CN111073699B

CN111073699B - Hydrotreating method

Info

Publication number: CN111073699B
Application number: CN201811226402.8A
Authority: CN
Inventors: 吕振辉; 彭绍忠; 薛冬; 杨占林
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2018-10-22
Filing date: 2018-10-22
Publication date: 2021-10-08
Anticipated expiration: 2038-10-22
Also published as: CN111073699A

Abstract

The invention discloses a hydrotreating method, which comprises the following steps: the hydrocracking raw material enters a hydrofining reaction zone for hydrogenation reaction, and the reaction effluent enters a cracking reaction zone and is subjected to hydrogenation reaction with a catalyst bed layer in a cracking reactor; the hydrofining catalyst bed layer is graded and filled with at least two stages of vulcanized hydrofining catalysts along the material flow direction, the average length of metal active phase platelets is gradually increased and the average layer number of the platelets is gradually reduced along the material flow direction of each stage of vulcanized hydrofining catalyst; the hydrocracking catalyst bed layer is filled with at least two stages of vulcanized hydrocracking catalysts in a grading manner along the material flow direction. The method realizes the matching reaction of the molecular size and the structure of reactants in each section with the active phase structure in the hydrofining reaction zone and the hydrocracking reaction zone, effectively utilizes the active center of the catalyst, improves the coupling reaction performance of the active center structure and the molecular structure, and produces high-quality naphtha, aviation kerosene, diesel oil and hydrocracking tail oil in more.

Description

Hydrotreating method

Technical Field

The present invention relates to a hydrotreating process.

Background

The hydrocracking technology has the main characteristics of strong raw material adaptability, flexible product scheme, high target product selectivity, good product quality, high added value and the like, and can be used for directly producing various high-quality petroleum products (such as gasoline, jet fuel, diesel oil, lubricating oil base oil and the like) and high-quality chemical raw materials (such as production raw materials of benzene, toluene, xylene, ethylene and the like). Therefore, with the gradual deterioration of crude oil quality, the continuous increase of the demand of the market for high-quality petroleum products and high-quality chemical raw materials and the successive emergence of new environmental regulations, the importance of hydrocracking technology is prominent day by day, the application is increasingly wide, the hydrocracking technology becomes the most suitable oil refining technology for reasonably utilizing limited petroleum resources and producing clean petroleum products and high-quality chemical raw materials to the maximum extent, and the hydrocracking technology is the core of the combination of oil refining, chemical refining and fiber in modern oil refining and petrochemical enterprises.

CN1293228A discloses a hydrocracking catalyst grading filling method, which can adopt molecular sieve type and/or amorphous silicon-aluminum hydrocracking catalysts commonly used in the oil refining industry, when selecting and filling hydrocracking catalysts for a hydrocracking device, selecting hydrocracking catalysts with different activities and/or different nitrogen resistance performances but basically equivalent target product selectivity, and carrying out reasonable matching, and can reduce 30-70% of the amount of quenching hydrogen used by a hydrocracking reactor and the amount of emergency cold hydrogen used by the hydrocracking device or improve the handling capacity of the hydrocracking device by 20-50%. But the method has little influence on improving the structure and the properties of the product.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a hydrotreating method, which realizes the matching reaction of the molecular size and the structure of reactants in each section with an active phase structure in a hydrofining reaction zone and a hydrocracking reaction zone, effectively utilizes a catalyst active center, improves the coupling reaction performance of the active center structure and the molecular structure, and produces high-quality naphtha, aviation kerosene, diesel oil and hydrocracking tail oil in more.

The hydrotreating method of the invention comprises the following steps: the hydrocracking raw material enters a hydrofining reaction zone and contacts a hydrofining catalyst bed layer in a refining reactor to carry out hydrogenation reaction, the refined reaction effluent enters the hydrocracking reaction zone and contacts a hydrocracking catalyst bed layer in a cracking reactor to carry out hydrogenation reaction, and the reaction product flows out of the reactor to carry out next fractionation; the hydrofining catalyst bed layer is graded and filled with at least two stages of vulcanized hydrofining catalysts along the material flow direction, the average length of metal active phase platelets is gradually increased and the average layer number of the platelets is gradually reduced along the material flow direction of each stage of vulcanized hydrofining catalyst; the hydrocracking catalyst bed layer is filled with at least two stages of vulcanization hydrocracking catalysts in a grading way along the material flow direction, and each stage of vulcanization hydrocracking catalysts increases the infrared acid amount step by step, increases the average length of metal active phase lamella crystal step by step and reduces the average layer number of the lamella crystal step by step along the material flow direction. The metal active phase is a metal sulfide.

In the method of the present invention, the hydrocracking raw material is a hydrocracking raw material conventional in the art, such as vacuum wax oil (VGO), coker wax oil (CGO), light deasphalted oil and other heavy distillate oil.

In the method, the vulcanized hydrofining/cracking catalyst is obtained by vulcanizing the oxidized hydrofining/cracking catalyst, the vulcanizing mode can adopt wet vulcanizing or dry vulcanizing, and the temperature rise speed, the vulcanizing temperature and the vulcanizing time in the vulcanizing process are adjusted according to the required metal active phase platelet structure. The vulcanizing agent adopted in the vulcanizing process is one or more of DMDS, CS2, SZ54 and the like.

In the method, the hydrofining reaction zone mainly carries out hydrodesulfurization, denitrification and aromatic saturation reaction, and 1 or more hydrofining reactors can be arranged as required; the hydrocracking reaction zone is mainly used for carrying out hydrocracking reaction, and 1 or more hydrocracking reactors can be arranged according to the requirement.

In the method of the present invention, the hydrofining catalyst (the hydrofining catalyst before sulfidation) is generally a hydrofining catalyst commonly used in the art, generally alumina or modified alumina is used as a carrier, VIII group and/or VIB group metal elements are used as active components, active metals are calculated by oxides based on the weight of the catalyst, the VIII group metal is 1wt% to 9wt%, preferably 1.0wt% to 9.0wt%, and the VIB group metal is 5wt% to 25wt%, and the hydrofining catalyst can be selected from one or more of the catalysts or commercially available products prepared by the method of the present invention, such as 3936, FF-14, FF-24, FF-16, FF-26, FF-36, FF-46, FF-56, FF-66, and the like.

In the method, the average length of the metal active phase lamella of each stage of the vulcanized hydrorefining catalyst is 1-9 nm, and the gradual increase amplitude is 1-5 nm, preferably 2-4 nm.

In the method, the average number of layers of metal active phase platelets of each stage of vulcanized hydrorefining catalyst is 1-9, and the stepwise reduction range is 1-5, preferably 2-4.

In the method, in the hydrofining reaction zone, the filling proportion of each level of sulfided catalyst is at least 10 percent by taking the total volume of the catalyst in the refining reactor as the reference. Taking filling of 2-4 stages as an example, along the logistics direction, when the two-stage filling proportion is: 10% -90%: 10% -90%; the third-level filling proportion is 10% -90%: 10% -40%: 20 to 80 percent; the four-stage filling proportion is as follows: 10% -40%: 10% -40%: 10% -40%: 10 to 40 percent, and the sum of the filling proportions of all levels is 100 percent.

In the method, the hydrofining catalysts subjected to 2-4-stage vulcanization are preferably sequentially loaded, and taking the loading of 3-stage as an example, the hydrofining catalysts I, II and III are sequentially loaded along the material flow direction.

Wherein the properties of the vulcanized hydrorefining catalyst I are as follows: the aluminum oxide catalyst comprises an aluminum oxide carrier and active metals, wherein the active metals are selected from one or more of VIII group and/or VIB group metal elements; based on the weight of the catalyst, the active metal is calculated by oxide, the VIII group metal is 1wt% -9 wt%, preferably 3.0wt% -9.0 wt%, and the VIB group metal is 5wt% -25 wt%, preferably 15wt% -25 wt%. The average number of layers of the active photo is 7.0-9.0, and the average length of the photo is 1.0-3.0 nm. The specific surface area is 150-200 m²(ii) a pore volume of 0.35 to 0.45 mL/g^-1. The hydrogenation catalyst I can be prepared by using a commercial product or according to the existing method, such as the following method: and supersaturating and dipping the alumina carrier by using a solution containing an active metal component to obtain a catalyst precursor, and drying and roasting to obtain the required hydrogenation catalyst I. The drying conditions are as follows: the drying temperature is 100-300 ℃, preferably 200-300 ℃, and the drying time is 1-5 hours, preferably 4-5 hours; the roasting conditions are as follows: the roasting temperature is 500-600 ℃, preferably 550-580 ℃, and the roasting time is 1-5 hours, preferably 4-5 hours; the heating rate is 2-5 ℃/min.

The preparation method of the vulcanized hydrofining catalyst I comprises the following steps: filling the catalyst I into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 150-170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 250-270 ℃ at the speed of 2-5 ℃/h, and keeping the temperature for 8-10 hours; and raising the temperature of the catalyst bed to 350-360 ℃ at the speed of 5-10 ℃/h, and keeping the temperature for 8-10 hours.

