Residual oil hydrodenitrification catalyst as well as preparation method and application thereof

Abstract

The invention discloses a residual oil hydrodenitrification catalyst as well as a preparation method and application thereof. The catalyst comprises a carrier and a second active metal component, the carrier comprises first active metal phosphide, first active metal carbide and aluminum oxide, and the molar ratio of the first active metal phosphide metered by first active metal to the first active metal carbide metered by the first active metal is 1: (0.20-0.40). The hydrodenitrification catalyst has the characteristics of good macromolecular diffusion performance, strong denitrification capability, strong metal capacity, good carbon deposition resistance and the like. The hydrodenitrogenation catalyst is especially suitable for a residual oil hydrodenitrogenation treatment process, and has good demetallization and denitrification activity and good activity stability.

Description

Technical Field

[0001] The invention belongs to the field of catalyst preparation, and in particular relates to a residual oil hydrodenitrogenation catalyst and a preparation method and application thereof. Background Art

[0002] In recent years, crude oil resources have shown a clear trend towards heavier and inferior quality, and processing inferior crude oil faces severe challenges. Residue hydroprocessing technology is mainly used to provide raw materials for catalytic cracking processes. The increase in nitrides and residual carbon values ​​in residue raw materials will cause the catalyst activity of downstream catalytic cracking units to decrease, and the product distribution will also deteriorate. Therefore, it is necessary to develop more active hydrodenitrogenation catalysts to improve the residue hydrodenitrogenation rate and residual carbon removal rate.

[0003] Due to the limitation of the properties of the residue hydrodenitrogenation catalyst in the prior art, the residue hydrodenitrogenation catalyst generally has only good denitrification function, but weak demetallization function, and can only use the outer surface of the catalyst for demetallization reaction, and the metal precipitate is precipitated in the gap. Therefore, in the residue hydrodenitrification series catalyst, when denitrification is carried out, the demetallization agent is required to remove the metal to the greatest extent possible, so that the metal content is as low as possible when entering the hydrodenitrogenation catalyst bed, so that the hydrodenitrogenation catalyst can meet the requirements of long-term operation.

[0004] CN1098433A discloses a method for preparing a hydrorefining catalyst. The method is to mix powdered basic nickel carbonate into the extrusion process of alumina monohydrate to provide the Ni content required by the catalyst, and at the same time mix a small amount of powdered industrial-grade ammonium molybdate, and then impregnate the final catalyst with a molybdenum ammonia solution once. The catalyst prepared by this method has a high hydrogenation denitrification performance, but the pores are too small to be conducive to the diffusion of macromolecules, and the metal cannot be precipitated inside the pores. CN1257103A discloses a method for preparing a hydrotreating catalyst. The method promotes metal dispersion by optimizing the kneading process of materials such as aluminum hydroxide monohydrate and metal salts. After all materials are kneaded into a plastic body once, they are extruded into strips and activated by water vapor-air high temperature to prepare the catalyst. The catalyst prepared by this method has too small pores, and cannot prepare a dual-function catalyst with both denitrification performance and high tolerance to metal impurities.

[0005] Generally speaking, the smaller the pores, the higher the catalytic activity of the catalyst. This is because small pores can increase the surface area of ​​the catalyst, increase the contact area between the catalyst and the reactants, and thus increase the reaction rate. However, as the quality of hydrogenation feedstocks deteriorates, a carrier with a larger pore structure is needed to prepare a hydrogenation catalyst with good mass transfer and diffusion performance. Therefore, for macromolecular reactants such as heavy oil and residual oil, the catalyst should not only have an appropriate specific surface area to allow the active center to have a high degree of dispersion, but also have a suitable pore structure to accommodate the diffusion of the reactants. Summary of the invention

[0006] In view of the deficiencies of the prior art, the present invention provides a residual oil hydrodenitrogenation catalyst and a preparation method and application thereof. The hydrodenitrogenation catalyst has the characteristics of good macromolecular diffusion performance, strong denitrification ability, strong metal tolerance, good anti-coking performance, etc. The hydrodenitrogenation catalyst is particularly suitable for residual oil hydrodenitrogenation treatment process, has good demetallization and denitrification activity and good activity stability.

