Ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst and preparation and application thereof

Abstract

The invention belongs to the technical field of catalysts, and particularly relates to a ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst and preparation and application thereof. The bifunctional catalyst comprises a ruthenium-based bimetal oxide and a mesoporous molecular sieve, the mass ratio of the ruthenium-based bimetal oxide to the mesoporous molecular sieve is (4: 1)-(1: 4), a metal additive M in the ruthenium-based bimetal oxide is selected from one or more of transition metal and rare earth metal, and the doped metal additive M not only can improve the distribution state of Ru metal electrons, but also can improve the catalytic activity of the mesoporous molecular sieve. The selectivity of part of products can be regulated and controlled; when the catalyst is applied to a reaction system for directly producing aviation kerosene from synthesis gas, the CO conversion rate is up to 50.5%, the CH4 selectivity is 6.7%, the C5 + selectivity is up to 76.4%, the C8-C16 selectivity is up to 53.5%, the isomerization ratio is 3.3, and the requirement of a process for directly producing aviation kerosene from synthesis gas can be well met.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysts, and specifically relates to a ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst and its preparation and application. Background Art

[0002] In recent years, with the global economic recovery and the rapid development of the world's aviation transportation industry, the annual consumption of global aviation kerosene has reached 1.5-1.7*10 9 barrels, China's demand for aviation kerosene is also huge, and it is showing an increasing trend year by year. In 2025, the consumption will reach 4.9*1.03 million tons. At present, aviation fuel mainly comes from traditional fossil fuels, which is unsustainable. In addition, aviation fuel carbon emissions account for a large proportion of the total carbon emissions of the aviation industry, accounting for about 2-3% of the total carbon footprint. It is crucial to reduce carbon emissions and emissions in the aviation industry, and new alternative production processes must be found. Therefore, the development of alternative technologies for the preparation of aviation kerosene is favored by researchers from all over the world.

[0003] The production of aviation fuel from syngas is an important reaction for the production of green fuel alternatives. It is also one of the important ways to prepare clean fuels and high value-added chemicals from non-petroleum sources such as coal, natural gas, and biomass. The difficulty of producing aviation kerosene by direct Fischer-Tropsch synthesis of syngas under the action of catalysts is that the product distribution is greatly affected by the chain growth factor ɑ. 8 ~C 16 Theoretically, the maximum fraction selectivity is only 41%. The key technology lies in the development of an improved dual-function Fischer-Tropsch catalyst that can simultaneously realize the hydrogenation of CO to generate long-chain hydrocarbons and the secondary hydrocracking / isomerization reaction on the acidic site of the molecular sieve to increase the C content of aviation kerosene. 8 ~C 16 Fraction selectivity, with the potential for development in large-scale industry.

[0004] The catalyst Co-M / Y described in patent CN110368983A is at 250°C, 2.0MPa, W / F=10ghmol -1 , H 2 / CO (v / v) = 1.0, CO conversion rate 31 ~ 40%, methane selectivity 9.5 ~ 12%, C 8 ~C 16 The selectivity is 43.1-72%, the isomerization ratio is 0.5-3.3, and the ASF product distribution of the Fischer-Tropsch reaction can be broken to obtain a highly selective aviation kerosene fraction. The catalyst Fe-M / ZnCrOx / HZSM-5 described in patent CN116870954A is at 275°C, 2.0MPa, WHSV=500mL / gh -1 , H 2 / CO (v / v) = 2.0, CO conversion rate is 13.7-37.4%, CO2 Selectivity 41.9~50.2%, C 8 ~C 16 Selectivity 55.2~64.6%, among which C 8 -C 12 Aromatic selectivity 30.2~49.8%, but CO 2 The selectivity is as high as 41.9%.

[0005] The above-mentioned synthesis gas is used to produce aviation kerosene through Co and Fe-based catalysts. Although the aviation kerosene selectivity can break through the ASF product distribution and obtain a highly selective aviation kerosene fraction, CH 4 Higher selectivity, or CO 2 High selectivity. The activity and stability of traditional Ru-based catalysts are limited by the ASF (Anderson-Schulz-Flory) carbon chain growth mechanism. The selectivity of heavy hydrocarbons in the Fischer-Tropsch synthesis products is high and the product distribution is wide. The selectivity of isomerized hydrocarbon-rich liquid fuels is low and is affected by many factors: such as Ru particle size, additives, active phase size and proximity. The added metal additives can not only improve the Ru metal electron distribution, but also regulate the selectivity of some products. For example, metal Mn can not only improve the CO hydrogenation activity and C by adjusting the Ru atomic dispersion, but also improve the selectivity of some products. 5 + selectivity, and can also improve olefin selectivity and inhibit the formation of methane. Metal Zr can adjust the surface acidity of the carrier and promote the surface RuO 2 Species enrichment, low-content Zr introduction can also increase C 5 + Selectivity. Alkali metal K can promote CO adsorption and dissociation by providing electrons to the surface, increase the selectivity of low-carbon hydrocarbons and the activity of water-gas shift reaction, etc.

