Oxidation state hydrocracking catalyst ex-situ activation continuous production method

Abstract

The invention relates to an ex-situ activation continuous production method of an oxidation-state hydrocracking catalyst. The method comprises the following steps: step 1, continuously inputting the oxidation-state hydrocracking catalyst into a moving bed reactor; step 2, arranging an inert activation atmosphere in the moving bed reactor; 3, spraying an inorganic activator solution into the moving bed reactor, and keeping the inorganic activator and the oxidation-state hydrocracking catalyst to move in the same direction; step 4, controlling the pressure, temperature and time of the activation reaction to perform activation treatment: controlling the operation pressure in the moving bed reactor to be 0.01-15MPa and the operation temperature to be 60-360 DEG C to perform activation treatment for 4-12 hours; and step 5, obtaining the activated hydrocracking catalyst. According to the present invention, the oxidation state hydrocracking catalyst can integrally complete the vulcanization and passivation processes in the activation reactor, the operation is simple, the continuous production is achieved, the efficiency is substantially improved compared with the batch reactor of the same scale, and the catalyst has characteristics of high self-heating stability and easy storage, transportation and filling.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrocracking catalyst production, and particularly relates to an ex-situ activation continuous production method for an oxidized hydrocracking catalyst. Background Art

[0002] Hydrocracking technology is one of the important means of deep processing of crude oil. It has many advantages such as strong raw material adaptability, flexible processing scheme, high liquid product yield, and good product quality. It is one of the pillar processes for modern refineries to "squeeze everything" and improve quality and efficiency. The core of the hydrocracking process is the hydrocracking catalyst, which has two functions: cracking and hydrogenation. Its cracking function is provided by carriers with acidic centers such as molecular sieves and amorphous silicon aluminum, and the hydrogenation active center is provided by sulfides of Mo and / or W of group VIB and Co and / or Ni of group VIII. For the hydrocracking catalyst, only the sulfidation of the metal component is completed without stabilization of the acidic component. In the early stage of the reaction, problems such as excessive cracking of the reaction raw materials and high heat release leading to temperature runaway are prone to occur. In addition, metal sulfides are prone to spontaneous combustion when in contact with oxygen, and have poor transportation and storage stability. Therefore, the ex situ activation process of the oxidized hydrocracking catalyst needs to take into account the two processes of metal component sulfidation and acidic component passivation.

[0003] At present, the process of ex-situ activation of oxidized hydrocracking catalysts is mainly based on the intermittent method, that is, the oxidized catalyst is loaded into the activation reactor, the sulfide and metal oxide are reacted under certain process conditions to produce metal sulfide, and then the sulfided catalyst is transferred to the passivation reactor or liquid ammonia, organic nitride and other passivators are injected into the original sulfidation reactor for acid center passivation. After the activation is completed, the temperature and pressure are lowered to normal pressure and room temperature, and the activated catalyst is unloaded, and the next batch of catalyst activation production is carried out. The order of the sulfidation and passivation processes in this activation process can be reversed, and the whole process is time-consuming, usually 3 to 7 days, and the production efficiency is low.

[0004] CN113509963A provides an off-site treatment method for a hydrocracking catalyst, which comprises impregnating an oxidized catalyst with an organic solution containing a nitrogen-containing compound, heat-treating the impregnated oxidized catalyst at 50°C to 200°C for 2h to 10h, and then performing a sulfidation treatment to obtain an activated hydrocracking catalyst.

[0005] CN113509964B provides a passivation method for a sulfided hydrocracking catalyst, wherein a sulfur-containing organic compound and a nitrogen-containing organic compound are impregnated and loaded onto a sulfided hydrocracking catalyst, wherein the nitrogen content is 0.1wt% to 5wt% of the catalyst, and the sulfur content is 0.1wt% to 5wt% of the catalyst, and then the catalyst is passivated at 0.01MPa to 0.5MPa and 10°C to 120°C for 0.5h to 10h. After the obtained catalyst is loaded into a reactor, the raw oil can be directly introduced under hydrocracking conditions to react with hydrogen. This method can complete the passivation and sulfidation process of the oxidized hydrocracking catalyst outside the reactor, but the material needs to be transferred between different reactors during the passivation and sulfidation process, and the operation is complicated.

[0006] CN107456974A provides a method for improving the desulfurization performance of hydrogenation catalysts, wherein the hydrogenation catalysts sulfurized with hydrogen sulfide are impregnated with an impregnation solution containing organic nitrogen compounds, and heat treated at 200°C to 450°C for 0.5h to 12h under the protection of inert gas. Compared with the in-vessel activation method of first passivating with NH3 molecules and then introducing low-nitrogen start-up oil, the use of organic nitrogen compounds for catalyst passivation is affected by the strong electronegativity of the lone pair of electrons of organic nitrogen, and is easy to produce strong covalent bond force adsorption with the strong acid center of the hydrogenation catalyst, and is not easy to desorb, causing the catalyst to be deactivated. In addition, after the catalyst is pretreated with an organic solution, organic matter will remain in the micropores of the catalyst, and self-decomposition reactions are prone to occur during storage, transportation and use, increasing the risk of catalyst self-heating.

