocity of 1 h⁻¹. -1 Solvent elution was performed for 8 hours; then, the organic solvent on the catalyst was removed by gas stripping and thermal elimination. The hydrogen gas rate was adjusted to 8 L / h, and the device was gradually heated to 100°C for 8 hours.

[0047] (2) Increase the hydrogen partial pressure of the device to 0.4 MPa, gradually raise the temperature of the device to 260°C, and carry out in-situ hydrogen thermal reduction operation for 5 hours.

[0048] (3) A primary oil containing 6% and 0.55% by mass of the active component precursors molybdenum dialkyl dithiocarbamate and cobalt naphthenate, respectively, was introduced into the catalyst bed as an activation oil to reactivate and restore the catalyst. The reaction temperature was gradually increased and the space velocity of the activation oil was 1 h⁻¹. -1 The hydrogen pressure was 1.0 MPa, the hydrogen-to-oil volume ratio was 200, the activation time was 16 h, the bed activation temperature of the first reactor was 320 °C, after the activation process was carried out for 8 h, the temperature of the first reactor was reduced to 140 °C, the bed temperature of the second reactor was gradually increased to 320 °C, after the activation process was carried out for 8 h, the temperature of both beds of the reactor was reduced to room temperature, and after the hydrogen was continued to purge for a period of time, the system pressure was reduced to 0.2 MPa.

[0049] Example 6

[0050] In step (3), instead of using two separate reactors for temperature-controlled activation, the reactor was directly heated to 320°C, activated oil was introduced, and the activation process lasted for 12 hours. Steps (1) and (2) and other operations are the same as in Example 1.

[0051] Example 7

[0052] A certain deactivated hydrogenation catalyst has W and Ni as its main active metals. Based on oxidation state, WO3 accounts for 14.0% of the catalyst by weight, and NiO accounts for 2.7%. Its hydrogenation reactor consists of two reactors connected in series, each loaded with the aforementioned catalyst.

[0053] (1) First, the reactor loaded with deactivated catalyst (where the catalyst bulk density is 1.02 g / mL and the catalyst volume in the device is 10 mL) was shut down, the temperature was lowered to 70 °C, the hydrogen pressure in the device was reduced to 0.15 MPa, the hydrogen flow rate was 6.5 L / h, and the organic solvent cyclohexane was introduced at a space velocity of 0.7 h⁻¹. -1 Solvent elution was performed for 14 hours; then, the organic solvent on the catalyst was removed by gas stripping and thermal elimination. The hydrogen gas rate was adjusted to 8 L / h, and the device was gradually heated to 100°C for 12 hours.

[0054] (2) Increase the hydrogen partial pressure of the device to 0.4 MPa, gradually raise the temperature of the device to 250°C, and carry out in-situ hydrogen thermal reduction operation for 5 hours.

[0055] (3) A constant-temperature oil containing 4.5% alkylarylaminodithiophosphate oxytungsten sulfide and 0.32% nickel naphthenate precursors was introduced into the catalyst bed as an activation oil to reactivate and restore the catalyst. The reaction temperature was gradually increased, and the space velocity of the activation oil was 0.8 h⁻¹. -1 The hydrogen pressure was 1.0 MPa, the hydrogen-to-oil volume ratio was 200, and the activation process lasted for 16 hours. The bed activation temperature of the first reactor was 320℃. After 8 hours of activation, the temperature of the first reactor was reduced to 140℃. The bed temperature of the second reactor was gradually increased to 320℃. After 8 hours of activation, the bed temperatures of both reactors were reduced to room temperature. After hydrogen purging continued for a period of time, the system pressure was reduced to 0.2 MPa, completing the active regeneration of the catalyst.

[0056] Comparative Example 1

[0057] Same as steps (1) and (2) in Example 1, except for step (3).

[0058] Comparative Example 2

[0059] For the same deactivated catalyst as in Example 1, steps (1) and (2) are skipped, and activation oil is directly introduced to perform step (3). The specific operating conditions are the same as step (3) in Example 1.

[0060] After the catalysts in the above embodiments and comparative examples underwent activation regeneration, an activity comparison experiment was conducted using mixed diesel oil from a refinery as feedstock. Reaction conditions: operating pressure 6.5 MPa, reaction temperature 365 °C, hydrogen-to-oil volume ratio 500, and volume hourly space velocity 1.0 h⁻¹. -1 The results of the property evaluation of the raw materials and products are shown in Table 1. The new catalyst is a Mo-Ni type catalyst, with a MoO3 content of 15.5% and a NiO content of 2.5%.

