A titanium-based hydrogenation catalyst, its preparation method and application

Abstract

The present invention provides a titanium-based hydrogenation catalyst, a preparation method thereof and an application thereof. The titanium-based hydrogenation catalyst comprises a carrier and an active component supported on the surface of the carrier; the active component is a non-noble metal, the active component comprises a Ti active component and a promoter active metal component, and the promoter active metal component is selected from at least one of iron, cobalt, nickel, copper, zinc and molybdenum; based on the total mass of the titanium-based hydrogenation catalyst, the mass percentage content of the carrier is 50-85%, the mass percentage content of the Ti active component is 9-42%, and the mass percentage content of the promoter active metal component is 2-17%. The titanium-based hydrogenation catalyst of the present invention uses a non-noble metal as the active component, the raw materials are cheap and environmentally friendly, and the catalyst also has excellent hydrogenation activity and significant industrial value.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and particularly relates to a titanium-based hydrogenation catalyst, a preparation method thereof, and an application thereof. Background Art

[0002] Hydrodesulfurization and denitrification, as an important process in petroleum refining, have always been taken seriously. At present, the commonly used hydrogenation catalysts in industry are supported Co(Ni)Mo(W) catalysts. However, the active components of the existing catalysts are costly, and there are potential pollution hazards. Therefore, it is necessary to provide a hydrogenation catalyst with cheap raw materials and environmental friendliness. Summary of the Invention

[0003] The present invention provides a titanium-based hydrogenation catalyst, which uses non-precious metals as active components, has cheap raw materials and is environmentally friendly, and the catalyst also has excellent hydrogenation activity and significant industrial value.

[0004] The present invention provides a preparation method of a titanium-based hydrogenation catalyst for preparing the above-mentioned titanium-based hydrogenation catalyst. The preparation method has a simple process and is suitable for wide promotion and application.

[0005] The present invention provides a catalytic hydrogenation method for oils, which is carried out using the above-mentioned titanium-based catalyst. The catalytic hydrogenation method can achieve efficient desulfurization and denitrification.

[0006] The present invention provides a titanium-based hydrogenation catalyst, which includes a carrier and an active component supported on the surface of the carrier;

[0007] The active component is a non-precious metal, and the active component includes a Ti active component and a promoter active metal component. The promoter active metal component is selected from at least one of iron, cobalt, nickel, copper, zinc, and molybdenum;

[0008] Based on the total mass of the titanium-based hydrogenation catalyst, the mass percentage of the carrier is 50-85%, the mass percentage of the Ti active component is 9-42%, and the mass percentage of the promoter active metal component is 2-17%.

[0009] For the titanium-based hydrogenation catalyst as described above, the mass of the Ti active component is 2-5 times the mass of the promoter active component.

[0010] For the titanium-based hydrogenation catalyst as described above, the specific surface area of the titanium-based hydrogenation catalyst is 160-250 m 2 / g.

[0011] For the titanium-based hydrogenation catalyst as described above, the total pore volume of the titanium-based hydrogenation catalyst is 0.4-0.6 cm 3 / g.

[0012] The titanium-based hydrogenation catalyst as described above, wherein the promoter metal component includes zinc, and after the titanium-based hydrogenation catalyst is sulfided, it includes Ti2ZnS4 with a crystal space group of and / or Ti4ZnS8 with a crystal space group of R3; and / or,

[0013] The promoter metal component includes nickel, and after the titanium-based hydrogenation catalyst is sulfided, it includes at least one of Ti3NiS6 with a crystal space group of P31, Ti2NiS4 with a crystal space group of C12 / m1, and Ti4NiS8 with a crystal space group of C12 / m1; and / or,

[0014] The promoter metal component includes iron, and after the titanium-based hydrogenation catalyst is sulfided, it includes at least one of Ti3FeS6 with a crystal space group of P31, Ti2FeS4 with a crystal space group of C12 / m1, and Ti4FeS8 with a crystal space group of C12 / m1; and / or,

[0015] The promoter metal component includes copper, and after the titanium-based hydrogenation catalyst is sulfided, it includes Ti2CuS4 with a crystal space group of and at least one of Ti3CuS6 with a crystal space group of P31 and Ti8Cu3S with a crystal space group of C12 / m1; and / or, 16

[0016] The promoter metal component includes cobalt, and after the titanium-based hydrogenation catalyst is sulfided, it includes at least one of Ti3CoS6 with a crystal space group of R3, Ti4CoS8 with a crystal space group of C12 / m1, and Ti2CoS4 with a crystal space group of C12 / m1; and / or,

[0017] The promoter metal component includes molybdenum, and after the titanium-based hydrogenation catalyst is sulfided, it includes Ti(MoS2)2 with a crystal space group of C12 / m1.