[0007] A first aspect of the present invention provides a residual oil hydrodenitrogenation catalyst, comprising a carrier and a second active metal component, wherein the carrier comprises a first active metal phosphide, a first active metal carbide and alumina, and the molar ratio of the first active metal phosphide calculated as the first active metal to the first active metal carbide calculated as the first active metal is 1:0.20-0.40.

[0008] According to the present invention, the first active metal is a Group VIII metal selected from one or more of Fe, Co, and Ni, preferably at least one of Co and Ni, and more preferably Ni.

[0009] According to the present invention, the second 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.

[0010] According to the present invention, the second active metal is present in the catalyst in the form of an oxide.

[0011] According to the present invention, the carrier further comprises carbon, and the carbon content of the alumina carrier is 0.5% to 14% by mass, preferably 2% to 9% by mass.

[0012] According to the present invention, based on the mass of the carrier, the mass content of aluminum oxide is 83% to 96%, and the content of the first active metal in terms of metal oxide is 2% to 8%.

[0013] According to the present invention, based on the mass of the catalyst, the mass content of the carrier is 74% to 85%, the content of the Group VIII metal in the second active metal in terms of oxide is 2% to 6%, and the content of the Group VIB metal in the second active metal in terms of oxide is 13% to 24%.

[0014] According to the present invention, the properties of the catalyst are as follows: the specific surface area is 170 to 280 m 2 / g, the pore volume is 0.5-1.3mL / g, the average pore diameter is 9-15nm, and the mechanical strength is 110-150N / cm.

[0015] According to the present invention, the pore distribution of the catalyst is as follows: the pore volume of pores with a pore diameter of less than 10 nm accounts for 5% to 8% of the total pore volume, the pore volume of pores with a pore diameter of 10 to 20 nm accounts for 63% to 69% of the total pore volume, and the pore volume of pores with a pore diameter of more than 20 nm accounts for 25% to 30% of the total pore volume.

[0016] The second aspect of the present invention provides a method for preparing the above-mentioned hydrodenitrogenation catalyst, comprising:

[0017] (1) dissolving a surfactant, an organic acid and a first active metal source in water to obtain a material I;

[0018] (2) mixing and kneading the pseudo-boehmite, the material I obtained in step (1), and the adhesive, and drying to obtain a carrier intermediate;

[0019] (3) mixing the carrier intermediate described in step (2) with a phosphorus source, and heating the mixture under the protection of an inert gas to obtain a carrier;

[0020] (4) impregnating the impregnation solution II containing the second active metal into the carrier described in step (3), and preparing a residual oil hydrodenitrogenation catalyst through curing, drying and calcining.

[0021] According to the present invention, the surfactant in step (1) is one or more of long-chain fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, fatty acid polyoxyethylene esters, polyoxyethylene alkylamines, polyoxyethylene alkylolamides, and polyethers; further, the carbon number of the surfactant is 30 to 50. The organic acid is one or more of fumaric acid, adipic acid, tartaric acid, citric acid, oxalic acid, acetic acid, salicylic acid, and malic acid.

[0022] According to the present invention, in step (1), the first active metal is a Group VIII metal selected from one or more of Fe, Co, and Ni, preferably at least one of Co and Ni, and more preferably Ni. The first active metal source is from a soluble salt, such as at least one of nitrate, citrate, carbonate, or acetate.

[0023] According to the present invention, in step (1), the mass ratio of surfactant: organic acid: first active metal source (calculated as first active metal oxide): water is 10-50:1-10:20-100:100, preferably 30-50:5-10:40-70:100.

[0024] According to the present invention, in step (2), the molding can be performed in a conventional molding manner, such as extrusion molding, and the molding shape is a conventional shape, such as a cylinder, a clover, a four-leaf clover, etc. The mass ratio of the amount of the pseudo-boehmite added in terms of alumina to the first active metal source in material I in terms of oxide is 1:0.03-0.08. The adhesive can be at least one of nitric acid, acetic acid, and citric acid. A molding aid can also be added during the molding process, such as an extrusion aid, and the extrusion aid can be sesbania powder. The amount of the adhesive and the extrusion aid added is added according to the actual molding needs, and the present invention has no special requirements, such as the amount of the adhesive added is 0.5wt%-5wt% of the mass of the pseudo-boehmite. The amount of the extrusion aid added is 0.5wt%-6wt% of the mass of the pseudo-boehmite. Water can also be added during the molding process, and it is added according to the actual molding needs, such as the amount of water added is 80wt%-130wt% of the mass of the pseudo-boehmite, preferably 90wt%-120wt%.

