Method for grading a residue hydroprocessing catalyst and use thereof

Abstract

The application discloses a method for grading residual oil hydrogenation catalysts and application thereof. The method comprises: sequentially filling a hydrogenation protective agent, a hydrogenation demetallization catalyst, a hydrogenation desulfurization catalyst and a hydrogenation denitrification catalyst along the flow direction of a liquid phase stream; the hydrogenation desulfurization catalyst comprises a carrier and an active metal component, wherein the carrier comprises gallium and fluorine modified metakaolin and aluminum oxide, and the mass ratio of the gallium and fluorine modified metakaolin to the aluminum oxide is 15-30:7-13; in the gallium and fluorine modified metakaolin, the mass content of gallium is 2.0%-5.0%, and the mass content of fluorine is 0.8%-1.5%. The method is used for residual oil hydrogenation reaction, and has a remarkable effect of deep desulfurization and denitrification.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of residual oil hydrogenation, and particularly relates to a method for grading residual oil hydrogenation catalysts and application thereof. BACKGROUND

[0002] In recent years, the processing proportion of heavy and poor crude oil in oil refining production is increasing, and residual oil hydrogenation technology can convert as much as possible heavy and poor crude oil into high-quality product oil and chemical raw materials, which is the main technical means for processing residual oil in refineries. Among them, the fixed bed residual oil hydrogenation treatment process can meet the needs of adapting to the deterioration of raw materials and long-term stable operation, and is the most mature, reliable and widely used process, accounting for 3 / 4 of the total processing capacity of residual oil hydrogenation.

[0003] Residual oil feedstock is complex and difficult to process, and needs to use catalysts with different properties to remove most of the metal, sulfur, nitrogen and other impurities therein, and to realize the hydrogenation conversion of residual carbon precursors and increase the hydrogen content. The fixed bed residual oil hydrogenation catalyst can be divided into protective agent, metal removal agent, desulfurization agent and residual carbon removal agent according to the function. Different properties and types of catalysts are usually filled in different parts of the reactor in a graded loading manner. According to the properties of the raw materials, operating conditions and requirements for product quality, the operation cycle of the residual oil hydrogenation device can be prolonged by using catalysts with reasonable gradation and reasonably distributing the reaction load. The basic principle of the gradation is that the particle size of the catalyst along the liquid phase flow direction is from large to small, the average pore size is from large to small, the porosity is from large to small, and the activity is from low to high.

[0004] CN1458236A discloses a preparation method of a heavy oil hydrogenation demetallization and desulfurization catalyst. The preparation method of the catalyst uses two different forms of aluminum-containing materials, one is calcined alumina, and the other is aluminum hydroxide dry gel powder, uses alkali metal and / or alkaline earth metal elements as an additive, the additive is pre-mixed with the aluminum hydroxide dry gel powder, and part of the additive is loaded on the catalyst by impregnation method, so that the additive is unevenly distributed on the catalyst. The average pore size of the catalyst obtained by the method is 15-19 nm, which is still too small for asphaltene agglomerates, which is not conducive to residual oil hydrogenation desulfurization and hydrodemetallization reactions, and the activity and stability need to be further improved.

[0005] CN1098433A discloses a preparation method of a hydrofining catalyst. The method mixes powdered basic nickel carbonate into the extrusion process of monohydrate alumina to provide the required Ni content of the catalyst, and then mixes a small amount of powdered industrial grade ammonium molybdate, and then impregnates a molybdenum ammonia water solution to prepare the final catalyst. The catalyst prepared by the method has high hydrodenitrogenation performance, but the pore is too small to be conducive to the diffusion of macromolecules, and the metal cannot be precipitated inside the pore.

[0006] CN1257103A discloses a preparation method of a hydroprocessing catalyst. The method promotes metal dispersion by optimizing kneading process of aluminum hydroxide monohydrate and metal salts and the like materials. After all the materials are kneaded into plastic body once, the plastic body is extruded into strips, and the catalyst is prepared by high-temperature activation of water vapor-air. The catalyst prepared by the method has too small pore channel, and cannot prepare a bifunctional catalyst having both denitrogenation performance and high metal impurity content. SUMMARY

[0007] In view of the deficiencies of the prior art, the application provides a grading method of a residue oil hydrogenation catalyst and application thereof. The grading method is used for residue oil hydrogenation reaction, and has significant effects of deep desulfurization and denitrogenation.

[0008] The application provides a grading method of a residue oil hydrogenation catalyst. The grading method comprises: sequentially filling a hydrogenation guard catalyst, a hydrogenation demetallization catalyst, a hydrogenation desulfurization catalyst and a hydrogenation denitrogenation catalyst along a liquid phase flow direction.

[0009] According to the application, the hydrogenation desulfurization catalyst comprises a carrier and an active metal component, wherein the carrier comprises gallium and fluorine modified metakaolin and alumina, and the mass ratio is 15-30:7-13; in the gallium and fluorine modified metakaolin, the mass content of gallium is 2.0%-5.0%, and the mass content of fluorine is 0.8%-1.5%.

[0010] According to the application, the active metal in the hydrogenation desulfurization catalyst comprises at least one metal component selected from Group VIII and at least one metal component selected from Group VIB; the Group VIII metal is preferably nickel and / or cobalt; and the Group VIB metal is preferably molybdenum and / or tungsten.

[0011] According to the application, in the hydrogenation desulfurization catalyst, the mass content of the carrier is 75%-85%, the content of the Group VIII metal in terms of oxide is 2%-6%, and the content of the Group VIB metal in terms of oxide is 10%-20%, based on the mass of the catalyst.

[0012] According to the application, the hydrogenation desulfurization catalyst has the following properties: the specific surface area is 180-220 m 2 / g, the pore volume is 0.5-0.7 mL / g, and the average pore diameter is 10.0-30.0 nm.

[0013] According to the application, the hydrogenation desulfurization catalyst is a shaped body, and the shape can be at least one of shapes commonly used for fixed-bed hydrogenation catalysts, such as strip, trilobal, quadrilobal, spherical and cylindrical shapes. The particle size of the hydrogenation desulfurization catalyst is 2-10 mm, and preferably 2.5-8.0 mm.

[0014] According to the present application, the preparation method of the hydrodesulfurization catalyst comprises:

[0015] (1) mixing metakaolin, gallium nitrate, ammonium fluoride and water, sealing and hydrothermal treatment, drying, calcination to obtain a modified material;

[0016] (2) mixing and kneading the modified material obtained in step (1), pseudoboehmite, adhesive, extrusion aid, pore-expanding agent and water into a shape, drying, calcination to obtain a catalyst carrier;

[0017] (3) preparing an impregnation solution containing amine, alcohol, thiourea and active metal;

[0018] (4) impregnating the catalyst carrier obtained in step (2) with the impregnation solution obtained in step (3), drying and calcination to obtain a hydrodesulfurization catalyst.

[0019] According to the present application, in the preparation method of the hydrodesulfurization catalyst, the mass ratio of gallium nitrate to ammonium fluoride in step (1) is 1-10:1, and the total mass of gallium nitrate and ammonium fluoride accounts for 5%-60% of the mass of metakaolin, preferably 15%-40%; and / or, the amount of water added in step (1) is 5:1-10:1 in terms of the mass ratio of water to the sum of metakaolin, gallium nitrate and ammonium fluoride. The metakaolin, gallium nitrate, ammonium fluoride and water can be mixed in any order, for example, water can be added to the mixture of metakaolin, gallium nitrate and ammonium fluoride, or metakaolin can be immersed in an aqueous solution of gallium nitrate and ammonium fluoride.

[0020] According to the present application, in the preparation method of the hydrodesulfurization catalyst, the sealing and hydrothermal treatment in step (1) is carried out under the following conditions: hydrothermal treatment temperature is 80-130℃, time is 3-10 hours; wherein the heating rate is 3-10℃ / min. The sealing and hydrothermal treatment is generally carried out in a high-pressure reaction kettle, and the hydrothermal treatment is carried out under autogenous pressure. Preferably, the hydrothermal treatment adopts two-stage hydrothermal treatment, and the temperature of the second stage is at least 20℃ higher than that of the first stage, preferably at least 30℃ higher.

[0021] According to the present application, in the preparation method of the hydrodesulfurization catalyst, the drying temperature in step (1) is 120-160℃, the drying time is 2-6 hours, the calcination temperature is 550-700℃, and the calcination time is 4-6 hours.

[0022] According to the present application, in the preparation method of the hydrodesulfurization catalyst, the mass ratio of the pseudoboehmite to the modifier in step (2) is 7-13:15-30 in terms of aluminum oxide. The adhesive can be at least one of nitric acid, acetic acid and citric acid, the extrusion aid can be sesbania powder, and the pore-expanding agent can be one or more of graphite, activated carbon, wood chips or cellulose. The adhesive and the extrusion aid are added according to the actual molding needs, and the present application does not have a special requirement. The addition amount of the pore-expanding agent is 4wt%-13wt% of the total mass of the pseudoboehmite in terms of aluminum oxide and the modifier.

[0023] According to the present application, in the preparation method of the hydrodesulfurization catalyst, the drying temperature in step (2) is 120-160℃, the drying time is 2-6 hours, the calcination temperature is 550-750℃, and the calcination time is 2-6 hours. The molding can be performed by using a conventional molding method, such as extrusion molding or tablet molding.

[0024] According to the present application, in the preparation method of the hydrodesulfurization catalyst, phosphoric acid can be added to the impregnation solution in step (3).

