Hydrogenation catalysts, processes for their preparation and use

Abstract

The application provides a hydrogenation catalyst, a preparation method and application thereof, the hydrogenation catalyst comprising 10-30% of molecular sieve, 20-40% of heteropolyacid compound in terms of metal oxide, and the rest being aluminum oxide; the structural formula of the heteropolyacid compound is selected from at least one of Ni3[H4P2Mo 12 Ni9O 56 (L)7]、[{Ni(L)2}2Mo8O 26 ] and at least one of the following: HL is at least one of acetic acid, 4-methyl-3,5-dihydroxybenzoic acid and 3-amino-2,5-dihydroxybenzoic acid. The catalyst has a highly dispersed II type active phase and can be applied to distillate oil hydrotreating to achieve high-efficiency hydrogenation.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, specifically relating to a hydrogenation catalyst, its preparation method, and its application. Background Technology

[0002] Hydrorefining improves the quality of petroleum products by inducing reactions such as hydrodesulfurization, hydronitrogenation, and hydrosaturation to remove impurities like sulfur and nitrogen. Currently, catalysts used in hydrorefining processes typically employ alumina and magnesium oxide as supports, with Group VIII and Group VIB metals as active components.

[0003] Patent document CN103157518A discloses a hydrodesulfurization catalyst with mesoporous magnesium oxide as support and Co and Mo as active components and its application. The catalyst prepared by supporting Co and Mo with mesoporous magnesium oxide has high catalytic activity for the hydrodesulfurization reaction of dibenzothiophene compounds. However, the stability of magnesium oxide support is much lower than that of alumina support, making it difficult to operate in industrial plants. The preparation route of the catalyst is complicated and the hydrogenation activity is not high.

[0004] Patent document CN103801345A discloses a method for preparing a hydrodesulfurization catalyst. A composite oxide precursor containing W, Ni, Al, and Mg is prepared by co-precipitation. This precursor is then shaped, washed, dried, and calcined to obtain a catalyst intermediate. This intermediate is then impregnated with an impregnation solution containing Co and Mo, followed by drying and calcination to obtain the hydrodesulfurization catalyst. While the catalyst prepared by this method exhibits high desulfurization activity, the preparation process is lengthy and production costs are high.

[0005] Patent document CN101590416A discloses a method for preparing a molybdenum-nickel hydrogenation catalyst. This method involves two steps: kneading and impregnation. First, molybdenum oxide, a titanium-containing compound, a phosphorus-containing compound, and alumina are mixed with nitric acid solution, kneaded, extruded into strips, dried, and calcined to obtain a titanium, phosphorus, and molybdenum-containing alumina molding. Then, the molding is impregnated with a nickel-containing phosphoric acid solution, and after drying and calcination, the molybdenum-nickel hydrogenation catalyst is obtained. The preparation route of this catalyst is complex and its hydrogenation activity is not high.

[0006] Patent document CN1052501A discloses a method for preparing a hydrogenation catalyst. This method involves adding promoters P, F, and B to an impregnation solution containing Co-W-Mo trimetallic compounds, impregnating the catalyst using a segmented impregnation method, and then drying and calcining it to obtain the finished catalyst. In the above method, after impregnating the supported active metal, the catalyst is calcined at high temperature. The interaction between the active metal components and the support is relatively strong, which affects the sulfidation effect of the catalyst. Furthermore, it can cause some active metal components to aggregate, affecting the dispersion of the active metal and thus the activity of the catalyst.

[0007] Patent document CN1302848A discloses a hydrogenation catalyst and its preparation method. The catalyst uses Group VIB and Group VIII metals as active components, fluorine as an auxiliary agent, and supports one or more of silicon, boron, magnesium, titanium, and phosphorus as auxiliary agents. It is prepared by co-precipitation method. The defects of this technology or the shortcomings of this invention are: although the catalyst prepared by this method has high desulfurization activity, the preparation process is long and the production cost is high.

[0008] Patent document CN102039148A discloses a method for preparing a paraffin hydrogenation refining catalyst. The main steps of this method include: adding a solution of 6%-17% silicon-containing compound and 2%-20% phosphorus-containing compound to boehmite dry gel powder, rolling and extruding the mixture, and then drying and calcining it to obtain a silicon and phosphorus-containing alumina support. The preparation route of this catalyst is complex and its hydrogenation activity is not high.