[0018] The present invention provides a method for preparing the titanium-based hydrogenation catalyst as described above, which includes:

[0019] Dissolve the titanium source and the promoter metal source in a solvent, and perform ultrasonic oscillation treatment to obtain a solution;

[0020] Impregnate the solution on the carrier, and successively perform ultrasonic oscillation treatment, static treatment, drying treatment, and microwave calcination treatment to obtain the titanium-based hydrogenation catalyst;

[0021] wherein the mass ratio of the total mass of the titanium source and the promoter metal source to the mass of the carrier is 1:(0.5 - 4.0);

[0022] ​The mass ratio of the titanium source to the co-active metal source is (1.5 - 7.2):1.

[0023] The preparation method as described above, wherein the time of the ultrasonic oscillation treatment is 20 - 60 min; and / or,

[0024] The time of the static treatment is 1 - 10 h; and / or,

[0025] In the drying treatment, the temperature is 50 - 75 °C and the time is 5 - 15 h; and / or,

[0026] In the microwave calcination treatment, the temperature is 400 - 700 °C and the time is 0.5 - 3 h.

[0027] The preparation method as described above, wherein the solvent includes at least one of acetone and methyl ethyl ketone, and also includes at least one of ethanol and propanol.

[0028] The preparation method as described above, wherein the solvent includes acetone and ethanol, and the mass ratio of the acetone to the ethanol is (9 - 18):(2 - 5).

[0029] The present invention provides a catalytic hydrogenation method for oil products, wherein the catalytic hydrogenation reaction is carried out using the titanium-based hydrogenation catalyst as described above.

[0030] The catalytic hydrogenation method as described above, wherein in the catalytic hydrogenation reaction, the temperature is 260 - 420 °C, the hydrogen pressure is 2 - 10 MPa, the hydrogen-oil volume ratio is (200 - 800):1, and the weight hourly space velocity is 1.0 - 5.0 h -1 .

[0031] The present invention provides a titanium-based hydrogenation catalyst, which uses inexpensive non-noble metals as active components, has excellent hydrogenation activity when used in hydrogenation catalyst reactions, and the titanium-based hydrogenation catalyst also has the advantages of safety and environmental protection, and is suitable for wide promotion and application.

[0032] The present invention provides a preparation method of a titanium-based hydrogenation catalyst, which can prepare the above-mentioned titanium-based hydrogenation catalyst and has a simple process.

[0033] The present invention provides a catalytic hydrogenation method for oil products, which is carried out using the above-mentioned titanium-based catalyst. This catalytic hydrogenation method can achieve efficient desulfurization and denitrification and has excellent economic benefits. Detailed implementation mode

[0034] In order to make the above objects, features, and advantages of the embodiments of the present invention more apparent and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the scope of protection of the present invention.

[0035] The first aspect of the present invention provides a titanium-based hydrogenation catalyst, which includes a carrier and an active component supported on the surface of the carrier.

[0036] The active component is a non-noble metal, and the active component includes a Ti active component and a promoter active metal component. The promoter active metal component is selected from at least one of iron, cobalt, nickel, copper, zinc, and molybdenum.

[0037] Based on the total mass of the titanium-based hydrogenation catalyst, the mass percentage content of the carrier is 50-85%, the mass percentage content of the Ti active component is 9-42%, and the mass percentage content of the promoter active metal component is 2-17%.

[0038] The titanium-based hydrogenation catalyst of the present invention includes a carrier and an active component supported on the surface of the carrier.

[0039] The carrier is used to support the active component. The present invention does not make special limitations on the carrier. The carrier can be a commonly used carrier in the art. Exemplarily, the carrier can be selected from at least one of Al2O3, mesoporous molecular sieve, silicon carbide, diatomaceous earth, and natural clay.

[0040] The active component is used for the hydrogenation catalytic reaction. The active component of the present invention is a non-noble metal, and the active component includes the main active metal component Ti and at least one of the promoter active metal components iron, cobalt, nickel, copper, zinc, and molybdenum.

[0041] Exemplarily, the titanium-based hydrogenation catalyst of the present invention can include a carrier and a Ti active component and a copper active component supported on the surface of the carrier; or, the titanium-based hydrogenation catalyst of the present invention can include a carrier and a Ti active component, a zinc active component, and a copper active component supported on the surface of the carrier.

[0042] In the titanium-based hydrogenation catalyst of the present invention, the mass percentage content of the carrier is 50-85%, the mass percentage content of the Ti active component is 9-42%, and the mass percentage content of the promoter active metal component is 2-17%. The titanium-based hydrogenation catalyst with a specific composition is helpful for improving the efficiency of the hydrogenation catalytic reaction and the desulfurization and denitrification efficiency when used for the hydrogenation catalytic reaction. Moreover, the titanium-based hydrogenation catalyst of the present invention also has the advantages of safety and environmental protection and is suitable for wide promotion and application.