[0007] CN113117762B provides a method for pretreating a hydrocracking catalyst, wherein an oxidized hydrocracking catalyst is mixed with ammonium sulfide and / or ammonium thiosulfate solution and sodium sulfide solution at 0.1MPa-8MPa and 120°C-200°C, and then treated for 1h-48h in a hydrogen atmosphere at 0.1MPa-8.0MPa and 200°C-350°C, and then switched to a nitrogen atmosphere, and the temperature is adjusted to 110°C-130°C for 0.5h-10h to obtain an activated catalyst. Sodium adsorption on the acidic center is one of the main reasons for permanent poisoning of the hydrocracking catalyst. This method is likely to cause excessive passivation of the hydrocracking catalyst, slow activity recovery, and even reduce the long-term operation stability of the catalyst, shorten the catalyst service life, and cannot achieve activity regeneration.

[0008] CN116059933A provides a hydrogenation catalyst activation device, including a rotary reactor capable of axial rotation and self-rotation, an activation liquid sprayer installed on the top of the reactor, and a material mixing device arranged in the reactor, which can evenly distribute the hydrogenation catalyst activation liquid composed of porous proppant, sulfurized oil, organic solvent and auxiliary agent in the reactor, so that the catalyst loaded in the reactor is evenly sprayed, and the activation reaction rate is improved. This method is an intermittent kettle operation, and the production efficiency is low.

[0009] In summary, in the prior art, the ex situ activation of oxidative hydrocracking catalysts is mostly performed in an intermittent manner, and no public documents are found on the continuous production process of the ex situ activation of oxidative hydrocracking catalysts. Summary of the invention

[0010] The purpose of the present invention is to overcome the shortcomings of the prior art and provide an ex situ activation continuous production method for an oxidized hydrocracking catalyst. The method adopts a continuous moving bed process and an inorganic activator to complete the ex situ activation production of the oxidized hydrogenation catalyst by a one-step method of sulfurization and passivation. The method not only effectively improves the ex situ activation production efficiency, but also avoids the residue of organic activation raw materials in the micropores of the catalyst, improves the self-heating tolerance of the catalyst, reduces the risk of spontaneous combustion of the activated catalyst during storage, transportation and loading, and effectively controls the catalyst activity, avoiding the risk of temperature runaway at start-up due to excessive catalyst activity.

[0011] The present invention solves the technical problem by the following technical solutions:

[0012] A method for continuous production of an oxidized hydrocracking catalyst by ex situ activation, characterized in that the steps of the production method are:

[0013] Step 1, continuously feeding an oxidized hydrocracking catalyst into a moving bed reactor;

[0014] Step 2, setting an inert activation atmosphere in the moving bed reactor;

[0015] Step 3, spraying an inorganic activator solution into the moving bed reactor, and keeping the inorganic activator and the oxidized hydrocracking catalyst moving in the same direction;

[0016] Step 4, controlling the activation reaction pressure, temperature and time for activation treatment: controlling the operating pressure in the moving bed reactor to 0.01MPa-15MPa and the operating temperature to 60°C-360°C for activation treatment for 4h-12h;

[0017] Step 5: obtaining an activated hydrocracking catalyst.

[0018] Furthermore, the moving bed reactor may be a horizontal activation reactor, a one-stage vertical activation reactor or a horizontal rotating drum activation reactor.

[0019] Moreover, the moving bed reactor preferably has an operating pressure of 0.1 MPa to 8 MPa, an operating temperature of 140° C. to 320° C., and an activation time of 6 h to 10 h.

[0020] Moreover, 6-12 temperature control points are arranged in the mobile reactor along the material moving direction to form a temperature control interval, which includes a first temperature zone: a pre-activation temperature zone, a second temperature zone: an activation temperature zone, and a third temperature zone: a passivation temperature zone.

[0021] Moreover, an activation atmosphere circulation system is arranged in the mobile reactor, including an activation atmosphere circulation fan and a tail gas emission absorption device.

[0022] Moreover, the moving bed reactor is provided with at least one inorganic activator nozzle in the pre-activation temperature zone and the activation temperature zone.

[0023] Moreover, the inorganic activator is any one of ammonium hydrogen sulfide, ammonium sulfide, ammonium polysulfide, and thiourea, or a combination of any two or more thereof.

[0024] Moreover, the oxidized hydrocracking catalyst comprises a carrier and a hydrogenation metal component; the main acidic component in the carrier comprises one or more of Y molecular sieve and Beta molecular sieve, and the content is 5wt% to 40wt% by weight of the oxide; the hydrogenation metal component mainly comprises a VIB group metal, selected from Mo and / or W, and the content is 3wt% to 28wt% by weight of the oxide; the hydrogenation metal component comprises a VIII group metal as an auxiliary hydrogenation component, selected from Ni, and the content is 2wt% to 12wt% by weight of the oxide.