[0006] In order to regulate the product distribution, it is necessary to couple the processes of hydrocracking and isomerization. Only through secondary reactions can suitable motor oil or aviation fuel be obtained. Therefore, it is necessary to develop a multifunctional catalyst with excellent performance to increase the C content of aviation fuel in the Fischer-Tropsch product. 8-16 Fraction selectivity has become a hot topic in solving the current shortage of aviation fuel. Summary of the invention

[0007] When a traditional ruthenium (Ru)-based catalyst is used for the Fischer-Tropsch reaction, the product is limited by the ASF (Anderson-Schulz-Flory) carbon chain growth mechanism. The selectivity of heavy hydrocarbons in the Fischer-Tropsch synthesis product is high and the product distribution is wide, and the selectivity of isomerized hydrocarbon-rich liquid fuel is low. In order to effectively regulate the selectivity of the product, the present invention adopts a new strategy, namely, by adding a metal additive M to adjust the chemical state, metal dispersion, surface electronic distribution, mesoporous molecular sieve acidity of the active metal Ru, improve the blending particles and proximity between active components, component mass ratio, etc., which can better break through the ASF distribution limitation of the Fischer-Tropsch synthesis product and obtain a highly selective target product.

[0008] In order to achieve the above-mentioned object and other related objects, the present invention provides a ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst, comprising a Ru-M ruthenium-based bimetallic oxide and a mesoporous molecular sieve, wherein the mass ratio of the Ru-M ruthenium-based bimetallic oxide to the mesoporous molecular sieve is (4:1) to (1:4), and the carrier of the Ru-M ruthenium-based bimetallic oxide is selected from SiO 2 、Al 2 O 3 、TiO 2 One or more of the above, wherein the mesoporous molecules are selected from one or more of mesoporous-ZSM-5, mesoporous-Y, and mesoporous-Beta.

[0009] The present invention also provides a method for preparing the ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst as described above, comprising the steps of: grinding and blending the Ru-M ruthenium-based bimetallic oxide and the mesoporous molecular sieve separately to obtain the ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst.

[0010] The present invention also provides a use of the ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst as described above in direct production of aviation kerosene by hydrogenation of synthesis gas.

[0011] The present invention also provides a method for directly preparing aviation kerosene by hydrogenating synthesis gas, wherein the ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst as described above is reduced, and then H is introduced. 2 / CO / N 2 The mixed gas is reacted to prepare aviation kerosene.

[0012] As described above, the present invention has the following beneficial effects:

[0013] 1. The improved Fischer-Tropsch catalyst developed by the present invention, a ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst, the added metal additive M can not only improve the electronic distribution state of Ru metal, but also regulate the selectivity of some products.

[0014] 2. The present invention adopts a co-impregnation method to prepare Ru-M ruthenium-based bimetallic oxide, and then precisely matches and couples it with a mesoporous molecular sieve to prepare a ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst, which can not only improve the synthesis gas conversion rate, but also improve the selectivity of aviation kerosene fractions.

[0015] 3. When the ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst provided by the present invention is used to directly produce aviation kerosene from synthesis gas, the CO conversion rate reaches 50.5%, and CH 4 Selectivity 6.7%, C 5 + The selectivity reached 76.4%, of which the selectivity of aviation kerosene reached 53.6%, C 8 -C 16 The isomerization ratio in the fraction is 3.3, which can better meet the requirements of the direct production of aviation kerosene by CO hydrogenation. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 The Ru-M / SiO particles after blending in Example 1 2 & Chromatographic distribution diagram of the composition analysis of the oil phase product obtained by hydrogenating syngas to aviation kerosene over mesoporous-ZSM-5 catalyst.

[0017] Figure 2 The Ru-M / SiO particles after blending in Example 1 2 &Picture of oil phase products obtained by hydrogenating syngas to jet fuel over mesoporous-ZSM-5 catalyst. DETAILED DESCRIPTION

[0018] The following describes the embodiments of the present invention through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention.

[0019] Please refer to the attached drawings. It should be noted that the illustrations provided in this embodiment are only used to illustrate the basic concept of the present invention in a schematic manner, and the drawings only show the components related to the present invention rather than the number, shape and size of the components in actual implementation. In actual implementation, the type, quantity and proportion of each component may be changed arbitrarily, and the component layout may also be more complicated.

[0020] The first aspect of the present invention provides a ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst, comprising a Ru-M ruthenium-based bimetallic oxide and a mesoporous molecular sieve, wherein the mass ratio of the Ru-M ruthenium-based bimetallic oxide to the mesoporous molecular sieve is (4:1) to (1:4), and the metal M in the Ru-M ruthenium-based bimetallic oxide is selected from one or more of transition metals or rare earth metals; the carrier in the Ru-M ruthenium-based bimetallic oxide is selected from SiO 2 、Al 2 O 3 、TiO 2 One or more of the mesoporous molecules are selected from one or more of mesoporous-ZSM-5, mesoporous-Y, and mesoporous-Beta.

[0021] Wherein, the mass ratio of the Ru-M ruthenium-based bimetallic oxide to the mesoporous molecular sieve can be (4:1) to (3:1), (3:1) to (2:1), (2:1) to (1:1), (1:1) to (1:2), (1:2) to (1:3) or (1:3) to (1:4). In a preferred embodiment of the present invention, the mass ratio of the Ru-M ruthenium-based bimetallic oxide to the mesoporous molecular sieve is (4:1) to (1:2), more preferably (2:1) to (1:1).