[0025] According to the present invention, the drying conditions in step (2) are: drying at 100-160° C. for 1-8 hours.

[0026] According to the present invention, the phosphorus source in step (3) is a substance containing P, which can be selected from substances that provide phosphorus under heating conditions, including but not limited to at least one of red phosphorus, phosphine, phosphoric acid, phosphates, hypophosphites, phosphonic acid, phosphinic acid and its derivatives, phosphine and its derivatives. The inert atmosphere can be at least one of nitrogen, helium, neon, argon and xenon, preferably nitrogen. The temperature of the heat treatment is 250-425°C, preferably 325-375°C, and more preferably 350-375°C; the heat treatment time is 1-24h, preferably 2-6h. After the heat treatment, it can be purged with gas, preferably a mixture of O2 and an inert gas (such as Ar), wherein the oxygen volume fraction is 0.1%-1%, and the purging time is 0.5-2h.

[0027] According to the present invention, in step (3), the molar ratio of the phosphorus source as P to the carrier intermediate as the first active metal is 1:1 to 30:1, preferably 10:1 to 20:1.

[0028] According to the present invention, the second active metal in step (4) includes 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 (4), the second active metal is calculated as metal oxide, wherein the content of Group VIB metal is 150-450 g / L, preferably 300-400 g / L, and the content of Group VIII metal is 10-120 g / L, preferably 40-60 g / L. When preparing the impregnation solution, the molybdenum source can be one or more of molybdenum trioxide, molybdate, and paramolybdate, preferably molybdenum trioxide; the tungsten source can be tungstate or tungsten oxide, preferably ammonium metatungstate; the nickel source can be one or more of nickel nitrate, nickel acetate, basic nickel carbonate, and nickel chloride, preferably basic nickel carbonate; the cobalt source can be one or more of cobalt nitrate, cobalt acetate, basic cobalt carbonate, and cobalt chloride, preferably basic cobalt carbonate.

[0029] According to the present invention, the impregnation solution containing the second active metal in step (4) contains a phosphorus-containing compound, and the phosphorus-containing compound is preferably phosphoric acid. The concentration of phosphorus in the impregnation solution is 20 to 80 g / L, preferably 30 to 50 g / L, calculated as phosphorus.

[0030] According to the present invention, the impregnation in step (4) can be carried out by a spray impregnation method, and a saturated impregnation method or a supersaturated impregnation method can be used during the impregnation.

[0031] According to the present invention, the curing in step (4) is to place the sample after impregnation under a closed condition of 10-30°C for 6-12 hours, and the curing pressure is not particularly limited, and can be autogenous pressure; and / or, the drying condition is drying at 100-160°C for 1-8 hours. The roasting condition is roasting at 450-650°C for 3-7 hours, preferably roasting at 480-600°C for 4-7 hours. The roasting atmosphere is an oxygen-containing gas, such as air.

[0032] According to the present invention, the properties of the catalyst in step (4) are as follows: the specific surface area is 170 to 280 m 2 / g, pore volume of 0.5-1.3mL / g, average pore diameter of 9-15nm, and mechanical strength of 110-150N / cm. The pore distribution of the catalyst is as follows: the pore volume of pores with a pore diameter of less than 10nm accounts for 5%-8% of the total pore volume, the pore volume of pores with a pore diameter of 10-20nm accounts for 63%-69% of the total pore volume, and the pore volume of pores with a pore diameter of more than 20nm accounts for 25%-30% of the total pore volume.

[0033] The third aspect of the present invention provides the use of the above-mentioned residue hydrodenitrogenation catalyst or the residue hydrodenitrogenation catalyst prepared by the above-mentioned preparation method in residue hydroprocessing.

[0034] Compared with the prior art, the present invention has the following advantages:

[0035] 1. The hydrodenitrogenation catalyst of the present invention comprises a carrier and an active metal component, wherein the carrier contains a phosphide and a carbide of a first active metal and has a suitable pore structure. The catalyst of the present invention is suitable for the hydrogenation conversion process of nitrides in asphaltene during the hydrotreatment of residual oil, has strong hydrodemetallization ability, high hydrodenitrogenation activity and good stability.