[0025] According to the present application, in the preparation method of the hydrodesulfurization catalyst, the alcohol compound in step (3) is one or more of pentaerythritol, ethylene glycol, glycerol, 1,2-propanediol, 1,4-butanediol and neopentyl glycol; the amine compound is one or more of hexamethylenetetramine, ethylenediamine, ethanolamine, diethanolamine and triethanolamine; the mass ratio of the alcohol compound to the amine compound is 1:1-16:1; the addition amount of thiourea is such that the concentration of thiourea in the impregnation solution is 5-70g / L, preferably 8-50g / L; and the concentration of the alcohol compound in the impregnation solution in step (3) is 5-60g / L, preferably 7-30g / L.

[0026] According to the present application, in the preparation method of the hydrodesulfurization catalyst, the active metal in step (3) comprises at least one metal component selected from Group VIII and at least one metal component selected from Group VIB. The Group VIII metal is preferably nickel and / or cobalt, and the Group VIB metal is preferably molybdenum and / or tungsten. The content of the active metal in the impregnation solution in step (3) is as follows: the content of the Group VIB metal is 150-450 g / L, preferably 300-400 g / L, the content of the Group VIII metal is 10-120 g / L, preferably 40-60 g / L, and the concentration of phosphorus is 20-80 g / L, preferably 40-60 g / L. The tungsten source can be a tungstate or a tungsten oxide, and is preferably ammonium metatungstate; the molybdenum source can be one or more of molybdenum trioxide, a molybdate, and a paramolybdate, and is preferably molybdenum trioxide; the nickel source can be one or more of nickel nitrate, nickel acetate, basic nickel carbonate, and nickel chloride, and is preferably basic nickel carbonate; and the cobalt source can be one or more of cobalt nitrate, cobalt acetate, basic cobalt carbonate, and cobalt chloride, and is preferably basic cobalt carbonate. The phosphorus-containing compound is phosphoric acid.

[0027] According to the present application, in the preparation method of the hydrodesulfurization catalyst, the impregnation in step (4) is performed by a spray impregnation method, and the impregnation is performed by an equal-volume impregnation method or a supersaturated impregnation method. Preferably, after the impregnation, the sample is placed in a closed environment at room temperature for 6-12 hours before the drying step is performed; and / or, in step (4), the drying is performed at a constant temperature of 100-160°C for 1-8 hours; and the calcination is performed at a constant temperature of 450-650°C for 2-7 hours, preferably at a constant temperature of 480-600°C for 2-7 hours.

[0028] According to the present application, the hydrodenitrogenation catalyst comprises a carrier and an active metal component, and the carrier comprises a modified Y molecular sieve and alumina. The modified Y molecular sieve is a small-crystal mesoporous modified Y molecular sieve, and has the following properties: the crystal particle size is 500 nm or less, preferably 300-500 nm; the molar ratio of silicon oxide to alumina is 8-55; the specific surface area is 640-800 m 2 / g; the unit cell parameter is 2.433-2.460 nm; and the average pore size is 10-30 nm.

[0029] According to the present application, the content of sodium in the modified Y molecular sieve is 1 wt% or less.

[0030] According to the present application, in the hydrodenitrogenation catalyst, the active metal comprises at least one metal component selected from Group VIII and at least one metal component selected from Group VIB; the Group VIII metal is preferably nickel and / or cobalt; and the Group VIB metal is preferably molybdenum and / or tungsten.

[0031] According to the present application, the mass content of the carrier in the hydrogenation denitrification catalyst is 74% to 85%, the content of the Group VIII metal in terms of oxides is 2% to 6%, and the content of the Group VIB metal in terms of oxides is 15% to 24%.

[0032] According to the present application, the content of the modified Y molecular sieve in the hydrogenation denitrification catalyst is 40% to 70% by mass of the carrier, and the content of the alumina is 14% to 40%.

[0033] According to the present application, the hydrogenation denitrification catalyst has the following properties: the specific surface area is 190 to 250 m 2 / g, the pore volume is 0.4 to 0.6 mL / g, and the average pore diameter is 10 to 20 nm.

[0034] According to the present application, the hydrogenation denitrification catalyst is a shaped body, which can have at least one of the shapes commonly used for fixed-bed hydrogenation catalysts, such as a strip, a trilobal, a quadrilobal, a spherical shape, a cylindrical shape, and the like, and has a particle size of 1.5 to 8 mm, preferably 2.0 to 6.0 mm.

[0035] According to the present application, the method for preparing the hydrogenation denitrification catalyst comprises:

[0036] (1) NaY molecular sieve is exchanged with ammonium ions, filtered and washed to obtain NH4Y molecular sieve filter cake;

[0037] (2) The NH4Y molecular sieve filter cake obtained in step (1) is mixed with an organic acid, a water-soluble polymer and water, and then subjected to hydrothermal treatment to obtain modified Y molecular sieve;

[0038] (3) The modified Y molecular sieve obtained in step (2), pseudoboehmite, a binder, a extrusion aid, a pore-expanding agent and water are mixed and kneaded into a shape, dried, and calcined to obtain a catalyst carrier;

[0039] (4) The catalyst carrier obtained in step (3) is immersed in a gallium nitrate solution, dried, and then subjected to high-temperature steam treatment to obtain a catalyst carrier;

[0040] (5) An impregnation solution containing an amine, an alcohol and thiourea, and an active metal is prepared;

[0041] (6) The catalyst carrier obtained in step (4) is impregnated with the impregnation solution obtained in step (5), dried and calcined to obtain a hydrogenation denitrification catalyst.

[0042] According to the present application, in the method for preparing the hydrogenation denitrification catalyst, the NaY molecular sieve in step (1) has the following properties: the molar ratio of silicon oxide to aluminum oxide is 3 to 7:1, and the sodium content is 6 wt% to 12 wt%.

[0043] According to the application, in the preparation method of the hydrodenitrogenation catalyst, step (1) the ammonium ion exchange of NaY molecular sieve is mixing and beating NaY molecular sieve with ammonium salt solution, adjusting the pH value of the slurry, ammonium ion exchange, and then filtering and washing to obtain NH4Y molecular sieve filter cake; wherein the mass ratio of NaY molecular sieve: water: ammonium salt is 1:6-25:0.2-0.4; the pH value of the slurry is adjusted to 3-4; the ammonium ion exchange temperature is adjusted to 70-90℃, the ammonium ion exchange time is 2-4 hours, and the ammonium ion exchange frequency is 1-3 times. The ammonium salt can be one or more of ammonium chloride, ammonium nitrate, ammonium sulfate, and ammonium phosphate.

[0044] According to the application, in the preparation method of the hydrodenitrogenation catalyst, step (1) the filtering and washing can be carried out by conventional methods, and deionized water can be used for washing.

[0045] According to the application, in the preparation method of the hydrodenitrogenation catalyst, step (2) the organic acid is at least one selected from fumaric acid, adipic acid, tartaric acid, citric acid, oxalic acid, acetic acid, salicylic acid, and malic acid. The water-soluble polymer is at least one selected from polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, and water-soluble polysaccharide (such as methyl cellulose). The water-soluble polymer has a weight average molecular weight of 10000-40000.

[0046] According to the application, in the preparation method of the hydrodenitrogenation catalyst, step (2) the mass ratio of NH4Y molecular sieve: organic acid: water-soluble polymer: water is =1:0.01-0.05:0.05-0.25:15-40.

[0047] According to the application, in the preparation method of the hydrodenitrogenation catalyst, step (2) the hydrothermal treatment conditions are as follows: the temperature is 100-150℃, and the treatment time is 5-12 hours; wherein the heating rate is 8-15℃ / min; preferably, the hydrothermal treatment adopts two-stage hydrothermal treatment, the temperature of the second stage is at least 15℃ higher than that of the first stage, preferably at least 20℃; the hydrothermal treatment is generally carried out in a sealed high-pressure reaction kettle under autogenous pressure. After step (2) hydrothermal treatment, drying is carried out, and the drying conditions are as follows: the drying temperature is 100-160℃, and the drying time is 3-8 hours.

[0048] According to the application, in the preparation method of the hydrodenitrogenation catalyst, the mass ratio of the pseudo-boehmite to the modified Y molecular sieve is 7-13:15-30 in step (3). The adhesive can be at least one of nitric acid, acetic acid and citric acid, the extrusion aid can be sesbania gum, and the pore-expanding agent can be one or more of graphite, activated carbon, wood chips or cellulose. The adhesive, the extrusion aid and water are added according to the actual molding needs, and the application does not have a special requirement. The pore-expanding agent is added in an amount of 2wt%-10wt% of the total mass of the pseudo-boehmite and the modified Y molecular sieve. The molding can be performed by using a conventional molding method, such as extrusion molding or tablet molding.

[0049] According to the application, in the preparation method of the hydrodenitrogenation catalyst, the drying temperature is 120-160℃, the drying time is 3-6 hours, the calcination temperature is 550-700℃, and the calcination time is 2-6 hours in step (3).

[0050] According to the application, in the preparation method of the hydrodenitrogenation catalyst, the concentration of the gallium nitrate solution is 0.5-2.5mol / L in step (4), the impregnation method is saturated impregnation or unsaturated impregnation, and the high-temperature water vapor treatment is performed under the conditions of a temperature of 500-700℃ and a time of 60-90min.

[0051] According to the application, in the preparation method of the hydrodenitrogenation catalyst, phosphoric acid can be added to the impregnation solution in step (5).

[0052] According to the application, in the preparation method of the hydrodenitrogenation catalyst, the alcohol compound is one or more of pentaerythritol, ethylene glycol, glycerol, 1,2-propanediol, 1,4-butanediol and neopentyl glycol, the amine compound is one or more of hexamethylenetetramine, ethylenediamine, ethanolamine, diethanolamine and triethanolamine, the mass ratio of the alcohol compound to the amine compound is 1:1-16:1, the addition amount of the thiourea is such that the concentration of the thiourea in the impregnation solution is 5-70g / L, preferably 8-50g / L, and the concentration of the alcohol compound in the impregnation solution is 2-60g / L, preferably 7-30g / L.