[0025] Moreover, the activated hydrocracking catalyst contains 7wt% to 12wt% sulfur by weight, and 3wt% to 8wt% nitrogen by weight.

[0026] The beneficial effects of the present invention are:

[0027] 1. The method for continuous production of oxidized hydrocracking catalyst by ex situ activation of the present invention can complete the sulfurization and passivation processes of the catalyst in an integrated manner in the activation reactor. The operation is simple and continuous production can be achieved. Compared with batch reactors of the same scale, the production capacity of a single reactor can reach up to 6 tons / day, and the production efficiency is increased by more than 4 times.

[0028] 2. The method for continuous production of off-site activation of oxidized hydrocracking catalysts of the present invention uses an inorganic activator that can simultaneously provide the sulfide required for the metal sulfidation reaction and the alkaline compound required for the passivation of the acidic center of the molecular sieve, thereby reducing the synergistic effect between the highly active metal sulfide produced by the sulfidation reaction and the acidic center of the molecular sieve, thereby improving the self-heating tolerance of the catalyst and ensuring the safety of the storage, transportation and filling process of the activated sulfided hydrocracking catalyst.

[0029] 3. The method for continuous production of ex situ activation of an oxidized hydrocracking catalyst of the present invention effectively passivates the acidic center of the obtained ex situ activated hydrocracking catalyst, reduces the risk of temperature runaway due to excessive catalyst activity, and can directly enter the stage of heating and oil feeding when starting up without any gas or liquid phase replacement operation, which greatly saves the start-up time and reduces the generation of waste gas and waste oil during the start-up process. DETAILED DESCRIPTION

[0030] The present invention is further described in detail below through specific examples. The following examples are only illustrative and not restrictive, and the protection scope of the present invention cannot be limited thereto.

[0031] A method for continuous production of an oxidized hydrocracking catalyst by ex situ activation, the production method comprising the following steps:

[0032] Step 1, continuously feeding an oxidized hydrocracking catalyst into a moving bed reactor;

[0033] The moving bed reactor used in the present invention can be a horizontal activation reactor, a one-stage vertical activation reactor or a horizontal drum activation reactor; the moving bed reactor is provided with at least one inorganic activator nozzle along the material moving direction. 6-12 temperature control points are arranged in the moving reactor along the material moving direction to form a temperature control interval, which includes a first temperature zone: a pre-activation temperature zone, a second temperature zone: an activation temperature zone, and a third temperature zone: a passivation temperature zone. The reactor is provided with an activator nozzle in the pre-activation temperature zone and the activation temperature zone to uniformly spray the activator.

[0034] The oxidized hydrocracking catalyst comprises a carrier and a hydrogenation metal component; the main acidic component in the carrier comprises one or more of Y molecular sieve and Beta molecular sieve, and the content thereof is 5wt% to 40wt% by weight of the oxide; the hydrogenation metal component mainly comprises a metal of Group VIB as a hydrogenation component, selected from Mo and / or W, and the content thereof is 3wt% to 28wt% by weight of the oxide; the hydrogenation metal component comprises a metal of Group VIII as a hydrogenation-aiding component, selected from Ni, and the content thereof is 2wt% to 12wt% by weight of the oxide.

[0035] Step 2, setting an inert activation atmosphere in the moving bed reactor;

[0036] An inert activation atmosphere such as nitrogen is arranged in the moving bed reactor, and an activation atmosphere circulation system is arranged in the moving reactor, including an activation atmosphere circulation fan and a tail gas emission absorption device.

[0037] Step 3, spraying an inorganic activator solution into the moving bed reactor, keeping the inorganic activator and the oxidized hydrocracking catalyst moving in the same direction; since the inlet and the middle of the reactor are provided with activator nozzles, the activator can be sprayed evenly. The inorganic activator is any one of ammonium hydrosulfide, ammonium sulfide, ammonium polysulfide, and thiourea, or a combination of any two or more thereof.

[0038] Step 4: Control the activation reaction pressure, temperature and time to perform activation treatment:

[0039] The oxidized hydrocracking catalyst is continuously fed into the activation reactor under nitrogen protection, and the operating pressure in the horizontal activation reactor is controlled to be 0.01MPa-15MPa and the operating temperature is 60℃-360℃ for activation treatment for 4h-12h; the preferred operating pressure in the moving bed reactor is 0.1MPa-8MPa, the operating temperature is 140℃-320℃, and the activation time is 6h-10h.

[0040] Step 5, obtaining an activated hydrocracking catalyst, wherein the sulfur content of the activated hydrocracking catalyst obtained after the above steps 1-5 is 7wt% to 12wt%, and the nitrogen content of the activated hydrocracking catalyst is 3wt% to 8wt%. After the activation is completed, the activated hydrocracking catalyst is sent out of the reactor, cooled to room temperature under nitrogen protection, and packaged to obtain an ex-situ activated hydrocracking catalyst.