[0043] In some embodiments of the present invention, when the mass of the Ti active component is 2-5 times the mass of the co-active component, it helps to further improve the reaction activity of the titanium-based hydrogenation catalyst.

[0044] In some embodiments of the present invention, the specific surface area of the titanium-based hydrogenation catalyst is 160-250 m 2 / g.

[0045] When the specific surface area of the titanium-based hydrogenation catalyst is within the above range, the catalytic effect of the hydrogenation catalytic treatment can be further improved.

[0046] In some embodiments of the present invention, when the total pore volume of the titanium-based hydrogenation catalyst is 0.4-0.6 cm 3 / g, the titanium-based catalyst not only has a long service life but also has high catalytic activity.

[0047] When the titanium-based hydrogenation catalyst of the present invention is used for hydrogenation catalyst treatment, the titanium-based hydrogenation catalyst can be sulfurized first to improve the treatment effect of the hydrogenation catalytic treatment. Among them, the sulfurization treatment can be a commonly used sulfurization treatment in the art. And the inventors found in the research that when the sulfurized titanium-based hydrogenation catalyst has a special crystal space group, the catalytic effect of the hydrogenation catalytic treatment can be further improved.

[0048] Exemplarily, in some embodiments of the present invention, the co-active metal component includes zinc. After the titanium-based hydrogenation catalyst is sulfurized, it includes Ti2ZnS4 with a crystal space group of and / or Ti4ZnS8 with a crystal space group of R3; and / or,

[0049] The co-active metal component includes nickel. After the titanium-based hydrogenation catalyst is sulfurized, it includes at least one of Ti3NiS6 with a crystal space group of P31, Ti2NiS4 with a crystal space group of C12 / m1, and Ti4NiS8 with a crystal space group of C12 / m1; and / or,

[0050] The co-active metal component includes iron. After the titanium-based hydrogenation catalyst is sulfurized, it includes at least one of Ti3FeS6 with a crystal space group of P31, Ti2FeS4 with a crystal space group of C12 / m1, and Ti4FeS8 with a crystal space group of C12 / m1; and / or,

[0051] The co-active metal component includes copper. After the titanium-based hydrogenation catalyst is sulfurized, it includes Ti2CuS4 with a crystal space group of and / or at least one of Ti3CuS6 with a crystal space group of P31 and Ti8Cu3S with a crystal space group of C12 / m1; and / or, 16 and / or,

[0052] The promoter metal component includes cobalt. After the titanium-based hydrogenation catalyst is sulfided, it includes at least one of Ti3CoS6 with a crystal space group of R3, Ti4CoS8 with a crystal space group of C12 / m1, and Ti2CoS4 with a crystal space group of C12 / m1; and / or,

[0053] The promoter metal component includes molybdenum. After the titanium-based hydrogenation catalyst is sulfided, it includes Ti(MoS2)2 with a crystal space group of C12 / m1.

[0054] In some embodiments of the present invention, XRD can be used to obtain the crystal space group of the sulfided titanium-based hydrogenation catalyst.

[0055] The second aspect of the present invention provides a preparation method of the above-mentioned titanium-based hydrogenation catalyst, which includes:

[0056] Dissolve the titanium source and the promoter metal source in a solvent, and perform ultrasonic oscillation treatment to obtain a solution;

[0057] Impregnate the solution on the carrier, and successively perform ultrasonic oscillation treatment, static treatment, drying treatment, and microwave calcination treatment to obtain the titanium-based hydrogenation catalyst;

[0058] Wherein, the mass ratio of the total mass of the titanium source and the promoter metal source to the mass of the carrier is 1:(0.5 - 4.0);

[0059] The mass ratio of the titanium source to the promoter metal source is (1.5 - 7.2):1.

[0060] The preparation method of the titanium-based hydrogenation catalyst of the present invention specifically includes: dissolving a specific mass of the titanium source and the promoter metal source in a solvent, and then performing ultrasonic oscillation treatment to fully disperse the titanium source and the promoter metal source in the solvent to obtain a solution; then impregnating the solution on a specific mass of the carrier, performing ultrasonic oscillation treatment to more fully disperse the solution in the carrier, then performing static treatment to allow more active components in the solution to be impregnated in the carrier, then performing drying treatment to remove excess solvent and moisture, and finally performing microwave calcination treatment to obtain the titanium-based hydrogenation catalyst of the present invention.

[0061] The microwave calcination treatment of the present invention has the advantages of uniform heating, safety, and controllability, which helps to obtain a titanium-based hydrogenation catalyst with excellent performance.

[0062] The present invention does not particularly limit the titanium source, as long as it can provide titanium elements. Exemplarily, the titanium source can be tetrabutyl titanate.