[0009] Patent document CN102851061A discloses a method for hydrorefining inferior gasoline and diesel. The catalyst uses Si-modified alumina and ETS-10 titanium-silicon molecular sieve with a grain size of less than 2μm as the support, and Fe, Co, Ni and Mo, W as the active components. The microporous ETS-10 molecular sieve used is not conducive to the reaction of large molecular sulfur and nitrogen compounds, and the hydrorefining activity needs to be improved.

[0010] The above-mentioned hydrogenation catalysts exhibit low catalytic activity and poor denitrification and desulfurization rates when used for the hydrotreating of high-sulfur and high-nitrogen oil products. Summary of the Invention

[0011] This invention provides a hydrogenation catalyst, its preparation method, and its application. The catalyst has a highly dispersed type II active phase and can be applied to the hydrogenation treatment of distillate oils to achieve efficient hydrogenation, effectively overcoming the shortcomings of the prior art.

[0012] In one aspect, the present invention provides a hydrogenation catalyst comprising, by weight of 100%, 10%-30% molecular sieve, 20%-40% heteropolyacid compound based on metal oxide, and the remainder being alumina; the heteropolyacid compound is selected from Ni3[H4P2Mo]. 12 Ni9O 56 [(L)7]、[{Ni(L)2}2Mo8O] 26 At least one of the following, wherein HL is at least one of acetic acid, 4-methyl-3,5-dihydroxybenzoic acid, and 3-amino-2,5-dihydroxybenzoic acid.

[0013] According to one embodiment of the present invention, Ni3[H4P2Mo 12 Ni9O 56 [L]7] is obtained by a preparation method including the following process: NaL, (NH4)12 [H2P2Mo 12 O 48 The nickel salt and water are mixed evenly, the pH is adjusted to 2.2-2.6, and the mixture is kept at 80℃-100℃ for 1-3 hours to obtain Ni3[H4P2Mo]. 12 Ni9O 56 [(L)7], of which NaL and (NH4) 12 [H2P2Mo 12 O 48 The molar ratio of nickel salt is 10:1:15; and / or, [{Ni(L)2}2Mo8O 26 The preparation method includes the following steps: NaL, (NH4)6Mo7O 24 Mix nickel salt and water thoroughly, adjust the pH to 1.5-1.8, and heat to boiling for 1-3 hours to obtain [{Ni(L)2}2Mo8O 26 ], including NaL, (NH4)6Mo7O 24 The molar ratio of nickel salt is 4:1:2.

[0014] According to one embodiment of the present invention, the heteropolyacid compound is Ni3[H4P2Mo] 12 Ni9O 56 [(L)7]、[{Ni(L)2}2Mo8O] 26 A mixture of Ni3[H4P2Mo] 12 Ni9O 56 [(L)7] and [{Ni(L)2}2Mo8O] 26 The molar ratio of ] is 1:(5-15).

[0015] According to one embodiment of the present invention, the molecular sieve includes a mesoporous ETS-10 molecular sieve.

[0016] According to one embodiment of the present invention, the diameter of the catalyst is 0.8 mm to 2.0 mm or greater than 2.5 mm.

[0017] In a second aspect, the present invention provides a method for preparing the above-mentioned hydrogenation catalyst, comprising the following steps: mixing boehmite, molecular sieve and water uniformly, and calcining the mixture to obtain a calcined product; impregnating the calcined product in an impregnation solution containing heteropolyacid compounds and inorganic acids, and drying the product to obtain the hydrogenation catalyst.

[0018] According to one embodiment of the present invention, the calcination conditions are: temperature of 400℃-550℃ and time of 2h-6h.

[0019] According to one embodiment of the present invention, the impregnation conditions are: temperature of 50°C-70°C and time of 1-3 hours.

[0020] According to one embodiment of the present invention, the drying conditions are: temperature of 100℃-150℃ and time of 2h-4h.

[0021] A third aspect of the present invention provides a hydrogenation method, comprising: subjecting a feedstock containing distillate oil to a hydrogenation reaction in the presence of a catalyst to obtain a hydrogenated product; the catalyst comprising the above-described hydrogenation catalyst or a hydrogenation catalyst prepared by the above-described preparation method.

[0022] The implementation of this invention has at least the following beneficial effects:

[0023] The hydrogenation catalyst of this invention contains a heteropolyacid compound with a specific configuration. This unique configuration gives the compound inherent dispersibility, resulting in a highly dispersed type II active phase. When used in hydrorefining, this catalyst allows the active metal to contact more of the hydrogenation feedstock, significantly improving its catalytic activity. Due to its high catalytic activity, efficient hydrogenation can be achieved even with low catalyst dosage, reducing the cost of hydrorefining. This hydrogenation catalyst exhibits high catalytic activity and can be used in the hydrorefining of oil products, particularly high-sulfur and high-nitrogen oil products, achieving a desulfurization rate of not less than 90.3% and a denitrification rate of not less than 87.5%.