[0053] According to the present invention, in the preparation method of the hydrodenitrification catalyst, the active metal in step (5) comprises at least one metal component selected from Group VIII and at least one metal component selected from Group VIB. The Group VIII metal is preferably nickel and / or cobalt, and the Group VIB metal is preferably molybdenum and / or tungsten. In the impregnation solution in step (5), the active metal, calculated as metal oxide, comprises a Group VIB metal content of 150–450 g / L, preferably 300–400 g / L, a Group VIII metal content of 10–120 g / L, preferably 40–60 g / L, and a phosphorus concentration of 20–80 g / L, preferably 40–60 g / L. The molybdenum source is one or more of molybdenum trioxide, molybdate, and paramolybdate, preferably molybdenum trioxide; the tungsten source is tungstate or tungsten oxide, preferably ammonium metatungstate; the nickel source is one or more of nickel nitrate, nickel acetate, basic nickel carbonate, and nickel chloride, preferably basic nickel carbonate; the cobalt source is one or more of cobalt nitrate, cobalt acetate, basic cobalt carbonate, and cobalt chloride, preferably basic cobalt carbonate. The phosphorus-containing compound is phosphoric acid.

[0054] According to the present invention, in the preparation method of the hydrodenitrification catalyst, the impregnation in step (6) is carried out by spray impregnation, and the impregnation is carried out by equal volume impregnation or supersaturated impregnation. Preferably, after impregnation, the sample is placed under closed conditions at room temperature for 6 to 12 hours before the drying step is carried out. In step (6), the drying conditions are constant temperature at 100 to 160°C for 1 to 8 hours; the calcination conditions are constant temperature at 450 to 650°C for 3 to 7 hours, preferably constant temperature at 480 to 600°C for 4 to 7 hours.

[0055] According to the present invention, in the method for grading the residual oil hydrotreating catalyst, the packing volume of the hydrodesulfurization catalyst accounts for 20% to 30% of the total catalyst packing volume. The packing volume of the hydrodenitrogenation catalyst accounts for 30% to 40% of the total catalyst packing volume. The packing volume of the hydroprotective agent accounts for 15% to 25% of the total catalyst packing volume. The packing volume of the hydrodemetallization catalyst accounts for 10% to 20% of the total catalyst packing volume.

[0056] According to the present invention, in the method for grading the residual oil hydrotreating catalyst, the packing volume of the hydrodesulfurization catalyst and the hydrodenitrogenation catalyst accounts for more than 50% of the total catalyst packing volume, preferably 50% to 70%.

[0057] According to the present invention, preferably, a foamed ceramic catalyst can be loaded before the hydrogenation protectant. The loading volume of the foamed ceramic catalyst accounts for 1% to 10% of the total catalyst loading volume.

[0058] According to the present invention, the foam ceramic catalyst, hydrogenation protectant, and hydrogenation demetallization catalyst can be conventional catalysts in the art. Generally, an alumina-based support is used, with Group VIB and / or Group VIII metals as the active metal component.

[0059] According to the present application, the foam ceramic catalyst has a content of Group VIB metals in the form of oxides of 0.5% to 2% and a content of Group VIII metals in the form of oxides of 0.1% to 1.0%, based on the weight of the catalyst.

[0060] According to the present application, the hydrogenation guard catalyst has a content of Group VIB metals in the form of oxides of 1.5% to 6% and a content of Group VIII metals in the form of oxides of 0.4% to 3.0%, based on the weight of the catalyst.

[0061] According to the present application, the hydrodemetallization catalyst has a content of Group VIB metals in the form of oxides of 3% to 14% and a content of Group VIII metals in the form of oxides of 0.5% to 5.0%, based on the weight of the catalyst.

[0062] According to the present application, the foam ceramic catalyst, the hydrogenation guard catalyst and the hydrodemetallization catalyst can be commercially available, such as the FZC series catalysts developed and produced by Fushun Petrochemical Research Institute of SINOPEC.

[0063] According to the present application, the hydrodesulfurization catalyst and the hydrodenitrogenation catalyst need to be sulfided before use, and can be subjected to conventional in-situ presulfurization or ex-situ presulfurization.

[0064] According to the present application, further, the sulfiding step comprises: contacting the catalyst with a sulfiding liquid and hydrogen to sulfide the catalyst, and the sulfiding process is divided into two stages, the first stage: heating to 150-180°C, and constant temperature sulfidation for 1-8 hours, the second stage: heating to 250-340°C, and constant temperature sulfidation for 1-8 hours.

[0065] According to the present application, further, in the method of sulfiding, the first stage heating rate is 0.1-5.0°C / min; and the second stage heating rate is 0.5-5.0°C / min.

[0066] According to the present application, further, in the method of sulfiding, the sulfiding liquid comprises a solvent and a sulfur-containing solute. The mass content of the sulfur-containing solute in the sulfiding liquid is 1.0%-10.0%, preferably 2.0%-8.0%.

[0067] According to the present application, further, in the method of sulfiding, the solvent is a liquid organic hydrocarbon. The liquid organic hydrocarbon is a hydrocarbon with a final boiling point not higher than 300°C. Preferably, the solvent is selected from one or more of alkanes with a carbon number of 6-10, and distillate oil. The alkanes with a carbon number of 6-10 are preferably saturated hydrocarbons. The distillate oil is preferably low-nitrogen distillate oil with a nitrogen content not higher than 20 μg / g.

[0068] According to the application, further, in the method for sulfuration, the sulfur-containing solute comprises at least one of CS2, dimethyl disulfide, dimethyl sulfoxide, tetramethyl sulfoxide and dodecyl sulfide.

[0069] According to the application, further, in the method for sulfuration, the amount of the sulfuration liquid is 0.5-6.0 g / h per gram of catalyst, preferably 1.0-5.0 g / h. The hydrogen is hydrogen with a purity of not less than 90 v%.

[0070] According to the application, further, in the method for sulfuration, the sulfuration conditions are as follows: the hydrogen pressure is 1.0-20.0 MPa, preferably 2.0-16.0 MPa; and the hydrogen flow rate is 3-20 mL / min per gram of catalyst, preferably 5-15 mL / min.

[0071] The second aspect of the application provides an application of the grading method in a residue oil hydrogenation reaction.

[0072] According to the application, the application method is specifically that: under the hydrogenation treatment reaction conditions, the residue oil is contacted with the catalyst packed by the above grading method to perform a hydrogenation reaction, and a hydrogenation treatment product is obtained.

[0073] According to the application, in the application, the residue oil raw material comprises at least one of atmospheric residue oil, vacuum residue oil and deasphalted oil.

[0074] According to the application, in the application, the operation conditions of each reaction zone are independently as follows: the reaction temperature is 340-400 ℃; the reaction pressure is 6.0-25.0 MPa; the hydrogen-oil volume ratio is 200:1-1200:1; the liquid hourly space velocity is 0.1-2.0 h -1 .

[0075] According to the application, in the application, the residue oil hydrogenation reaction adopts a fixed-bed hydrogenation treatment process.

[0076] According to the application, the hydrogenated product oil obtained by the residue oil hydrogenation treatment is used as feed of a catalytic cracking device, or as feed of a hydrocracking device, or as feed of a deep catalytic cracking device (DCC).

[0077] Compared with the prior art, the application has the following advantages:

[0078] 1. The residue oil fixed-bed hydrogenation treatment method of the application adopts the grading packing of the above hydrogen desulfurization catalyst and the hydrogen denitrogenation catalyst, the particle size gradually decreases, the average pore size gradually decreases, and the activity gradually increases, so that the sulfides in the asphaltene and the nitrides can be deeply converted, the hydrogenation activity is high, and the stability is good.

[0079] 2. In the preparation process of the hydrodenitrification catalyst of the present invention, the impregnation solution containing alcohols, amines, thiourea and active metals can enable group VIII metal ions to form complexes and simultaneously form phosphomolybdate (tungstate). The Ga species located in the surface and near-surface regions effectively prevent the formation of strong Mo(W)-O-Al bonds, thereby further weakening the acid regulation and interaction between the active metal and the support. This is beneficial for the hydrodesulfurization and denitrification catalyst to have suitable acid content and acid distribution, and the catalyst has strong anti-coking properties, which is beneficial for improving the hydrodesulfurization activity and stability.

[0080] 3. In the preparation process of the hydrodesulfurization catalyst of the present invention, metakaolin is first modified by hydrothermal treatment in the presence of gallium nitrate and ammonium fluoride. While removing aluminum to increase the silicon-to-aluminum ratio, gallium species are introduced to form Si-O-Ga bonds. Due to the removal of aluminum, more coordinated unsaturated aluminum ions and silicon oxide are exposed on the surface of the silicon-aluminum material. Then, a support is prepared with alumina, a pore-expanding agent, etc., and the support is impregnated with an impregnation solution containing alcohols, amines, thiourea, and active metals. During the contact process between the active metal ions in the impregnation solution and the mixture of alcohols, amines, and thiourea with the support, the coordinated unsaturated sites and SH groups generate Lewis acids and SH groups on the support surface, respectively. Acid sites were identified, resulting in a catalyst with suitable pore structure, high acid content, and appropriate acid strength distribution, which is particularly suitable for hydrodesulfurization of residual oil.

[0081] In addition, the preparation process of hydrodesulfurization catalysts involves forming complexes of Group VIII metal ions and forming phosphomolybdate (tungstate) structures of Group VIB metals, which helps to generate high-quality active phases. Detailed Implementation

[0082] The technical solution of the present invention will be described in detail below with reference to the embodiments.