[0022] In the bifunctional catalyst of the present invention, the transition metal is selected from one or more of Mn, Zn, and Zr; the rare earth metal is selected from one or more of La and Ce; that is, M in the Ru-M ruthenium-based bimetallic oxide is selected from one or more of Mn, Zn, Zr, La, and Ce. In a preferred embodiment of the present invention, M in the Ru-M ruthenium-based bimetallic oxide is selected from one or more of Mn, Zn, and La.

[0023] In the bifunctional catalyst of the present invention, the mass ratio of metal Ru / M in the Ru-M ruthenium-based bimetallic oxide is (1-6): 3 (based on the mass of the carrier, unit: g), for example, (1-2): 3, (2-3): 3, (3-4): 3, (4-5): 3 or (5-6): 3. In a preferred embodiment of the present invention, the mass ratio of metal Ru / M in the Ru-M ruthenium-based bimetallic oxide is (1-3): 3 (based on the mass of the carrier, unit: g).

[0024] In the bifunctional catalyst of the present invention, the mass ratio of the total mass of the ruthenium source and the metal M source to the carrier is (4-11):10, which can be (4-5):10, (5-6):10, (6-7):10, (7-8):10, (8-9):10, (9-10):10 or (10-11):10.

[0025] In the bifunctional catalyst of the present invention, the particle size of the Ru-M ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst is 20 to 120 meshes, for example, 20 to 30 meshes, 30 to 40 meshes, 40 to 50 meshes, 50 to 60 meshes, 60 to 70 meshes, 70 to 80 meshes, 80 to 90 meshes, 90 to 100 meshes, 100 to 110 meshes or 110 to 120 meshes.

[0026] In the bifunctional catalyst of the present invention, the Ru-M ruthenium-based bimetallic oxide is prepared by a co-impregnation method. The carrier used in the co-impregnation method is selected from SiO 2 、Al 2 O 3 、TiO 2 In a preferred embodiment of the present invention, the carrier used in the impregnation method is SiO 2 , with a specific surface area of ​​100 to 480 m 2 / g, for example, 100 to 150 m 2 / g, 150~200m 2 / g, 200~250m 2 / g, 250~300m 2 / g, 300~350m 2 / g, 350~400m 2 / g, 400~450m 2 / g, 450~480m 2 In a preferred embodiment of the present invention, the specific surface area is 300 to 480 m 2 / g.

[0027] In the bifunctional catalyst of the present invention, the mesoporous molecular sieve is treated with hydrogen; specifically, the mesoporous-ZSM-5 molecular sieve is derived from mesoporous-HZSM-5; the mesoporous-Y molecular sieve is derived from mesoporous-HY, for example, it can be H-USY molecular sieve; the mesoporous-Beta molecular sieve is derived from mesoporous-HBeta. In a preferred embodiment of the present invention, the mesoporous molecular sieve is derived from mesoporous-HZSM-5.

[0028] The SiO in the mesoporous ZSM-5 molecular sieve 2 / Al 2 O 3The molar ratio is 25 to 300. For example, 25 to 35, 35 to 45, 45 to 55, 55 to 65, 65 to 75, 75 to 85, 85 to 95, 95 to 100, 100 to 120, 120 to 140, 140 to 160, 160 to 180, 180 to 200, 200 to 220, 220 to 240, 240 to 260, 260 to 280 or 280 to 300. In some embodiments of the present invention, the SiO 2 / Al 2 O 3 The molar ratio is 25-200, preferably 25-150, more preferably 25-100, further preferably 25-75, and even more preferably 25-50.

[0029] The second aspect of the present invention provides a method for preparing the ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst as described above, comprising the steps of: grinding and blending the Ru-M ruthenium-based bimetallic oxide and the mesoporous molecular sieve separately to obtain the ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst.

[0030] In the preparation method of the present invention, the mass ratio of the Ru-M ruthenium-based bimetallic oxide to the mesoporous molecular sieve is (4:1) to (1:4), for example, (4:1) to (3:1), (3:1) to (2:1), (2:1) to (1:1), (1:1) to (1:2), (1:2) to (1:3) or (1:3) to (1:4).

[0031] In the preparation method of the present invention, the grinding is grinding to 40-60 mesh, for example, 40-50 mesh or 50-60 mesh. In a preferred embodiment of the present invention, tableting is also included before grinding, that is, Ru-M ruthenium-based bimetallic oxide and mesoporous molecular sieve are respectively tableted and then ground to 40-60 mesh.

[0032] In the preparation method of the present invention, the preparation method of the Ru-M ruthenium-based bimetallic oxide comprises: dissolving a ruthenium source and a metal M source in a solvent to form a mixed solution A, placing a carrier in a round-bottom flask, and then slowly dripping the mixed solution A into the carrier, stirring and impregnating, washing, drying, and calcining to obtain the Ru-M ruthenium-based bimetallic oxide.

[0033] The concentration of the ruthenium (Ru) source in the solution A is 0.5 to 2.0 mol / L, for example, 0.5 to 1.0 mol / L, 1.0 to 1.5 mol / L, or 1.5 to 2.0 mol / L.

[0034] The concentration of the metal M source in the solution A is 0.1 to 0.5 mol / L, for example, 0.1 to 0.2 mol / L, 0.2 to 0.3 mol / L, 0.3 to 0.4 mol / L, or 0.4 to 0.5 mol / L.