[0063] The present invention does not particularly limit the promoter metal source, as long as it can provide the promoter metal component. Exemplarily, the promoter metal source can be selected from at least one of nitrates, sulfates, chlorides, organic acid salts, and phosphates including the promoter metal component.

[0064] In the present invention, when the carrier is a composite carrier of Al2O3 and MCM-41, the precursor of Al2O3, pseudoboehmite, can be crushed and mixed with MCM-41 to obtain the composite carrier of Al2O3 and MCM-41. In some embodiments, when in the composite carrier of Al2O3 and MCM-41, the mass ratio of pseudoboehmite (calculated based on containing 78.1% of Al2O3) to MCM-41 can be (5-15):(2-5).

[0065] The preparation method of the titanium-based hydrogenation catalyst of the present invention can prepare the above-mentioned titanium-based hydrogenation catalyst, and this preparation method is simple to operate.

[0066] In the present invention, various process parameters in the preparation process can be further selected to obtain a titanium-based hydrogenation catalyst with more excellent performance.

[0067] In some embodiments of the present invention, the time of ultrasonic oscillation treatment is 20-60 min; and / or,

[0068] The time of static treatment is 1-10 h; and / or,

[0069] In the drying treatment, the temperature is 50-75 °C and the time is 5-15 h; and / or,

[0070] In the microwave calcination treatment, the temperature is 400-700 °C and the time is 0.5-3 h.

[0071] Furthermore, the time of ultrasonic oscillation treatment is 25-45 min; and / or,

[0072] The time of static treatment is 2-5 h; and / or,

[0073] In the drying treatment, the temperature is 50-75 °C and the time is 5-10 h.

[0074] In some embodiments of the present invention, the solvent includes at least one of acetone and methyl ethyl ketone, and also includes at least one of ethanol and propanol.

[0075] Exemplarily, the solvent can be composed of acetone and ethanol, or can be composed of acetone, methyl ethyl ketone, and propanol. In the present invention, when the solvent is the above substances, the titanium source and the promoter metal source can be more fully dispersed, and thus a titanium-based hydrogenation catalyst with excellent performance can be obtained.

[0076] Further, when the solvent includes acetone and ethanol and the mass ratio of acetone to ethanol is (9 - 18):(2 - 5), the titanium source and the co-active metal source can be further dispersed, improving the comprehensive performance of the titanium-based hydrogenation catalyst.

[0077] The third aspect of the present invention provides a method for catalytic hydrogenation of oil products, wherein the above-mentioned titanium-based hydrogenation catalyst is used for the catalytic hydrogenation reaction.

[0078] The oil products of the present invention are not particularly limited, and the oil products can be heavy oil and / or diesel. Using the titanium-based hydrogenation catalyst of the present invention for the catalytic hydrogenation reaction of oil products helps to improve the efficiency of the catalytic hydrogenation reaction and the efficiency of desulfurization and denitrification.

[0079] In a specific embodiment, the titanium-based hydrogenation catalyst needs to be sulfided. The titanium-based hydrogenation catalyst of the present invention can also shorten the sulfiding time and improve the efficiency of catalytic hydrogenation.

[0080] In the present invention, the process parameters in the catalytic hydrogenation reaction can also be further selected to further improve the efficiency of the catalytic hydrogenation reaction. In some embodiments of the present invention, in the catalytic hydrogenation reaction, the temperature is 260 - 420 °C, the hydrogen pressure is 2 - 10 MPa, the hydrogen-oil volume ratio is (200 - 800):1, and the weight hourly space velocity is 1.0 - 5.0 h -1 。

[0081] Hereinafter, the technical solutions of the present invention will be introduced in detail through specific examples.

[0082] Example 1

[0083] The titanium-based hydrogenation catalyst of this example was prepared by a method including the following steps:

[0084] Take 20.42 g of tetrabutyl titanate and 8.92 g of zinc nitrate and dissolve them in a solvent composed of 102.87 g of acetone and 10.28 g of ethanol, perform ultrasonic oscillation treatment for 30 minutes to prepare a solution;

[0085] Dropwise add the solution onto a composite support composed of 40.14 g of pseudo-boehmite and 9.64 g of MCM-41, perform ultrasonic oscillation treatment for 30 minutes, stand for 2 hours, then perform drying treatment at a temperature of 60 °C for 9 hours, and perform microwave calcination treatment at a temperature of 500 °C for 2.5 hours to obtain a titanium-based hydrogenation catalyst;

[0086] The Optima 7300DV inductively coupled plasma atomic emission spectrometer (ICP-OES) was used to determine the mass percentage content of each component in the titanium-based hydrogenation catalyst. After testing, in the titanium-based hydrogenation catalyst, the total mass percentage content of titanium oxide and zinc oxide is 15.0%, the mass percentage content of titanium oxide is 10.0%, and the mass percentage content of zinc oxide is 5.0%.