[0083] In this invention, the determination of total infrared acid, L-acid, or Brønsted acid is performed using infrared spectroscopy. The instrument used is a Nicot Fourier Transform Infrared Spectrometer-6700 (USA). The determination method is as follows: Weigh 20 mg of sample with a particle size less than 200 mesh, press it into a thin sheet with a diameter of 20 mm, and place it on the sample holder of the absorption cell. Place 200 mg of sample into the instrument's hanging cup, connect the absorption cell and adsorption tube, and perform vacuum treatment to achieve a vacuum degree of 4 × 10⁻⁶. -2Pa, temperature is raised to 500℃ and kept for 1 hour to remove the adsorbed substances on the surface of the sample, after the temperature is lowered to room temperature, pyridine is adsorbed to saturation, then the temperature is continuously raised to 160℃ and kept for 1 hour to desorb the physically adsorbed pyridine, and then the acid amount of total infrared acid, B acid and L acid can be obtained, wherein the acid amount unit is mmol / g. Then the temperature is raised to 250℃, 350℃ and 450℃ in sequence, and each is kept for 1 hour to obtain the acid amount of corresponding infrared acid, B acid and L acid respectively. The absorption peak near 1450cm -1 is L acid, and the absorption peak near 1540cm -1 is B acid.

[0084] In the present application, the specific surface area, pore volume and pore distribution are measured by using the ASAP2420 full-automatic physical adsorption instrument of American Micromeritics Company, and the measurement method is as follows: after the sample is treated at 300℃ and 0.1MPa for 4 hours, liquid N2 is used as adsorbate, the adsorption temperature is -196℃, and after accurate weighing, the analysis test is carried out. The specific surface area is calculated by BET method, and the pore volume and pore distribution are calculated by BJH method.

[0085] In the present application, the hydrogen desulfurization rate (HDS) and the hydrogen denitrogenation rate (HDN) are calculated according to the following formula:

[0086] The hydrogen desulfurization rate (HDS) = (mass fraction of S in raw material-mass fraction of S in product) / mass fraction of S in raw material × 100%;

[0087] The hydrogen denitrogenation rate (HDN) = (mass fraction of N in raw material-mass fraction of N in product) / mass fraction of N in raw material × 100%.

[0088] Example 1

[0089] 360g of metakaolin, 88g of gallium nitrate, 36g of ammonium fluoride, 2520g of distilled water are added to the above-mentioned materials and stirred for 20 minutes, the above-mentioned materials are transferred into a high-pressure kettle and sealed, then the temperature is raised to 80℃ at a speed of 10℃ / min and kept for 3 hours, then the temperature is raised to 110℃ at a speed of 5℃ / min and kept for 5 hours, after filtration and washing, the materials are dried at 120℃ for 6 hours, and then calcined at 600℃ for 5 hours to obtain gallium and fluorine modified material I (the mass content of gallium is 3.6%, and the mass content of fluorine is 1.1%). 179g of pseudoboehmite (the mass content of aluminum oxide is 69.1%), 269g of material I, 9g of sesbania powder, 4.5g of nitric acid, 3g of citric acid, 18g of activated carbon with a particle size of 4 microns, and 228g of water are kneaded and formed, then dried at 120℃ for 3 hours and calcined at 700℃ for 4 hours to obtain catalyst carrier A-0.

[0090] Take 100 g of catalyst carrier A-0, measure its water absorption rate of 0.9, take molybdenum trioxide (containing 99 wt% of molybdenum oxide) 202 g, basic nickel carbonate (containing 52 wt% of nickel oxide) 96.2 g, phosphoric acid solution (containing 26.7 wt% of phosphorus) 52.4 g, add clean water and stir to gradually heat to boiling until the raw materials are completely dissolved, and then reduce to room temperature after constant temperature for 40 minutes, and get the impregnation solution. Slowly add a mixture of pentaerythritol and diethanolamine and thiourea to the above solution under stirring, the mass ratio of pentaerythritol and diethanolamine is 3:1, the amount of thiourea is 20 g / L in the impregnation solution, and the amount of pentaerythritol is 16 g / L in the impregnation solution. The solution is constant volume 90 mL for use. The above impregnation solution is impregnated on the carrier A-0 by spraying to obtain A-1. A-1 is placed in a sealed container at room temperature for 6 hours, then dried at 120°C for 4 hours, and finally calcined at 550°C for 4 hours to obtain CA-1.

[0091] Example 2

[0092] Take 500 g of metakaolin, 92 g of gallium nitrate, 25 g of ammonium fluoride, add 4388 g of distilled water to the above materials and stir for 30 minutes, then transfer the above materials into a high-pressure kettle and seal, then heat to 90°C at a rate of 8°C / min and keep constant temperature for 4 hours, then heat to 120°C at a rate of 10°C / min and keep constant temperature for 3 hours, then filter, wash, and then dry the materials at 130°C for 4 hours, and then calcine at 650°C for 4 hours to obtain gallium and fluorine modified material I (the mass content of gallium is 2.8%, and the mass content of fluorine is 1.3%). Take 146 g of pseudo-boehmite (the mass content of alumina is 68.6%), 358 g of material I, 12 g of sesbania powder, 6 g of nitric acid, 4 g of citric acid, 22 g of activated carbon with a particle size of 4 microns, and 304 g of water, and then knead and shape, then dry at 130°C for 2 hours, and then calcine at 730°C for 3 hours to obtain catalyst carrier B-0.

[0093] Take 100 g of catalyst carrier B-0, measure its water absorption rate of 0.88, take molybdenum trioxide (containing 99 wt% of molybdenum oxide) 182 g, basic nickel carbonate (containing 52 wt% of nickel oxide) 96.2 g, phosphoric acid solution (containing 26.7 wt% of phosphorus) 59.9 g, add clean water and stir to gradually heat to boiling until the raw materials are completely dissolved, and then reduce to room temperature after constant temperature for 60 minutes, to obtain an impregnation solution. Slowly add 1,4-butanediol and ethylenediamine and thiourea mixture to the above solution under stirring, the mass ratio of 1,4-butanediol and ethylenediamine is 6:1, and the amount of thiourea is 32 g / L in the impregnation solution, and the amount of 1,4-butanediol is 22 g / L in the impregnation solution. The solution is constant volume 88 mL for use. The above impregnation solution is impregnated on the carrier B-0 by spraying to obtain B-1. B-1 is placed in a sealed container at room temperature for 8 hours, then dried at 130°C for 2 hours, and finally calcined at 530°C for 3 hours to obtain CB-1.

[0094] Example 3

[0095] Take 600 g of metakaolin, 102 g of gallium nitrate, and 36 g of ammonium fluoride. Add 5540 g of distilled water to the above materials and stir for 60 minutes. Transfer the above materials to an autoclave and seal. Heat to 80°C at a rate of 6°C / min, and then maintain the temperature for 3 hours. Then heat to 130°C at a rate of 8°C / min, and then maintain the temperature for 3 hours. Filter and wash, then dry the materials at 120°C for 3 hours, and then calcine at 600°C for 5 hours to obtain gallium and fluorine modified material I (mass content of gallium is 2.6%, mass content of fluorine is 0.9%). Take 224 g of pseudoboehmite (mass content of alumina is 69%), 538 g of material I, 15 g of sesbania powder, 7 g of nitric acid, 5 g of citric acid, 36 g of activated carbon with a particle size of 4 microns, and 462 g of water. Knead and shape, then dry at 120°C for 2 hours, and then calcine at 750°C for 3 hours to obtain catalyst carrier C-0.

[0096] Take 100 g of catalyst carrier C-0, measure its water absorption rate of 0.93, take molybdenum trioxide (containing molybdenum oxide 99wt%) 192g, basic nickel carbonate (containing nickel oxide 52wt%) 101g, phosphoric acid solution (containing phosphorus 26.7wt%) 52.4g, add clean water after stirring, gradually heating to boiling until the raw materials are completely dissolved, constant temperature for 60 minutes, then reduce to room temperature for standby, get the impregnation solution. Slowly add glycol and hexamethyl tetramine and thiourea mixture to the above solution under stirring, the mass ratio of glycol and hexamethyl tetramine is 4:1, the amount of thiourea is 43g / L in the impregnation solution, the amount of glycol is 19g / L in the impregnation solution, and the solution is constant volume 93mL for standby. The above impregnation solution is impregnated on the carrier C-0 by spraying to obtain C-1. C-1 is placed in a closed container at room temperature for 8 hours, then dried at 120℃ for 2 hours, and finally calcined at 500℃ for 3 hours to obtain CC-1.

[0097] Example 4

[0098] Take 750g of metakaolin, 132g of gallium nitrate, 44g of ammonium fluoride, add 5741g of distilled water to the above materials and stir for 90 minutes, then transfer the above materials into an autoclave and seal, then heat to 90℃ at a rate of 5℃ / min, then constant temperature for 4 hours, then heat to 130℃ at a rate of 8℃ / min, then constant temperature for 3 hours, then filter, wash, then dry the materials at 140℃ for 2 hours, then calcine at 550℃ for 5 hours to obtain gallium and fluorine modified material I (mass content of gallium is 3.8%, mass content of fluorine is 1.0%). Take 251g of pseudoboehmite (mass content of alumina is 67.9%), 532g of material I, 15g of sesbania powder, 7g of nitric acid, 5g of citric acid, 36g of activated carbon with a particle size of 4 microns, and 462g of water, then mix and shape, then dry at 120℃ for 2 hours, then calcine at 750℃ for 3 hours to obtain catalyst carrier D-0.

