An external activation method for a bifunctional hydrogenation catalyst

Abstract

This invention provides an external activation method for a bifunctional hydrogenation catalyst. The steps of this external activation method are as follows: during the external activation process, inorganic sulfur compounds and inorganic nitrogen compounds are used to complete the sulfidation and passivation process of the bifunctional hydrogenation catalyst, avoiding the residue of organic matter in the micropores of the catalyst and improving the self-heating tolerance of the catalyst; the feedstock oil can be directly introduced for start-up operation by heating, which greatly shortens the start-up time of the industrial plant and effectively reduces the risk of overheating due to excessive catalyst activity.

Description

Technical Field

[0001] This invention belongs to the field of petrochemical catalysis technology, and in particular relates to an external activation treatment method for a bifunctional hydrogenation catalyst. Background Technology

[0002] Hydrogenation is one of the most effective means of producing clean fuels, and efficient hydrogenation catalysts are key to this process. Hydrogenation catalysts are typically bifunctional catalysts with both acidic and hydrogenation-active centers. The acidic centers are provided by supports such as alumina, amorphous silica-alumina, and molecular sieves, while the hydrogenation-active centers are provided by sulfides of Group VIB Mo and / or W and Group VIII Co and / or Ni.

[0003] Industrially, hydrogenation catalysts are typically produced in a high-temperature, oxygen-rich environment using oxidized metal components supported on a carrier. This facilitates transportation, storage, and loading. However, the metal components require sulfidation before use. For bifunctional hydrogenation catalysts, simply sulfiding the metal components results in unstable metal sulfides that are prone to spontaneous combustion upon contact with oxygen. Furthermore, the acidic components remain unstabilized, leading to problems such as excessive cracking of the reactants and excessive heat release causing runaway reactions in the initial stages of the reaction. Therefore, the external activation process for bifunctional hydrogenation catalysts must consider both metal component sulfidation and acidic component passivation.

[0004] Currently, most hydrocracking catalysts are activated in-reactor, where the oxidized catalyst is loaded into the reactor, and under the reaction process conditions, H2S reacts with metal oxides to produce metal sulfides. Liquid ammonia and low-NOx distillate oil are then injected sequentially for acid center passivation before the feedstock is introduced for start-up. CN1074466A provides a hydrocracking start-up method that first loads the hydrocracking catalyst with 1%–6% low-carbon organic amines, then introduces low-NOx start-up oil, hydrogen, and a sulfiding agent into the low-temperature phase reactor, and sulfides at 220℃–330℃. After sulfidation, the reactor temperature can be raised to normal process conditions before gradually introducing the feedstock oil. This method eliminates the need for passivation during start-up, but the sulfidation process remains relatively cumbersome. Due to the long activation time, complex system switching, and equipment corrosion associated with in-reactor activation, external activation of the catalyst has become a current research focus.

[0005] CN113509964B provides a passivation method for a sulfurized hydrocracking catalyst. Sulfur-containing organic compounds and nitrogen-containing organic compounds are impregnated and loaded onto the sulfurized hydrocracking catalyst. The nitrogen content is 0.1 wt%–5 wt% of the catalyst, and the sulfur content is 0.1 wt%–5 wt%. The catalyst is then passivated at 10℃–120℃ and 0.01 MPa–0.5 MPa for 0.5 h–10 h. After being loaded into the reactor, the resulting catalyst can be directly fed with feedstock oil to react with hydrogen under hydrocracking conditions, effectively shortening the start-up time. CN113509963A provides an external treatment method for a hydrocracking catalyst. An oxidized catalyst is impregnated with an organic solution containing nitrogen-containing compounds. The impregnated oxidized catalyst is then heat-treated at 50℃–200℃ for 2 h–10 h, followed by sulfurization treatment to obtain an activated hydrocracking catalyst. This method allows for the passivation and sulfurization of the oxidized hydrocracking catalyst to be completed in one external process. CN107456974A discloses a method for improving the desulfurization performance of hydrotreating catalysts. The method involves impregnating a hydrotreating catalyst, after hydrogen sulfide sulfidation, with an impregnation solution containing organic nitrogen compounds, and then heat-treating it at 200℃~450℃ for 0.5h~12h under inert gas protection. Compared to the in-process activation method of first passivating with NH3 molecules and then introducing low-NOx operating oil, using organic nitrogen compounds for catalyst passivation, due to the strong electronegativity of the lone pairs of electrons in the organic nitrogen compounds, easily forms strong covalent bonds with the strongly acidic centers of the hydrotreating catalyst, making desorption difficult and leading to catalyst deactivation. Furthermore, after pretreating the catalyst with an organic solution, organic matter may remain in the micropores of the catalyst, which is prone to self-decomposition reactions during storage, transportation, and use, increasing the risk of catalyst self-heating.