[0035] The mass of the carrier is 6 to 20 g, for example, 6 to 10 g, 10 to 15 g, or 15 to 20 g.

[0036] The mass ratio of the total mass of the ruthenium source and the metal M source to the carrier is (4-11):10, for example (4-4.5):10, (4.5-5.0):10, (5.0-6.0):10, (6.0-8.0):10 or (8.0-11):10.

[0037] Wherein, the ruthenium source is selected from one or more of ruthenium nitrosyl nitrate, ruthenium chloride, and ruthenium acetylacetonate;

[0038] The metal M source is selected from one or more of nitrates, chlorides or acetates of M;

[0039] The solvent is deionized water.

[0040] The co-impregnation temperature is 25-40°C, for example, 25-30°C, 30-35°C or 35-40°C.

[0041] The co-immersion time is 24 to 48 hours, for example 24 to 36 hours, 36 to 48 hours.

[0042] The drying temperature is 60-80°C, for example, 60-65°C, 65-70°C, 70-75°C or 75-80°C.

[0043] The drying time is 12 to 24 hours, for example 12 to 16 hours, 16 to 20 hours or 20 to 24 hours.

[0044] The calcination temperature is 200-400°C, for example, 200-220°C, 220-240°C, 240-260°C, 260-280°C, 280-300°C, 300-320°C, 320-340°C, 340-360°C, 360-380°C or 380-400°C.

[0045] The calcination time is 4 to 6 hours, for example 4 to 5 hours or 5 to 6 hours.

[0046] In the preparation method of the present invention, the pretreatment of the mesoporous molecular sieve before grinding includes: treating the mesoporous molecular sieve with an alkaline solution, then washing, drying, roasting, and then using NH 4 NO 3The solution is subjected to proton exchange treatment, washed again, dried, and calcined for later use.

[0047] Wherein, the alkaline solution is NaOH solution.

[0048] The concentration of the alkaline solution is 0.2-1.0 mol / L. For example, 0.2-0.3 mol / L, 0.3-0.4 mol / L, 0.4-0.6 mol / L, 0.6-0.8 mol / L or 0.8-1.0 mol / L. In a preferred embodiment of the present invention, the concentration of the alkaline solution is 0.4-0.6 mol / L.

[0049] The temperature of the alkali treatment is 60-80°C, for example, 60-65°C, 65-70°C, 70-75°C or 75-80°C.

[0050] The drying temperature is 100-120°C, for example, 100-105°C, 105-110°C, 110-115°C or 115-120°C.

[0051] The calcination temperature is 400-500°C, for example, 400-410°C, 410-420°C, 420-430°C, 430-440°C, 440-450°C, 450-460°C, 460-470°C, 470-480°C, 480-490°C or 490-500°C.

[0052] The calcination time is 4 to 6 hours, for example 4 to 5 hours or 5 to 6 hours.

[0053] The proton exchange treatment time is 1 to 3 hours, for example 1 to 2 hours or 2 to 3 hours.

[0054] A third aspect of the present invention provides a use of the ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst as described above in direct production of aviation kerosene from synthesis gas.

[0055] The positive effect of the ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst of the present invention is that CO is hydrogenated on the Ru-M bimetallic active center, and the metal additive M can adjust the functions such as the dispersion of Ru metal and the surface electronic structure, so as to obtain high-carbon hydrocarbons through chain growth better. The intermediate product generated then continues to catalyze secondary reactions such as cracking and isomerization reactions on the acidic center of the zeolite molecular sieve. If the intensity of the secondary reaction can be better controlled, the selectivity of the target product can be regulated to obtain a higher C 8 -C 16 The catalyst has broad application prospects due to its selectivity for aviation kerosene.

[0056] The fourth aspect of the present invention provides a method for directly preparing aviation kerosene from synthesis gas, comprising reducing the ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst as described above, and then introducing H 2 / CO / N 2 The mixed gas is reacted to prepare aviation kerosene.

[0057] The reduction is carried out at 260-320°C and 0.1-0.5Mpa. For example, the temperature may be 260-270°C, 270-280°C, 280-290°C, 290-300°C, 300-310°C, 310-320°C, and the pressure may be 0.1-0.2Mpa, 0.2-0.3Mpa, 0.3-0.4Mpa or 0.4-0.5Mpa.

[0058] The reduction was carried out in pure H 2 Conditions are carried out.

[0059] The H 2 / CO / N 2 H in the synthesis gas 2 ,CO,N 2 The molar volume ratio is (64.7-72.8): (24.2-32.3): 3.0. For example, (64.7-65.0): (24.2-32.3): 3.0, (65.0-66.0): (24.2-32.3): 3.0, (66.0-67.0): (24.2-32.3): 3.0, (67.0-68.0): (24.2-32.3): 3.0, (68.0-69.0) :(24.2~32.3):3.0、(69.0~70.0):(24.2~32.3):3.0、(70.0~71.0):(24.2~32.3):3.0、(71.0~72.0):(24.2~32.3):3.0、(72.0~72.8):(24.2~32.3):3. 0, (64.7-72.8): (24.2-25.0): 3.0, (64.7-72.8): (25.0-26.0): 3.0, (64.7-72.8): (26.0-27.0): 3.0, (64.7-72.8): (27.0-28.0): 3.0, (64.7-72.8): ( 28.0~29.0): 3.0, (64.7~72.8): (29.0~30.0): 3.0, (64.7~72.8): (30.0~31.0): 3.0, (64.7~72.8): (31.0~32.0): 3.0, (64.7~72.8): (32.0~32.3): 3.0.