Wherein the properties of the vulcanized hydrofining catalyst II are as follows: the aluminum oxide catalyst comprises an aluminum oxide carrier and active metals, wherein the active metals are selected from one or more of VIII group and/or VIB group metal elements; based on the weight of the catalyst, the active metal is calculated by oxide, the VIII group metal is 1wt% -9 wt%, preferably 3.0wt% -9.0 wt%, and the VIB group metal is5wt% -25 wt%, preferably 15wt% -25 wt%, and the balance being alumina carrier. The average number of layers of the active photo is 4.0-6.0, and the average length of the photo is 4.0-6.0 nm. The specific surface area is 150-200 m²(ii) a pore volume of 0.35 to 0.45 mL/g^-1. The hydrogenation catalyst II can be prepared by using a commercial product or according to the existing method, such as the following method: impregnating the catalyst support with an organic compound solution; heat-treating the obtained organic compound additive-loaded support; and loading the active metal component on the obtained organic matter-loaded carrier to obtain a catalyst precursor, and drying and roasting the catalyst precursor to obtain the required hydrogenation catalyst II. The organic compound may specifically be a compound containing at least two oxygen atom groups and 2 to 5 carbon atoms. In particular compounds containing at least two hydroxyl groups and 2 to 5 carbon atoms. Suitable organic additives include, for example, alcohols, ethers or sugars, for example, suitable alcohols may include ethylene glycol, propylene glycol, glycerol, and the like, suitable ethers may include diethylene glycol, propylene glycol, and the like, and suitable sugars include monosaccharides. One or more of the organic compounds may be selected. The drying temperature is 100-300 ℃, preferably 150-200 ℃, and the drying time is 1-5 hours, preferably 2-3 hours; the roasting temperature is 400-500 ℃, preferably 450-480 ℃, and the roasting time is 1-5 hours, preferably 2-3 hours; the temperature rise rate is 5-10 ℃/min. The dosage of the organic compound is 5-10% of the weight of the catalyst carrier.

The preparation method of the vulcanized hydrofining catalyst II comprises the following steps: filling the hydrogenation catalyst II into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 150-170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 210-230 ℃ at a speed of 5-10 ℃/h, and keeping the temperature for 5-7 hours; and raising the temperature of the catalyst bed to 330-340 ℃ at a speed of 10-15 ℃/h, and keeping the temperature for 5-7 hours.

Wherein the properties of the vulcanized hydrofining catalyst III are as follows: the aluminum oxide catalyst comprises an aluminum oxide carrier and active metals, wherein the active metals are selected from one or more of VIII group and/or VIB group metal elements; based on the weight of the catalyst, the active metal is 1wt percent calculated by oxide and the VIII group metal9wt%, preferably 3.0wt% to 9.0wt%, group VIB metal 5wt% to 25wt%, preferably 15wt% to 25wt%, the balance being alumina support. The average number of layers of the active photo is 1.0-3.0, and the average length of the photo is 7.0-9.0 nm. The specific surface area is 150-200 m²(ii) a pore volume of 0.35 to 0.45 mL/g^-1。

The preparation can be carried out by using a commercially available product or according to the existing method, for example, by using the following method: and (3) saturating and dipping the alumina carrier by using a solution containing an active metal component and an organic compound to obtain a catalyst precursor, and drying to obtain the required hydrogenation catalyst III. The organic compound may specifically be a compound containing at least two oxygen atom groups and 5 to 20 carbon atoms. In particular compounds containing at least two hydroxyl groups and 5 to 20 carbon atoms. Suitable organic additives include, for example, alcohols, ethers or sugars, for example, suitable alcohols may include glycerol and the like, suitable ethers may include triethylene glycol, tributylene glycol or tetraethylene glycol and the like, suitable sugars include polysaccharides, which may include lactose, maltose or sucrose. One or more of the organic compounds may be selected. The drying temperature is 100-300 ℃, preferably 100-150 ℃, and the drying time is 1-5 h, preferably 1-1.5 h; the heating rate is 2-5 ℃/min. The dosage of the organic compound is 15-20% of the weight of the catalyst carrier.

The preparation method of the vulcanized hydrofining catalyst III comprises the following steps: filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 150-170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 180-200 ℃ at a speed of 10-15 ℃/h, and keeping the temperature for 2-4 hours; and raising the temperature of the catalyst bed to 310-320 ℃ at a speed of 15-20 ℃/h, and keeping the temperature for 2-4 hours.

Taking the weight of the catalyst in the hydrofining reaction zone as a reference, the proportion of the hydrogenation catalyst I is 10-90 percent; the proportion of the hydrogenation catalyst II is 10 to 40 percent; the proportion of the hydrogenation catalyst III is 20-80%. The filling method of the hydrogenation catalyst grading system generally adopts bag filling or dense phase filling, and is conventional operation in the field.

In the method of the present invention, the hydrocracking catalyst (hydrocracking catalyst before sulfidation) is generally a hydrocracking catalyst commonly used in the art, and generally amorphous silica-alumina, silica-magnesium, zeolite molecular sieve and alumina are used as carriers, the group VIII and/or group VIB metal elements are used as active components, based on the weight of the catalyst, the active metals are calculated by oxides, the group VIII metal is 1wt% -9 wt%, preferably 1.0wt% -9.0 wt%, the group VIB metal is 5wt% -25 wt%, and the specific surface area is 100-800 m²A pore volume of 0.20 to 0.50 ml/g^-1It may be selected from the catalysts prepared by the process of the present invention or commercially available products, such as HC-14, HC-24, HC-28, HC-29, HC-190, HC-185, DHC-32, DHC-215, DHC-115, HC-150, ICR-210, ICR-220, ICR-120, ICR-209, ICR-141, ICR-126, FC-14, FC-20, FC-30, FC-40, FC-50, FC-60, FC-16, FC-12, FC-32, FC-24, RT-1, RT-5, RT-25, RT-30, RHC-1, RHC-5, etc.

In the method, the infrared acid amount of each stage of the vulcanization hydrocracking catalyst is 0.3-1.1 mol/g, and the gradual increase amplitude is 0.1-0.5 mol/g, preferably 0.2-0.4 mol/g.

In the method, the average length of the metal active phase lamella of each stage of the vulcanization hydrocracking catalyst is 1-9 nm, and the gradual increase amplitude is 1-5 nm, preferably 2-4 nm.

In the method, the average number of layers of metal active phase platelets of each stage of the vulcanization hydrocracking catalyst is 1-9, and the stepwise reduction range is 1-5, preferably 2-4.

In the method, in the hydrocracking reaction zone, the filling proportion of each stage of the vulcanization catalyst is at least 10 percent by taking the total volume of the catalyst in the cracking reactor as the reference. Along the material flow direction, when the two-stage filling proportion is: 10% -90%: 10% -90%; the third-level filling proportion is 10% -90%: 10% -40%: 20 to 80 percent; the four-stage filling proportion is as follows: 10% -40%: 10% -40%: 10% -40%: 10 to 40 percent, and the sum of the filling proportions of all levels is 100 percent.

In the method, the vulcanized hydrocracking catalyst is obtained by vulcanizing the oxidized hydrocracking catalyst, the vulcanization mode can adopt wet vulcanization or dry vulcanization, and the temperature rise speed, the vulcanization temperature and the vulcanization time in the vulcanization process are adjusted according to the required metal active phase platelet structure. The vulcanizing agent adopted in the vulcanizing process is one or more of DMDS, CS2, SZ54 and the like.

In the method, 2-4 stages of the vulcanization hydrocracking catalyst are preferably and sequentially loaded, and taking the loading of 3 stages as an example, the vulcanization hydrocracking catalyst I, II and III are sequentially loaded along the material flow direction.

The properties of the vulcanized hydrocracking catalyst I are as follows: the aluminum oxide catalyst comprises an aluminum oxide carrier and active metals, wherein the active metals are selected from one or more of VIII group and/or VIB group metal elements; based on the weight of the catalyst, the active metal is calculated by oxide, the VIII group metal is 1wt% -9 wt%, preferably 3.0wt% -9.0 wt%, the VIB group metal is 5wt% -25 wt%, preferably 15wt% -25 wt%, and the balance is an alumina carrier. The average number of layers of the active photo is 7.0-9.0, and the average length of the photo is 1.0-3.0 nm. The specific surface area is 100-350 m²(ii) a pore volume of 0.35 to 0.45 mL/g^-1The amount of the infrared acid is 0.3 to 0.5 mol/g. The hydrocracking catalyst I can be prepared by using a commercial product or according to the existing method, such as the following method: and supersaturating and dipping the alumina carrier by using a solution containing an active metal component to obtain a catalyst precursor, and drying and roasting to obtain the required hydrogenation catalyst I. The drying temperature is 100-300 ℃, preferably 200-300 ℃, and the drying time is 1-5 h, preferably 4-5 h; the roasting temperature is 500-600 ℃, preferably 550-580 ℃, and the roasting time is 1-5 h, preferably 4-5 h; the heating rate is 2-5 ℃/min.

The preparation method of the vulcanization hydrocracking catalyst I comprises the following steps: filling the hydrocracking catalyst I into a vulcanization reactor, introducing vulcanized oil into the reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 150-170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 250-270 ℃ at the speed of 2-5 ℃/h, and keeping the temperature for 8-10 hours; and raising the temperature of the catalyst bed to 350-360 ℃ at the speed of 5-10 ℃/h, and keeping the temperature for 8-10 hours.