[0006] CN113117762B discloses a method for pretreating hydrocracking catalysts. The method involves mixing an oxidized hydrocracking catalyst with ammonium sulfide and / or ammonium thiosulfate solution and a sodium sulfide solution at 0.1 MPa–8 MPa and 120°C–200°C, then treating it under a hydrogen atmosphere at 0.1 MPa–8.0 MPa and 200°C–350°C for 1–48 hours. The mixture is then switched to a nitrogen atmosphere, and the temperature is adjusted to 110°C–130°C for 0.5–10 hours to obtain an activated catalyst. Sodium adsorption on acidic sites is one of the main causes of permanent poisoning in hydrocracking catalysts. This method easily leads to excessive passivation of the hydrocracking catalyst, slow activity recovery, and may even reduce the long-term operational stability of the catalyst, shorten its service life, and fail to achieve activity regeneration. Summary of the Invention

[0007] The purpose of this invention is to overcome the shortcomings of the prior art and provide an external activation method for bifunctional hydrogenation catalysts. By using external activation, inorganic sulfur compounds and inorganic nitrogen compounds are used to simultaneously sulfide and passivate the bifunctional hydrogenation catalyst, avoiding the residue of organic matter in the micropores of the catalyst and improving the catalyst's self-heating tolerance. The feedstock oil can be directly introduced for start-up operation, which greatly shortens the start-up time of industrial plants and effectively reduces the risk of system overheating due to excessive catalyst activity and over-reaction.

[0008] The technical problem solved by this invention is achieved through the following technical solution:

[0009] An off-site activation method for a bifunctional hydrogenation catalyst, characterized by comprising the following steps:

[0010] 1) The bifunctional hydrogenation catalyst is packed into the activation reactor and heated to 60℃ to 160℃ in an environment with nitrogen and / or inert gas content of 90v% to 100v%.

[0011] 2) After the treatment in step 1) is completed, the first activation gas is introduced, and the activation treatment is carried out in stages at 0.01MPa~10MPa and 60℃~360℃ for 4~72h.

[0012] 3) After the treatment in step 2) is completed, stop the first activation gas and switch to the second activation gas. Adjust the temperature to 120℃~240℃ and treat at 0.01MPa~10MPa for 1h~24h.

[0013] 4) After the treatment in step 2) is completed, switch to nitrogen and / or inert gas and cool down to 15℃~35℃ to obtain the activated bifunctional hydrogenation catalyst.

[0014] Moreover, the bifunctional hydrogenation catalyst mentioned in step 1) is a hydrocracking catalyst, a hydrotreatment catalyst, a hydrodeoxygenation catalyst, or a hydroisomerization catalyst.

[0015] Moreover, the first activating gas mentioned in step 2) is a mixed gas containing inorganic sulfur compounds, with a content of 1000 μg / L to 50000 μg / L based on the weight of sulfur element; the inorganic sulfur compounds are one or more of COS, CS2, and H2S, and the mixed gas also contains one or more of H2O, N2, and inert gases.

[0016] Furthermore, the sulfur content in the mixed gas containing inorganic sulfur compounds is preferably 2000 μg / L to 20000 μg / L.