[0060] The temperature at which the synthesis gas is reacted is 220-300°C, for example, 220-230°C, 230-240°C, 240-250°C, 250-260°C, 260-270°C, 270-280°C, 280-290°C or 290-300°C.

[0061] The reaction pressure of the synthesis gas is 1.0-3.0 MPa, for example, 1.0-1.5 MPa, 1.5-2.0 MPa, 2.0-2.5 MPa or 2.5-3.0 MPa.

[0062] The space velocity of the synthesis gas reaction is 2000-3000h -1 . For example, 2000~2200h -1 , 2200~2400h -1 , 2400~2600h -1 , 2600~2800h -1 , 2800~3000h -1 .

[0063] Example 1

[0064] 1. Preparation of 3Ru-3Mn / SiO by co-impregnation method 2 Bimetallic Oxide Steps:

[0065] Weigh 0.616 g of ruthenium chloride (RuCl 3 )、1.955g 50% manganese nitrate (Mn(NO 3 ) 2 ) solution was completely dissolved in 29.6 ml of deionized water (DI), and then SiO 2 10.0 g of -380 carrier was added to a 100 ml flask and impregnated for 24 h under stirring at room temperature. After filtration and washing, the filter cake was dried at 60 ° C for 12 h and calcined at 300 ° C for 5 h to obtain 3Ru-3Mn / SiO with Ru = 3.0 wt% -Mn = 3.0 wt% 2 Bimetallic oxides.

[0066] 2. Preparation steps of mesoporous ZSM-5 molecular sieve:

[0067] Prepare 400 mL of NaOH solution with a molar concentration of 0.5 mol / L, pour it into a 1000 mL three-necked flask, and then weigh the prepared H-ZSM-5 molecular sieve (SiO 2 / Al 2 O 3 molar ratio = 50) 40.0 g was added into NaOH solution, and alkali treated for 1 h in a 70 ° C water bath with stirring, filtered, washed, dried at 120 ° C overnight, calcined at 500 ° C for 5 h, and then NH 4 NO3 The solution (1.0 mol / L) was subjected to proton exchange treatment for 1 h in a water bath at 80° C. with stirring, filtered, washed, dried at 120° C. overnight, and calcined at 500° C. for 5 h, to finally obtain a mesoporous H-ZSM-5-50-0.5M molecular sieve.

[0068] 3. Preparation steps of ruthenium (Ru) based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst:

[0069] The 3Ru-3Mn / SiO 2 Oxide and Mesoporous-ZSM-5-50-0.5M Molecular Sieve (SiO 2 / Al 2 O 3 The molar ratio = 50) was firstly tableted and ground to 40-60 mesh, and then the particles were blended at a mass ratio of 1:1 to obtain Ru = 3.0% - Mn = 3.0% / SiO 2 / Mesoporous-ZSM-5-50-0.5M bifunctional catalyst for direct production of aviation kerosene from synthesis gas by hydrogenation.

[0070] 4. Catalyst evaluation was carried out in a fixed bed microreactor, which used a stainless steel reaction tube with an inner diameter of Φ9 mm. The catalyst was first reduced with pure hydrogen at 300°C and 0.5 MPa for 3 h in the reactor, and then switched to synthesis gas (H 2 / CO / N 2 =64.7 / 32.3 / 3.0, mol%), at 260°C, 2.0MPa, 2400h -1 The reaction was carried out under the following conditions, the obtained gas phase product was detected online by gas chromatography, and the oil phase product was analyzed offline by FID chromatography. The reaction results are shown in Table 1.

[0071] Example 2

[0072] 1. Preparation of 3Ru-3Zn / SiO by co-impregnation method 2 Bimetallic Oxide Steps:

[0073] Weigh 0.616 g of ruthenium chloride (RuCl 3 )、1.365g zinc nitrate (Zn(NO 3 ) 2 ) was completely dissolved in 29.6 ml of deionized water (DI), and then SiO 2 10.0 g of -380 carrier was added to a 100 ml flask and impregnated for 24 h under stirring at room temperature. After filtration and washing, the filter cake was dried at 60 ° C for 12 h and calcined at 300 ° C for 5 h to obtain 3Ru-3Zn / SiO with Ru = 3.0 wt% -Zn = 3.0 wt% 2 Bimetallic oxides.

[0074] 2. Preparation steps of mesoporous ZSM-5 molecular sieve:

[0075] The same steps as described in Example 1 for the mesoporous H-ZSM-5-50-0.5M molecular sieve.

[0076] 3. Preparation steps of ruthenium (Ru) based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst:

[0077] The 3Ru-3Zn / SiO 2 Oxide and Mesoporous-ZSM-5-50-0.5M Molecular Sieve (SiO 2 / Al 2 O 3 The molar ratio = 50) was firstly tableted and ground to 40-60 mesh, and then the particles were blended at a mass ratio of 1:1 to obtain Ru = 3.0% - Zn = 3.0% / SiO 2 / Mesoporous-ZSM-5-50-0.5M bifunctional catalyst for direct production of aviation kerosene from synthesis gas by hydrogenation.