[0087] Example 2

[0088] The titanium-based hydrogenation catalyst of this example was prepared by a method including the following steps:

[0089] 17.02 g of tetrabutyl titanate and 6.73 g of iron nitrate were dissolved in a solvent composed of 57.31 g of acetone and 5.73 g of ethanol, and ultrasonic oscillation treatment was carried out for 30 minutes to prepare a solution;

[0090] The solution was added dropwise to a composite support composed of 14.37 g of pseudo-boehmite and 3.74 g of MCM-41, ultrasonic oscillation treatment was carried out for 30 minutes, static treatment was carried out for 3 hours, then drying treatment was carried out at a temperature of 70 °C for 5 hours, and microwave calcination treatment was carried out at a temperature of 550 °C for 2 hours to obtain a titanium-based hydrogenation catalyst;

[0091] The method in Example 1 was used to test the content of each component in the titanium-based hydrogenation catalyst. After testing, in the titanium-based hydrogenation catalyst, the total mass percentage content of titanium oxide and iron oxide is 20.0%, the mass percentage content of titanium oxide is 15.0%, and the mass percentage content of iron oxide is 5.0%.

[0092] Example 3

[0093] The titanium-based hydrogenation catalyst of this example was prepared by a method including the following steps:

[0094] 17.02 g of tetrabutyl titanate and 3.02 g of copper nitrate were dissolved in a solvent composed of 36.97 g of acetone and 3.69 g of ethanol, and ultrasonic oscillation treatment was carried out for 30 minutes to prepare a solution;

[0095] The solution was added dropwise to a composite support composed of 14.37 g of pseudo-boehmite and 3.74 g of MCM-41, ultrasonic oscillation treatment was carried out for 30 minutes, static treatment was carried out for 4 hours, then drying treatment was carried out at a temperature of 60 °C for 7 hours, and microwave calcination treatment was carried out at a temperature of 600 °C for 1 hour to obtain a titanium-based hydrogenation catalyst;

[0096] The method in Example 1 was used to test the content of each component in the titanium-based hydrogenation catalyst. After testing, in the titanium-based hydrogenation catalyst, the total mass percentage content of titanium oxide and copper oxide is 25.0%, the mass percentage content of titanium oxide is 20.0%, and the mass percentage content of copper oxide is 5.0%.

[0097] Example 4

[0098] The titanium-based hydrogenation catalyst of this example is prepared by a method including the following steps:

[0099] Take 20.42 g of tetrabutyl titanate, 3.30 g of iron nitrate and 2.18 g of nickel nitrate and dissolve them in a solvent composed of 87.77 g of acetone and 8.77 g of ethanol, perform ultrasonic oscillation treatment for 30 minutes to prepare a solution;

[0100] Dropwise add the solution onto a composite support composed of 34.55 g of pseudo-boehmite and 6.75 g of MCM-41, perform ultrasonic oscillation treatment for 30 minutes, let it stand for 4 hours, then perform drying treatment at a temperature of 65 °C for 7 hours, and perform microwave calcination treatment at a temperature of 500 °C for 2.5 hours to obtain the titanium-based hydrogenation catalyst;

[0101] Use the method in Example 1 to test the content of each component in the titanium-based hydrogenation catalyst. After detection, in the titanium-based hydrogenation catalyst, the total mass percentage content of titanium oxide and cobalt oxide is 15.0%, the mass percentage content of titanium oxide is 12.08%, the mass percentage content of iron oxide is 1.51%, and the mass percentage content of nickel oxide is 1.41%.

[0102] Example 5

[0103] The titanium-based hydrogenation catalyst of this example is prepared by a method including the following steps:

[0104] Take 20.42 g of tetrabutyl titanate, 1.81 g of copper nitrate and 3.03 g of iron nitrate and dissolve them in a solution composed of 62.33 g of acetone and 6.23 g of ethanol, perform ultrasonic oscillation treatment for 30 minutes to prepare a solution;

[0105] Dropwise add the solution onto a composite support composed of 24.54 g of pseudo-boehmite and 4.79 g of MCM-41, perform ultrasonic oscillation treatment for 30 minutes, let it stand for 3 hours, then perform drying treatment at a temperature of 70 °C for 5 hours, and perform microwave calcination treatment at a temperature of 550 °C for 2 hours to obtain the titanium-based hydrogenation catalyst;

[0106] Use the method in Example 1 to test the content of each component in the titanium-based hydrogenation catalyst. After detection, in the titanium-based hydrogenation catalyst, the total mass percentage content of titanium oxide, copper oxide and iron oxide is 20.0%, the mass percentage content of titanium oxide is 16.0%, the mass percentage content of copper oxide is 2.0%, and the mass percentage content of iron oxide is 2.0%.