Wherein the properties of the vulcanized hydrocracking catalyst II are as follows: comprises amorphous silica-alumina or silica-magnesium carrier and active metalWherein the active metal is selected from one or more of VIII group and/or VIB group metal elements; based on the weight of the catalyst, the active metal is calculated by oxide, the VIII group metal is 1wt% -9 wt%, preferably 3.0wt% -9.0 wt%, and the VIB group metal is 5wt% -25 wt%, preferably 15wt% -25 wt%. The average number of layers of the active photo is 4.0-6.0, and the average length of the photo is 4.0-6.0 nm. The specific surface area is 400-500 m²(ii) a pore volume of 0.35 to 0.45 mL/g^-1The amount of the infrared acid is 0.6 to 0.8 mol/g. The hydrocracking catalyst II can be prepared by using a commercial product or according to the existing method, such as the following method: impregnating the support with an organic compound solution; heat-treating the obtained organic compound additive-loaded support; and loading the active metal component on the obtained organic matter-loaded carrier to obtain a catalyst precursor, and drying and roasting the catalyst precursor to obtain the required hydrogenation catalyst II. The organic compound may specifically be a compound containing at least two oxygen atom groups and 2 to 5 carbon atoms. In particular compounds containing at least two hydroxyl groups and 2 to 5 carbon atoms. Suitable organic additives include, for example, alcohols, ethers or sugars, for example, suitable alcohols may include ethylene glycol, propylene glycol, glycerol, and the like, suitable ethers may include diethylene glycol, propylene glycol, and the like, and suitable sugars include monosaccharides. One or more of the organic compounds may be selected. The drying temperature is 100-300 ℃, preferably 150-200 ℃, and the drying time is 1-5 hours, preferably 2-3 hours; the roasting temperature is 400-500 ℃, preferably 450-480 ℃, and the roasting time is 1-5 hours, preferably 2-3 hours; the temperature rise rate is 5-10 ℃/min. The dosage of the organic compound is 5-10% of the weight of the catalyst carrier.

The preparation method of the vulcanization hydrocracking catalyst II comprises the following steps: filling the hydrocracking catalyst II into a vulcanization reactor, introducing vulcanized oil into the reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 150-170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 210-230 ℃ at a speed of 5-10 ℃/h, and keeping the temperature for 5-7 hours; and raising the temperature of the catalyst bed to 330-340 ℃ at a speed of 10-15 ℃/h, and keeping the temperature for 5-7 hours.

In which a hydrocracking catalyst III is sulfidedThe properties were as follows: comprises a modified zeolite molecular sieve carrier and active metals, wherein the active metals are selected from one or more of VIII group and/or VIB group metal elements; based on the weight of the catalyst, the active metal is calculated by oxide, the VIII group metal is 1wt% -9 wt%, preferably 3.0wt% -9.0 wt%, the VIB group metal is 5wt% -25 wt%, preferably 15wt% -25 wt%, and the balance is carrier. The average number of layers of the active photo is 1.0-3.0, and the average length of the photo is 7.0-9.0 nm. The specific surface area is 500-700 m²A pore volume of 0.35 to 0.45 ml/g^-1The amount of the infrared acid is 0.9 to 1.1 mol/g. The hydrocracking catalyst III may be prepared from a commercially available product or according to a conventional method, for example, as follows: and (3) saturating and impregnating the carrier by using a solution containing an active metal component and an organic compound to obtain a catalyst precursor, and drying to obtain the required hydrocracking catalyst III. The organic compound may specifically be a compound containing at least two oxygen atom groups and 5 to 20 carbon atoms. In particular compounds containing at least two hydroxyl groups and 5 to 20 carbon atoms. Suitable organic additives include, for example, alcohols, ethers or sugars, for example, suitable alcohols may include glycerol and the like, suitable ethers may include triethylene glycol, tributylene glycol or tetraethylene glycol and the like, suitable sugars include polysaccharides, which may include lactose, maltose or sucrose. One or more of the organic compounds may be selected. The drying temperature is 100-300 ℃, preferably 100-150 ℃, and the drying time is 1-5 h, preferably 1-1.5 h; the heating rate is 2-5 ℃/min. The dosage of the organic compound is 15-20% of the weight of the catalyst carrier.

The preparation method of the vulcanization hydrocracking catalyst III comprises the following steps: filling the hydrocracking catalyst III into a vulcanization reactor, introducing vulcanized oil into the reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 150-170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 180-200 ℃ at a speed of 10-15 ℃/h, and keeping the temperature for 2-4 hours; and raising the temperature of the catalyst bed to 310-320 ℃ at a speed of 15-20 ℃/h, and keeping the temperature for 2-4 hours.

Taking the weight of the vulcanized hydrocracking catalyst as a reference, the vulcanized hydrocracking catalyst I accounts for 20-80 percent; the proportion of the vulcanization hydrocracking catalyst II is 20-80 percent; the proportion of the vulcanization hydrocracking catalyst III is 20-80%. The filling method of the hydrocracking catalyst grading system generally adopts bag filling or dense phase filling, and is conventional operation in the field.

The hydrocracking catalyst grading process of the present invention may be used under any hydrocracking processing conditions suitable in the art. Typical hydrocracking process conditions are: the average reaction temperature is 360-450 ℃, preferably 350-430 ℃; the reaction hydrogen partial pressure is 8.0-20.0 MPa, preferably 10.0-18.0 MPa; liquid hourly volume space velocity of 0.15h^-1～3.0h^-1Preferably 0.2h^-1～3.0h^-1(ii) a The volume ratio of hydrogen to oil is 300-2000, preferably 500-1500.

Compared with the prior art, the hydrocracking treatment method provided by the invention has the following advantages:

1. in the method, in the hydrofining section and the hydrocracking section, each reaction section is graded with various active phase catalysts with different structures according to the molecular size and the structure of the reactant along the flow direction of the reactant, so that the coupling reaction of the molecular size and the structure of the reactant and the active phase structure is realized, the utilization rate of active metal is improved, and the technical problem that the molecular size and the structure of the reactant are contradictory to the active phase structure is solved.

2. In the method, in the hydrofining section, along the flowing direction of reactants, reactants such as polycyclic thiophene sulfides and the like which are firstly contacted with the catalyst are complex in structure and large in steric hindrance, and reaction impurities are difficult to remove under the influence of the steric hindrance, so that the metal active photo crystal of the catalyst adopting the method is short in length and large in the number of layers, the steric hindrance effect can be remarkably reduced, the utilization rate of an active phase is improved, and the impurities with large steric hindrance are easier to remove; through the preliminary hydrogenation reaction, the molecular structure of the reactant is simplified, and the steric hindrance is reduced, so the catalyst adopting the method has moderate metal active photo crystal length and moderate number of the photo crystal layers, can be more effectively coupled with the reaction molecules of the structure for reaction, and further improves the reaction performance to the reactant molecules; finally, molecules of hydrogenation and hydrogenolysis reaction are subjected to ring opening and chain scission to form small molecular reactants such as thiophene sulfides which are simple in structure, smaller in steric hindrance and more difficult to react, and finally the catalyst adopting the method disclosed by the invention is longer in metal active photo crystal length and less in the number of layers of the photo crystal, so that the small molecules with smaller steric hindrance are subjected to further hydrogenation reaction, impurities contained in the small molecules which are more difficult to remove are removed, the utilization rate of active metals is improved, and effective reaction on the reactant molecules is realized;

3. in the method, in the hydrocracking section along the flowing direction of reactants, the reactants which are firstly contacted with the catalyst, such as polycyclic aromatic hydrocarbon, cycloparaffin, long-chain alkane and the like, have more complex structures and larger steric hindrance, and are difficult to remove under the influence of the steric hindrance, so that the metal active photo crystal of the catalyst adopting the method has shorter length and more layers, can obviously reduce the steric hindrance effect and improve the utilization rate of an active phase, and the aromatic hydrocarbon, the cycloparaffin and the long-chain alkane with larger steric hindrance are easier to open and break chains; through the preliminary hydrogenation reaction, the molecular structure of the reactant is simplified, and the steric hindrance is reduced, so the catalyst adopting the method has moderate metal active photo crystal length and moderate number of the photo crystal layers, can be more effectively coupled with the reaction molecules of the structure for reaction, and further improves the reaction performance to the reactant molecules; finally, molecules of hydrogenation and hydrogenolysis reaction are subjected to ring opening and chain scission to form a micromolecule reactant which is simple in structure, smaller in steric hindrance and more difficult to react, and finally the catalyst adopting the method has the advantages that the length of the metal active photo crystal is longer, the number of the layers of the photo crystal is less, the micromolecule with smaller steric hindrance is subjected to further hydrogenation reaction, the utilization rate of active metal is improved, and effective reaction on reactant molecules is realized;

4. the catalyst preparation method and the grading technology adopted in the method can obviously improve the utilization rate of active metal of the catalyst, carry out optimized grading according to the properties of raw materials and the requirements of products, and can produce high-quality naphtha, aviation kerosene, diesel oil and hydrocracking tail oil in large quantity according to the requirements.

Drawings

FIGS. 1, 2 and 3 are TEM spectra of sulfided hydrofinishing catalysts I, II and III of example 1 of this invention.

FIGS. 4, 5 and 6 are TEM spectra of the sulfided hydrocracking catalysts I, II and III of example 1 of the present invention.

Detailed Description

The preparation and grading process of the hydrorefining and hydrocracking catalysts of the present invention are described in more detail below by way of specific examples. The examples are merely illustrative of specific embodiments of the process of the present invention and do not limit the scope of the invention. In the method, the length and the number of layers of the catalyst are statistically analyzed by a Transmission Electron Microscope (TEM) (30 transmission electron microscope pictures are manually counted to obtain an average value); the pore structure of the catalyst is determined by adopting nitrogen adsorption-desorption; the infrared acid content of the catalyst adopts NH₃TPD. The hydrofining catalyst carrier used is alumina carrier with specific surface area of 298m²Per g, pore volume of 0.85 mL/g^-1(ii) a The hydrocracking catalyst carrier I used is an alumina carrier with the specific surface area of 350m²Per g, pore volume of 1.10 mL. g^-1(ii) a The hydrocracking catalyst carrier II is amorphous silica-alumina with the specific surface area of 500m²Per g, pore volume of 0.95ml g^-1(ii) a The hydrocracking catalyst carrier III is a modified zeolite molecular sieve, and the specific surface area of the modified zeolite molecular sieve is 800m²Per g, pore volume of 0.84 mL/g^-1(ii) a The vulcanizing agent is DMDS.