[0017] Furthermore, the first activation gas volume hourly space velocity (VHSV) mentioned in step 2) is 0.1 h⁻¹ of the bifunctional hydrogenation catalyst loading volume.-1 ~50h -1 0.5h is preferred -1 ~25h -1 The reaction pressure is 0.01MPa to 10MPa, preferably 0.5MPa to 6MPa, and the activation treatment is carried out in stages at 60℃ to 360℃ for 12h to 72h, preferably at 80℃ to 160℃ for 4h to 12h, 160℃ to 240℃ for 4h to 36h, and 280℃ to 320℃ for 4h to 24h.

[0018] Furthermore, the second activating gas mentioned in step 3) is a mixture of inorganic nitrogen compound NH3 and carrier gas, with a nitrogen content of 0.1 g / L to 10 g / L, preferably 0.5 g / L to 5 g / L, based on the weight of nitrogen. The carrier gas can be one or more of nitrogen, carbon dioxide, and inert gases.

[0019] Furthermore, the second activation gas volume space velocity mentioned in step 3) is 0.1 h⁻¹ of the catalyst loading volume. -1 ~2h -1 0.5h is preferred -1 ~1h -1 The activation temperature is 120℃~240℃, preferably 150℃~200℃; the activation pressure is 0.01MPa~10MPa, preferably 0.5MPa~6MPa; and the activation time is 1h~24h, preferably 6h~12h.

[0020] Furthermore, in the activated bifunctional hydrogenation catalyst described in step 4), the sulfur content is 2 wt% to 12 wt% by weight, and the nitrogen content is 2 wt% to 8 wt% by weight.

[0021] The advantages and beneficial effects of this invention are as follows:

[0022] 1. The external activation method of the bifunctional hydrogenation catalyst of the present invention, compared with the existing external activation technology, adopts a gas-phase activation process of inorganic sulfur compounds and inorganic nitrogen compounds, which avoids the residue of organic matter in the micropores of the catalyst and improves the self-heating resistance of the catalyst.

[0023] 2. The off-reactor activation method of the bifunctional hydrogenation catalyst of the present invention can complete the sulfidation and passivation operations in the same reactor sequentially without the need to transfer the intermediate catalyst under nitrogen protection, which is simple to operate.

[0024] 3. The external activation method of the bifunctional hydrogenation catalyst of the present invention can be cooled to room temperature under nitrogen protection after activation, which can keep the micropores of the catalyst completely filled with inert gas, prevent the active components of the catalyst from reacting with O2 and water in the air, and improve the safety of catalyst storage, transportation and loading.

[0025] 4. The off-site activation method of the bifunctional hydrogenation catalyst of the present invention allows the pre-activated bifunctional hydrogenation catalyst obtained by the present invention to directly enter the heating and oil feeding stage during the start-up of industrial plants without any gas or liquid phase replacement operation, which greatly saves start-up time, reduces the amount of waste gas and waste oil generated during start-up, and effectively reduces the risk of overheating due to excessive catalyst activity. Detailed Implementation

[0026] The present invention will be further described in detail below through specific embodiments. The following embodiments are merely descriptive and not limiting, and should not be used to limit the scope of protection of the present invention.

[0027] In both the embodiments and comparative examples of this invention, the catalyst activation reactors are vertical isothermal tubular furnace reactors, with the reaction tubes made of stainless steel or quartz and a height-to-diameter ratio of 3 to 10. The catalyst is naturally loaded into the isothermal zone of the reactor, and both the upper and lower ends of the reactor are filled with inert ceramic balls or silicon carbide particles as proppant.

[0028] The oxidized bifunctional hydrogenation catalysts in the embodiments and comparative examples of this invention are commercially available hydrocracking catalysts, hydrotreatment catalysts, hydrodeoxygenation catalysts, and hydroisomerization catalysts, or they can be prepared according to existing publicly available methods in the art.

[0029] Example 1

[0030] An oxidized hydrocracking catalyst was obtained, with WO3 content of 28% and NiO content of 7%, and strong acid centers provided by the molecular sieve support accounting for 40% of the total number of acid centers.