[0041] Embodiment 1:

[0042] A method for continuous production of an oxidized hydrocracking catalyst by ex situ activation, the production method comprising the following steps:

[0043] Step 1, continuously feeding an oxidized hydrocracking catalyst into a moving bed reactor;

[0044] This embodiment adopts a horizontal activation reactor; the horizontal activation reactor is provided with at least one inorganic activator nozzle along the material moving direction. This embodiment is provided with an activator nozzle at the entrance and the middle of the horizontal activation reactor, and the activator can be evenly sprayed. 12 temperature control points are set in the mobile reactor along the material moving direction to form a temperature control interval, which includes the first temperature zone: pre-activation temperature zone, the second temperature zone: activation temperature zone, and the third temperature zone: passivation temperature zone. Each temperature interval can respectively realize the activator diffusion in the catalyst micropores and the adsorption function of the active center, the metal sulfide activation and the shielding function of the molecular sieve acid center, and the step-by-step release function of the molecular sieve part of the acid center. The temperatures of the 12 temperature control points are 80°C, 160°C, 230°C, 230°C, 230°C, 280°C, 320°C, 320°C, 280°C, 200°C, and 200°C.

[0045] The oxidized hydrocracking catalyst of this embodiment includes a carrier and a hydrogenation metal component; including WO3 (tungsten trioxide) content of 23%, NiO (nickel oxide) content of 7% and Y molecular sieve content of 18% calculated as oxide.

[0046] The oxidized hydrocracking catalyst is placed on a gas-permeable track of a horizontal activation reactor and moves horizontally, and the moving speed is controlled by a frequency regulator.

[0047] Step 2, setting an inert activation atmosphere in a horizontal activation reactor;

[0048] In this embodiment, an inert activation atmosphere of nitrogen is set in the horizontal activation reactor. An activation atmosphere circulation system is set in the horizontal activation reactor, including an activation atmosphere circulation fan and a tail gas emission absorption device. The nitrogen activation atmosphere is filled and circulated in the horizontal activation reactor.

[0049] Step 3, spraying an inorganic activator solution into a horizontal activation reactor, and keeping the inorganic activator and the oxidized hydrocracking catalyst moving horizontally in the same direction;

[0050] In this embodiment, ammonium hydrosulfide is used as an activator. The ammonium hydrosulfide is prepared into a 50% by mass aqueous solution, and the activator nozzles are provided at the inlet and the middle of the reactor to evenly spray the oxidized hydrocracking catalyst surface. The activator nozzles move horizontally in the same direction as the oxidized hydrocracking catalyst along the air-permeable crawler of the horizontal activation reactor.

[0051] Step 4: Control the activation reaction pressure, temperature and time to perform activation treatment: The oxidized hydrocracking catalyst is continuously fed into the activation reactor under nitrogen protection. The system operating pressure is 6 MPa and the circulating fan flow rate is 1 m / s. 3 / h. The moving rate of the oxidized hydrogenation catalyst is 200kg / h, and the residence time in the reactor is 10h; the injection rate of the ammonium hydrogen sulfide aqueous solution at the reactor inlet is 36kg / h, and the injection rate in the middle is 14kg / h.

[0052] Step 5: obtaining an activated hydrocracking catalyst.

[0053] After the above steps 1-5, an activated hydrocracking catalyst is obtained, wherein the sulfur content is 9.21wt% by weight, the nitrogen content is 5.05wt% by weight, and the degree of sulfurization is 98.3%. The activated hydrocracking catalyst is sent out of the horizontal activation reactor, cooled to room temperature under nitrogen protection, and packaged, which is the ex-situ activated hydrocracking catalyst A1, see Table 1.

[0054] Embodiment 2:

[0055] A method for continuous production of an oxidized hydrocracking catalyst by ex situ activation, the production method comprising the following steps:

[0056] Step 1, continuously feeding an oxidized hydrocracking catalyst into a moving bed reactor;

[0057] This embodiment uses a one-stage vertical activation reactor; 10 heating points are arranged along the axial direction to control the temperature distribution. The oxidized hydrocracking catalyst moves downward through the rotation of the turntable inside the vertical activation reactor, and the movement rate is controlled by the turntable frequency regulator; the finished catalyst is discharged from the reactor through a butterfly valve. An activator nozzle is arranged on the top of the one-stage vertical activation reactor to uniformly spray the activator.

[0058] Ten temperature control points are set in the one-stage vertical activation reactor along the material moving direction to form a temperature control zone, which includes the first temperature zone: pre-activation temperature zone, the second temperature zone: activation temperature zone, and the third temperature zone: passivation temperature zone. Each temperature zone can respectively realize the activator diffusion in the catalyst micropores and the adsorption function of the active center, the metal sulfide activation and the shielding function of the molecular sieve acid center, and the step-by-step release function of some of the molecular sieve acid centers.

[0059] The temperatures of the 10 temperature control points of the one-stage vertical activation reactor are 60°C, 120°C, 200°C, 200°C, 250°C, 285°C, 350°C, 350°C, 300°C, and 190°C, respectively.