Example 1

This example shows a catalyst grading combination and a preparation of a graded catalyst. Adopting a catalyst grading scheme, filling a refining reactor with a catalyst, and filling a bed layer with a sulfurized hydrofining catalyst I, a sulfurized hydrofining catalyst II and a sulfurized hydrofining catalyst III from top to bottom; the cracking reactor is filled with a catalyst, and a bed layer is filled with a sulfurized hydrocracking catalyst I, a sulfurized hydrocracking catalyst II and a sulfurized hydrocracking catalyst III from top to bottom.

The preparation method of the vulcanized hydrofining catalyst I comprises the following steps: hydrogenation is carried outMoO-containing carrier for purification₃And supersaturation impregnation is carried out on the active component of NiO to obtain a catalyst precursor, the precursor is dried for 4h at the temperature of 200 ℃, the temperature is raised to 600 ℃ at the speed of 5 ℃/min, and the required catalyst is obtained after constant-temperature roasting for 4.0 h. The catalyst MoO₃20.01 percent and NiO is 3.8 percent; the specific surface area is 189m²Per g, pore volume of 0.35ml g^-1. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 150 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 250 ℃ at a speed of 10 ℃/h, and keeping the temperature for 9 hours; the temperature of the catalyst bed is raised to 360 ℃ at the speed of 8 ℃/h, and the temperature is kept for 10 hours. The average number of layers of the active photo is 8.5, and the average length of the plate is 2.5 nm.

The preparation method of the vulcanized hydrofining catalyst II comprises the following steps: the hydrofining carrier contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and diglycol (the dosage is 6 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 180 ℃ for 2.5h, heating to 450 ℃ at 5 ℃/min, and roasting at constant temperature for 3.0h to obtain the required catalyst. The catalyst MoO₃21.5 percent of NiO and 3.8 percent of NiO; the specific surface area is 195m²Per g, pore volume of 0.38ml g^-1. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 230 ℃ at the speed of 5 ℃/h, and keeping the temperature for 6.5 hours; the temperature of the catalyst bed is raised to 340 ℃ at the speed of 10 ℃/h, and the temperature is kept constant for 5.5 hours. The average number of layers of the active photo is 4.9, and the average length of the plate is 5.9 nm.

The preparation method of the vulcanized hydrofining catalyst III comprises the following steps: the hydrofining carrier contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and cane sugar (the dosage is 16 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, and drying the precursor at 120 ℃ for 1.5h to obtain the required catalyst. The catalyst MoO₃21.0 percent of NiO and 4.0 percent of NiO; the specific surface area is 200m²Per g, pore volume of 0.38ml·g^-1. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 200 ℃ at a speed of 12 ℃/h, and keeping the temperature for 3.0 hours; the temperature of the catalyst bed is raised to 320 ℃ at 18 ℃/h and kept constant for 2.5 hours. The average number of layers of the active photo is 1.8, and the average length of the plate crystal is 7.8 nm.

The preparation method of the vulcanized hydrocracking catalyst I comprises the following steps: adding the hydrocracking carrier I with the catalyst containing MoO₃And supersaturation impregnation is carried out on the active component of NiO to obtain a catalyst precursor, the precursor is dried for 4h at the temperature of 200 ℃, the temperature is raised to 600 ℃ at the speed of 4 ℃/min, and the required catalyst is obtained after constant-temperature roasting for 4.0 h. The catalyst MoO₃20.01 percent and NiO is 3.8 percent; the specific surface area is 189m²Per g, pore volume of 0.40ml g^-1The amount of infrared acid was 0.50 mol/g. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 150 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 250 ℃ at a speed of 10 ℃/h, and keeping the temperature for 9 hours; the temperature of the catalyst bed is raised to 360 ℃ at the speed of 8 ℃/h, and the temperature is kept for 10 hours. The average number of layers of the active photo is 8.4, and the average length of the plate is 2.3 nm.

The preparation method of the vulcanized hydrogenation catalyst II comprises the following steps: the hydrocracking carrier II contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and diglycol (the dosage is 6 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 180 ℃ for 2.5h, heating to 450 ℃ at 5 ℃/min, and roasting at constant temperature for 3.0h to obtain the required catalyst. The catalyst MoO₃21.5 percent of NiO and 3.8 percent of NiO; the specific surface area is 401m²Per g, pore volume of 0.45ml g^-1The infrared acid amount was 0.80 mol/g. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is raised to 230 ℃ at a speed of 5 ℃/h and is constantWarming for 6.5 hours; the temperature of the catalyst bed is raised to 340 ℃ at the speed of 10 ℃/h, and the temperature is kept constant for 5.5 hours. The average number of layers of the active photo is 5.0, and the average length of the plate crystal is 6.0 nm.

The preparation method of the vulcanized hydrogenation catalyst III comprises the following steps: adding the hydrocracking carrier III with the catalyst containing MoO₃And saturating and dipping the mixed solution of the active component of NiO and cane sugar (the dosage is 16 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, and drying the precursor at 120 ℃ for 1.5h to obtain the required catalyst. The catalyst MoO₃21.0 percent of NiO and 4.0 percent of NiO; specific surface area of 605m²Per g, pore volume of 0.35ml g^-1The infrared acid amount was 1.00 mol/g. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 200 ℃ at a speed of 12 ℃/h, and keeping the temperature for 3.0 hours; the temperature of the catalyst bed is raised to 320 ℃ at 18 ℃/h and kept constant for 2.5 hours. The average number of layers of the active photo is 1.8, and the average length of the plate crystal is 7.8 nm.

Example 2

This example shows the preparation of a catalyst grading composition.

The preparation method of the vulcanized hydrofining catalyst I comprises the following steps: the hydrofining carrier contains MoO₃And supersaturation impregnation is carried out on the active component of NiO to obtain a catalyst precursor, the precursor is dried for 5h at the temperature of 300 ℃, the temperature is raised to 550 ℃ at the speed of 4 ℃/min, and the required catalyst is obtained after constant-temperature roasting for 4.5 h. The catalyst MoO₃22.5 percent of NiO and 4.1 percent of NiO; specific surface area of 198m²Per g, pore volume of 0.37ml g^-1. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 270 ℃ at a speed of 3 ℃/h, and keeping the temperature for 8 hours; the temperature of the catalyst bed is raised to 350 ℃ at the speed of 5 ℃/h, and the temperature is kept for 9 hours. The average number of layers of the active photo is 7.9, and the average length of the plate crystal is 2.5 nm.

Catalyst for hydrogenation refining in sulfurized stateThe preparation method of the reagent II comprises the following steps: the hydrofining carrier contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and glucose (the dosage is 8 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 150 ℃ for 3.0h, heating to 470 ℃ at the speed of 10 ℃/min, and roasting at constant temperature for 2.0h to obtain the required catalyst. The catalyst MoO₃21.5 percent of NiO and 4.2 percent of NiO; specific surface area 187m²Per g, pore volume of 0.41ml g^-1. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 230 ℃ at a speed of 10 ℃/h, and keeping the temperature for 6 hours; the temperature of the catalyst bed is raised to 330 ℃ at a speed of 15 ℃/h, and the temperature is kept for 5 hours. The average number of layers of the active photo is 4.9, and the average length of the plate is 5.2 nm.

The preparation method of the vulcanized hydrofining catalyst III comprises the following steps: the hydrofining carrier contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and tributyl glycol (the dosage is 20 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, and drying the precursor at 100 ℃ for 1.0h to obtain the required catalyst. The catalyst MoO₃22.7 percent of NiO and 4.5 percent of NiO; specific surface area 175m²Per g, pore volume of 0.41ml g^-1. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 150 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 180 ℃ at a speed of 10 ℃/h, and keeping the temperature for 2.5 hours; the temperature of the catalyst bed is raised to 320 ℃ at the speed of 15 ℃/h, and the temperature is kept constant for 3.5 hours. The average number of layers of the active photo is 2.1, and the average length of the plate crystal is 8.8 nm.

The preparation method of the vulcanized hydrocracking catalyst I comprises the following steps: the hydrocracking catalyst carrier I contains MoO₃And supersaturation impregnation is carried out on the active component of NiO to obtain a catalyst precursor, the precursor is dried for 5h at the temperature of 300 ℃, the temperature is raised to 550 ℃ at the speed of 4 ℃/min, and the required catalyst is obtained after constant-temperature roasting for 4.5 h. The catalyst MoO₃22.0% of NiO4.5 percent; specific surface area of 285m²Per g, pore volume of 0.37ml g^-1The infrared acid amount was 0.35 mol/g. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 250 ℃ at the speed of 3 ℃/h, and keeping the temperature for 8 hours; the temperature of the catalyst bed is raised to 360 ℃ at the speed of 5 ℃/h, and the temperature is kept for 9 hours. The average number of layers of the active photo is 7.8, and the average length of the plate is 2.7 nm.

The preparation method of the vulcanized hydrocracking catalyst II comprises the following steps: the hydrocracking catalyst carrier II contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and glucose (the dosage is 8 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 130 ℃ for 3.0h, heating to 460 ℃ at 10 ℃/min, and roasting at constant temperature for 2.0h to obtain the required catalyst. The catalyst MoO₃23.5 percent and NiO is 4.7 percent; the specific surface area is 450m²Per g, pore volume of 0.41ml g^-1The infrared acid amount was 0.70 mol/g. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 230 ℃ at a speed of 10 ℃/h, and keeping the temperature for 6 hours; the temperature of the catalyst bed is raised to 340 ℃ at a speed of 15 ℃/h, and the temperature is kept constant for 5 hours. The average number of layers of the active photo is 5.0, and the average length of the plate is 5.1 nm.