[0099] Take 100g of catalyst carrier D-0, measure its water absorption rate of 0.93, take molybdenum trioxide (containing molybdenum oxide 99wt%) 192g, basic nickel carbonate (containing nickel oxide 52wt%) 101g, phosphoric acid solution (containing phosphorus 26.7wt%) 52.4g, add clean water after stirring, gradually heating to boiling until the raw materials are completely dissolved, constant temperature for 60 minutes, then reduce to room temperature for standby. Slowly add glycerol and ethanolamine and thiourea mixture to the above solution under stirring, the mass ratio of glycerol and ethanolamine is 6:1, the amount of thiourea is 52g / L in the impregnation solution, the amount of glycerol is 26g / L in the impregnation solution, and the solution is constant volume 93mL for standby. The above impregnation solution is impregnated on the carrier D-0 by spraying to obtain D-1. D-1 is placed in a closed container at room temperature for 8 hours, then dried at 130℃ for 3 hours, and finally calcined at 490℃ for 3 hours to obtain CD-1.

[0100] Example 5

[0101] Take 360 g of metakaolin, 88 g of gallium nitrate, 36 g of ammonium fluoride, add 2520 g of distilled water to the above materials and stir for 20 minutes, then seal the materials in an autoclave and heat at a rate of 5°C / min to 110°C and maintain for 5 hours, then filter, wash, dry the materials at 120°C for 6 hours, and then calcine at 600°C for 5 hours to obtain gallium and fluorine modified material I (mass content of gallium 3.6%, mass content of fluorine 1.1%). Take 179 g of pseudoboehmite (mass content of alumina 69.1%), 269 g of material I, 9 g of sesbania powder, 4.5 g of nitric acid, 3 g of citric acid, 18 g of activated carbon with a particle size of 4 microns, and 228 g of water, and knead and shape, then dry at 120°C for 3 hours and calcine at 700°C for 4 hours to obtain catalyst carrier E-0.

[0102] Take 100 g of catalyst carrier E-0 and measure its water absorption rate to be 0.9, take 202 g of molybdenum trioxide (containing 99 wt% of molybdenum trioxide), 96.2 g of basic nickel carbonate (containing 52 wt% of nickel oxide), 52.4 g of phosphoric acid solution (containing 26.7 wt% of phosphorus), add clean water and stir to gradually heat to boiling until the raw materials are completely dissolved, maintain the temperature for 40 minutes, then cool to room temperature for use, to obtain an impregnation solution. Slowly add a mixture of pentaerythritol and diethanolamine and thiourea to the above solution under stirring, the mass ratio of pentaerythritol to diethanolamine is 3:1, the amount of thiourea added is to make its concentration in the impregnation solution 20 g / L, and the amount of pentaerythritol added is to make its concentration in the impregnation solution 16 g / L, then make the solution to a constant volume of 90 mL for use. Use a spraying method to impregnate the above impregnation solution on the carrier E-0 to obtain E-1. Place E-1 in a sealed container at room temperature for 6 hours, then dry at 120°C for 4 hours, and finally calcine at 550°C for 4 hours to obtain CE-1.

[0103] Example 6

[0104] Take 100 g NaY molecular sieve (properties as follows: molar ratio of silicon oxide to aluminum oxide is 6:1, sodium content is 7 wt%), 20 g ammonium chloride and 800 g deionized water are mixed, beaten, the slurry pH is adjusted to about 3.5 with hydrochloric acid, ion exchange is carried out at 90℃ for 2 hours, the ammonium ion exchange times is 2, then filtered and washed to obtain NH4Y molecular sieve filter cake; the obtained NH4Y molecular sieve filter cake, 3 g citric acid, 20 g polyvinyl alcohol (molecular weight is 25000) are added to 1500 g deionized water and stirred uniformly, and the above-mentioned material is transferred into an autoclave for hydrothermal treatment, after sealing, the temperature is raised to 100℃ at a rate of 15℃ / min, then the temperature is kept constant for 3 hours, then the temperature is raised to 140℃ at a rate of 10℃ / min, and kept constant for 6 hours, then filtered, washed, and then the material is dried at 120℃ for 6 hours to obtain a modified molecular sieve.

[0105] Take 179 g pseudo-boehmite (alumina mass content is 69.2%), 269 g modified molecular sieve, 9 g sesbania powder, 4.5 g nitric acid, 3 g citric acid, 12 g activated carbon with a particle size of 4 microns, 178 g water are mixed and kneaded into a shape, then dried at 120℃ for 3 hours and calcined at 550℃ for 3 hours to obtain a catalyst carrier F. The obtained carrier F is saturatedly immersed in a 1.5 mol / L gallium nitrate solution under the condition of 100% water vapor at 550℃ for 90 min to obtain a catalyst carrier F-0.

[0106] Take 100 g of the catalyst carrier F-0, and measure the water absorption rate to be 0.9, take 202 g of molybdenum trioxide (containing 99 wt% of molybdenum oxide), 96.2 g of basic nickel carbonate (containing 52 wt% of nickel oxide), 52.4 g of phosphoric acid solution (containing 26.7 wt% of phosphorus), add clean water and stir to gradually heat to boiling until all the raw materials are dissolved, then keep the temperature constant for 40 minutes, and then reduce to room temperature for standby, to obtain an impregnation solution. Under stirring, slowly add a mixture of pentaerythritol and diethanolamine and thiourea to the above-mentioned solution, the ratio of pentaerythritol and diethanolamine is 3:1, the amount of thiourea added is to make its concentration in the impregnation solution be 20 g / L, and the amount of pentaerythritol added is to make its concentration in the impregnation solution be 16 g / L, and the solution is made up to 90 mL for standby. The above-mentioned impregnation solution is impregnated on the carrier F-0 by spraying to obtain F-1. After placing F-1 in a closed container at room temperature for 6 hours, it is dried at 120℃ for 4 hours, and finally calcined at 500℃ for 4 hours to obtain CF-1.

[0107] Example 7

[0108] Take 200 g NaY molecular sieve (properties as follows: molar ratio of silicon oxide to aluminum oxide is 4:1, sodium content is 11 wt%), 40 g ammonium chloride and 1400 g deionized water are mixed, beaten, the slurry pH is adjusted to about 4 with nitric acid, ion exchange is carried out at 85°C for 3 hours, the ammonium ion exchange times is 2, then filtration, washing, NH4Y molecular sieve filter cake is obtained; the obtained NH4Y molecular sieve filter cake, 6 g citric acid, 20 g methyl cellulose (molecular weight is 20000) are added to 4000 g deionized water and stirred uniformly, the above-mentioned material is transferred into an autoclave, hydrothermal treatment is carried out, after sealing, the temperature is increased to 110°C at a rate of 10°C / min, then constant temperature is kept for 2.5 hours, then the temperature is increased to 130°C at a rate of 10°C / min, constant temperature is kept for 6 hours, filtration, washing; then the material is dried at 120°C for 4 hours to obtain a modified molecular sieve.

[0109] Take 147 g pseudoboehmite (alumina mass content is 68.7%), 359 g modified molecular sieve, 12 g sesbania powder, 6 g nitric acid, 4 g citric acid, 22 g activated carbon with a particle size of 4 microns, 258 g water are mixed and kneaded into a shape, then dried at 140°C for 3 hours, calcined at 550°C for 3 hours to obtain catalyst carrier G. The obtained carrier G is saturatedly immersed in a 2.0 mol / L gallium nitrate solution under the condition of 100% water vapor at 550°C for 70 min to obtain catalyst carrier G-0.

[0110] Take 100 g catalyst carrier G-1, measure its water absorption rate as 0.88, take molybdenum trioxide (containing 99 wt% of molybdenum oxide) 183 g, basic nickel carbonate (containing 52 wt% of nickel oxide) 96.2 g, phosphoric acid solution (containing 26.7 wt% of phosphorus) 59.9 g, add clean water, stir and gradually heat to boiling until the raw materials are completely dissolved, keep constant temperature for 60 minutes, then reduce to room temperature for standby. In a stirred state, slowly add a mixture of 1,4-butanediol and diethanolamine and thiourea to the above-mentioned solution, the ratio of 1,4-butanediol and diethanolamine is 5:1, the amount of thiourea added is to make its concentration in the impregnation solution be 33 g / L, the amount of 1,4-butanediol added is to make its concentration in the impregnation solution be 22 g / L, the solution is constant volume 88 mL for standby. The above-mentioned impregnation solution is impregnated on the carrier G-0 by spraying to obtain G-1. The G-1 is placed in a closed container at room temperature for 8 hours, then dried at 120°C for 4 hours, finally calcined at 490°C for 4 hours to obtain CG-1.

[0111] Example 8

[0112] Take 152 g NaY molecular sieve (properties as follows: molar ratio of silicon oxide to aluminum oxide is 5:1, sodium content is 7 wt%), 46 g ammonium chloride and 1672 g deionized water are mixed, beaten, the slurry pH is adjusted to about 3.5 with nitric acid, ion exchange is carried out at 90℃ for 3 hours, the number of ammonium ion exchange is 2 times, then filtration and washing are carried out, and an NH4Y molecular sieve filter cake is obtained; the obtained NH4Y molecular sieve filter cake, 5 g adipic acid, 17 g polyvinylpyrrolidone (molecular weight is 30000), 3200 g deionized water are added and stirred uniformly, and the above-mentioned materials are transferred into an autoclave for hydrothermal treatment, after sealing, the temperature is increased to 110℃ at a rate of 10℃ / min, then constant temperature is kept for 4 hours, then the temperature is increased to 130℃ at a rate of 10℃ / min, constant temperature is kept for 6 hours, filtration and washing are carried out, and then the materials are dried at 130℃ for 4 hours to obtain a modified molecular sieve.

[0113] Take 251 g pseudoboehmite (alumina mass content is 69%), 532 g modified molecular sieve, 9 g sesbania powder, 4.5 g nitric acid, 3 g citric acid, 17 g activated carbon with a particle size of 4 microns, 328 g water are mixed and kneaded into a shape, then dried at 130℃ for 4 hours and calcined at 650℃ for 3 hours to obtain a catalyst carrier H. The obtained carrier H is saturatedly immersed in a 1.7 mol / L gallium nitrate solution under the condition of 100% water vapor and 600℃ for 60 min to obtain a catalyst carrier H-0.