[0031] 100g of oxidized hydrocracking catalyst was loaded into the activation reactor, sealed, and purged with nitrogen until the nitrogen content reached 99%. The system was pressurized to 6MPa, and the catalyst bed temperature was raised to 100℃ at a heating rate of 30℃ / h. The first activation gas (composed of COS, H2O, and N2, with a sulfur content of 10000μg / L) was introduced at a gas hourly space velocity (GHSV) of 2h⁻¹. -1 Under the continuous presence of the first activating gas, the catalyst was activated at a constant temperature of 100℃ for 10 hours, at 200℃ for 24 hours, and at 300℃ for 8 hours, with a heating rate of 20℃ / h for each stage.

[0032] After sulfidation, while maintaining the system pressure, the catalyst bed temperature was lowered to 180°C, and a second activation gas (composed of NH3 and N2, with a nitrogen content of 1 g / L) was introduced at a gas hourly space velocity of 1 h⁻¹. -1 The catalyst was activated at a constant temperature of 180°C for 9 hours in the continuous presence of the second activating gas.

[0033] After activation, the system pressure is kept constant, nitrogen gas is introduced, and the temperature is lowered to room temperature to obtain the activated bifunctional hydrocracking catalyst with a sulfur content of 9.44 wt% and a nitrogen content of 6.00 wt%.

[0034] After passivation, the catalyst was subjected to a reaction pressure of 14.5 MPa, a reaction temperature of 375 °C, a hydrogen-to-oil volume ratio of 1000:1, and a hydrocracking feedstock volume hourly space velocity of 1.5 h⁻¹. -1 Under the specified reaction conditions, the reaction was initiated. The catalyst activity stabilization time is shown in Table 1.

[0035] Example 2

[0036] An oxidized hydrocracking catalyst was obtained, with WO3 content of 25% and NiO content of 5%, and strong acid centers provided by molecular sieve support accounting for 20% of the total number of acid centers.

[0037] 100g of oxidized hydrocracking catalyst was loaded into an activation reactor, sealed, and purged with nitrogen until the nitrogen content reached 98%. The system was pressurized to 5MPa, and the catalyst bed temperature was raised to 120℃ at a heating rate of 30℃ / h. The first activation gas (composed of COS and H2O, with a sulfur content of 9000μg / L) was introduced at a gas hourly space velocity (GHSV) of 1.5h⁻¹. -1 Under the continuous presence of the first activating gas, the catalyst was activated at a constant temperature of 120℃ for 8 hours, at 180℃ for 28 hours, and at 320℃ for 20 hours, with a heating rate of 20℃ / h at each stage.

[0038] After sulfidation, while maintaining the system pressure, the catalyst bed temperature was lowered to 150°C, and a second activation gas (composed of NH3 and N2, with a nitrogen content of 4 g / L) was introduced at a gas hourly space velocity of 2 h⁻¹. -1 The catalyst was activated at a constant temperature of 150°C for 8.5 hours in the presence of the second activating gas.

[0039] After activation, the system pressure is kept constant, nitrogen gas is introduced, and the temperature is lowered to room temperature to obtain the activated bifunctional hydrocracking catalyst with a sulfur content of 8.60 wt% and a nitrogen content of 2.35 wt%.

[0040] Example 3

[0041] An oxidized hydrocracking catalyst was obtained with WO3 content of 27%, MoO3 content of 5%, and NiO content of 8%, and strong acid centers provided by the molecular sieve support accounted for 40% of the total number of acid centers.

[0042] 1000g of oxidized hydrocracking catalyst was loaded into an activation reactor, sealed, and purged with helium until the helium content reached 97%. The system was pressurized to 8MPa, and the catalyst bed temperature was raised to 140℃ at a heating rate of 30℃ / h. The first activation gas (composed of COS, H2O, and He, with a sulfur content of 15000μg / L) was then introduced at a gas hourly space velocity (GHSV) of 1.2h. -1 Under the continuous presence of the first activating gas, the catalyst was activated at a constant temperature of 140℃ for 12 hours, at 230℃ for 36 hours, and at 290℃ for 24 hours, with a heating rate of 20℃ / h at each stage.