[0024] The method for preparing the hydrogenation catalyst provided by this invention involves uniformly mixing boehmite and molecular sieve water, followed by calcination to obtain a calcined product. The calcined product is then impregnated in an impregnation solution containing heteropolyacid compounds and inorganic acids, and dried to obtain the hydrogenation catalyst. This method of calcination followed by impregnation ensures that only weak van der Waals forces exist between the active metal and the support, further improving the dispersibility of the active components in the catalyst. Therefore, it effectively enhances the catalyst's reactivity, resulting in a highly active and stable catalyst.

[0025] Furthermore, the preparation method of the hydrogenation catalyst provided by this invention has the advantages of simple preparation process and easy operation, which is conducive to industrial production and application. Attached Figure Description

[0026] Figure 1 These are the adsorption isotherms and pore size distribution diagrams of the hydrogenation catalyst C in Example 3;

[0027] Figure 2 This is a transmission electron microscope (TEM) image of hydrogenation catalyst C from Example 3. Detailed Implementation

[0028] The specific embodiments listed below are merely descriptions of the principles and features of the present invention. The examples given are only for explaining the present invention and are not intended to limit the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] This invention provides a hydrogenation catalyst, comprising, by mass of 100%, 10%-30% molecular sieve, 20%-40% heteropolyacid compound (based on metal oxide), and the remainder being alumina; the heteropolyacid compound has a structural formula selected from Ni3[H4P2Mo]. 12 Ni9O 56 [(L)7]、[{Ni(L)2}2Mo8O] 26 At least one of the following, wherein HL is at least one of acetic acid, 4-methyl-3,5-dihydroxybenzoic acid, and 3-amino-2,5-dihydroxybenzoic acid.

[0030] The above-mentioned heteropolyacid compounds contain metals Ni and Mo. The mass of the heteropolyacid compounds is calculated based on metal oxides, which are nickel oxide and molybdenum trioxide.

[0031] The aforementioned hydrogenation catalyst uses alumina and molecular sieves as supports for the active components, with a heteropolyacid compound of a specific configuration as the active component. This hydrogenation catalyst exhibits high catalytic activity and can be used in the hydrotreating of oil products, especially high-sulfur and high-nitrogen oil products. The inventors hypothesize that due to the specific configuration of the heteropolyacid compound, it possesses high dispersibility, thus forming a highly dispersed type II active phase in the hydrogenation catalyst. When this hydrogenation catalyst is used in hydrorefining, it allows the active metal to contact more of the hydrogenation feedstock, not only improving the utilization rate of the active metal but also significantly enhancing the catalytic activity of the hydrogenation catalyst.

[0032] In some embodiments, Ni3[H4P2Mo] 12 Ni9O 56 [L]7] is obtained by a preparation method including the following process: NaL, (NH4) 12 [H2P2Mo 12 O 48 The nickel salt and water are mixed evenly, the pH is adjusted to 2.2-2.6, and the mixture is kept at 80℃-100℃ for 1-3 hours to obtain Ni3[H4P2Mo]. 12 Ni9O 56 [(L)7], of which NaL and (NH4) 12 [H2P2Mo 12 O 48 The molar ratio of nickel salt is 10:1:15.

[0033] In the above embodiments, NaL was mixed with water to form a NaL-containing solution, and (NH4) was added sequentially during stirring. 12 [H2P2Mo 12 O 48 A mixture of nickel salts was obtained, and the pH of the mixture was adjusted to 2.2-2.6. The mixture was then heated to promote the reaction. After the reaction was completed, the precipitate was washed and dried to obtain Ni3[H4P2Mo]. 12 Ni9O 56 (L)7], wherein the nickel salt includes nickel nitrate; the reaction temperature is 80℃-100℃, for example, 80℃, 82℃, 85℃, 88℃, 90℃, 92℃, 95℃, 98℃, 100℃ or any two of these ranges; the reaction time is 1h-3h, for example, 1h, 1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.8h, 3h or any two of these ranges.

[0034] In some embodiments, [{Ni(L)2}2Mo8O 26 The preparation method includes the following steps: NaL, (NH4)6Mo7O 24 Mix nickel salt and water thoroughly, adjust the pH to 1.5-1.8, and heat to boiling for 1-3 hours to obtain [{Ni(L)2}2Mo8O 26 ], including NaL, (NH4)6Mo7O 24 The molar ratio of nickel salt is 4:1:2.