The preparation method of the vulcanized hydrocracking catalyst III comprises the following steps: using a hydrocracking catalyst carrier III containing MoO₃And saturating and dipping the mixed solution of the active component of NiO and tributyl glycol (the dosage is 20 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, and drying the precursor at 100 ℃ for 1.0h to obtain the required catalyst. The catalyst MoO₃24.7 percent of NiO and 5.0 percent of NiO; specific surface area of 652m²Per g, pore volume of 0.41ml g^-1The infrared acid amount was 0.92 mol/g. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the bed temperature toInjecting a vulcanizing agent at 150 ℃; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 200 ℃ at a speed of 10 ℃/h, and keeping the temperature for 2.5 hours; the temperature of the catalyst bed is raised to 320 ℃ at the speed of 15 ℃/h, and the temperature is kept constant for 3.5 hours. The average number of layers of the active photo is 2.0, and the average length of the plate crystal is 8.9 nm.

Example 3

This example shows the preparation of a catalyst grading composition.

The preparation method of the vulcanized hydrofining catalyst I comprises the following steps: the hydrofining carrier contains MoO₃And supersaturation impregnation is carried out on the active component of NiO to obtain a catalyst precursor, the precursor is dried for 5h at the temperature of 300 ℃, the temperature is raised to 550 ℃ at the speed of 4 ℃/min, and the required catalyst is obtained after constant-temperature roasting for 4.5 h. The catalyst MoO₃22.5 percent of NiO and 3.7 percent of NiO; specific surface area is 179m²Per g, pore volume of 0.36ml g^-1. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 260 ℃ at the speed of 5 ℃/h, and keeping the temperature for 9.0 hours; the temperature of the catalyst bed is raised to 360 ℃ at the speed of 10 ℃/h, and the temperature is kept for 9 hours. The average number of layers of the active photo is 7.4, and the average length of the plate crystal is 2.1 nm.

The preparation method of the vulcanized hydrofining catalyst II comprises the following steps: the hydrofining carrier contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and glucose (the dosage is 8 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 150 ℃ for 3.0h, heating to 480 ℃ at the speed of 10 ℃/min, and roasting at constant temperature for 2.0h to obtain the required catalyst. The catalyst MoO₃21.5 percent of NiO and 4.2 percent of NiO; specific surface area 187m²Per g, pore volume of 0.41ml g^-1. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 230 ℃ at a speed of 10 ℃/h, and keeping the temperature for 6.0 hours; the temperature of the catalyst bed is increased to 15 ℃/hThe temperature was maintained at 330 ℃ for 6.0 hours. The average number of layers of the active photo is 4.7, and the average length of the plate crystal is 5.3 nm.

The preparation method of the vulcanized hydrofining catalyst III comprises the following steps: the hydrofining carrier contains MoO₃And saturating and impregnating the mixed solution of the active component of NiO and lactose (the dosage is 17 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, and drying the precursor at 120 ℃ for 1.5h to obtain the required catalyst. The catalyst MoO₃22.7 percent of NiO and 4.5 percent of NiO; specific surface area 187m²Per g, pore volume of 0.41ml g^-1. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 160 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 195 ℃ at a speed of 10 ℃/h, and keeping the temperature for 4.0 hours; the temperature of the catalyst bed is raised to 310 ℃ at 20 ℃/h and kept constant for 2.5 hours. The average number of layers of the active photo is 1.3, and the average length of the plate crystal is 8.3 nm.

The preparation method of the vulcanized hydrocracking catalyst I comprises the following steps: adding the hydrocracking carrier I with the catalyst containing MoO₃And supersaturation impregnation is carried out on the active component of NiO to obtain a catalyst precursor, the precursor is dried for 5h at the temperature of 300 ℃, the temperature is raised to 550 ℃ at the speed of 4 ℃/min, and the required catalyst is obtained after constant-temperature roasting for 4.5 h. The catalyst MoO₃24.3 percent of NiO and 4.8 percent of NiO; the specific surface area is 575m²Per g, pore volume of 0.37ml g^-1The infrared acid amount was 0.42 mol/g. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 250 ℃ at a speed of 5 ℃/h, and keeping the temperature for 9.0 hours; the temperature of the catalyst bed is raised to 360 ℃ at the speed of 10 ℃/h, and the temperature is kept for 9 hours. The average number of layers of the active photo is 7.8, and the average length of the plate is 2.3 nm.

The preparation method of the vulcanized hydrocracking catalyst II comprises the following steps: the hydrocracking carrier II contains MoO₃Saturated impregnation of mixed solution of active component of NiO and glucose (the dosage is 8 percent of the mass of the catalyst carrier) to obtain the catalystDrying the precursor at 150 ℃ for 3.0h, heating to 480 ℃ at the speed of 10 ℃/min, and roasting at constant temperature for 2.0h to obtain the required catalyst. The catalyst MoO₃24.5 percent and NiO is 5.0 percent; specific surface area is 485m²Per g, pore volume of 0.42ml g^-1The infrared acid amount was 0.81 mol/g. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 230 ℃ at a speed of 10 ℃/h, and keeping the temperature for 6.0 hours; the temperature of the catalyst bed is raised to 340 ℃ at a speed of 15 ℃/h, and the temperature is kept constant for 6.0 hours. The average number of layers of the active photo is 4.8, and the average length of the plate is 5.2 nm.

The preparation method of the vulcanized hydrocracking catalyst III comprises the following steps: adding the hydrocracking carrier III with the catalyst containing MoO₃And saturating and impregnating the mixed solution of the active component of NiO and lactose (the dosage is 17 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, and drying the precursor at 120 ℃ for 1.5h to obtain the required catalyst. The catalyst MoO₃23.7 percent of NiO and 4.9 percent of NiO; specific surface area of 587m²Per g, pore volume of 0.35ml g^-1The amount of infrared acid was 1.10 mol/g. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 160 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 200 ℃ at a speed of 10 ℃/h, and keeping the temperature for 4.0 hours; the temperature of the catalyst bed is raised to 320 ℃ at the speed of 20 ℃/h, and the temperature is kept for 2.5 hours. The average number of layers of the active photo is 1.2, and the average length of the plate crystal is 8.7 nm.

Example 4

This example shows the preparation of a catalyst grading composition.

The preparation method of the vulcanized hydrofining catalyst I comprises the following steps: the hydrofining carrier contains MoO₃And supersaturation impregnation is carried out on the active component of NiO to obtain a catalyst precursor, the precursor is dried for 4h at the temperature of 300 ℃, the temperature is raised to 550 ℃ at the speed of 5 ℃/min, and the catalyst is roasted at constant temperature for 4.0h to obtain the required catalyst. The catalyst MoO₃21.8 percent of NiO3.9 percent; specific surface area of 177m²Per g, pore volume of 0.35ml g^-1. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 265 ℃ at the speed of 5 ℃/h, and keeping the temperature for 8.5 hours; the temperature of the catalyst bed is raised to 360 ℃ at the speed of 5 ℃/h, and the temperature is kept for 9.0 hours. The average number of layers of the active photo is 7.7, and the average length of the plate crystal is 2.3 nm.

The preparation method of the vulcanized hydrofining catalyst II comprises the following steps: the hydrofining carrier contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and glucose (the dosage is 10 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 170 ℃ for 2.0h, heating to 450 ℃ at 10 ℃/min, and roasting at constant temperature for 2.0h to obtain the required catalyst. The catalyst MoO₃21.7 percent of NiO and 4.4 percent of NiO; the specific surface area is 180m²Per g, pore volume of 0.37ml g^-1. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 220 ℃ at a speed of 10 ℃/h, and keeping the temperature for 7.5 hours; the temperature of the catalyst bed was raised to 335 ℃ at 15 ℃/h and held constant for 6.5 hours. The average number of layers of the active photo is 5.2, and the average length of the plate is 6.0 nm.

The preparation method of the vulcanized hydrofining catalyst III comprises the following steps: the hydrofining carrier contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and lactose (the dosage is 20 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, and drying the precursor at 120 ℃ for 1.0h to obtain the required catalyst. The catalyst MoO₃22.7 percent of NiO and 5.0 percent of NiO; the specific surface area is 167m²Per g, pore volume of 0.39 ml.g^-1. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 160 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, the temperature of the catalyst bed layer is controlled at 18 DEG CRaising the temperature to 185 ℃ in h, and keeping the temperature for 3 hours; the temperature of the catalyst bed was raised to 315 ℃ at 15 ℃/h and maintained at that temperature for 3.5 hours. The average number of layers of the active photo is 2.0, and the average length of the plate crystal is 8.1 nm.

The preparation method of the vulcanized hydrocracking catalyst I comprises the following steps: adding the hydrocracking carrier I with the catalyst containing MoO₃And supersaturation impregnation is carried out on the active component of NiO to obtain a catalyst precursor, the precursor is dried for 4h at the temperature of 300 ℃, the temperature is raised to 550 ℃ at the speed of 5 ℃/min, and the catalyst is roasted at constant temperature for 4.0h to obtain the required catalyst. The catalyst MoO₃22.8 percent of NiO and 5.1 percent of NiO; the specific surface area is 289m²Per g, pore volume of 0.35ml g^-1The amount of infrared acid was 0.50 mol/g. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 250 ℃ at the speed of 5 ℃/h, and keeping the temperature for 8.5 hours; the temperature of the catalyst bed is raised to 360 ℃ at the speed of 5 ℃/h, and the temperature is kept for 9.0 hours. The average number of layers of the active photo is 7.8, and the average length of the plate crystal is 2.1 nm.