[0036] 2. In the preparation process of the hydrodenitrogenation catalyst of the present invention, the surfactant helps the first active metal salt to be evenly distributed on the surface of the carrier, and at the same time helps the molding and extrusion of the carrier; the organic acid can form a complex with nickel, which is conducive to the formation of Ni3C during carbonization, and can also delay the sulfidation of part of the nickel, which is conducive to the formation of Ni-Mo-S active phase in the catalyst. In addition, during the reaction process, the carbonization of the surfactant and the organic acid, as well as the phosphating of the first active metal, generate the first active metal phosphide and the first active metal carbide, which interacts synergistically, not only increasing the surface of the carrier, but also The number of acid sites can generate more coordinated unsaturated sites and enable the catalyst to form a suitable macroporous structure. The hydrodenitrification catalyst is used in the residual oil hydroprocessing process and has the characteristics of strong hydrodemetallization ability, high hydrodenitrification activity and good stability.

[0037] In the preparation process of the hydrodenitrogenation catalyst of the present invention, by doping P and C elements on the catalyst carrier, Ni-Al and Ni-P and C can interact synergistically, which can reduce the interaction between the active metal and alumina and improve the dispersibility of the metal on the one hand, and effectively inhibit metal agglomeration, carbon deposition, phase change and other deactivation factors on the other hand, thereby better playing an important role in regulating the performance of the catalyst.

[0038] 3. The hydrodenitrogenation catalyst of the present invention is used in the process of residual oil hydrotreating and has the characteristics of strong hydrodemetallization ability, high hydrodenitrogenation activity and good stability. DETAILED DESCRIPTION

[0039] The technical scheme and effects of the present invention are further illustrated by examples below, but the following examples do not constitute a limitation to the method of the present invention.

[0040] In the present invention, % refers to mass fraction unless otherwise specified.

[0041] In the present invention, the specific surface area, pore volume and pore distribution are measured by using the ASAP2420 fully automatic physical adsorption instrument of the American Micromeritics Instrument Company, and the measuring method is as follows: the sample is treated at 300°C and 0.1MPa for 4 hours, liquid N2 is used as the adsorbent, the adsorption temperature is -196°C, and the analysis test is performed after accurate weighing. The specific surface area is calculated according to the BET method, and the pore volume and pore distribution are calculated according to the BJH method.

[0042] In the present invention, the mechanical strength is measured by using a ZQJ-III particle strength tester produced by Dalian Intelligent Testing Machine Factory. The catalyst in each embodiment and comparative example is formed into an extruded strip with a diameter of 1.3 mm and a length of 4.0 mm.

[0043] In the present invention, the catalyst composition is tested by spectrophotometry, and the testing instrument is a Lambda 365 ultraviolet spectrophotometer.

[0044] In the present invention, the room temperature described in each example is 25°C.

[0045] Example 1

[0046] (1) Take 135 g of nickel nitrate hexahydrate and 6.5 g of citric acid and add them to 80 g of water. After they are completely dissolved, add 32 g of dodecyl fatty alcohol polyoxyethylene ether to obtain material I.

[0047] (2) Take 172 g of pseudo-boehmite (with an aluminum oxide mass content of 69.2%), 52 g of material I, 6 g of sesbania powder, and 4.5 g of nitric acid (with a mass concentration of 67%), add 186 g of water, knead and shape, and then dry at 120°C for 3 hours to obtain a catalyst carrier intermediate A-1.

[0048] (3) The catalyst carrier intermediate A-1 and sodium hypophosphite were weighed and placed in a quartz tube at a molar ratio of 10.15:1 between the phosphorus source (P) and the first active metal (the carrier intermediate). The tube was purged with argon (100 mL / min) for 30 min, and then the reaction system was evacuated with a vacuum pump and sealed. The temperature was raised to 350°C and maintained for 3 h. The temperature was lowered to room temperature and the pressure was released. The tube was purged with O2 / Ar (O2 volume fraction: 0.5%) for 1 h to obtain a carrier.