[0035] In the above embodiments, NaL is mixed with water to form a solution containing NaL, and (NH4)6Mo7O is added sequentially during stirring. 24 A mixture of nickel salts was obtained, and the pH of the mixture was adjusted to 1.5-1.8. The mixture was then heated to promote the reaction. After the reaction was completed, the precipitate was washed and dried to obtain [{Ni(L)2}2Mo8O]. 26 The nickel salt includes nickel nitrate; the reaction time is 1h-3h, for example, 1h, 1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.8h, 3h or any combination thereof.

[0036] In some embodiments, the heteropolyacid compound is Ni3[H4P2Mo 12 Ni9O 56 [(L)7]、[{Ni(L)2}2Mo8O] 26 A mixture of Ni3[H4P2Mo] 12 Ni9O 56 [(L)7] and [{Ni(L)2}2Mo8O]26 The molar ratio of ] is 1:(5-15), for example, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15 or any two of these ranges.

[0037] In some embodiments, the molecular sieve includes a mesoporous ETS-10 molecular sieve, the framework of which is composed of six-coordinated (TiO6). 2- Together with a four-coordinated (SiO4) structure, the above-mentioned mesoporous ETS-10 molecular sieve has a pore volume of 0.25 cm³ in some embodiments. 3 / g.

[0038] In the above embodiments, the mesoporous ETS-10 molecular sieve can be obtained by conventional methods, specifically by the synthesis method of mesoporous ETS-10 disclosed in patent document CN109264738A.

[0039] The hydrogenation catalyst of the present invention further includes an extrusion aid, wherein the aid can be at least one of guar gum powder, polyvinyl alcohol, methylcellulose, and polyethylene glycol, and the aid is 1%-10% based on 100% of the catalyst mass.

[0040] The hydrogenation catalyst of the present invention also includes a binder, which may be at least one of nitric acid and citric acid, and the binder comprises 1%-10% of the catalyst by mass.

[0041] The particle size of the catalyst is controlled according to actual needs. In some embodiments, the diameter of the catalyst is 0.8 mm to 2.0 mm, for example, a range of 0.8 mm, 0.9 mm, 1 mm, 1.2 mm, 1.3 mm, 1.5 mm, 1.8 mm, 2 mm, or any combination thereof. When the catalyst is used in large-scale production, in other embodiments, the diameter of the catalyst is greater than 2.5 mm.

[0042] To achieve the above objectives, the present invention also provides a method for preparing the above-mentioned hydrogenation catalyst, comprising the following steps: mixing boehmite, molecular sieve and water evenly, and calcining to obtain a calcined product; impregnating the calcined product in an impregnation solution containing heteropolyacid compounds and inorganic acids, and drying to obtain the hydrogenation catalyst.

[0043] The method for preparing a hydrogenation catalyst provided by this invention involves calcining boehmite and molecular sieves to obtain a catalyst support, followed by impregnation to load a heteropolyacid compound with a specific configuration onto the support, thereby obtaining the catalyst. This process of calcination followed by impregnation weakens the interaction between the support and the active component, thus precisely controlling the active phase structure of the catalyst and forming highly dispersed type II phase hydrogenation active centers.

[0044] In the above preparation method, pseudoboehmite, molecular sieve and water are mixed evenly to obtain a mixture. An extrusion aid and a binder can also be added to the mixture to promote the bonding of pseudoboehmite and molecular sieve. After the mixture is calcined, a calcined product is obtained, which is the catalyst support.

[0045] Prior to the aforementioned calcination, the mixture is further subjected to extrusion molding, which involves extruding the mixture into a product of a certain shape through a perforated nozzle and then drying and shaping it. The specific shape obtained is adjusted according to the shape of the actual catalyst. For example, the shape of the product can be controlled to be strip-shaped, clover-shaped, granular, or toothed spherical during the extrusion molding process.

[0046] In the above embodiments, the drying and molding conditions are: a temperature of 80-150°C, for example, 80°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, or any combination thereof; in some embodiments, the above calcination conditions are: a temperature of 400°C-550°C, for example, 400°C, 410°C, 420°C, 430°C, 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, or any combination thereof; and a time of 2h-6h, for example, 2h, 3h, 4h, 5h, 6h, or any combination thereof.