The preparation method of the vulcanized hydrocracking catalyst II comprises the following steps: the hydrocracking carrier II contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and glucose (the dosage is 10 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 170 ℃ for 2.0h, heating to 450 ℃ at 10 ℃/min, and roasting at constant temperature for 2.0h to obtain the required catalyst. The catalyst MoO₃22.7 percent of NiO and 4.9 percent of NiO; specific surface area of 451m²Per g, pore volume of 0.37ml g^-1The infrared acid amount was 0.82 mol/g. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 230 ℃ at a speed of 10 ℃/h, and keeping the temperature for 7.5 hours; the temperature of the catalyst bed is raised to 340 ℃ at a speed of 15 ℃/h, and the temperature is kept constant for 6.5 hours. The average number of layers of the active photo is 5.3, and the average length of the plate is 5.9 nm.

The preparation method of the vulcanized hydrocracking catalyst III comprises the following steps: will addMoO-containing hydrogen cracking carrier III₃And saturating and dipping the mixed solution of the active component of NiO and lactose (the dosage is 20 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, and drying the precursor at 120 ℃ for 1.0h to obtain the required catalyst. The catalyst MoO₃24.7 percent of NiO and 5.0 percent of NiO; specific surface area of 652m²Per g, pore volume of 0.39 ml.g^-1The amount of infrared acid was 1.01 mol/g. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 160 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 200 ℃ at 18 ℃/h, and keeping the temperature for 3 hours; the temperature of the catalyst bed is raised to 320 ℃ at the speed of 15 ℃/h, and the temperature is kept constant for 3.5 hours. The average number of layers of the active photo is 2.1, and the average length of the plate crystal is 8.2 nm.

Example 5

This example shows the preparation of a catalyst grading composition.

The preparation method of the vulcanized hydrofining catalyst II comprises the following steps: the hydrofining carrier II contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and glucose (the dosage is 10 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 170 ℃ for 2.5h, heating to 450 ℃ at 10 ℃/min, and roasting at constant temperature for 3.5h to obtain the required catalyst. The catalyst MoO₃21.8 percent of NiO and 4.8 percent of NiO; the specific surface area is 170m²Per g, pore volume of 0.35ml g^-1. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 230 ℃ at a speed of 10 ℃/h, and keeping the temperature for 6.5 hours; the temperature of the catalyst bed was raised to 340 ℃ at 15 ℃/h and maintained at that temperature for 7 hours. The average number of layers of the active photo is 5.5, and the average length of the plate is 5.4 nm.

The preparation method of the vulcanized hydrofining catalyst III comprises the following steps: the hydrofining carrier III contains MoO₃Mixed solution of active component of NiO and lactose (the dosage is 20 percent of the mass of the catalyst carrier)Saturated dipping to obtain a catalyst precursor, and drying the precursor at 120 ℃ for 1.0h to obtain the required catalyst. The catalyst MoO₃25.0 percent and NiO 6.5 percent; specific surface area of 198m²Per g, pore volume of 0.51ml g^-1(ii) a The aperture of the glass can be as small as 8.5 nm. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 160 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 200 ℃ at 18 ℃/h, and keeping the temperature for 2 hours; the temperature of the catalyst bed is raised to 320 ℃ at the speed of 15 ℃/h, and the temperature is kept for 2.5 hours. The average number of layers of the active photo is 2.2, and the average length of the plate crystal is 8.0 nm.

The preparation method of the vulcanized hydrocracking catalyst II comprises the following steps: the hydrocracking carrier II contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and glucose (the dosage is 10 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 170 ℃ for 2.5h, heating to 450 ℃ at 10 ℃/min, and roasting at constant temperature for 3.5h to obtain the required catalyst. The catalyst MoO₃24.8 percent of NiO and 4.9 percent of NiO; specific surface area of 445m²Per g, pore volume of 0.37ml g^-1The infrared acid amount was 0.65 mol/g. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 230 ℃ at a speed of 10 ℃/h, and keeping the temperature for 6.5 hours; the temperature of the catalyst bed was raised to 340 ℃ at 15 ℃/h and maintained at that temperature for 7 hours. The average number of layers of the active photo is 5.6, and the average length of the plate is 5.3 nm.

The preparation method of the vulcanized hydrocracking catalyst III comprises the following steps: adding the hydrocracking carrier III with the catalyst containing MoO₃And saturating and dipping the mixed solution of the active component of NiO and lactose (the dosage is 20 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, and drying the precursor at 120 ℃ for 1.0h to obtain the required catalyst. The catalyst MoO₃25.0 percent and NiO 6.5 percent; the specific surface area is 689m²Per g, pore volume of 0.45ml g^-1The infrared acid amount is 1.05 mol/g; tea tableThe aperture is 8.5 nm. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 160 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 200 ℃ at 18 ℃/h, and keeping the temperature for 2 hours; the temperature of the catalyst bed is raised to 320 ℃ at the speed of 15 ℃/h, and the temperature is kept for 2.5 hours. The average number of layers of the active photo is 2.1, and the average length of the plate crystal is 8.8 nm.

Comparative example 1

This example shows the preparation of a catalyst grading composition.

The preparation method of the hydrofining catalyst I comprises the following steps: the hydrofining carrier contains MoO₃And supersaturation impregnation is carried out on the active component of NiO to obtain a catalyst precursor, the precursor is dried for 5h at the temperature of 300 ℃, the temperature is raised to 550 ℃ at the speed of 5 ℃/min, and the catalyst is roasted at constant temperature for 4.0h to obtain the required catalyst. The catalyst MoO₃22.0 percent and 4.7 percent of NiO; the specific surface area is 180m²Per g, pore volume of 0.35ml g^-1。

The preparation method of the hydrofining catalyst II comprises the following steps: the hydrofining carrier contains MoO₃And supersaturating and dipping the active component solution of NiO to obtain a catalyst precursor, drying the precursor at 300 ℃ for 5.5h, heating to 580 ℃ at the speed of 5 ℃/min, and roasting at constant temperature for 4.0h to obtain the required catalyst. The catalyst MoO₃22.5 percent of NiO and 4.6 percent of NiO; the specific surface area is 170m²Per g, pore volume of 0.38ml g^-1。

The preparation method of the hydrofining catalyst III comprises the following steps: the hydrofining carrier contains MoO₃And supersaturation dipping the active component solution of NiO to obtain a catalyst precursor, drying the precursor at 300 ℃ for 5h, heating to 550 ℃ at 4 ℃/min, and roasting at constant temperature for 5.0h to obtain the required catalyst. The catalyst MoO₃22.5 percent of NiO and 4.7 percent of NiO; the specific surface area is 178m²Per g, pore volume of 0.41ml g^-1。

Loading a hydrofining catalyst I, a catalyst II and a catalyst III into a vulcanization reactor from top to bottom according to a proportion, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 160 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 250 ℃ at the speed of 5 ℃/h, and keeping the temperature for 8 hours; the temperature of the catalyst bed is raised to 360 ℃ at the speed of 10 ℃/h, and the temperature is kept constant for 8 hours. The average number of layers of active photo crystals of the hydrogenation catalyst I in a sulfurized state is 7.8, and the average length of the photo crystals is 2.3 nm; the average number of layers of the active photo of the hydrogenation catalyst II in a vulcanized state is 8.5, and the average length of the plate crystals is 2.8 nm; the average number of layers of the active photo of the hydrogenation catalyst III in a vulcanized state is 8.3, and the average length of the photo is 2.9 nm.

The preparation method of the hydrocracking catalyst I comprises the following steps: adding the hydrocracking carrier I with the catalyst containing MoO₃And supersaturation impregnation is carried out on the active component of NiO to obtain a catalyst precursor, the precursor is dried for 5h at the temperature of 300 ℃, the temperature is raised to 550 ℃ at the speed of 5 ℃/min, and the catalyst is roasted at constant temperature for 4.0h to obtain the required catalyst. The catalyst MoO₃23.0 percent and NiO is 4.7 percent; the specific surface area is 209m²Per g, pore volume of 0.35ml g^-1The infrared acid amount was 0.35 mol/g.

The preparation method of the hydrocracking catalyst II comprises the following steps: the hydrocracking carrier II contains MoO₃And supersaturating and dipping the active component solution of NiO to obtain a catalyst precursor, drying the precursor at 300 ℃ for 5.5h, heating to 580 ℃ at the speed of 5 ℃/min, and roasting at constant temperature for 4.0h to obtain the required catalyst. The catalyst MoO₃25.5 percent of NiO and 4.6 percent of NiO; specific surface area of 452m²Per g, pore volume of 0.38ml g^-1The infrared acid amount was 0.41 mol/g.

The preparation method of the hydrocracking catalyst comprises the following steps: adding the hydrocracking carrier III with the catalyst containing MoO₃And supersaturation dipping the active component solution of NiO to obtain a catalyst precursor, drying the precursor at 300 ℃ for 5h, heating to 550 ℃ at 4 ℃/min, and roasting at constant temperature for 5.0h to obtain the required catalyst. The catalyst MoO₃25.5 percent of NiO and 4.9 percent of NiO; specific surface area of 678m²Per g, pore volume of 0.45ml g^-1The infrared acid amount was 0.38 mol/g.

Filling a hydrocracking catalyst I, a hydrocracking catalyst II and a hydrocracking catalyst III into a vulcanization reactor from top to bottom according to a proportion, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 160 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 250 ℃ at the speed of 5 ℃/h, and keeping the temperature for 8 hours; the temperature of the catalyst bed is raised to 360 ℃ at the speed of 10 ℃/h, and the temperature is kept constant for 8 hours. The average number of layers of active photo crystals of the hydrogenation catalyst I is 8.8, and the average length of the photo crystals is 2.4 nm; the average number of layers of active photo crystals of the hydrogenation catalyst II is 8.3, and the average length of the photo crystals is 2.9 nm; the average number of layers of active photo crystal of hydrogenation catalyst III is 8.4, and the average length of the photo crystal is 2.7 nm.