[0107] Example 6

[0108] The titanium-based hydrogenation catalyst of this example is prepared by a method including the following steps:

[0109] Take 20.42 g of tetrabutyl titanate, 2.98 g of zinc nitrate and 1.45 g of nickel nitrate and dissolve them in a solvent composed of 46.53 g of acetone and 4.65 g of ethanol, perform ultrasonic oscillation treatment for 25 minutes to prepare a solution;

[0110] Dropwise add the solution onto a composite support composed of 18.32 g of pseudo-boehmite and 3.58 g of MCM-41, perform ultrasonic oscillation treatment for 25 minutes, stand for 4 hours, then perform drying treatment at a temperature of 60 °C for 7 hours, and perform microwave calcination treatment at a temperature of 600 °C for 1 hour to obtain the titanium-based hydrogenation catalyst;

[0111] Use the method in Example 1 to test the content of each component in the titanium-based hydrogenation catalyst. After detection, in the titanium-based hydrogenation catalyst, the total mass percentage content of titanium oxide, zinc oxide and nickel oxide is 25.0%, the mass percentage content of titanium oxide is 20.0%, the mass percentage content of zinc oxide is 3.33%, and the mass percentage content of nickel oxide is 1.57%.

[0112] Example 7

[0113] The titanium-based hydrogenation catalyst of this example is prepared by a method including the following steps:

[0114] Take 20.42 g of tetrabutyl titanate, 4.04 g of iron nitrate and 1.46 g of cobalt nitrate and dissolve them in a solvent composed of 46.58 g of acetone and 4.65 g of ethanol, perform ultrasonic oscillation treatment for 25 minutes to prepare a solution;

[0115] Dropwise add the solution onto a composite support composed of 18.34 g of pseudo-boehmite and 3.58 g of MCM-41, perform ultrasonic oscillation treatment for 25 minutes, stand for 4 hours, then perform drying treatment at a temperature of 60 °C for 7 hours, and perform microwave calcination treatment at a temperature of 600 °C for 1 hour to obtain the titanium-based hydrogenation catalyst;

[0116] Use the method in Example 1 to test the content of each component in the titanium-based hydrogenation catalyst. After detection, in the titanium-based hydrogenation catalyst, the total mass percentage content of titanium oxide, iron oxide and cobalt oxide is 25.0%, the mass percentage content of titanium oxide is 20.0%, the mass percentage content of iron oxide is 3.35%, and the mass percentage content of cobalt oxide is 1.65%.

[0117] Example 8

[0118] The titanium-based hydrogenation catalyst of this example is prepared by a method including the following steps:

[0119] Take 20.42 g of tetrabutyl titanate, 2.21 g of copper nitrate, 1.49 g of zinc nitrate and 1.45 g of nickel nitrate and dissolve them in a solvent composed of 46.60 g of acetone and 4.66 g of ethanol, and perform ultrasonic oscillation treatment for 25 minutes to prepare a solution;

[0120] Dropwise add the solution onto a composite support composed of 18.35 g of pseudo-boehmite and 3.58 g of MCM-41, perform ultrasonic oscillation treatment for 25 minutes, stand for 4 hours, then perform drying treatment at a temperature of 60 °C for 7 hours, and perform microwave calcination treatment at a temperature of 600 °C for 1 hour to obtain a titanium-based hydrogenation catalyst;

[0121] Use the method in Example 1 to test the content of each component in the titanium-based hydrogenation catalyst. After detection, in the titanium-based hydrogenation catalyst, the total mass percentage content of titanium oxide, copper oxide, zinc oxide and nickel oxide is 25.0%, the mass percentage content of titanium oxide is 20.0%, the mass percentage content of copper oxide is 1.67%, the mass percentage content of zinc oxide is 1.70%, and the mass percentage content of nickel oxide is 1.57%.

[0122] Example 9

[0123] The titanium-based hydrogenation catalyst of this example is prepared by a method including the following steps:

[0124] Take 20.42 g of tetrabutyl titanate and 17.85 g of zinc nitrate and dissolve them in a solvent composed of 72.54 g of acetone and 7.28 g of ethanol, and perform ultrasonic oscillation treatment for 30 minutes to prepare a solution;

[0125] Dropwise add the solution onto a composite support composed of 28.42 g of pseudo-boehmite and 6.83 g of MCM-41, perform ultrasonic oscillation treatment for 30 minutes, stand for 3 hours, then perform drying treatment at a temperature of 65 °C for 5 hours, and perform microwave calcination treatment at a temperature of 550 °C for 1 hour to obtain a titanium-based hydrogenation catalyst;

[0126] Use the method in Example 1 to test the content of each component in the titanium-based hydrogenation catalyst. After detection, in the titanium-based hydrogenation catalyst, the total mass percentage content of titanium oxide and zinc oxide is 25.0%, the mass percentage content of titanium oxide is 12.4%, and the mass percentage content of zinc oxide is 12.6%.