[0047] In this invention, the impregnation process includes: first, forming an inorganic acid solution with an inorganic acid and water; then, mixing a heteropolyacid compound with the inorganic acid solution and stirring until uniform to form an impregnation liquid; then, mixing the calcined product that meets the above requirements with the impregnation liquid to ensure full contact between the calcined product and the impregnation liquid, thereby achieving the impregnation process.

[0048] Specifically, during the impregnation process, the calcined product is brought into full contact with the impregnation solution, and the heteropolyacid compounds in the impregnation solution are loaded onto the calcined product. In addition, the calcined product is impregnated in the above-mentioned impregnation solution system containing inorganic acids, so that the catalyst has suitable acidity, which helps to improve its hydrogenation catalytic activity. The inorganic acids include phosphoric acid.

[0049] In the above embodiments, the impregnation process can be carried out by the equal volume impregnation method or by the excessive impregnation method, and the equal volume impregnation method is preferred.

[0050] In practice, the saturated adsorption capacity of the calcined product can be detected first, and then the volume of the impregnation solution can be determined based on the adsorption capacity of the calcined product. Impregnation can then be carried out according to the equal volume method or the excess impregnation method described above.

[0051] In some embodiments, the impregnation conditions are: a temperature of 50°C-70°C, for example, a range of 50°C, 55°C, 60°C, 65°C, 70°C or any two thereof; and a time of 1h-3h, for example, a range of 1h, 1.5h, 2h, 2.5h, 3h or any two thereof.

[0052] In the above embodiments, drying is performed to remove residual moisture from the impregnated product. In some embodiments, the drying conditions are: a temperature of 100°C-150°C, such as 100°C, 110°C, 120°C, 130°C, 140°C, 150°C or any combination thereof; and a time of 2h-4h, such as 2h, 2.5h, 3h, 3.5h, 4h or any combination thereof.

[0053] The hydrogenation method provided by the present invention includes: subjecting a feedstock containing distillate oil to a hydrogenation reaction under the action of a catalyst to obtain a hydrogenated product; the catalyst includes the above-mentioned hydrogenation catalyst or a hydrogenation catalyst prepared by the above-mentioned preparation method.

[0054] Specifically, the catalyst is placed in a reactor, and the hydrogenation feedstock containing distillate oil is introduced into the reactor to contact the catalyst, carrying out a hydrogenation catalytic reaction to obtain the hydrogenated product. In the above embodiments, the catalyst needs to be pre-sulfurized before contacting the hydrogenation feedstock to further improve the catalyst's hydrogenation activity.

[0055] To achieve the above objectives, the conditions for the hydrogenation reaction are as follows: a reaction temperature of 300℃-400℃, for example, 300℃, 320℃, 350℃, 380℃, 400℃, or any combination thereof; a hydrogen partial pressure of 6MPa-12MPa, for example, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, or any combination thereof; a hydrogen-to-oil volume ratio of 300:1-600:1; and a volume hourly space velocity of 0.5 h⁻¹. -1 -2.0h -1 .

[0056] The hydrogenation method provided by this invention uses a specific hydrogenation catalyst to hydrogenate oil products, which can achieve high desulfurization and denitrification rates, improve the oil products, and reduce environmental pollution.

[0057] To make the objectives, technical solutions, and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention.

[0058] In all the embodiments and comparative examples, the other chemicals used were commercially available chemically pure reagents; Example 1

[0059] (1) Mix 100g of pseudoboehmite and 11.2g of mesoporous ETS-10 molecular sieve evenly, then add 4g of guar gum powder, 4g of nitric acid and 4g of citric acid aqueous solution to form a 1.5mm clover shape. After drying and calcination, the calcined product, i.e., the carrier, is obtained. The drying temperature is 120℃. The calcination conditions are: temperature 550℃ and time 4h.

[0060] (2) (NH4) 12 [H2P2Mo 12 O 48 [The mixture was] thoroughly mixed with CH3COONa and water, and Ni(NO3)3 was added while stirring. After thorough mixing, the pH of the solution was adjusted to 2.2-2.6, and the mixture was heated to 90℃ for 2 hours. The reaction product was washed and dried to obtain Ni3[H4P2Mo]. 12 Ni9O 56 [(CH3COO)7]; where CH3COONa and (NH4) are present. 12 [H2P2Mo 12 O 48 The molar ratio of Ni(NO3)3 is 10:1:15;

[0061] (NH4)6Mo7O 24 Mix CH3COONa and water thoroughly, then add Ni(NO3)3 while stirring. After mixing thoroughly, adjust the pH of the solution to 1.5-1.8, heat to boiling, and react for 2 hours. Wash and dry the reaction product to obtain [{Ni(CH3COO)2}2Mo8O 26 ]; including CH3COONa, (NH4)6Mo7O 24 The molar ratio of Ni(NO3)3 is 4:1:2;