Comparative example 2

This example shows the preparation of a catalyst grading composition.

The preparation method of the hydrofining catalyst I comprises the following steps: the hydrofining carrier contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and glycol (the dosage is 5 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 250 ℃ for 5h, heating to 550 ℃ at the speed of 5 ℃/min, and roasting at constant temperature for 5.0h to obtain the required catalyst. The catalyst MoO₃21.2 percent of NiO and 4.9 percent of NiO; the specific surface area is 170m²Per g, pore volume of 0.38ml g^-1。

The preparation method of the hydrofining catalyst II comprises the following steps: the hydrofining carrier contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and glycol (the dosage is 8 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 150 ℃ for 3.0h, heating to 450 ℃ at the speed of 10 ℃/min, and roasting at constant temperature for 2.0h to obtain the required catalyst. The catalyst MoO₃22.0 percent and 4.7 percent of NiO; the specific surface area is 160m²Per g, pore volume of 0.40ml g^-1。

The preparation method of the hydrofining catalyst III comprises the following steps: the hydrofining carrier contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and glycol (the dosage is 10 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 170 ℃ for 2.0h, heating to 480 ℃ at 8 ℃/min, and roasting at constant temperature for 2.5h to obtain the required catalyst. The catalyst MoO₃22.8 percent of NiO and 4.7 percent of NiO; specific surface area of 180m²Per g, pore volume of 0.45ml g^-1。

Loading a hydrofining catalyst I, a catalyst II and a catalyst III into a vulcanization reactor from top to bottom according to a proportion, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 160 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 230 ℃ at a speed of 10 ℃/h, and keeping the temperature for 8 hours; the temperature of the catalyst bed is increased to 340 ℃ at a speed of 15 ℃/h, and the temperature is kept constant for 8 hours. The average number of crystal layers of an active photo of the hydrogenation catalyst I in a sulfurized state is 4.2, and the average length of the plate crystal is 5.2 nm; the average number of crystal layers of an active photo of the hydrogenation catalyst II in a vulcanized state is 4.3, and the average length of the plate crystals is 5.4 nm; the average number of layers of the active photo of the hydrogenation catalyst III in a vulcanized state is 5.3, and the average length of the photo is 5.9 nm.

The preparation method of the hydrocracking catalyst I comprises the following steps: adding the hydrocracking carrier I with the catalyst containing MoO₃And saturating and dipping the mixed solution of the active component of NiO and glycol (the dosage is 5 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 250 ℃ for 5h, heating to 550 ℃ at the speed of 5 ℃/min, and roasting at constant temperature for 5.0h to obtain the required catalyst. The catalyst MoO₃24.2 percent and NiO is 4.9 percent; the specific surface area is 208m²Per g, pore volume of 0.38ml g^-1The infrared acid amount was 0.75 mol/g.

The preparation method of the hydrocracking catalyst II comprises the following steps: the hydrocracking carrier II contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and glycol (the dosage is 8 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 150 ℃ for 3.0h, heating to 450 ℃ at the speed of 10 ℃/min, and roasting at constant temperature for 2.0h to obtain the required catalyst. The catalyst MoO₃24.0 percent and NiO is 4.9 percent; specific surface area of 452m²Per g, pore volume of 0.40ml g^-1The infrared acid amount was 0.80 mol/g.

The preparation method of the hydrocracking catalyst III comprises the following steps: adding the hydrocracking carrier III with the catalyst containing MoO₃Saturating and dipping the NiO active component and the mixed solution of glycol (the dosage is 10 percent of the mass of the catalyst carrier) to obtain the catalyst precursorAnd drying the precursor at 170 ℃ for 2.0h, heating to 480 ℃ at 8 ℃/min, and roasting at constant temperature for 2.5h to obtain the required catalyst. The catalyst MoO₃25.8 percent of NiO and 4.9 percent of NiO; the specific surface area is 657m²Per g, pore volume of 0.45ml g^-1The infrared acid amount was 0.78 mol/g.

Filling a hydrocracking catalyst I, a hydrocracking catalyst II and a hydrocracking catalyst III into a vulcanization reactor from top to bottom according to a proportion, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 160 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 230 ℃ at a speed of 10 ℃/h, and keeping the temperature for 8 hours; the temperature of the catalyst bed is increased to 340 ℃ at a speed of 15 ℃/h, and the temperature is kept constant for 8 hours. The average number of layers of active photo crystals of the hydrogenation catalyst I is 4.1, and the average length of the photo crystals is 5.1 nm; the average number of layers of active photo crystals of the hydrogenation catalyst II is 4.2, and the average length of the photo crystals is 5.3 nm; the average number of layers of active photo crystal of hydrogenation catalyst III is 5.2, and the average length of the photo crystal is 5.8 nm.

Comparative example 3

This example shows the preparation of a catalyst grading composition.

The preparation method of the hydrofining catalyst I comprises the following steps: the hydrofining carrier contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and tetraethyleneglycol (the dosage is 15 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 150 ℃ for 5 hours, heating to 500 ℃ at 4 ℃/min, and roasting at constant temperature for 4.0 hours to obtain the required catalyst. The catalyst MoO₃21.5 percent of NiO and 4.8 percent of NiO; the specific surface area is 180m²Per g, pore volume of 0.39 ml.g^-1。

The preparation method of the hydrofining catalyst II comprises the following steps: the hydrofining carrier contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and tetraethyleneglycol (the dosage is 18 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 140 ℃ for 3.0h, heating to 450 ℃ at 10 ℃/min, and roasting at constant temperature for 2.0h to obtain the required catalyst. The catalyst MoO₃22.5 percent of NiO and 4.8 percent of NiO; specific surface area of 176m²Per g, pore volume of 0.37ml·g^-1。

The preparation method of the hydrofining catalyst III comprises the following steps: the hydrofining carrier contains MoO₃And saturating and dipping the mixed solution of the active component of NiO and tetraethyleneglycol (the dosage is 20 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 120 ℃ for 2.0h, heating to 480 ℃ at 8 ℃/min, and roasting at constant temperature for 2.5h to obtain the required catalyst. The catalyst MoO₃22.8 percent of NiO and 4.5 percent of NiO; the specific surface area is 195m²Per g, pore volume of 0.38ml g^-1。

Loading a hydrofining catalyst I, a catalyst II and a catalyst III into a vulcanization reactor from top to bottom according to a proportion, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 160 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 200 ℃ at a speed of 12 ℃/h, and keeping the temperature for 4 hours; the catalyst bed temperature was raised to 320 ℃ at 18 ℃/h and held constant for 4 hours. The average number of layers of active photo crystals of the hydrogenation catalyst I in a sulfurized state is 2.3, and the average length of the photo crystals is 7.8 nm; the average number of layers of the active photo of the hydrogenation catalyst II in a vulcanized state is 2.4, and the average length of the plate crystals is 7.7 nm; the average number of layers of the active photo of the hydrogenation catalyst III in a vulcanized state is 2.9, and the average length of the photo is 7.3 nm.

The preparation method of the hydrocracking catalyst I comprises the following steps: adding the hydrocracking carrier I with the catalyst containing MoO₃And saturating and dipping the mixed solution of the active component of NiO and tetraethyleneglycol (the dosage is 15 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 150 ℃ for 5 hours, heating to 500 ℃ at 4 ℃/min, and roasting at constant temperature for 4.0 hours to obtain the required catalyst. The catalyst MoO₃24.5 percent of NiO and 4.9 percent of NiO; the specific surface area is 252m²Per g, pore volume of 0.35ml g^-1The infrared acid amount was 0.35 mol/g.

The preparation method of the hydrocracking catalyst II comprises the following steps: the hydrocracking carrier II contains MoO₃Saturating and dipping the mixed solution of the active component of NiO and tetraethyleneglycol (the dosage is 18 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 140 ℃ for 3.0h, and raising the temperature at 10 ℃/minAnd roasting at the constant temperature of 450 ℃ for 2.0h to obtain the required catalyst. The catalyst MoO₃24.5 percent of NiO and 4.9 percent of NiO; the specific surface area is 489m²Per g, pore volume of 0.35ml g^-1The infrared acid amount was 0.59 mol/g.

The preparation method of the hydrocracking catalyst III comprises the following steps: adding the hydrocracking carrier III with the catalyst containing MoO₃And saturating and dipping the mixed solution of the active component of NiO and tetraethyleneglycol (the dosage is 20 percent of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 120 ℃ for 2.0h, heating to 480 ℃ at 8 ℃/min, and roasting at constant temperature for 2.5h to obtain the required catalyst. The catalyst MoO₃24.8 percent of NiO and 4.9 percent of NiO; the specific surface area is 658m²Per g, pore volume of 0.35ml g^-1The infrared acid amount was 0.88 mol/g.

Filling a hydrocracking catalyst I, a hydrocracking catalyst II and a hydrocracking catalyst III into a vulcanization reactor from top to bottom according to a proportion, introducing vulcanized oil into the vulcanization reactor, and wetting a catalyst bed layer; then adjusting the temperature of the bed layer to 160 ℃, and injecting a vulcanizing agent; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 200 ℃ at a speed of 12 ℃/h, and keeping the temperature for 4 hours; the catalyst bed temperature was raised to 320 ℃ at 18 ℃/h and held constant for 4 hours. The average number of layers of active photo crystals of the hydrogenation catalyst I is 2.2, and the average length of the photo crystals is 7.7 nm; the average number of layers of active photo crystals of the hydrogenation catalyst II is 2.3, and the average length of the photo crystals is 7.3 nm; the average number of layers of active photo crystals of the hydrogenation catalyst III is 2.5, and the average length of the photo crystals is 7.6 nm.