[0060] The oxidized hydrocracking catalyst of this embodiment includes a carrier and a hydrogenation metal component; the WO3 content is 25%, the NiO content is 5%, and the Y molecular sieve content is 22% calculated as oxide.

[0061] The oxidized hydrocracking catalyst is continuously introduced into a one-stage vertical activation reactor under nitrogen protection.

[0062] Step 2, setting an inert activation atmosphere in a one-stage vertical activation reactor;

[0063] In this embodiment, an inert activation atmosphere of nitrogen is set in the one-stage vertical activation reactor, and an activation atmosphere circulation system is set at the lower end of the one-stage vertical activation reactor, including an activation atmosphere circulation fan and a tail gas emission absorption device, and the nitrogen activation atmosphere is filled and circulated in the one-stage vertical activation reactor.

[0064] Step 3, spraying an inorganic activator solution into a one-stage vertical activation reactor, and keeping the inorganic activator and the oxidized hydrocracking catalyst moving horizontally in the same direction;

[0065] In this embodiment, ammonium sulfide is used as an activator. The ammonium hydrosulfide is prepared into an aqueous solution with a mass content of 8%. The activator nozzle is provided on the top of the reactor, and the activator is evenly sprayed on the surface of the oxidized hydrocracking catalyst. The activator moves in the same direction as the oxidized hydrocracking catalyst along the turntable of the one-stage vertical activation reactor.

[0066] Step 4: Control the activation reaction pressure, temperature and time to perform activation treatment: The oxidized hydrocracking catalyst is continuously fed into a one-stage vertical activation reactor under nitrogen protection. The system operating pressure is 8 MPa and the circulating fan flow rate is 0.3 m / s. 3 / h, adjust the rotating speed of the turntable to control the catalyst downward movement rate of 100kg / h; spray ammonium sulfide aqueous solution at the top of the reactor at a rate of 270kg / h.

[0067] Step 5: obtaining an activated hydrocracking catalyst.

[0068] After the above steps 1-5, an activated hydrocracking catalyst is obtained, wherein the sulfur content is 8.83wt% by weight, the nitrogen content is 4.35wt% by weight, and the degree of sulfurization is 97.5%. The activated hydrocracking catalyst is sent out of a one-stage vertical activation reactor, cooled to room temperature under nitrogen protection, and packaged, i.e., an ex-situ activated hydrocracking catalyst A2, see Table 1.

[0069] Embodiment 3:

[0070] A method for continuous production of an oxidized hydrocracking catalyst by ex situ activation, the production method comprising the following steps:

[0071] Step 1, continuously feeding an oxidized hydrocracking catalyst into a moving bed reactor;

[0072] The moving bed reactor of this embodiment adopts a two-stage split drum reactor, including a front-stage drum reactor and a rear-stage drum reactor. The front-stage drum reactor and the rear-stage drum reactor are connected by a coaxial mechanical seal chamber. The oxidized hydrocracking catalyst is driven forward by the rotation of the front-stage drum reactor and the rear-stage drum reactor, and the moving rate is controlled by the reactor frequency regulator; the front-stage drum reactor and the rear-stage drum reactor are both provided with an activator nozzle at the head end to uniformly spray the activator. The end of the rear-stage drum reactor is provided with an activation atmosphere circulation fan and an exhaust gas emission absorption device. The front-stage drum reactor is provided with a 6-point heating control temperature distribution to form a temperature control interval. The temperature control interval is a pre-activation temperature zone, which can realize the diffusion of the activator in the catalyst micropores and the adsorption function of the active center. The rear-stage drum reactor is provided with 6-point heating control to form a temperature control interval; the temperature control interval includes the second temperature zone: the activation temperature zone, the third temperature zone: the passivation temperature zone, and each temperature zone can respectively realize the metal sulfidation activation and the shielding function of the molecular sieve acid center and the step-by-step release function of the molecular sieve acid center.

[0073] The injection rate of ammonium polysulfide solution at the inlet of the front-stage rotary drum reactor is 95 kg / h. The temperatures of the six temperature control points of the front-stage rotary drum reactor are 90°C, 140°C, 200°C, 240°C, 240°C, and 240°C, respectively. The flow rate of the circulating fan is 1 m3 / h; the injection rate of ammonium polysulfide solution at the inlet of the rear-stage rotary drum reactor is 65kg / h, and the temperatures of the six temperature control points of the rear-stage rotary drum reactor are 285°C, 350°C, 350°C, 320°C, 240°C, and 180°C, respectively.

[0074] The oxidized hydrocracking catalyst of this embodiment includes a carrier and a hydrogenation metal component; including a WO3 content of 27%, a MoO3 (molybdenum trioxide) content of 5%, a NiO content of 8%, and a Y molecular sieve content of 28% calculated as oxide.