[0062] (3) Ni3[H4P2Mo 12 Ni9O 56 (CH3COO)7] and [{Ni(CH3COO)2}2Mo8O 26 The impregnation solution was prepared by mixing Ni3[H4P2Mo] with phosphoric acid solution and stirring at 60°C for 1 hour. 12 Ni9O 56 (CH3COO)7] and [{Ni(CH3COO)2}2Mo8O 26 The molar ratio of ] is 1:12;

[0063] The calcined product obtained in step (1) is impregnated in an impregnation solution of equal volume and then dried to obtain hydrogenation catalyst A.

[0064] Example 2

[0065] (1) Mix 100g of pseudoboehmite and 70g of mesoporous ETS-10 molecular sieve evenly, then add 4g of guar gum powder, 4g of nitric acid and 4g of citric acid aqueous solution to form a 1.5mm clover shape. After drying and calcination, the calcined product, i.e., the carrier, is obtained. The drying temperature is 120℃. The calcination conditions are: temperature 550℃, time 4h.

[0066] (2) (NH4) 12 [H2P2Mo 12 O 48 [Ni3[H4P2Mo]] was mixed thoroughly with sodium 4-methyl-3,5-dihydroxybenzoate and water. Ni(NO3)3 was added while stirring, and after thorough mixing, the pH of the solution was adjusted to 2.2-2.6. The mixture was heated to 90℃ and reacted for 2 hours. The reaction product was washed and dried to obtain Ni3[H4P2Mo]. 12 Ni9O 56 [(L)7]; including sodium 4-methyl-3,5-dihydroxybenzoate, (NH4) 12 [H2P2Mo 12 O 48 The molar ratio of Ni(NO3)3 is 10:1:15;

[0067] (NH4)6Mo7O 24 The mixture was thoroughly mixed with sodium 4-methyl-3,5-dihydroxybenzoate and water. Ni(NO3)3 was added while stirring, and after thorough mixing, the pH of the solution was adjusted to 1.5-1.8. The mixture was heated to boiling and reacted for 2 hours. The reaction product was washed and dried to obtain [{Ni(L)2}2Mo8O]. 26 ]; including sodium 4-methyl-3,5-dihydroxybenzoate, (NH4)6Mo7O 24 The molar ratio of Ni(NO3)3 is 4:1:2; where HL is 4-methyl-4-methyl-3,5-dihydroxybenzoic acid;

[0068] (3) Ni3[H4P2Mo 12 Ni9O 56 [(L)7] and [{Ni(L)2}2Mo8O] 26 The impregnation solution was prepared by mixing Ni3[H4P2Mo] with phosphoric acid solution and stirring at 60°C for 1 hour. 12 Ni9O 56 [CH3COO)7] and [{Ni(L)2}2Mo8O] 26 The molar ratio of ] is 1:12;

[0069] The calcined product obtained in step (1) is impregnated in an impregnation solution of equal volume and then dried to obtain hydrogenation catalyst B.

[0070] Example 3

[0071] (1) Mix 100g of pseudoboehmite and 21.5g of mesoporous ETS-10 molecular sieve evenly, then add 4g of guar gum powder, 4g of nitric acid and 4g of citric acid aqueous solution to form a 1.5mm clover shape. After drying and calcination, the calcined product, i.e., the carrier, is obtained. The drying temperature is 120℃. The calcination conditions are: temperature 550℃ and time 4h.

[0072] (2) (NH4) 12 [H2P2Mo 12 O 48 [Ni(NO3)3] was mixed thoroughly with sodium 3-amino-2,5-dihydroxybenzoate and water. Ni(NO3)3 was added while stirring, and after thorough mixing, the pH of the solution was adjusted to 2.2-2.6. The mixture was heated to 90℃ and reacted for 2 hours. The reaction product was washed and dried to obtain Ni3[H4P2Mo]. 12 Ni9O 56 [(L)7]; including sodium 3-amino-2,5-dihydroxybenzoate, (NH4) 12 [H2P2Mo 12 O 48 The molar ratio of Ni(NO3)3 is 10:1:15;