[0114] Take 100 g of the catalyst carrier H-1, and measure the water absorption rate to be 0.9. Take 202 g of molybdenum trioxide (containing 99 wt% of molybdenum trioxide), 96.2 g of basic nickel carbonate (containing 52 wt% of nickel oxide), and 52.4 g of phosphoric acid solution (containing 26.7 wt% of phosphorus), add clean water, stir and gradually heat to boiling until all the raw materials are dissolved, then keep the temperature constant for 40 minutes and then reduce to room temperature for standby. In a stirred state, slowly add a mixture of pentaerythritol and diethanolamine and thiourea to the above-mentioned solution, the ratio of pentaerythritol and diethanolamine is 3:1, the amount of thiourea added is to make its concentration in the impregnation solution be 20 g / L, and the amount of pentaerythritol added is to make its concentration in the impregnation solution be 19 g / L, and the solution is made up to 90 mL for standby. The above-mentioned impregnation solution is impregnated on the carrier H-0 by spraying to obtain H-1. The H-1 is placed in a closed container at room temperature for 6 hours, then dried at 120℃ for 4 hours, and finally calcined at 550℃ for 4 hours to obtain CH-1.

[0115] Example 9

[0116] Take 100 g NaY molecular sieve (properties as follows: molar ratio of silicon oxide to aluminum oxide is 7:1, sodium content is 10 wt%), 25 g ammonium chloride and 800 g deionized water are mixed, beaten, the slurry pH is adjusted to about 3.5 with hydrochloric acid, ion exchange is carried out at 90°C for 2 hours, the number of ammonium ion exchange is 3 times, then filtration and washing are carried out, and NH4Y molecular sieve filter cake is obtained; the obtained NH4Y molecular sieve filter cake, 3 g citric acid, 20 g methyl cellulose (molecular weight is 20000) and 1500 g deionized water are stirred uniformly, and the above-mentioned materials are transferred into an autoclave for hydrothermal treatment, after sealing, the temperature is increased to 100°C at a rate of 15°C / min, then the temperature is kept constant for 3 hours, then the temperature is increased to 140°C at a rate of 10°C / min, and the temperature is kept constant for 6 hours, then filtration and washing are carried out; then the materials are dried at 120°C for 6 hours to obtain modified molecular sieve.

[0117] Take 224 g pseudo-boehmite (alumina mass content is 67.8%), 538 g modified molecular sieve, 15 g sesbania powder, 7 g nitric acid, 5 g citric acid, 36 g activated carbon with a particle size of 4 microns, and 462 g water are mixed and kneaded into a shape, then dried at 120°C for 3 hours and calcined at 550°C for 3 hours to obtain catalyst carrier I. The obtained carrier I is saturatedly immersed in a 1.5 mol / L gallium nitrate solution under the condition of 100% water vapor and 600°C for 80 min to obtain catalyst carrier I-0.

[0118] Take 100 g catalyst carrier I-1, and measure the water absorption rate to be 0.93; take 192 g molybdenum trioxide (containing 99 wt% molybdenum oxide), 102 g basic nickel carbonate (containing 52 wt% nickel oxide), 52.4 g phosphoric acid solution (containing 26.7 wt% phosphorus), and add clean water, then stir and gradually heat to boiling until the raw materials are completely dissolved, keep the temperature constant for 70 min, then reduce to room temperature for standby. In a stirred state, slowly add a mixture of neopentyl glycol and hexamethylenetetramine and thiourea to the above-mentioned solution, the ratio of neopentyl glycol and hexamethylenetetramine is 4:1, the amount of thiourea added is to make its concentration in the impregnation solution be 39 g / L, and the amount of neopentyl glycol added is to make its concentration in the impregnation solution be 27 g / L, and the solution is made up to 93 mL for standby. The above-mentioned impregnation solution is impregnated on the carrier I-0 by spraying to obtain I-1. The I-1 is placed in a closed container at room temperature for 6 hours, then dried at 120°C for 4 hours, and finally calcined at 495°C for 4 hours to obtain CI-1.

[0119] Example 10

[0120] Take 100 g NaY molecular sieve (properties as follows: molar ratio of silicon oxide to aluminum oxide is 6:1, sodium content is 7 wt%), 20 g ammonium chloride and 800 g deionized water are mixed, beaten, the slurry pH is adjusted to about 3.5 with hydrochloric acid, ion exchange is carried out at 90°C for 2 hours, the ammonium ion exchange times is 2, then filtration, washing, NH4Y molecular sieve filter cake is obtained; the obtained NH4Y molecular sieve filter cake, 3 g citric acid, 20 g polyvinyl alcohol (molecular weight is 25000) are added to 1500 g deionized water and stirred uniformly, the above-mentioned material is transferred into an autoclave for hydrothermal treatment, the temperature is raised to 140°C at a rate of 10°C / min and kept constant for 6 hours, filtration, washing, then the material is dried at 120°C for 6 hours to obtain the modified molecular sieve.

[0121] Take 179 g pseudo-boehmite (alumina mass content is 69.2%), 269 g modified molecular sieve, 9 g sesbania powder, 4.5 g nitric acid, 3 g citric acid, 12 g activated carbon with a particle size of 4 microns, 178 g water are mixed and kneaded into a shape, then dried at 120°C for 3 hours and calcined at 550°C for 3 hours to obtain catalyst carrier J. The obtained carrier J is saturatedly immersed in a 1.5 mol / L gallium nitrate solution under the condition of 100% water vapor at 550°C for 90 min to obtain catalyst carrier J-0.

[0122] Take 100 g catalyst carrier J-1, measure its water absorption rate as 0.9, take molybdenum trioxide (containing 99 wt% of molybdenum oxide) 202 g, basic nickel carbonate (containing 52 wt% of nickel oxide) 96.2 g, phosphoric acid solution (containing 26.7 wt% of phosphorus) 52.4 g, add clean water and stir to gradually heat to boiling until the raw materials are completely dissolved, keep constant temperature for 40 min, then reduce to room temperature for standby, to obtain an impregnation solution. Under stirring, slowly add a mixture of pentaerythritol and diethanolamine and thiourea to the above-mentioned solution, the ratio of pentaerythritol and diethanolamine is 3:1, the amount of thiourea is added to make its concentration in the impregnation solution be 20 g / L, the amount of pentaerythritol is added to make its concentration in the impregnation solution be 16 g / L, the solution is constant volume 90 mL for standby. The above-mentioned impregnation solution is impregnated on the carrier J-0 by spraying to obtain J-1. The J-1 is placed in a closed container at room temperature for 6 hours, then dried at 120°C for 4 hours, finally calcined at 500°C for 4 hours to obtain CJ-1.

[0123] Examples 11-15

[0124] The catalysts obtained in Examples 1-10 were sulfided, and the sulfidation process was as follows: the catalysts were loaded into a tubular reactor, and pre-sulfidation of the catalysts was carried out, the sulfidation liquid was a 5.0% by mass CS2 solution in cyclohexane, the flow rate of the sulfidation liquid was 2.1 g / g catalyst, the hydrogen pressure was 5.0 MPa, the hydrogen flow rate was 10 mL / min per gram of catalyst, the reaction was divided into two temperature stages, the first stage was from 80°C, the temperature was raised at a rate of 2.0°C / min, and after reaching 160°C, the temperature was kept constant for 4.0 h; the second stage was from 160°C, the temperature was raised at a rate of 2.0°C / min, and after reaching 300°C, the temperature was kept constant for 2.0 h, and the sulfidation was completed.

[0125] The sulfided catalysts obtained in Examples 1-10 were graded and loaded. The properties of the residual oil feedstock used are shown in Table 4. A fixed bed process was used. Along the flow direction of the liquid phase, the foam ceramic catalyst, the hydrogenation guard, the hydrodemetallization catalyst, the hydrodesulfurization catalyst, and the hydrodenitrogenation catalyst were loaded in sequence. Based on the total catalyst loading volume ratio, the loading volumes of the foam ceramic catalyst, the hydrogenation guard, the hydrodemetallization catalyst, the hydrodesulfurization catalyst, and the hydrodenitrogenation catalyst were 5%, 20%, 15%, 25%, and 35%, respectively. The foam ceramic catalyst, the hydrogenation guard, and the hydrodemetallization catalyst were produced by the Fushun Petrochemical Research Institute of SINOPEC. The types were: foam ceramic catalyst (FGF-02), hydrogenation guard (FZC-100B), and hydrodemetallization catalyst (FZC-204A). The grading method parameters of the hydrodesulfurization catalyst and the hydrodenitrogenation catalyst are shown in Tables 5-1 to 5-3.

[0126] The operating conditions of each reaction zone were as follows: reaction temperature 350°C, reaction pressure 7.5 MPa, hydrogen to oil volume ratio 550:1, liquid hourly space velocity 0.5 h -1 The evaluation results of the reaction are shown in Tables 5-1 to 5-3.

[0127] Comparative Example 1

[0128] Comparative Example 1 was the same as Example 1, except that the metakaolin was not modified and was directly mixed and kneaded with the pseudoboehmite, etc. to prepare the carrier, and the comparative hydrodesulfurization catalyst DCA-1 was prepared.

[0129] Comparative Example 2

[0130] Comparative Example 2 was the same as Example 1, except that the metakaolin was simply mechanically modified with gallium nitrate and ammonium fluoride, and the above materials were not sealed and hydrothermally treated in an autoclave, and the comparative hydrodesulfurization catalyst DCA-2 was prepared.

[0131] Comparative Example 3

[0132] Comparative hydrogenation desulfurization catalyst DCA-3 was prepared by impregnating the carrier with the conventional impregnation solution without adding the mixture of pentaerythritol, diethanolamine and thiourea in the preparation process of the impregnation solution compared with Example 1.