[0075] Step 2, setting an inert activation atmosphere in a two-stage split drum reactor;

[0076] In this embodiment, an inert activation atmosphere of nitrogen is set in the two-stage split drum reactor, an activation atmosphere circulation system is set in the two-stage split drum reactor, an activation atmosphere circulation fan and a tail gas emission absorption device are provided at the end of the rear-stage rotary drum reactor, and the nitrogen activation atmosphere is filled and circulated in the two-stage split drum reactor.

[0077] Step 3, spraying an inorganic activator solution into a two-stage split drum reactor, and keeping the inorganic activator and the oxidized hydrocracking catalyst moving horizontally in the same direction;

[0078] In this embodiment, ammonium polysulfide is used as an activator. The ammonium polysulfide is prepared into an aqueous solution with a sulfur content of 15% by mass and an NH3 content of 21% by mass. The head ends of the front-stage rotary drum reactor and the rear-stage rotary drum reactor are both provided with activator nozzles, which are evenly sprayed on the surface of the oxidized hydrocracking catalyst and move in the same direction as the oxidized hydrocracking catalyst as the two-stage split rotary drum reactor rotates.

[0079] Step 4, control the activation reaction pressure, temperature and time for activation treatment: the oxidized hydrocracking catalyst is continuously fed into the front-stage rotary drum reactor under nitrogen protection, the catalyst movement rate is 150kg / h, and the system operating pressure is 1.5MPa. The injection rate of ammonium polysulfide solution at the inlet of the front-stage rotary drum reactor is 95kg / h, and the temperatures of the six temperature control points of the front-stage rotary drum reactor are 90℃, 140℃, 200℃, 240℃, 240℃, 240℃, and the circulating fan flow rate is 1m 3 / h; the injection rate of ammonium polysulfide solution at the inlet of the rear drum reactor is 65kg / h, the temperatures of the six temperature control points of the reactor are 285℃, 350℃, 350℃, 320℃, 240℃, and 180℃ respectively, and the circulation fan flow rate is 0.5m 3 / h.

[0080] Step 5: obtaining an activated hydrocracking catalyst.

[0081] After the above steps 1-5, an activated hydrocracking catalyst is obtained, wherein the sulfur content is 12.75wt% by weight, the nitrogen content is 6.72wt% by weight, and the degree of sulfurization is 97.1%. The activated hydrocracking catalyst is sent out of a two-stage split drum reactor, cooled to room temperature under nitrogen protection, and packaged, i.e., an ex-situ activated hydrocracking catalyst A3, see Table 1.

[0082] Embodiment 4:

[0083] A method for continuous production of an oxidized hydrocracking catalyst by ex situ activation, the production method comprising the following steps:

[0084] Step 1, continuously feeding an oxidized hydrocracking catalyst into a moving bed reactor;

[0085] This embodiment adopts a horizontal drum activation reactor; the horizontal drum activation reactor is provided with at least one inorganic activator nozzle along the material moving direction. This embodiment is provided with an activator nozzle at the entrance of the horizontal drum activation reactor, which can spray the activator evenly, and an activation atmosphere circulation fan and a tail gas emission absorption device are provided at the end. Eight temperature control points are set along the material moving direction in the mobile reactor to form a temperature control interval, which includes the first temperature zone: pre-activation temperature zone, the second temperature zone: activation temperature zone, and the third temperature zone: passivation temperature zone. Each temperature interval can respectively realize the activator diffusion in the catalyst micropores and the adsorption function of the active center, the metal sulfide activation and the shielding function of the molecular sieve acid center, and the step-by-step release function of the molecular sieve part of the acid center.

[0086] The temperatures of the 8 temperature control points are 180°C, 250°C, 250°C, 265°C, 295°C, 310°C, 310°C, and 220°C respectively.

[0087] The oxidized hydrocracking catalyst of this embodiment includes a carrier and a hydrogenation metal component; the WO3 content is 23%, the NiO content is 5%, and the Beta molecular sieve content is 8% calculated as oxide.

[0088] The oxidized hydrocracking catalyst moves horizontally along with the rotation of the horizontal drum activation reactor, and the movement rate is controlled by a frequency regulator.

[0089] Step 2, setting an inert activation atmosphere in a horizontal rotary drum activation reactor;

[0090] In this embodiment, an inert activation atmosphere of nitrogen is set in the horizontal rotary drum activation reactor. An activation atmosphere circulation system is set in the horizontal rotary drum activation reactor, including an activation atmosphere circulation fan and a tail gas emission absorption device. The nitrogen activation atmosphere is filled and circulated in the horizontal rotary drum activation reactor.

[0091] Step 3, spraying an inorganic activator solution into a horizontal rotary drum activation reactor, and keeping the inorganic activator and the oxidized hydrocracking catalyst moving horizontally in the same direction;

[0092] Thiourea is used as an activator, which is melted into a solution and evenly sprayed on the surface of the oxidized hydrocracking catalyst through activator nozzles provided at the inlet and middle of the reactor. The oxidized hydrocracking catalyst moves horizontally in the same direction as the air-permeable crawler of the horizontal rotary drum activation reactor.