[0073] (NH4)6Mo7O 24 The mixture was thoroughly mixed with sodium 3-amino-2,5-dihydroxybenzoate and water. Ni(NO3)3 was added while stirring, and after thorough mixing, the pH of the solution was adjusted to 1.5-1.8. The mixture was then heated to boiling and reacted for 2 hours. The reaction product was washed and dried to obtain [{Ni(L)2}2Mo8O]. 26 ]; including sodium 3-amino-2,5-dihydroxybenzoate, (NH4)6Mo7O 24 The molar ratio of Ni(NO3)3 is 4:1:2; where HL is 3-amino-2,5-dihydroxybenzoic acid;

[0074] (3) Ni3[H4P2Mo 12 Ni9O 56 [(L)7] and [{Ni(L)2}2Mo8O] 26 The impregnation solution was prepared by mixing Ni3[H4P2Mo] with phosphoric acid solution and stirring at 60°C for 1 hour. 12 Ni9O 56 [CH3COO)7] and [{Ni(L)2}2Mo8O] 26 The molar ratio of ] is 1:12;

[0075] The calcined product obtained in step (1) is impregnated in an impregnation solution of equal volume and then dried to obtain hydrogenation catalyst C.

[0076] Example 4

[0077] Compared with Example 2, the 70g mesoporous ETS-10 molecular sieve in step (1) was replaced with 21.5g mesoporous ETS-10 molecular sieve; other conditions remained unchanged, and hydrogenation catalyst D was obtained.

[0078] Example 5

[0079] Compared with Example 1, the 11.2g mesoporous ETS-10 molecular sieve in step (1) was replaced with 21.5g mesoporous ETS-10 molecular sieve; other conditions remained unchanged, and hydrogenation catalyst E was obtained.

[0080] Example 6

[0081] Compared with Example 3, the Ni3[H4P2Mo] in step (3) is changed. 12 Ni9O 56 [(L)7] and [{Ni(L)2}2Mo8O] 26 The molar ratio of 1:12 was replaced with a molar ratio of 1:15; other conditions remained unchanged, and hydrogenation catalyst F was obtained.

[0082] Example 7

[0083] Compared with Example 3, the Ni3[H4P2Mo] in step (3) is changed. 12 Ni9O 56 [(L)7] and [{Ni(L)2}2Mo8O] 26 The molar ratio of 1:12 was replaced with a molar ratio of 1:5; other conditions remained unchanged, and hydrogenation catalyst G was obtained.

[0084] Comparative Example 1

[0085] Hydrogenation catalyst H was prepared by impregnating alumina with a co-impregnation solution of nickel nitrate and ammonium molybdate, drying at 100℃~120℃ for 4h, and calcining at 500℃~600℃ for 4h.

[0086] Comparative Example 2

[0087] Hydrogenation catalyst I was prepared by impregnating alumina containing ETS-10 molecular sieve with a co-impregnation solution prepared from nickel nitrate and ammonium molybdate, drying at 100℃~120℃ for 4h, and calcining at 500℃~600℃ for 4h.

[0088] The physicochemical properties of the catalysts prepared in Examples 1-7 and Comparative Examples 1-2 are shown in Table 1;

[0089] The catalysts of Examples 1-7 and Comparative Examples 1-2 were hydrogenated using the following methods:

[0090] Using coking diesel with a sulfur content of 1260 ppm and a nitrogen content of 1178 ppm as the evaluation feedstock, 8 g of catalyst was weighed and hydrotreated in a 10 mL microreactor. The reaction conditions during hydrotreating were: reaction temperature 340℃, hydrogen partial pressure 6.4 MPa, hydrogen-to-oil volume ratio 500:1, and volume hourly space velocity (VHSV) 2.0 h⁻¹. -1 The microreactor evaluation results of the hydrogenation catalyst obtained by hydrogenation using coking diesel as feedstock are shown in Table 2.

[0091] Using wax oil (distillation range 225℃-521℃) with a sulfur content of 900 ppm and a nitrogen content of 726 ppm as the evaluation feedstock, 8 g of catalyst was weighed and hydrogenated in a 10 mL microreactor. The reaction conditions during hydrogenation were: reaction temperature 360℃, hydrogen partial pressure 12 MPa, hydrogen-to-oil volume ratio 800:1, and volume hourly space velocity (VHSV) 1.5 h⁻¹. -1 The microreactor evaluation results of the hydrogenation catalyst obtained by hydrogenation using wax oil as raw material are shown in Table 3.