[0049] (4) 36 g of molybdenum oxide, 17.3 g of basic nickel carbonate, and 10.8 g of phosphoric acid were mixed into 90 mL of impregnation solution, which was then impregnated onto 100 g of the carrier by spraying. The carrier was placed in a sealed container at room temperature for 6 hours, dried at 120°C for 4 hours, and finally calcined at 500°C for 4 hours to obtain catalyst CA-1.

[0050] In the catalyst carrier, the molar ratio of the first active metal phosphide calculated as the first active metal to the first active metal carbide calculated as the first active metal is 1:0.36.

[0051] Example 2

[0052] (1) Take 140 g of nickel nitrate hexahydrate and 5.4 g of citric acid and add them to 80 g of water. After they are completely dissolved, add 31.5 g of dodecyl fatty alcohol polyoxyethylene ether to obtain material I.

[0053] (2) Take 202 g of pseudo-boehmite (with an aluminum oxide mass content of 69.2%), 73 g of material I, 6 g of sesbania powder, and 6 g of nitric acid (with a mass concentration of 67%), add 223 g of water, knead and shape, and then dry at 120°C for 3 hours to obtain a catalyst carrier intermediate B-1.

[0054] (3) The catalyst carrier intermediate B-1 and sodium hypophosphite were weighed and placed in a quartz tube at a molar ratio of 10.38:1 between the phosphorus source (P) and the first active metal (the carrier intermediate). The tube was purged with nitrogen (100 mL / min) for 30 min, and then the reaction system was evacuated with a vacuum pump and sealed. The temperature was raised to 350°C and maintained for 2 h. The temperature was lowered to room temperature and the pressure was released. The tube was purged with O2 / Ar (O2 volume fraction: 0.5%) for 1 h to obtain the carrier.

[0055] (4) 38 g of molybdenum oxide, 14.62 g of basic nickel carbonate, and 10.25 g of phosphoric acid were prepared into 95 mL of impregnation solution, which was then impregnated onto 100 g of the carrier by spraying. The carrier was placed in a sealed container at room temperature for 6 hours, dried at 120° C. for 4 hours, and finally calcined at 490° C. for 6 hours to obtain catalyst CB-1.

[0056] In the catalyst carrier, the molar ratio of the first active metal phosphide calculated as the first active metal to the first active metal carbide calculated as the first active metal is 1:0.25.

[0057] Example 3

[0058] (1) 135 g of nickel nitrate hexahydrate and 6.5 g of citric acid were added to 80 g of water, and after they were completely dissolved, 32 g of nonylphenol polyoxyethylene ether OP-10 was added to obtain material I.

[0059] (2) Take 172 g of pseudo-boehmite (with an aluminum oxide mass content of 69.2%), 52 g of material I, 6 g of sesbania powder, and 4.5 g of nitric acid (with a mass concentration of 67%), add 186 g of water, knead and shape, and then dry at 120°C for 3 hours to obtain a catalyst carrier intermediate C-1.

[0060] (3) The catalyst carrier intermediate C-1 and red phosphorus were weighed and placed in a quartz tube at a molar ratio of 10.33:1 between the phosphorus source (P) and the first active metal (the carrier intermediate). The tube was purged with argon (100 mL / min) for 30 min, and then the reaction system was evacuated with a vacuum pump and sealed. The temperature was raised to 350°C and maintained for 2 h. The temperature was lowered to room temperature and the pressure was released. The tube was purged with O2 / Ar (O2 volume fraction: 0.5%) for 1 h to obtain a carrier.

[0061] (4) 36 g of molybdenum oxide, 17.3 g of basic nickel carbonate, and 10.8 g of phosphoric acid were prepared into 90 mL of impregnation solution, which was then impregnated onto 100 g of the carrier by spraying. The carrier was placed in a sealed container at room temperature for 6 hours, dried at 120° C. for 4 hours, and finally calcined at 550° C. for 4 hours to obtain catalyst CC-1.

[0062] In the catalyst carrier, the molar ratio of the first active metal phosphide calculated as the first active metal to the first active metal carbide calculated as the first active metal is 1:0.27.