[0093] Step 4: Control the activation reaction pressure, temperature and time for activation treatment: the moving rate of the oxidized hydrocracking catalyst is 250 kg / h, and the system operating pressure is 0.5 MPa. The injection rate of the thiourea solution at the reactor inlet is 62.5 kg / h, and the temperatures of the 8 temperature control points of the oxidized hydrocracking catalyst are 180°C, 250°C, 250°C, 265°C, 295°C, 310°C, 310°C, and 220°C, respectively. The circulating fan flow rate is 0.6 m / s. 3 / h.

[0094] Step 5: obtaining an activated hydrocracking catalyst.

[0095] After the above steps 1-5, an activated hydrocracking catalyst is obtained, wherein the sulfur content is 8.39wt% by weight, the nitrogen content is 3.03wt% by weight, and the degree of sulfurization is 98.6%. The activated hydrocracking catalyst is sent out of the horizontal drum activation reactor, cooled to room temperature under nitrogen protection, and packaged, which is the ex-situ activated hydrocracking catalyst A4, see Table 1.

[0096] Comparative Example 1

[0097] This comparative example uses the same oxidized hydrocracking catalyst as in Example 1, including 23% WO3 content, 7% NiO content and 18% Y molecular sieve content calculated as oxide.

[0098] Adopt the fixed bed ex situ activation method commonly used in industry:

[0099] The catalyst loading is 8 tons, the reactor is pressurized to a hydrogen partial pressure of 12.5 MPa, and the circulating hydrogen space velocity is 1300 h -1 The catalyst bed was heated from room temperature to 185°C at a rate of 15°C / h. After the catalyst bed temperature reached 185°C, the sulfiding agent dimethyl disulfide (DMDS) was injected into the reactor at a rate of 26 kg / h / (10000 Nm 3Circulating hydrogen). After DMDS is injected, the heating rate is controlled at 5℃ / h, and the catalyst bed temperature is raised to 230℃, and then kept at this temperature for 20h. Since the decomposition and sulfidation reaction of DMDS will release a large amount of heat, the catalyst bed temperature will rise. During the heating and constant temperature period, the DMDS injection amount can be reduced to ensure that the catalyst bed temperature does not exceed 230℃.

[0100] At the end of the 230℃ constant temperature period, the DMDS injection rate was increased to 50kg / h / (10000Nm 3 Circulating hydrogen) until the hydrogen sulfide content in the circulating hydrogen reaches 0.5-1.0v%, then the reactor bed temperature is raised to 290°C at a rate of 4°C / h and kept at this temperature for 4h. Then the reactor bed temperature is raised to 370°C at a rate of 5°C / h, the DM DS injection rate is kept unchanged, and the reactor bed temperature is kept at 370°C for 8h, and the sulfidation is completed.

[0101] After the sulfidation is completed, the catalyst bed is cooled to 150°C at a rate of 10°C / h while maintaining the hydrogen sulfide content in the circulating gas at not less than 0.5v%, and straight-run light diesel is introduced into the reactor as a raw material for catalyst wetting, and then anhydrous liquid ammonia is introduced for catalyst passivation. The anhydrous liquid ammonia injection rate is 40kg / h, and DMDS is injected at the same time as the ammonia injection to ensure that the hydrogen sulfide concentration in the circulating hydrogen is not less than 0.1% (V). After 2 hours of liquid ammonia injection, water is injected into the circulating hydrogen separator at a water injection rate of 50kg / h to wash the ammonia in the circulating hydrogen. After the catalyst bed temperature is raised to 325°C at a heating rate of 15°C / h, the temperature is maintained for 8 hours. The total amount of ammonia injected is 8wt% of the cracking agent loading.

[0102] The above steps were carried out for 120 hours in total to obtain an activated hydrocracking catalyst B1, which contained 9.12 wt% sulfur, 5.05 wt% nitrogen, and a sulfurization degree of 96.7%. See Table 1.

[0103] Comparative Example 2

[0104] This comparative example uses the same oxidized hydrocracking catalyst as in Example 2, including WO3 content of 25%, NiO content of 5% and Y molecular sieve content of 22% calculated as oxide.

[0105] Adopt the fixed bed ex situ activation method commonly used in industry:

[0106] The fixed bed reactor was loaded with 10 tons of catalyst. After N2 replacement, the system was pressurized to 5 MPa. H2S was introduced into the system to maintain the H2S concentration at 0.75v%, and the hydrogen volume space velocity was 300h -1; Raise the catalyst bed temperature to 230°C at a heating rate of 4°C / min and maintain for 16 hours, then raise it to 300°C at a heating rate of 3°C / min and maintain for 8 hours, and finally raise it to 350°C at a heating rate of 3°C / min and maintain for 8 hours to complete the catalyst sulfidation.

[0107] After the vulcanization is completed, the temperature is lowered to 180℃ at a rate of 10℃ / h and replaced with N2 atmosphere. A mixture of NH3 and N2 is introduced, N2 / NH3=200:1, and the mixed gas air velocity is 1.0h -1 , and maintain the temperature at this space velocity for 15 hours.