[0078] 4. Catalyst evaluation was carried out in a fixed bed microreactor, which used a stainless steel reaction tube with an inner diameter of Φ9 mm. The catalyst was first reduced with pure hydrogen at 280°C and 0.5 MPa for 3 h in the reactor, and then switched to synthesis gas (H 2 / CO / N 2 =64.7 / 32.3 / 3.0, mol%), at 270°C, 2.0MPa, 2400h -1 The reaction was carried out under the following conditions, the obtained gas phase product was detected online by gas chromatography, and the oil phase product was analyzed offline by FID chromatography. The reaction results are shown in Table 1.

[0079] Example 3

[0080] 1. Preparation of 3Ru-3Zr / SiO by co-impregnation method 2 Bimetallic Oxide Steps:

[0081] Weigh 0.616 g of ruthenium chloride (RuCl 3 )、1.412 g zirconium nitrate (Zr(NO 3 ) 4 Completely dissolve in 29.6 ml of deionized water (DI), then weigh SiO 2 10.0 g of -380 carrier was added to a 100 ml flask and impregnated for 24 h under stirring at room temperature. After filtration and washing, the filter cake was dried at 60 ° C for 12 h and calcined at 300 ° C for 5 h to obtain 3Ru-3Zr / SiO with Ru = 3.0 wt% -Zr = 3.0 wt% 2 Bimetallic oxides.

[0082] 2. Preparation steps of mesoporous ZSM-5 molecular sieve:

[0083] The same steps as described in Example 1 for the mesoporous H-ZSM-5-50-0.5M molecular sieve.

[0084] 3. Preparation steps of ruthenium (Ru) based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst:

[0085] The 3Ru-3Zr / SiO 2 Oxide and Mesoporous-ZSM-5-50-0.5M Molecular Sieve (SiO 2 / Al 2 O 3 The molar ratio = 50) was firstly pressed into tablets, ground into 40-60 mesh, and then the particles were blended at a mass ratio of 1:1 to obtain Ru = 3.0% - Zr = 3.0% / SiO 2 / Mesoporous-ZSM-5-50-0.5M bifunctional catalyst for direct production of aviation kerosene from synthesis gas by hydrogenation.

[0086] 4. Catalyst evaluation was carried out in a fixed bed microreactor, which used a stainless steel reaction tube with an inner diameter of Φ9 mm. The catalyst was first reduced with pure hydrogen at 300°C and 0.5 MPa for 3 h in the reactor, and then switched to synthesis gas (H 2 / CO / N 2 =64.7 / 32.3 / 3.0, mol%), at 280°C, 2.0 MPa, 2800 h -1 The reaction was carried out under the following conditions, the obtained gas phase product was detected online by gas chromatography, and the oil phase product was analyzed offline by FID chromatography. The reaction results are shown in Table 1.

[0087] Example 4

[0088] 1. Preparation of 3Ru-3La / SiO by co-impregnation method 2 Bimetallic Oxide Steps:

[0089] Weigh 0.616 g of ruthenium chloride (RuCl 3 ), 0.935 g lanthanum nitrate (La(NO 3 ) 3 Completely dissolve in 29.6 ml of deionized water (DI), then weigh SiO 2 10.0 g of -380 carrier was added to a 100 ml flask and impregnated for 24 h under stirring at room temperature. After filtration and washing, the filter cake was dried at 60 ° C for 12 h and calcined at 300 ° C for 5 h to obtain 3Ru-3La / SiO with Ru = 3.0 wt% -La = 3.0 wt% 2 Bimetallic oxides.

[0090] 2. Preparation steps of mesoporous ZSM-5 molecular sieve:

[0091] The same steps as described in Example 1 for the mesoporous H-ZSM-5-50-0.5M molecular sieve.

[0092] 3. Preparation steps of ruthenium (Ru) based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst:

[0093] The 3Ru-3La / SiO 2 Oxide and Mesoporous-ZSM-5-50-0.5M Molecular Sieve (SiO 2 / Al 2 O 3 The molar ratio = 50) was firstly pressed into tablets, ground into 40-60 mesh, and then the particles were blended at a mass ratio of 1:1 to obtain Ru = 3.0% - La = 3.0% / SiO 2 / Mesoporous-ZSM-5-50-0.5M bifunctional catalyst for direct production of aviation kerosene from synthesis gas by hydrogenation.

[0094] 4. Catalyst evaluation was carried out in a fixed bed microreactor, which used a stainless steel reaction tube with an inner diameter of Φ9 mm. The catalyst was first reduced with pure hydrogen at 300°C and 0.5 MPa for 3 h in the reactor, and then switched to synthesis gas (H 2 / CO / N 2 =64.7 / 32.3 / 3.0, mol%), at 260°C, 1.0 MPa, 2600 h -1 The reaction was carried out under the following conditions, the obtained gas phase product was detected online by gas chromatography, and the oil phase product was analyzed offline by FID chromatography. The reaction results are shown in Table 1.