[0063] Example 4

[0064] (1) Take 200 g of nickel nitrate hexahydrate and 5.6 g of citric acid and add them to 80 g of water. After they are completely dissolved, add 24 g of dodecyl fatty alcohol polyoxyethylene ether to obtain material I.

[0065] (2) Take 202 g of pseudo-boehmite (with an aluminum oxide mass content of 69.2%), 42 g of material I, 7 g of sesbania powder, and 8 g of nitric acid (with a mass concentration of 67%), add 201 g of water, knead and shape, and then dry at 120°C for 3 hours to obtain a catalyst carrier intermediate D-1.

[0066] (3) The obtained catalyst carrier intermediate D-1 and sodium hypophosphite were weighed and placed in a quartz tube at a molar ratio of 14.85:1 between the phosphorus source (P) and the first active metal (the carrier intermediate). After purging with nitrogen (100 mL / min) for 30 min, the reaction system was evacuated with a vacuum pump and sealed. The temperature was raised to 350°C and maintained for 2 h. After the temperature was lowered to room temperature, the pressure was released and purged with O2 / Ar (O2 volume fraction of 0.5%) for 1 h to obtain the carrier.

[0067] (4) 36 g of molybdenum oxide, 17.3 g of basic nickel carbonate, and 10.8 g of phosphoric acid were mixed into 90 mL of impregnation solution, which was then impregnated onto 100 g of the carrier by spraying. The carrier was placed in a sealed container at room temperature for 6 hours, dried at 120°C for 4 hours, and finally calcined at 490°C for 6 hours to obtain catalyst CD-1.

[0068] In the catalyst carrier, the molar ratio of the first active metal phosphide calculated as the first active metal to the first active metal carbide calculated as the first active metal is 1:0.34.

[0069] Comparative Example 1

[0070] Compared with Example 1, the difference is that there is no step (1) for preparing material I, and step (2) is changed to: 27.7 g nickel nitrate hexahydrate and 1.3 g citric acid, 6.6 g dodecyl fatty alcohol polyoxyethylene ether and 172 g pseudo-boehmite (alumina mass content is 69.2%), 6 g sesbania powder, 4.5 g nitric acid (mass concentration is 67%), 202.4 g water is added and kneaded into shape, and then dried at 120°C for 3 hours to obtain a catalyst carrier intermediate.

[0071] Steps (3) and (4) are the same as in Example 1.

[0072] A comparative hydrodenitrogenation catalyst DCA-1 was prepared.

[0073] In the catalyst carrier, the molar ratio of the first active metal phosphide calculated as the first active metal to the first active metal carbide calculated as the first active metal is 1:0.6.

[0074] Comparative Example 2

[0075] Compared with Example 1, the difference is that no organic acid is added when preparing material I in step (1).

[0076] A comparative hydrodenitrogenation catalyst DCA-2 was prepared.

[0077] In the catalyst carrier, the molar ratio of the first active metal phosphide calculated as the first active metal to the first active metal carbide calculated as the first active metal is 1:0.19.

[0078] Comparative Example 3

[0079] Compared with Example 1, in step (3), the carrier is not subjected to phosphating reaction but is heated in an inert gas Ar at 350° C. for 3 h. After cooling to room temperature, the pressure is released and purged with O2 / Ar (O2 volume fraction is 0.5%) for 1 h to obtain a carrier.

[0080] A comparative hydrodenitrogenation catalyst DCA-3 was prepared.

[0081] Table 1 Composition and properties of the catalysts obtained in each example

[0082]

[0083] Application Examples

[0084] The catalysts obtained in the examples and comparative examples were evaluated for residual oil hydrogenation reaction using the feedstock oil shown in Table 2. The properties of the feedstock oil and the reaction conditions are shown in Table 2. The evaluation results are shown in Table 3.