[0108] In the above step 155h, an activated hydrocracking catalyst B2 is obtained, wherein the sulfur content is 8.65wt% by weight, the nitrogen content is 4.21wt% by weight, and the sulfurization degree is 95.5%. See Table 1.

[0109] Table 1

[0110]

[0111] The autothermal reaction of the activated hydrocracking catalyst is mainly a chain reaction triggered by the reaction of sulfided metal with O2 to produce elemental sulfur or SO2. Therefore, the activated bifunctional hydrogenation catalysts obtained in Examples 1 to 4 were subjected to an oxygen autothermal evaluation test at normal pressure and 80°C. The changes in the sulfur and nitrogen loadings of the catalysts are shown in Table 2.

[0112] Table 2

[0113]

[0114] It can be seen from the above embodiments that the ex situ activation continuous production method of the oxidized hydrogenation catalyst provided by the present invention can directly provide a completely sulfided and passivated catalyst with high production efficiency; moreover, since the acidic center of the molecular sieve is shielded while the metal component is in the activation reaction, the interaction between the active metal sulfide and the molecular sieve carrier is reduced, so that the active component is stabilized, the catalyst has strong self-heating tolerance, can be directly loaded and used in an industrial device, and no other treatment measures are required, which can save a lot of start-up time for the refinery, and has the advantages of time saving, safety, and environmental protection.

[0115] Although the embodiments of the present invention are disclosed for illustrative purposes, those skilled in the art will appreciate that various substitutions, changes and modifications are possible without departing from the spirit and scope of the present invention and the appended claims. Therefore, the scope of the present invention is not limited to the contents disclosed in the embodiments.

Claims

1. A method for continuous production of an oxidized hydrocracking catalyst by ex situ activation, characterized in that: The steps of the production method are: Step 1, continuously feeding an oxidized hydrocracking catalyst into a moving bed reactor; Step 2, setting an inert activation atmosphere in the moving bed reactor; Step 3, spraying an inorganic activator solution into the moving bed reactor, and keeping the inorganic activator and the oxidized hydrocracking catalyst moving in the same direction; Step 4, controlling the activation reaction pressure, temperature and time for activation treatment: controlling the operating pressure in the moving bed reactor to 0.01MPa-15MPa and the operating temperature to 60°C-360°C for activation treatment for 4h-12h; Step 5: obtaining an activated hydrocracking catalyst.

2. The method for continuous production of an oxidized hydrocracking catalyst by ex situ activation according to claim 1, characterized in that: The moving bed reactor can be a horizontal activation reactor, a one-stage vertical activation reactor or a horizontal rotating drum activation reactor.

3. The method for continuous production of an oxidized hydrocracking catalyst by ex situ activation according to claim 1, characterized in that: The moving bed reactor preferably has an operating pressure of 0.1 MPa to 8 MPa, an operating temperature of 140° C. to 320° C., and an activation time of 6 h to 10 h.

4. The method for continuous production of an oxidized hydrocracking catalyst by ex situ activation according to claim 1, characterized in that: 6-12 temperature control points are arranged in the moving reactor along the material moving direction to form a temperature control interval, which includes a first temperature zone: a pre-activation temperature zone, a second temperature zone: an activation temperature zone, and a third temperature zone: a passivation temperature zone.

5. The method for continuous production of an oxidized hydrocracking catalyst by ex situ activation according to claim 1, characterized in that: An activated atmosphere circulation system is arranged in the mobile reactor, comprising an activated atmosphere circulation fan and a tail gas emission absorption device.

6. The method for continuous production of an oxidized hydrocracking catalyst by ex situ activation according to claim 1, characterized in that: The moving bed reactor is provided with at least one inorganic activator nozzle in the pre-activation temperature zone and the activation temperature zone.

7. The method for continuous production of an oxidized hydrocracking catalyst by ex situ activation according to claim 1, characterized in that: The inorganic activator is any one of ammonium hydrosulfide, ammonium sulfide, ammonium polysulfide and thiourea, or a combination of any two or more thereof.

8. The method for continuous production of an oxidized hydrocracking catalyst by ex situ activation according to claim 1, characterized in that: The oxidized hydrocracking catalyst comprises a carrier and a hydrogenation metal component; the main acidic component in the carrier comprises one or more of Y molecular sieve and Beta molecular sieve, and the content is 5wt% to 40wt% by weight of the oxide; the hydrogenation metal component mainly comprises a metal of Group VIB as a hydrogenation component, selected from Mo and / or W, and the content is 3wt% to 28wt% by weight of the oxide; the hydrogenation metal component comprises a metal of Group VIII as an auxiliary hydrogenation component, selected from Ni, and the content is 2wt% to 12wt% by weight of the oxide.

9. The method for continuous production of an oxidized hydrocracking catalyst by ex situ activation according to claim 1, characterized in that: The activated hydrocracking catalyst contains 7wt% to 12wt% sulfur by weight, and 3wt% to 8wt% nitrogen by weight.

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