[0133] Comparative Example 4

[0134] Comparative hydrogenation desulfurization catalyst DCA-4 was prepared by impregnating the carrier with the impregnation solution containing pentaerythritol and diethanolamine without adding thiourea in the preparation process of the impregnation solution compared with Example 1.

[0135] Comparative Example 5

[0136] Comparative hydrogenation desulfurization catalyst DCA-5 was prepared by modifying the metakaolin with gallium only without adding ammonium fluoride, and the other material dosages and preparation conditions were the same as those in Example 1 compared with Example 1.

[0137] Comparative Example 6

[0138] Comparative hydrogenation desulfurization catalyst DCA-6 was prepared by modifying the metakaolin with fluorine only without adding gallium nitrate, and the other material dosages and preparation conditions were the same as those in Example 1 compared with Example 1.

[0139] Comparative Example 7

[0140] Comparative hydrogenation denitrogenation catalyst DCF-1 was prepared by kneading the carrier with pseudo-boehmite and the like without modifying the NH4Y molecular sieve with organic acid and water-soluble polymer compared with Example 6.

[0141] Comparative Example 8

[0142] Comparative hydrogenation denitrogenation catalyst DCF-2 was prepared by not impregnating the catalyst carrier in gallium nitrate solution and treating it with high-temperature steam compared with Example 6.

[0143] Comparative Example 9

[0144] Comparative hydrogenation denitrogenation catalyst DCF-3 was prepared by impregnating the carrier with the conventional impregnation solution I without adding the mixture of pentaerythritol, diethanolamine and thiourea in the preparation process of the impregnation solution compared with Example 6.

[0145] Comparative Example 10

[0146] Comparative hydrogenation denitrogenation catalyst DCF-4 was prepared by impregnating the carrier with the impregnation solution containing pentaerythritol and diethanolamine without adding thiourea in the preparation process of the impregnation solution compared with Example 6.

[0147] Comparative Examples 11-20

[0148] The catalysts obtained in Comparative Examples 1-10 were sulfided, and the sulfidation method was the same as that in Examples 11-15.

[0149] The sulfided catalysts obtained in Comparative Examples 1-10 were graded and packed. The properties of the residual oil feedstock used are shown in Table 4. A fixed bed process was used. In the direction of flow of the liquid phase stream, the foam ceramic catalyst, hydrogenation guard catalyst, hydrodemetallization catalyst, hydrodesulfurization catalyst, and hydrodenitrogenation catalyst were packed in sequence. The volume ratio of the foam ceramic catalyst, hydrogenation guard catalyst, hydrodemetallization catalyst, hydrodesulfurization catalyst, and hydrodenitrogenation catalyst was 5%, 20%, 15%, 25%, and 35%, respectively, based on the total volume of the catalyst packing. The foam ceramic catalyst, hydrogenation guard catalyst, and hydrodemetallization catalyst were produced by Fushun Petrochemical Research Institute of SINOPEC. The types were: foam ceramic catalyst (FGF-02), hydrogenation guard catalyst (FZC-100B), and hydrodemetallization catalyst (FZC-204A). The grading method parameters for the hydrodesulfurization catalyst and hydrodenitrogenation catalyst are shown in Tables 5-1 to 5-3.

[0150] The operating conditions of each reaction zone were as follows: reaction temperature 350°C, reaction pressure 7.5 MPa, hydrogen to oil volume ratio 550:1, liquid hourly space velocity 0.5 h -1 The evaluation results of the reaction are shown in Tables 5-1 to 5-3.

[0151] Table 1-1 Catalyst composition and properties of the examples

[0152] Item Example 1 Example 2 Example 3 Example 4 Example 5 Composition MoO3, wt.% 15.2 15.8 15.4 15.6 15.5 NiO, wt% 3.7 3.9 3.8 3.6 3.7 Property Specific surface area, m 2 / g]] 187 185 192 188 181 Pore volume, cm3 / g 3 / g]]> 0.52 0.59 0.57 0.61 0.50 Average pore diameter, nm 11.45 10.66 11.29 13.18 10.09

[0153] Table 1-2 Catalyst composition and properties of the examples

[0154] Item Example 6 Example 7 Example 8 Example 9 Example 10 Composition MoO3, wt.% 18.2 18.8 18.4 18.4 18.5 NiO, wt% 4.7 4.9 4.8 4.8 4.6 Property Specific surface area, m 2 / g]] 215 207 232 197 194 Pore volume, cm3 / g 3 / g]]> 0.52 0.59 0.47 0.55 0.57 Average pore diameter, nm 11.9 12.2 13.7 11.3 11.9

[0155] Table 1-3 Catalyst composition and properties of the comparative examples

[0156]

[0157]

[0158] Table 1-4 Catalyst composition and properties of the comparative examples

[0159] Item Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Composition MoO3, wt.% 15.9 15.2 18.6 18.1 18.9 18.8 NiO, wt% 3.5 3.1 4.5 4.7 4.8 4.6 Property Specific surface area, m 2 / g]] 168 171 157 168 195 189 Pore volume, cm3 / g 3 / g]]> 0.43 0.46 0.33 0.43 0.47 0.44 Average pore diameter, nm 8.20 9.30 7.9 9.7 9.6 10.1

[0160] Table 2-1 Properties of modified Y zeolites of the examples and comparative examples

[0161] Property Example 6 Example 7 Example 8 Example 9 Example 10 Crystal grain size, nm 463 436 391 401 495 molar ratio of SiO2 / Al2O3 25 19 31 37 10 Specific surface area, m 2 / g]]> 705 668 683 711 643 Lattice parameter, nm 2.442 2.453 2.449 2.452 2.435 Average pore diameter, nm 12.5 11.9 11.1 12.4 10.3

[0162] Table 2-2 Properties of modified Y zeolites of the examples and comparative examples

[0163] Property Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Crystal grain size, nm 658 461 472 456 molar ratio of SiO2 / Al2O3 7 21 23 24 Specific surface area, m 2 / g]] 382 598 630 625 Lattice parameter, nm 2.128 2.448 2.446 2.444 Average pore diameter, nm 8.2 10.8 10.9 12.2

[0164] Table 3 Infrared acid properties of catalysts of each example and comparative example

[0165]

[0166]

[0167] Table 4 Properties of raw oil and reaction conditions

[0168] Item Property Feed oil property Density / kg m -3 ]] 970.0 S / wt% 2.2 N / wt% 0.54 [Ni + V] / μg·g -1 ]] 72 Reaction condition Reaction temperature / °C 350 Pressure / MPa 7.5 Volume space velocity / h -1 ]] 0.5 Hydrogen / oil volume ratio 550

[0169] Table 5-1 Catalyst activity evaluation results

[0170]

[0171] Table 5-2 Catalyst activity evaluation results

[0172]

[0173]

[0174] Table 5-3 Catalyst activity evaluation results

[0175] Item Operation time, h Comparative Example 17 Comparative Example 18 Comparative Example 19 Comparative Example 20 Desulfurization catalyst No. / CA-1 CA-1 CA-1 CA-1 Denitrogenation catalyst No. / DCF-1 DCF-2 DCF-3 DCF-4 HDS, % 2000 43.8 / / / HDN, % 2000 51.2 / / / HDS, % 200 67.2 68.9 70.2 73.1 HDN, % 200 76.2 77.5 81.7 79.2

[0176] From the catalyst evaluation results, the desulfurization and denitrification performance of the catalyst grading method of the present application is superior to the comparative example.

Claims

1. A method of grading a residue hydroprocessing catalyst, comprising: The hydrogenation protectant, the hydrogenation demetallization catalyst, the hydrogenation desulfurization catalyst and the hydrogenation denitrification catalyst are sequentially filled along the liquid phase flow direction. The hydrogenation desulfurization catalyst comprises a carrier and an active metal component, wherein the carrier comprises gallium and fluorine modified metakaolin and alumina, and the mass ratio of the gallium and fluorine modified metakaolin to the alumina is 15-30:7-13; in the gallium and fluorine modified metakaolin, the mass content of gallium is 2.0%-5.0%, and the mass content of fluorine is 0.8%-1.5%. The hydrogenation denitrification catalyst comprises a carrier and an active metal component, the carrier comprises modified Y molecular sieve and alumina, the modified Y molecular sieve is small crystal grain mesoporous modified Y molecular sieve, and has the following properties: the crystal grain size is 500 nm or less, the molar ratio of silicon oxide to aluminum oxide is 8-55, the specific surface area is 640-800 m 2 / g, the cell parameter is 2.433-2.460 nm, and the average pore size is 10-30 nm. The hydrodesulfurization catalyst has the following properties: a specific surface area of 180 to 220 m 2 / g, a pore volume of 0.5 to 0.7 mL / g, and an average pore diameter of 10.0 to 30.0 nm. The preparation method of the hydrogenation desulfurization catalyst comprises the following steps: (11) mixing metakaolin, gallium nitrate, ammonium fluoride and water, sealing and hydrothermally treating, drying, and calcining to obtain a modified material; (12) mixing and kneading the modified material obtained in step (11), pseudo-boehmite, a glue adhesive, a co-extrusion agent, a pore-expanding agent and water, drying, and calcining to obtain a catalyst carrier; (13) preparing an impregnation solution containing amines, alcohols, thiourea and active metals; (14) impregnating the catalyst carrier obtained in step (12) with the impregnation solution obtained in step (13), and drying and calcining to obtain a hydrogenation desulfurization catalyst; The preparation method of the hydrogenation denitrification catalyst comprises the following steps: (21) ammonium ion exchanging NaY molecular sieve, filtering and washing to obtain NH4Y molecular sieve filter cake; (22) mixing the NH4Y molecular sieve filter cake obtained in step (21) with an organic acid, a water-soluble polymer and water, and then performing hydrothermal treatment to obtain modified Y molecular sieve; (23) mixing and kneading the modified Y molecular sieve obtained in step (22), pseudo-boehmite, a glue adhesive, a co-extrusion agent, a pore-expanding agent and water, drying, and calcining to obtain a catalyst carrier; (24) impregnating the catalyst carrier obtained in step (23) into a gallium nitrate solution, drying, and then performing high-temperature water vapor treatment to obtain a catalyst carrier; (25) preparing an impregnation solution containing amines, alcohols, thiourea and active metals; (26) impregnating the catalyst carrier obtained in step (24) with the impregnation solution obtained in step (25), and drying and calcining to obtain a hydrogenation denitrification catalyst.