[0043] After sulfidation, while maintaining a constant system pressure, the catalyst bed temperature was lowered to 140°C, and a second activation gas (composed of NH3 and He, with a nitrogen content of 2 g / L) was introduced at a gas hourly space velocity of 0.5 h⁻¹. -1 The catalyst was activated at a constant temperature of 140℃ for 12 hours in the continuous presence of the second activating gas.

[0044] After activation, the system pressure is kept constant, nitrogen gas is introduced, and the temperature is lowered to room temperature to obtain the activated bifunctional hydrocracking catalyst with a sulfur content of 10.85 wt% and a nitrogen content of 8.75 wt%.

[0045] Example 4

[0046] An oxidized hydroisomerization catalyst was obtained with a NiO content of 3% and strong acid centers provided by a molecular sieve support accounting for 55% of the total number of acid centers.

[0047] 500g of oxidized hydroisomerization catalyst was loaded into an activation reactor, sealed, and replaced with carbon dioxide until the carbon dioxide content reached 98.5%. The system was pressurized to 4MPa, and the catalyst bed temperature was raised to 80℃ at a heating rate of 30℃ / h. The first activation gas (composed of COS and N2, with a sulfur content of 2000μg / L) was introduced at a gas hourly space velocity of 3h⁻¹. -1 Under the continuous presence of the first activating gas, the catalyst was activated at 80℃ for 6 hours, at 220℃ for 16 hours, and at 280℃ for 4 hours, with a heating rate of 20℃ / h at each stage.

[0048] After sulfidation, while maintaining a constant system pressure, the catalyst bed temperature was lowered to 240℃, and a second activation gas (composed of NH3 and carbon dioxide, with a nitrogen content of 2.5 g / L) was introduced at a gas hourly space velocity of 0.75 h⁻¹. -1 The catalyst was activated at a constant temperature of 240℃ for 6 hours in the continuous presence of the second activating gas.

[0049] After activation, the system pressure is kept constant, nitrogen gas is introduced, and the temperature is lowered to room temperature to obtain the activated bifunctional hydroisomer catalyst with a sulfur content of 1.35 wt% and a nitrogen content of 7.55 wt%.

[0050] Example 5

[0051] An oxidized hydrodeoxygenation catalyst was obtained with a MoO3 content of 18%, a NiO content of 2%, a CoO content of 5%, and strong acid centers provided by modified alumina accounting for 5% of the total number of acid centers.

[0052] 200g of oxidized hydrodeoxygenation catalyst was loaded into an activation reactor, sealed, and purged with nitrogen until the nitrogen content reached 99%. The system was pressurized to 2MPa, and the catalyst bed temperature was raised to 120℃ at a heating rate of 30℃ / h. The first activation gas (composed of COS, H2S, and H2O, with a sulfur content of 1000μg / L) was introduced at a gas hourly space velocity of 25h⁻¹. -1 Under the continuous presence of the first activating gas, the catalyst was activated at a constant temperature of 120℃ for 12 hours, at 230℃ for 24 hours, and at 350℃ for 8 hours, with a heating rate of 20℃ / h at each stage.

[0053] After sulfidation, while maintaining a constant system pressure, the catalyst bed temperature was lowered to 240°C, and a second activation gas (composed of NH3 and N2, with a nitrogen content of 0.5 g / L) was introduced at a gas hourly space velocity of 1 h⁻¹. -1 The catalyst was activated at a constant temperature of 240℃ for 8 hours in the continuous presence of the second activating gas.

[0054] After activation, the system pressure is kept constant, nitrogen gas is introduced, and the temperature is lowered to room temperature to obtain the activated bifunctional hydrodeoxygenation catalyst with a sulfur content of 10.15 wt% and a nitrogen content of 2.25 wt%.

[0055] Example 6

[0056] An oxidized hydrogenation catalyst was obtained with a MoO3 content of 23%, a NiO content of 5%, and strong acid centers provided by modified alumina accounting for 8% of the total number of acid centers.