[0092] Table 1 Physicochemical properties of catalysts

[0093]

[0094] Table 2 Evaluation results of catalyst microreactor hydrogenation

[0095]

[0096] Table 3 Evaluation results of microreactor hydrogenation

[0097]

[0098] Figure 1 These are the adsorption isotherms and pore size diagrams of the hydrogenation catalyst C in Example 3; Figure 2 This is a transmission electron microscope (TEM) image of hydrogenation catalyst C from Example 3, based on... Figure 2 It can be seen that the catalyst of the present invention did not agglomerate, but formed a layered structure and has high dispersibility.

[0099] As shown in Tables 2 and 3, when using coking diesel or wax oil as raw materials for hydrotreating, the catalyst of the present invention achieves a desulfurization rate of up to 99% and a denitrification rate of 98.5%, exhibiting high desulfurization and denitrification activity, which is significantly higher than that of Comparative Example 1. The hydrorefining catalyst of the present invention is particularly suitable for high-nitrogen raw materials.

[0100] In summary, the hydrogenation catalyst of the present invention contains a heteropolyacid compound with a specific configuration, which is highly dispersed. The hydrogenation catalyst has a highly dispersed Class II active phase and high catalytic activity. It can be used in the hydrotreating of oil products, especially in high-sulfur and high-nitrogen oil products, and can achieve a desulfurization rate of not less than 90.3% and a denitrification rate of not less than 87.5%.

[0101] The preferred embodiments and experimental verifications of the present invention have been described in detail above. It should be understood that those skilled in the art can make numerous modifications and variations based on the concept of the present invention without creative effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning, or limited experimentation on the basis of existing technology should be within the scope of protection defined by the claims.

Claims

1. A hydrogenation catalyst, characterized in that, Based on the mass of the catalyst, it includes 10%-30% molecular sieve, 20%-40% heteropolyacid compounds based on metal oxides, and the remainder is alumina; The heteropolyacid compound is Ni3[H4P2Mo] 12 Ni9O 56 [(L)7]、[{Ni(L)2}2Mo8O] 26 A mixture of Ni3[H4P2Mo] 12 Ni9O 56 [(L)7] and [{Ni(L)2}2Mo8O] 26 The molar ratio of [ ] is 1:(5-15); wherein L is at least one selected from acetate, 4-methyl-3,5-dihydroxybenzoate, and 3-amino-2,5-dihydroxybenzoate; the molecular sieve includes mesoporous ETS-10 molecular sieve; wherein the pore volume of the mesoporous ETS-10 molecular sieve is 0.25 cm³. 3 / g; The Ni3[H4P2Mo] 12 Ni9O 56 (L)7] is obtained by a preparation method including the following process: NaL, (NH4) 12 [H2P2Mo 12 O 48 The nickel salt and water are mixed evenly, the pH is adjusted to 2.2-2.6, and the mixture is kept at 80℃-100℃ for 1-3 hours to obtain the Ni3[H4P2Mo] 12 Ni9O 56 [(L)7], of which NaL and (NH4) 12 [H2P2Mo 12 O 48 The molar ratio of nickel salts is 10:1:15; and / or, The [{Ni(L)2}2Mo8O 26 It is obtained through a preparation method including the following processes: NaL, (NH4)6Mo7O 24 The nickel salt and water are mixed evenly, the pH is adjusted to 1.5-1.8, and the mixture is heated to boiling for 1-3 hours to obtain the [{Ni(L)2}2Mo8O] 26 ], including NaL, (NH4)6Mo7O 24 The molar ratio of nickel salt is 4:1:

2.

2. The hydrogenation catalyst according to claim 1, characterized in that, The catalyst has a diameter of 0.8 mm to 2.0 mm or greater than 2.5 mm.

3. The method for preparing the hydrogenation catalyst according to any one of claims 1-2, characterized in that, Includes the following steps: The pseudoboehmite, molecular sieve, and water are mixed evenly and then calcined to obtain the calcined product. The calcined product is impregnated in an impregnation solution containing heteropolyacid compounds and inorganic acids, and then dried to obtain the hydrogenation catalyst.

4. The preparation method according to claim 3, characterized in that, The roasting conditions are: temperature 400℃-550℃, time 2h-6h.

5. The preparation method according to claim 3, characterized in that, The impregnation conditions are: temperature 50℃-70℃, time 1h-3h.

6. The preparation method according to claim 3, characterized in that, The drying conditions are: temperature 100℃-150℃, time 2h-4h.

7. A hydrogenation method, characterized in that, include: The feedstock containing distillate oil is subjected to a hydrogenation reaction under the action of a catalyst to obtain a hydrogenated product; the catalyst includes the hydrogenation catalyst according to any one of claims 1-2 or the hydrogenation catalyst prepared by the preparation method according to any one of claims 3-6.

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