[0095] Example 5

[0096] 1. Preparation of 2Ru-3Mn / SiO by co-impregnation method 2 Bimetallic Oxide Steps:

[0097] Weigh 0.411 g of ruthenium chloride (RuCl 3 )、1.955g 50% manganese nitrate (Mn(NO 3 ) 2 ) solution was completely dissolved in 29.6 ml of deionized water (DI), and then SiO 2 10.0 g of -380 carrier was added to a 100 ml flask and impregnated for 24 h under stirring at room temperature. After filtration and washing, the filter cake was dried at 60 ° C for 12 h and calcined at 300 ° C for 5 h to obtain 2Ru-3Mn / SiO with Ru = 2.0 wt% -Mn = 3.0 wt% 2 Bimetallic oxides.

[0098] 2. Preparation steps of mesoporous ZSM-5 molecular sieve:

[0099] The same steps as described in Example 1 for the mesoporous H-ZSM-5-50-0.5M molecular sieve.

[0100] 3. Preparation steps of ruthenium (Ru) based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst:

[0101] The 2Ru-3Mn / SiO 2 Oxide and Mesoporous-ZSM-5-50-0.5M Molecular Sieve (SiO 2 / Al 2 O 3 The molar ratio = 50) was firstly tableted and ground to 40-60 mesh, and then the particles were blended at a mass ratio of 1:1 to obtain Ru = 2.0% - Mn = 3.0% / SiO 2 / Mesoporous-ZSM-5-50-0.5M bifunctional catalyst for direct production of aviation kerosene from synthesis gas by hydrogenation.

[0102] 4. Catalyst evaluation was carried out in a fixed bed microreactor, which used a stainless steel reaction tube with an inner diameter of Φ9 mm. The catalyst was first reduced with pure hydrogen at 320°C and 0.5 MPa for 3 h in the reactor, and then switched to synthesis gas (H 2 / CO / N 2 =64.7 / 32.3 / 3.0, mol%), at 260°C, 2.0MPa, 2400h -1 The reaction was carried out under the following conditions, the obtained gas phase product was detected online by gas chromatography, and the oil phase product was analyzed offline by FID chromatography. The reaction results are shown in Table 1.

[0103] Example 6

[0104] 1. Preparation of 1.5Ru-3Mn / SiO by co-impregnation method 2 Bimetallic Oxide Steps:

[0105] Weigh 0.308 g of ruthenium chloride (RuCl 3 )、1.955g 50% manganese nitrate (Mn(NO 3 ) 2 ) solution was completely dissolved in 29.6 ml of deionized water (DI), and then SiO 2 10.0 g of -380 carrier was added to a 100 ml flask and impregnated for 24 h under stirring at room temperature. After filtration and washing, the filter cake was dried at 60 ° C for 12 h and calcined at 300 ° C for 5 h to obtain 1.5 wt% Ru-3Mn / SiO 2 Bimetallic oxides.

[0106] 2. Preparation steps of mesoporous ZSM-5 molecular sieve:

[0107] The same steps as described in Example 1 for the mesoporous H-ZSM-5-50-0.5M molecular sieve.

[0108] 3. Preparation steps of ruthenium (Ru) based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst:

[0109] The 1.5Ru-3Mn / SiO 2 Oxide and Mesoporous-ZSM-5-50-0.5M Molecular Sieve (SiO 2 / Al 2 O 3 The molar ratio = 50) was firstly tableted and ground to 40-60 mesh, and then the particles were blended at a mass ratio of 1:1 to obtain Ru = 1.5% - Mn = 3.0% / SiO 2 / Mesoporous-ZSM-5-50-0.5M bifunctional catalyst for direct production of aviation kerosene from synthesis gas by hydrogenation.

[0110] 4. Catalyst evaluation was carried out in a fixed bed microreactor, which used a stainless steel reaction tube with an inner diameter of Φ9 mm. The catalyst was first reduced with pure hydrogen at 300°C and 0.5 MPa for 3 h in the reactor, and then switched to synthesis gas (H 2 / CO / N 2 =64.7 / 32.3 / 3.0, mol%), at 260°C, 2.0MPa, 3000h -1 The reaction was carried out under the following conditions, the obtained gas phase product was detected online by gas chromatography, and the oil phase product was analyzed offline by FID chromatography. The reaction results are shown in Table 1.

[0111] Example 7

[0112] 1. Preparation of 1Ru-3Mn / SiO by co-impregnation method 2 Bimetallic Oxide Steps:

[0113] Weigh 0.205 g of ruthenium chloride (RuCl 3 )、1.955g 50% manganese nitrate (Mn(NO 3 ) 2 ) solution was completely dissolved in 29.6 ml of deionized water (DI), and then SiO 2 10.0 g of -380 carrier was added to a 100 ml flask and impregnated for 24 h under stirring at room temperature. After suction filtration and washing, the filter cake was dried at 60 ° C for 12 h and calcined at 300 ° C for 5 h to obtain 1Ru-3Mn / SiO with Ru = 1.0 wt% -Mn = 3.0 wt% 2 Bimetallic oxides.

[0114] 2. Preparation steps of mesoporous ZSM-5 molecular sieve:

[0115] The same steps as described in Example 1 for the mesoporous H-ZSM-5-50-0.5M molecular sieve.