[0057] 500g of oxidized hydrotreating catalyst was loaded into an activation reactor, sealed, and purged with nitrogen until the nitrogen content reached 96%. The system was pressurized to 3.5MPa, and the catalyst bed temperature was raised to 90℃ at a rate of 30℃ / h. A first activation gas (composed of COS and H2O, with a sulfur content of 12000μg / L) was introduced at a gas hourly space velocity (GHSV) of 1.5h⁻¹. -1Under the continuous presence of the first activating gas, the catalyst was activated at a constant temperature of 90℃ for 12 hours, at 210℃ for 32 hours, and at 340℃ for 22 hours, with a heating rate of 20℃ / h at each stage.

[0058] After sulfidation, while maintaining a constant system pressure, the catalyst bed temperature was lowered to 230°C, and a second activation gas (composed of NH3 and N2, with a nitrogen content of 1.2 g / L) was introduced at a gas hourly space velocity of 0.4 h⁻¹. -1 The catalyst was activated at a constant temperature of 230°C for 7 hours in the continuous presence of the second activating gas.

[0059] After activation, the system pressure is kept constant, nitrogen gas is introduced, and the temperature is lowered to room temperature to obtain the activated bifunctional hydrogenation catalyst with a sulfur content of 11.60 wt% and a nitrogen content of 2.30 wt%.

[0060] Example 7

[0061] 1000g of the oxidized hydrocracking catalyst used in Example 1 was loaded into an activation reactor. After sealing, the reactor was purged with nitrogen until the nitrogen content reached 99.5%. The system was pressurized to 14.5MPa, and the catalyst bed temperature was raised to 60°C at a heating rate of 50°C / h. The first activation gas (composed of COS, H2O, and N2, with a sulfur content of 1000μg / L) was introduced at a gas hourly space velocity (GHSV) of 2h. -1 Under the continuous presence of the first activating gas, the catalyst was activated at a constant temperature of 60℃ for 4 hours, at 260℃ for 12 hours, and at 360℃ for 12 hours, with a heating rate of 25℃ / h at each stage.

[0062] After sulfidation, while maintaining a constant system pressure, the catalyst bed temperature was lowered to 100°C, and a second activation gas (composed of NH3 and N2, with a nitrogen content of 0.4 g / L) was introduced at a gas hourly space velocity of 2 h⁻¹. -1 The catalyst was activated at a constant temperature of 100°C for 6 hours in the continuous presence of the second activating gas.

[0063] After activation, the system pressure is kept constant, nitrogen gas is introduced, and the temperature is lowered to room temperature to obtain the activated bifunctional hydrocracking catalyst with a sulfur content of 9.39 wt% and a nitrogen content of 5.95 wt%.

[0064] After passivation, the catalyst was subjected to a reaction pressure of 14.5 MPa, a reaction temperature of 375 °C, a hydrogen-to-oil volume ratio of 1000:1, and a hydrocracking feedstock volume hourly space velocity of 1.5 h⁻¹. -1 Under the specified reaction conditions, the reaction was initiated. The catalyst activity stabilization time is shown in Table 1.

[0065] Comparative Example 1

[0066] 100g of the oxidized hydrocracking catalyst used in Example 1 was loaded into an activation reactor and activated using a conventional industrial gas-phase sulfidation passivation process. The sulfiding agent was DMDS and the passivation agent was liquid ammonia. After activation, the catalyst had a sulfur content of 9.40wt% and a nitrogen content of 5.90wt%.

[0067] Example 8

[0068] Excessively high catalyst activity not only results in a long stabilization time but also a low reaction temperature after stabilization, leading to a high yield of cracking byproduct gases. The catalysts activated in Examples 1, 7, and Comparative Example 1 were used in a hydrocracking reaction at a pressure of 14.5 MPa, a temperature of 375°C, a hydrogen-to-oil volume ratio of 1000:1, and a hydrocracking feedstock volume hourly space velocity of 1.5 h⁻¹. -1 Under the reaction conditions, an on-board activity stability test was conducted, and the results are shown in Table 1.