[0127] Comparative Example 1

[0128] The titanium-based hydrogenation catalyst of this comparative example is prepared by a method including the following steps:

[0129] Take 17.02 g of tetrabutyl titanate and dissolve it in a solvent composed of 28.10 g of acetone and 2.81 g of ethanol, and perform ultrasonic oscillation treatment for 30 minutes to prepare a solution;

[0130] The solution was added dropwise to a composite support composed of 11.50 g of pseudo-boehmite and 2.99 g of MCM-41, followed by ultrasonic oscillation treatment for 30 minutes, static treatment for 2 hours, then drying treatment at 60 °C for 8 hours, and microwave calcination treatment at 500 °C for 2.5 hours to obtain a titanium-based hydrogenation catalyst;

[0131] The method in Example 1 was used to test the contents of each component in the titanium-based hydrogenation catalyst. After detection, the mass percentage content of titanium oxide in the titanium-based hydrogenation catalyst was 25.0%.

[0132] Comparative Example 2

[0133] The titanium-based hydrogenation catalyst of this comparative example was prepared by a method including the following steps:

[0134] 3.81 g of tetrabutyl titanate and 2.69 g of iron nitrate were dissolved in a solvent composed of 108.88 g of acetone and 10.88 g of ethanol, followed by ultrasonic oscillation treatment for 30 minutes to prepare a solution;

[0135] The solution was added dropwise to a composite support composed of 43.20 g of pseudo-boehmite and 6.75 g of MCM-41, followed by ultrasonic oscillation treatment for 30 minutes, static treatment for 3 hours, then drying treatment at 65 °C for 5 hours, and microwave calcination treatment at 550 °C for 1 hour to obtain a titanium-based hydrogenation catalyst;

[0136] The method in Example 1 was used to test the contents of each component in the titanium-based hydrogenation catalyst. After detection, the total mass percentage content of titanium oxide and iron oxide in the titanium-based hydrogenation catalyst was 5.0%, the mass percentage content of titanium oxide was 3.7%, and the mass percentage content of iron oxide was 1.3%.

[0137] Performance Test

[0138] 1. The BET surface area and total pore volume of the hydrogenation catalysts in the examples and comparative examples were tested using a Micromeritics ASAP 2010 surface area analyzer. The test results are shown in Table 1;

[0139] The specific test method included: subjecting the hydrogenation catalyst to vacuum degassing pretreatment at 300 °C for 2 h, and testing using the BJH method.

[0140] Table 1

[0141] <![CDATA[Specific surface area, m 2 / g]]> <![CDATA[Total pore volume, cm 3 / g]]> Example 1 225 0.571 Example 2 211 0.531 Example 3 204 0.525 Example 4 219 0.577 Example 5 208 0.511 Example 6 195 0.494 Example 7 192 0.489 Example 8 197 0.496 Example 9 218 0.566 Comparative Example 1 181 0.478 Comparative Example 2 236 0.596

[0142] As can be seen from Table 1, the titanium-based hydrogenation catalyst in the present invention has a comparable BET surface area and total pore volume to those of the comparative examples, and with the increase in the content of the active component, the BET surface area and total pore volume of the catalyst decrease.

[0143] 2. Use the titanium-based hydrogenation catalysts in the examples and comparative examples to conduct hydrocatalytic treatment on coker diesel respectively, and calculate the desulfurization rate and denitrification rate. The results are shown in Table 2. The specific gravity (d4 20 ) of coker diesel is 0.8532 (the relative density of coker diesel at 20 °C to water at 4 °C), the sulfur content is 952 ppm, and the total nitrogen content is 819 ppm;

[0144] Specifically, it includes:

[0145] First, sulfide the titanium-based hydrogenation catalyst, and then use the sulfided titanium-based hydrogenation catalyst to conduct hydrocatalytic treatment on coker diesel;

[0146] Among them, in the sulfidation treatment, the sulfiding oil is a n-decane solution containing 5 wt% CS2, the temperature of the sulfidation treatment is 320 °C, the pressure is 4 MPa, and the weight hourly space velocity is 1.5 h -1 , and the hydrogen-oil volume ratio is 300:1;

[0147] In the hydrocatalytic treatment, use a high-temperature and high-pressure hydro-microreactor with an inner diameter of 10 mm and a tube length of 500 mm, the temperature is 380 °C, the pressure is 4 MPa, and the weight hourly space velocity is 4.0 h -1 , the hydrogen-oil volume ratio is 400:1, and the mass of the hydrogenation catalyst is 2 g;

[0148] Adopt the D8 Focus type X-ray diffractometer of Bruker Company in Germany to conduct XRD tests on the sulfided hydrogenation catalyst to obtain the crystal space group of the sulfided hydrogenation catalyst. The results are shown in Table 2. The test conditions of XRD are: the working voltage of the Cu target X-ray tube is 40.0 kV, the working current is 40.0 mA, and the angle scanning range is 5° - 95°.