Example 6

This example is a comparative test of the activity of the catalyst assemblies of examples 1, 2, 3, 4, 5 and comparative examples 1, 2, 3 on a 200ml fixed bed small scale hydrogenation unit. The properties of the stock oils were evaluated as shown in Table 1; the evaluation conditions are shown in Table 2; the catalyst assembly scheme is shown in table 3; the results of the catalyst combination schemes are shown in table 4.

TABLE 1 Properties of the stock oils

Table 2 evaluation of the Process conditions

TABLE 3 catalyst combination system grading scheme

TABLE 4 catalyst combination evaluation results

Claims

1. A hydroprocessing method, comprising: the hydrocracking raw material enters a hydrofining reaction zone and contacts a hydrofining catalyst bed layer in a refining reactor to carry out hydrogenation reaction, the refined reaction effluent enters the hydrocracking reaction zone and contacts a hydrocracking catalyst bed layer in a cracking reactor to carry out hydrogenation reaction, and the reaction product flows out of the reactor to carry out next fractionation; the method is characterized in that: the hydrofining catalyst bed layer is graded and filled with at least two stages of vulcanized hydrofining catalysts along the material flow direction, the average length of metal active phase platelets is gradually increased and the average layer number of the platelets is gradually reduced along the material flow direction of each stage of vulcanized hydrofining catalyst; the hydrocracking catalyst bed layer is filled with at least two stages of vulcanization hydrocracking catalysts in a grading way along the material flow direction, and each stage of vulcanization hydrocracking catalysts increases the infrared acid amount step by step, increases the average length of metal active phase platelets step by step and reduces the average layer number of platelets step by step along the material flow direction; the infrared acid amount of each stage of the vulcanization hydrocracking catalyst is 0.3-1.1 mol/g, and the gradual increase amplitude is 0.1-0.5 mol/g; the average length of metal active phase platelets of each stage of the vulcanization hydrocracking catalyst is 1-9 nm, and the gradual increase amplitude is 1-5 nm; the average number of layers of metal active phase platelets of each stage of the vulcanization hydrocracking catalyst is 1-9, and the gradual reduction range is 1-5.

2. The method of claim 1, wherein: the hydrofining reaction zone is mainly used for carrying out hydrodesulfurization, denitrification and aromatic saturation reaction, and is provided with 1 or more hydrofining reactors; the hydrocracking reaction zone is mainly used for carrying out hydrocracking reaction, and 1 or more hydrocracking reactors are arranged.

3. The method of claim 1, wherein: before the vulcanization, the vulcanized hydrorefining catalyst is an oxidized hydrorefining catalyst, the oxidized hydrorefining catalyst takes alumina or modified alumina as a carrier, VIII group and/or VIB group metal elements as active components, and the active metals are calculated by oxides, the VIII group metal accounts for 1-9 wt%, and the VIB group metal accounts for 5-25 wt% based on the weight of the catalyst.

4. The method of claim 1, wherein: the average length of metal active phase platelets of each stage of vulcanized hydrorefining catalyst is 1-9 nm, and the gradual increase range is 1-5 nm.

5. The method of claim 1, wherein: the average number of layers of metal active phase platelets of each stage of vulcanized hydrorefining catalyst is 1-9, and the gradual reduction range is 1-5.

6. The method of claim 1, wherein: in the hydrofining reaction zone, the filling proportion of each stage of sulfurized hydrofining catalyst is at least 10% and the sum of the filling proportions of each stage is 100% based on the total volume of the catalyst in the refining reactor.

7. The method of claim 1, wherein: sequentially filling 2-4 stages of vulcanization hydrofining catalysts in a hydrofining reaction zone along the material flow direction; based on the total volume of the catalyst in the refining reactor, when the two-stage filling proportion is as follows: 10% -90%: 10% -90%; the third-level filling proportion is 10% -90%: 10% -40%: 20 to 80 percent; the four-stage filling proportion is as follows: 10% -40%: 10% -40%: 10% -40%: 10% -40%; the sum of the filling proportions of all the stages is 100 percent.

8. The method of claim 1, wherein: sequentially filling 3-stage vulcanization hydrofining catalysts, and sequentially filling vulcanization hydrofining catalysts I, II and III along the material flow direction; wherein the properties of the vulcanized hydrorefining catalyst I are as follows: the aluminum oxide catalyst comprises an aluminum oxide carrier and active metals, wherein the active metals are selected from one or more of VIII group and/or VIB group metal elements; based on the weight of the catalyst, the active metal is calculated by oxide, the VIII group metal is 1-9 wt%, the VIB group metal is 5-25 wt%, the average number of crystal layers of the active photo is 7.0-9.0, and the average length of the plate crystal is 1.0-3.0 nm; the properties of the sulfided hydrofining catalyst II are as follows: the aluminum oxide catalyst comprises an aluminum oxide carrier and active metals, wherein the active metals are selected from one or more of VIII group and/or VIB group metal elements; based on the weight of the catalyst, the active metal is calculated by oxide, the VIII group metal is 1-9 wt%, the VIB group metal is 5-25 wt%, the average number of crystal layers of the active photo is 4.0-6.0, and the average length of the plate crystal is 4.0-6.0 nm; the properties of the sulfided hydrofining catalyst III are as follows: the aluminum oxide catalyst comprises an aluminum oxide carrier and active metals, wherein the active metals are selected from one or more of VIII group and/or VIB group metal elements; based on the weight of the catalyst, the active metal is calculated by oxide, the VIII group metal is 1wt% -9 wt%, and the VIB group metal is 5wt% -25 wt%; the average number of layers of the active photo is 1.0-3.0, and the average length of the photo is 7.0-9.0 nm.

9. The method of claim 8, wherein: taking the weight of the catalyst in the hydrofining reaction zone as a reference, the proportion of the vulcanized hydrofining catalyst I is 10-90 percent; the proportion of the vulcanization hydrofining catalyst II is 10-40 percent; the proportion of the vulcanization hydrofining catalyst III is 20-80%.

10. The method of claim 1, wherein: before vulcanization, the vulcanized hydrocracking catalyst is an oxidation state hydrocracking catalyst which is hydrogenated in an oxidation stateThe cracking catalyst takes one or more of amorphous silica-alumina, silicon-magnesium, zeolite molecular sieve and alumina as a carrier, VIII group and/or VIB group metal elements as active components, and the active metals are calculated by oxides based on the weight of the catalyst, wherein the VIII group metal accounts for 1-9 wt%, the VIB group metal accounts for 5-25 wt%, and the specific surface area is 100-800 m²(iii) a pore volume of 0.20 to 0.50 mL/g^-1。

11. The method of claim 1, wherein: in the hydrocracking reaction zone, the filling proportion of each stage of the vulcanized hydrocracking catalyst is at least 10 percent and the sum of the filling proportions of each stage is 100 percent on the basis of the total volume of the catalyst in the cracking reactor.

12. The method of claim 1, wherein: sequentially filling 2-4 stages of vulcanization hydrocracking catalysts.

13. The method of claim 1, wherein: filling a 3-stage vulcanization hydrocracking catalyst, and sequentially filling vulcanization hydrocracking catalysts I, II and III along the material flow direction; the properties of the sulfided hydrocracking catalyst I are as follows: the aluminum oxide catalyst comprises an aluminum oxide carrier and active metals, wherein the active metals are selected from one or more of VIII group and/or VIB group metal elements; based on the weight of the catalyst, the active metal is calculated by oxide, the VIII group metal is 1wt% -9 wt%, and the VIB group metal is 5wt% -25 wt%; the average number of layers of the active photo is 7.0-9.0, and the average length of the plate crystal is 1.0-3.0 nm; the infrared acid amount is 0.3-0.5 mol/g; the properties of the sulfided hydrocracking catalyst II were as follows: the catalyst comprises an amorphous silica-alumina or silica-magnesium carrier and active metal, wherein the active metal is selected from one or more of VIII group and/or VIB group metal elements; based on the weight of the catalyst, the active metal is calculated by oxide, the VIII group metal is 1wt% -9 wt%, and the VIB group metal is 5wt% -25 wt%; the average number of crystal layers of the active photo is 4.0-6.0, the average length of the plate crystal is 4.0-6.0 nm, and the amount of infrared acid is 0.6-0.8 mol/g; the properties of the sulfided hydrocracking catalyst III were as follows: comprises a modified zeolite molecular sieve carrier and active metals, wherein the active metals are selected from one or more of VIII group and/or VIB group metal elements; based on the weight of the catalyst, the active metal is calculated by oxide, the VIII group metal is 1wt% -9 wt%, and the VIB group metal is 5wt% -25 wt%; the average number of crystal layers of the active photo is 1.0-3.0, the average length of the plate crystal is 7.0-9.0 nm, and the amount of infrared acid is 0.9-1.1 mol/g; taking the weight of the vulcanized hydrocracking catalyst as a reference, the vulcanized hydrocracking catalyst I accounts for 20-80 percent; the proportion of the vulcanization hydrocracking catalyst II is 20-80 percent; the proportion of the vulcanization hydrocracking catalyst III is 20-80%.

14. The method of claim 1, wherein: the hydrocracking treatment process conditions are as follows: the average reaction temperature is 360-450 ℃, the reaction hydrogen partial pressure is 8.0-20.0 MPa, and the liquid hourly volume space velocity is 0.15h^-1～3.0h^-1The volume ratio of hydrogen to oil is 300-2000.