[0069] Table 1 Results of the activity stability test of the externally activated catalyst

[0070]

[0071] As can be seen from the above embodiments, the off-site activation method of the bifunctional hydrogenation catalyst provided by the present invention can directly provide a fully sulfidated and passivated catalyst. The catalyst has strong self-heating resistance and can be directly loaded and used in industrial plants without other treatment measures. It can save refineries a lot of start-up time and has the advantages of saving time, safety and environmental protection. It effectively reduces the risk of system overheating caused by excessive catalyst activity and excessive reaction, and the yield of cracking by-product gas is appropriate after stabilization.

[0072] Although embodiments of the invention have been disclosed for illustrative purposes, those skilled in the art will understand that various substitutions, variations, and modifications are possible without departing from the spirit and scope of the invention and the appended claims. Therefore, the scope of the invention is not limited to the contents disclosed in the embodiments.

Claims

1. An ex situ activation method of a bifunctional hydrog enation catalyst, characterized in that: The method comprises the following steps: 1) loading the bifunctional hydrogenation catalyst into an activation reactor, and heating to 60-160°C in an environment containing 90-100% nitrogen and / or inert gas; 2) after the treatment of step 1) is completed, introducing a first activation gas, and activating in stages at 0.01-10 MPa and 60-360°C for 4-72 hours; The first activation gas in step 2) is a mixed gas containing inorganic sulfur compounds; the inorganic sulfur compounds are one or more of COS, CS2, and H2S; the mixed gas also contains one or more of H2O, N2, and inert gas; 3) after the treatment of step 2) is completed, stopping the introduction of the first activation gas, switching to the introduction of a second activation gas, adjusting the temperature to 120-240°C, and treating at 0.01-10 MPa for 1-24 hours; The second activation gas is a mixed gas containing inorganic nitrogen compound NH3 and carrier gas; The content is 0.5-5 g / L by weight of nitrogen; the carrier gas is one or more of nitrogen, carbon dioxide, and inert gas; 4) after the treatment of step 2) is completed, switching to the introduction of nitrogen and / or inert gas, and cooling to 15-35°C to obtain the activated bifunctional hydrogenation catalyst.

2. The method for ex-situ activation of a bifunctional hydrog enation catalyst according to claim 1, characterized in that: The bifunctional hydrogenation catalyst in step 1) is a hydrocracking catalyst, a hydrodeoxygenation catalyst, or a hydroisomerization catalyst.

3. The method for ex situ activation of a bifunctional hydrog enation catalyst according to claim 1, characterized in that: The content of the mixed gas containing inorganic sulfur compounds is 1000-50000 μg / L by weight of sulfur.

4. The method for ex situ activation of a bifunctional hydrog enation catalyst according to claim 1, characterized in that: The content of sulfur in the mixed gas containing inorganic sulfur compounds is 2000-20000 μg / L.

5. The method for ex situ activation of a bifunctional hydrog enation catalyst according to claim 1, characterized in that: The first activated gas volume space velocity in the step 2) is 0.5h -1 ~ 25h -1 , the reaction pressure is 0.5MPa~6MPa, the 60℃~360℃ phased activation treatment is 12h~72h, the 80℃~160℃ activation is 4h~12h, the 160℃~240℃ activation is 4h~36h, and the 280℃~320℃ activation is 4h~24h.

6. The method for ex situ activation of a bifunctional hydrog enation catalyst according to claim 1, characterized in that: The second activation gas volume space velocity in the step 3) is 0.5h -1 ~1h -1 , the activation temperature is 150℃~200℃, the activation pressure is 0.5MPa~6MPa, and the activation time is 6h~12h.

7. The method for ex situ activation of a bifunctional hydrog enation catalyst according to claim 1, characterized in that: The content of sulfur in the activated bifunctional hydrogenation catalyst in step 4) is 2-12 wt%, and the content of nitrogen is 2-8 wt%.

Images