[0061] Table 1.

[0062]

Claims

1. A method for restoring the activity of a deactivated hydrogenation catalyst, comprising the following steps: (1) Organic solvent is introduced into the catalyst bed of the reactor to remove soluble carbon in situ from the catalyst, remove oil and coke precursors from the catalyst surface, and then the catalyst bed is stripped to remove the organic solvent. (2) Hydrogen gas is introduced into the catalyst bed of the reactor for thermal reduction to remove catalyst coke; (3) Activated oil is introduced into the catalyst bed of the reactor to restore the activity of the precursor. The activated oil includes conventional first-line oil and active component precursor.

2. The method according to claim 1, characterized in that, The organic solvent in step (1) is selected from at least one of methanol, ethanol, isopropanol, n-butanol, isobutanol, tetrahydrofuran, ethyl acetate, butyl acetate, acetone, diethyl ether, petroleum ether, dichloromethane, chloroform, cyclohexane and n-hexane.

3. The method according to claim 1, characterized in that, The conditions for in-situ soluble carbon removal by introducing organic solvent in step (1) are: the pressure inside the reactor is 0.10-0.5 MPa, wherein the system pressure is provided by hydrogen or an inert atmosphere, or a mixture of hydrogen and an inert atmosphere.

4. The method according to claim 1, characterized in that, In step (1), the space velocity of the organic solvent introduced is 0.1-3.5 h⁻¹. -1 The time for soluble carbon removal is 5-24 hours, and the temperature is 50-150℃.

5. The method according to claim 1, characterized in that, The stripping process uses hydrogen or an inert atmosphere, or a mixture of hydrogen and an inert atmosphere, with a volume hourly space velocity (VHSV) of 1 h⁻¹ relative to the catalyst. -1 .

6. The method according to claim 1, characterized in that, The temperature of the air stripping treatment is 65-180℃, and the air stripping time is 5-20h.

7. The method according to claim 1, characterized in that, In step (2), the temperature for thermal reduction by introducing hydrogen gas is 180-360℃, the pressure of hydrogen gas is 0.15-0.8MPa, the reduction time is 1-10h, and the volume hourly space velocity of hydrogen gas relative to the catalyst is preferably 0.5-1.5h. -1 .

8. The method according to claim 1, characterized in that, The active component precursor mentioned in step (3) is an oil-soluble organometallic compound containing an active metal element of a catalyst.

9. The method according to claim 8, characterized in that, The catalyst is a diesel hydrotreating catalyst, and its active components are mainly Group VIB metals and Group VIII metals. The Group VIB metals are molybdenum and tungsten, and the corresponding active component precursors are at least one of organomolybdenum and organotungsten. The Group VIII metals are cobalt and nickel, and the corresponding active component precursors are at least one of organonitrile and organcobalt.

10. The method according to claim 9, characterized in that, The organic molybdenum and organic tungsten are selected from one or more of dialkyl dithiophosphate molybdenum oxide, dialkyl dithiocarbamate molybdenum, naphthenate molybdenum, alkyl salicylate molybdenum, alkyl arylamino dithiophosphate sulfide tungsten oxide, and dialkyl dithiophosphate sulfide tungsten oxide; the organic nickel and organic cobalt are selected from at least one of nickel oleate, nickel bipyridine complex, nickel naphthenate, cobalt naphthenate, and cobalt oleate.

11. The method according to claim 1, characterized in that, In step (3), the mass concentration of the Group VIB active component precursor in the activated oil is 2.5-6%; the mass concentration of the Group VIII active component precursor in the activated oil is 0.31-0.75%.

12. The method according to claim 1, characterized in that, In step (3), the space velocity of the active oil introduced is 0.6-1.3 h⁻¹. -1 The activation time is 12-76 hours, the hydrogen-to-oil volume ratio is 50-400, and the activation pressure is 0.5-3.0 MPa.

13. The method according to claim 1, characterized in that, In step (3), when the deactivated catalyst is connected in series in two reactors, a gradient activity recovery method is adopted. First, the temperature of the catalyst bed in the first reactor is controlled at 220-360℃, and the temperature of the bed in the second reactor is controlled at 100-150℃. After the catalyst bed in the first reactor is deposited, the temperature of the first reactor is reduced to 100-150℃, and the temperature of the bed in the second reactor is increased to 220-360℃ to restore the activity of the catalyst in the second reactor. After completion, allow it to cool to room temperature.

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