[0085] Table 2 Raw oil properties and reaction conditions

[0086]

[0087]

[0088] Table 3 Activity evaluation results of various catalysts

[0089] Removal rate Operation time, h Example 1 Example 2 Example 3 Example 4 HDN, % 200 95.3 96.1 94.6 95.1 HDN, % 2000 90.6 89.8 91.4 90.5 HDM, % 200 78.2 81.5 82.3 79.4 HDM, % 2000 71.7 75.2 73.8 72.8

[0090] Table 3

[0091] Removal rate Operation time, h Comparative Example 1 Comparative Example 2 Comparative Example 3 HDN, % 200 71.8 74.2 76.4 HDN, % 2000 42.8 47.3 45.1 HDM, % 200 64.5 63.2 65.3 HDM, % 2000 32.2 33.5 34.1

[0092] The above describes the specific implementation of the present invention in detail, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the various technical features being combined in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A residual oil hydrodenitrogenation catalyst, comprising a carrier and a second active metal component, wherein the carrier comprises a first active metal phosphide, a first active metal carbide and alumina; the molar ratio of the first active metal phosphide calculated as the first active metal to the first active metal carbide calculated as the first active metal is 1:0.20-0.

40.

2. The catalyst according to claim 1, characterized in that The first active metal is a Group VIII metal selected from one or more of Fe, Co, and Ni, preferably at least one of Co and Ni, and more preferably Ni.

3. The catalyst according to claim 1, characterized in that The second active metal includes at least one metal component selected from Group VIII and at least one metal component selected from Group VIB; further, the Group VIII metal is preferably nickel and / or cobalt, and the Group VIB metal is preferably molybdenum and / or tungsten.

4. The catalyst according to claim 1, characterized in that The properties of the catalyst are as follows: specific surface area of ​​170 to 280 m 2 / g; and / or, a pore volume of 0.5 to 1.3 mL / g; and / or, a mechanical strength of 110 to 150 N / cm; And / or, the pore distribution of the catalyst is as follows: the pore volume of pores with a pore diameter of less than 10 nm accounts for 5% to 8% of the total pore volume, the pore volume of pores with a pore diameter of 10 to 20 nm accounts for 63% to 69% of the total pore volume, and the pore volume of pores with a pore diameter of more than 20 nm accounts for 25% to 30% of the total pore volume; And / or, the average pore size of the catalyst is 9 to 15 nm.

5. A method for preparing the catalyst according to any one of claims 1 to 4, comprising: (1) dissolving a surfactant, an organic acid and a first active metal source in water to obtain a material I; (2) mixing and kneading the pseudo-boehmite, the material I obtained in step (1), and the adhesive, and drying to obtain a carrier intermediate; (3) mixing the carrier intermediate described in step (2) with a phosphorus source, and heating the mixture under the protection of an inert gas to obtain a carrier; (4) impregnating the impregnation solution II containing the second active metal into the carrier described in step (3), and preparing a residual oil hydrodenitrogenation catalyst through curing, drying and calcining.

6. The preparation method according to claim 5, characterized in that: The surfactant in step (1) is one or more of long-chain fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, fatty acid polyoxyethylene esters, polyoxyethylene alkylamines, polyoxyethylene alkylolamides, and polyethers; And / or, the organic acid is one or more of fumaric acid, adipic acid, tartaric acid, citric acid, oxalic acid, acetic acid, salicylic acid, and malic acid.

7. The preparation method according to claim 5 or 6, characterized in that: In step (1), the mass ratio of surfactant: organic acid: first active metal source (calculated as first active metal oxide): water is 10-50:1-10:20-100:

100.

8. The preparation method according to claim 5, characterized in that: The mass ratio of the amount of the pseudo-boehmite added in step (2) calculated as alumina to the mass ratio of the first active metal source in material I calculated as oxide is 1:0.03-0.

08.

9. The preparation method according to claim 5, characterized in that: The temperature of the heating treatment in step (3) is 250-425°C, preferably 325-375°C, and more preferably 350-375°C; the heating treatment time is 1-24h, preferably 2-6h.

10. The preparation method according to claim 5, characterized in that: In step (3), the molar ratio of the phosphorus source as P to the carrier intermediate as the first active metal is 1:1 to 30:1, preferably 10:1 to 20:

1.

11. The preparation method according to claim 5, characterized in that: The impregnation solution containing the second active metal in step (4) contains a phosphorus-containing compound, and the phosphorus-containing compound is preferably phosphoric acid; preferably, the concentration of phosphorus in the impregnation solution is 20 to 80 g / L, preferably 30 to 50 g / L, calculated as phosphorus.

12. Use of the catalyst according to any one of claims 1 to 4 or the catalyst prepared by the preparation method according to any one of claims 5 to 11 in residual oil hydroprocessing.

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