2. The method of claim 1, wherein, In the hydrogenation denitrification catalyst, the crystal particle size of the modified Y molecular sieve is 300-500 nm.

3. The method of claim 1, wherein, The filling volume of the hydrogenation desulfurization catalyst accounts for 20%-30% of the total catalyst filling volume; The filling volume of the hydrogenation denitrification catalyst accounts for 30%-40% of the total catalyst filling volume; The filling volume of the hydrogenation protectant accounts for 15%-25% of the total catalyst filling volume; The filling volume of the hydrogenation demetallization catalyst accounts for 10%-20% of the total catalyst filling volume.

4. The method of claim 1 or 3, wherein The filling volume of the hydrogenation desulfurization catalyst and the hydrogenation denitrification catalyst accounts for more than 50% of the total catalyst filling volume.

5. The method of claim 4, wherein, The filling volume of the hydrogenation desulfurization catalyst and the hydrogenation denitrification catalyst accounts for 50%-70% of the total catalyst filling volume.

6. The method of claim 1, wherein, The hydrogenation protectant and / or the hydrogenation demetallization catalyst adopts an alumina-based carrier, and takes metals in Group VIB and / or Group VIII as active metal components.

7. The method of claim 6, wherein, The content of metals in Group VIB in terms of oxides in the hydrogenation protectant is 1.5%-6% based on the weight of the catalyst, and the content of metals in Group VIII in terms of oxides is 0.4%-3.0%. And / or, the hydrogen demetallization catalyst, the content of Group VIB in terms of oxides is 3% to 14% and the content of Group VIII metal in terms of oxides is 0.5% to 5.0% based on the weight of the catalyst.

8. The method of claim 1, wherein, In the preparation method of the hydrogen desulfurization catalyst, the mass ratio of the gallium nitrate to the ammonium fluoride in step (11) is 1 to 10:1, and the total mass of the gallium nitrate and the ammonium fluoride accounts for 5% to 60% of the mass of the metakaolin; and / or, the water is added in step (11) in an amount of 5:1 to 10:1 in terms of the mass ratio of water to the sum of the metakaolin, the gallium nitrate and the ammonium fluoride.

9. The method of claim 8, wherein, In the preparation method of the hydrogen desulfurization catalyst, the total mass of the gallium nitrate and the ammonium fluoride in step (11) accounts for 15% to 40% of the mass of the metakaolin.

10. The method of claim 1, wherein, In the preparation method of the hydrogen desulfurization catalyst, the sealing hydrothermal treatment in step (11) is carried out under the conditions of a hydrothermal treatment temperature of 80 to 130 ℃ and a time of 3 to 10 hours.

11. The method of claim 10, wherein, In the preparation method of the hydrogen desulfurization catalyst, the hydrothermal treatment in step (11) is carried out in two stages, and the temperature of the second stage is at least 20 ℃ higher than that of the first stage.

12. The method of claim 11, wherein, In the preparation method of the hydrogen desulfurization catalyst, the hydrothermal treatment in step (11) is carried out in two stages, and the temperature of the second stage is at least 30 ℃ higher than that of the first stage.

13. The method of claim 1, wherein, In the preparation method of the hydrogen desulfurization catalyst, the alcohol compound in step (13) is one or more of pentaerythritol, ethylene glycol, glycerol, 1,2-propanediol, 1,4-butanediol and neopentyl glycol; the amine compound is one or more of hexamethylenetetramine, ethylenediamine, ethanolamine, diethanolamine and triethanolamine; the mass ratio of the alcohol compound to the amine compound is 1:1 to 16:1; the addition amount of thiourea is such that the concentration of thiourea in the impregnation solution is 5 to 70 g / L; and the concentration of the alcohol compound in the impregnation solution in step (13) is 5 to 60 g / L.

14. The method of claim 13, wherein, In the preparation method of the hydrogen desulfurization catalyst, the addition amount of thiourea in step (13) is such that the concentration of thiourea in the impregnation solution is 8 to 50 g / L; and the concentration of the alcohol compound in the impregnation solution in step (13) is 7 to 30 g / L.

15. The method of claim 1, wherein, In the hydrogen denitrification catalyst, the active metal includes at least one metal component selected from Group VIII and at least one metal component selected from Group VIB.

16. The method of claim 15, wherein, The Group VIII metal is nickel and / or cobalt, and the Group VIB metal is molybdenum and / or tungsten.

17. The method of claim 15, wherein, The mass content of the carrier is 74% to 85%, the content of Group VIII in terms of oxides is 2% to 6%, and the content of Group VIB metal in terms of oxides is 15% to 24% based on the mass of the catalyst; and the content of the modified Y molecular sieve is 40% to 70% and the content of alumina is 14% to 40% based on the mass of the carrier.

18. The method of claim 1, wherein, In the preparation method of the hydrodenitrogenation catalyst, the NaY molecular sieve in step (21) has the following properties: the molar ratio of silicon oxide to aluminum oxide is 3-7:1, and the sodium content is 6 wt%-12 wt%; the NaY molecular sieve in step (21) is exchanged into an ammonium ion by mixing the NaY molecular sieve with an ammonium salt solution, adjusting the pH value of the slurry, and performing ammonium ion exchange, and then the NH4Y molecular sieve filter cake is obtained after filtration and washing; wherein the mass ratio of the NaY molecular sieve, water, and ammonium salt is 1:6-25:0.2-0.4; the pH value of the slurry is adjusted to 3-4; the ammonium ion exchange temperature is adjusted to 70-90 DEG C, the ammonium ion exchange time is 2-4 hours, and the ammonium ion exchange frequency is 1-3 times.

19. The method of claim 1, wherein, In the preparation method of the hydrodenitrogenation catalyst, the organic acid in step (22) is at least one selected from the group consisting of fumaric acid, adipic acid, tartaric acid, citric acid, oxalic acid, acetic acid, salicylic acid, and malic acid, and the water-soluble polymer is at least one selected from the group consisting of polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, and water-soluble polysaccharide with a weight average molecular weight of 10,000-40,000; and / or, the mass ratio of the NH4Y molecular sieve, the organic acid, the water-soluble polymer, and water in step (22) is =1:0.01-0.05:0.05-0.25:15-40.

20. The method of claim 1, wherein, In the preparation method of the hydrodenitrogenation catalyst, the hydrothermal treatment in step (22) has the following conditions: the temperature is 100-150 DEG C, and the treatment time is 5-12 hours; and / or, after the hydrothermal treatment in step (22), drying is performed, and the drying conditions are as follows: the drying temperature is 100-160 DEG C, and the drying time is 3-8 hours.

21. The method of claim 20, wherein, In the preparation method of the hydrodenitrogenation catalyst, the hydrothermal treatment in step (22) is two-stage hydrothermal treatment, and the temperature of the second stage is at least 15 DEG C higher than that of the first stage.

22. The method of claim 21, wherein, In the preparation method of the hydrodenitrogenation catalyst, the hydrothermal treatment in step (22) is two-stage hydrothermal treatment, and the temperature of the second stage is at least 20 DEG C higher than that of the first stage.

23. The method of claim 1, wherein In the preparation method of the hydrodenitrogenation catalyst, the mass ratio of the pseudoboehmite to the modified Y molecular sieve in step (23) is 7-13:15-30; the addition amount of the pore-expanding agent is 2 wt%-10 wt% of the total mass of the pseudoboehmite and the modified Y molecular sieve; and / or, the drying temperature in step (23) is 120-160 DEG C, the drying time is 3-6 hours, the calcination temperature is 550-700 DEG C, and the calcination time is 2-6 hours.

24. The method of claim 1, wherein, In the preparation method of the hydrodenitrogenation catalyst, the concentration of the gallium nitrate solution in step (24) is 0.5-2.5 mol / L; the impregnation method in step (24) is saturated impregnation or unsaturated impregnation; and the high-temperature water vapor treatment has the following conditions: the temperature is 500-700 DEG C, and the time is 60-90 min.

25. The method of claim 1, wherein In the preparation method of the hydrodenitrogenation catalyst, the alcohol compound in step (25) is one or more of pentaerythritol, ethylene glycol, glycerol, 1,2-propanediol, 1,4-butanediol, and neopentyl glycol; the amine compound is one or more of hexamethylenetetramine, ethylenediamine, ethanolamine, diethanolamine, and triethanolamine; the mass ratio of the alcohol compound to the amine compound is 1:1-16:1; the addition amount of the thiourea is such that the concentration of the thiourea in the impregnation solution is 5-70 g / L; and the concentration of the alcohol compound in the impregnation solution in step (25) is 2-60 g / L.

26. The method of claim 25, wherein, In the preparation method of the hydrodenitrogenation catalyst, the addition amount of the thiourea in step (25) is such that the concentration of the thiourea in the impregnation solution is 8-50 g / L; and the concentration of the alcohol compound in the impregnation solution in step (25) is 7-30 g / L.

27. Use of the grading method according to any one of claims 1-26 in a residue hydroprocessing reaction.

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