[0149] Table 2

[0150]

[0151] It can be seen from Table 2 that when the titanium-based hydrogenation catalyst in the examples of the present invention is used for catalytic hydrogenation treatment of coker diesel, it has a high desulfurization rate and denitrification rate.

[0152] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A titanium-based hydrogenation catalyst, characterized in that, The precursor of the titanium-based hydrogenation catalyst comprises a carrier and an active component supported on the surface of the carrier; The active component is a non-noble metal, and the active component comprises a Ti active component and a promoter active metal component. The promoter active metal component is zinc, or iron and nickel, or iron and copper, or iron and cobalt, or copper, zinc and nickel; Based on the total mass of the precursor of the titanium-based hydrogenation catalyst, the mass percentage of the carrier is 50-85%, the mass percentage of the Ti active component is 9-42%, and the mass percentage of the promoter active metal component is 2-17%; The titanium-based hydrogenation catalyst is obtained by subjecting the precursor of the titanium-based hydrogenation catalyst to a sulfidation treatment; The mass of the Ti active component is 2-5 times the mass of the promoter active component; The promoter metal component includes zinc, and the titanium-based hydrogenation catalyst includes Ti2ZnS4 with a crystal space group of ; The promoter active metal component comprises nickel, and the titanium-based hydrogenation catalyst comprises at least one of Ti2NiS4 with a crystal space group of C12 / m1 and Ti4NiS8 with a crystal space group of C12 / m1; The promoter active metal component comprises iron, and the titanium-based hydrogenation catalyst comprises at least one of Ti2FeS4 with a crystal space group of C12 / m1 and Ti4FeS8 with a crystal space group of C12 / m1; The promoter metal component includes copper, and the titanium-based hydrogenation catalyst includes at least one of Ti2CuS4 with a crystal space group of and Ti8Cu3S with a crystal space group of C12 / m1 16 ; The promoter active metal component comprises cobalt, and the titanium-based hydrogenation catalyst comprises at least one of Ti4CoS8 with a crystal space group of C12 / m1 and Ti2CoS4 with a crystal space group of C12 / m1; The preparation method of the precursor of the titanium-based hydrogenation catalyst comprises: Dissolving a titanium source and a promoter active metal source in a solvent, and performing ultrasonic oscillation treatment to obtain a solution; Impregnating the solution on the carrier, and successively performing ultrasonic oscillation treatment, static treatment, drying treatment and microwave calcination treatment to obtain the precursor of the titanium-based hydrogenation catalyst; in the microwave calcination treatment, the temperature is 400-700 °C and the time is 0.5-3 h.

2. The titanium-based hydrogenation catalyst according to claim 1, wherein The specific surface area of the titanium-based hydrogenation catalyst is 160-250 m 2 / g; and / or, The total pore volume of the titanium-based hydrogenation catalyst is 0.4-0.6 cm 3 / g.

3. The titanium-based hydrogenation catalyst according to claim 1, wherein The preparation method of the precursor of the titanium-based hydrogenation catalyst comprises: The mass ratio of the total mass of the titanium source and the promoter active metal source to the mass of the carrier is 1:(0.5-4.0); The mass ratio of the titanium source to the promoter active metal source is (1.5-7.2):

1.

4. The titanium-based hydrogenation catalyst according to claim 3, characterized in that, The time of the ultrasonic oscillation treatment is 20-60 min; and / or, The time of the static treatment is 1-10 h; and / or, In the drying treatment, the temperature is 50-75 °C and the time is 5-15 h.

5. The titanium-based hydrogenation catalyst according to claim 3 or 4, characterized in that, The solvent comprises acetone and ethanol.

6. The titanium-based hydrogenation catalyst according to claim 5, wherein The mass ratio of the acetone to the ethanol is (9-18):(2-5).

7. A catalytic hydrogenation method for an oil product, characterized in that, Use the titanium-based hydrogenation catalyst according to any one of claims 1-6 for catalytic hydrogenation reaction.

8. The catalytic hydrogenation method according to claim 7, wherein In the catalytic hydrogenation reaction, the temperature is 260 - 420 °C, the hydrogen pressure is 2 - 10 MPa, the hydrogen-oil volume ratio is (200 - 800):1, and the weight hourly space velocity is 1.0 - 5.0 h -1 .

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