[0116] 3. Preparation steps of ruthenium (Ru) based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst:

[0117] The 1Ru-3Mn / SiO 2 Oxide and Mesoporous-ZSM-5-50-0.5M Molecular Sieve (SiO 2 / Al 2 O 3 The molar ratio = 50) was firstly tableted and ground to 40-60 mesh, and then the particles were blended at a mass ratio of 1:1 to obtain Ru = 1.0% - Mn = 3.0% / SiO 2 / Mesoporous-ZSM-5-50-0.5M bifunctional catalyst for direct production of aviation kerosene from synthesis gas by hydrogenation.

[0118] 4. Catalyst evaluation was carried out in a fixed bed microreactor, which used a stainless steel reaction tube with an inner diameter of Φ9 mm. The catalyst was first reduced with pure hydrogen at 280°C and 0.5 MPa for 3 h in the reactor, and then switched to synthesis gas (H 2 / CO / N 2 =64.7 / 32.3 / 3.0, mol%), at 270°C, 2.0MPa, 2400h -1 The reaction was carried out under the following conditions, the obtained gas phase product was detected online by gas chromatography, and the oil phase product was analyzed offline by FID chromatography. The reaction results are shown in Table 1.

[0119] Example 8

[0120] 1. Preparation of 3Ru-3Mn / TiO by co-impregnation method 2 Bimetallic Oxide Steps:

[0121] Weigh 0.616 g of ruthenium chloride (RuCl 3 )、1.955g 50% manganese nitrate (Mn(NO 3 ) 2 ) solution was completely dissolved in 29.6 ml of deionized water (DI), and then TiO 2 10.0 g of the carrier was added to a 100 ml flask and impregnated for 24 h under stirring at room temperature. After filtration and washing, the filter cake was dried at 60 ° C for 12 h and calcined at 300 ° C for 5 h to obtain 3Ru-3Mn / TiO with Ru = 3.0 wt% -Mn = 3.0 wt% 2 Bimetallic oxides.

[0122] 2. Preparation steps of mesoporous H-Beta molecular sieve:

[0123] Prepare 400 mL of NaOH solution with a molar concentration of 0.15 mol / L, pour it into a 1000 mL three-necked flask, and then weigh the prepared H-Beta molecular sieve (SiO 2 / Al 2 O 3 molar ratio = 30) 10.0 g, put it into NaOH solution, stir in a water bath at 70 ° C for 1 h, filter, wash, dry at 120 ° C overnight, calcine at 500 ° C for 5 h, and then use NH 4 NO 3 The solution (1.0 mol / L) was subjected to proton exchange treatment for 1 h, and then filtered, washed, dried at 120° C. overnight, and calcined at 500° C. for 5 h, to finally obtain the mesoporous-H-Beta-30-0.15M molecular sieve.

[0124] 3. Preparation steps of ruthenium (Ru) based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst:

[0125] The 3Ru-3Mn / TiO 2 Oxide and Mesoporous-H-Beta-30-0.15M Molecular Sieve (SiO 2 / Al 2 O 3 The molar ratio = 30) was firstly pressed into tablets, ground into 40-60 mesh, and then the particles were blended at a mass ratio of 1:1 to obtain Ru = 3.0% - Mn = 3.0% / TiO 2 / Mesoporous-H-Beta-30-0.15M bifunctional catalyst for direct production of aviation kerosene from synthesis gas by hydrogenation.

[0126] 4. Catalyst evaluation was carried out in a fixed bed microreactor, which used a stainless steel reaction tube with an inner diameter of Φ9 mm. The catalyst was first reduced with pure hydrogen at 300°C and 0.5 MPa for 3 h in the reactor, and then switched to synthesis gas (H 2 / CO / N 2 =64.7 / 32.3 / 3.0, mol%), at 260°C, 1.0MPa, 2200h -1 The reaction was carried out under the following conditions, the obtained gas phase product was detected online by gas chromatography, and the oil phase product was analyzed offline by FID chromatography. The reaction results are shown in Table 1.

[0127] Example 9

[0128] 1. Preparation of 3Ru-3Mn / γ-Al by co-impregnation method 2 O 3 Bimetallic Oxide Steps:

[0129] Weigh 0.616 g of ruthenium chloride (RuCl 3 )、1.955g 50% manganese nitrate (Mn(NO 3 ) 2 ) solution was completely dissolved in 29.6 ml of deionized water (DI), and then γ-Al 2 O 3 10.0 g of the carrier was added to a 100 ml flask and immersed for 24 h under stirring at room temperature. After filtration and washing, the filter cake was dried at 60 ° C for 12 h and calcined at 300 ° C for 5 h to obtain 3Ru-3Mn / γ-Al with Ru = 3.0 wt% -Mn = 3.0 wt% 2 O 3 Bimetallic oxides.

[0130] 2. Preparation steps of mesoporous USY molecular sieve:

[0131] Prepare 400 mL of NaOH solution with a molar concentration of 0.4 mol / L, pour it into a 1000 mL three-necked flask, and then weigh the prepared USY molecular sieve (SiO 2 / Al 2 O 3 molar ratio = 5) 10.0g, which was charged into NaOH solution, treated with alkali for 1h under stirring in a 70℃ water bath, filtered, washed, dried at 120℃ overnight, calcined at 500℃ for 5h, and then treated with NH 4 NO 3 The solution (1.0 mol / L) was subjected to proton exchange treatment for 1 h, then filtered, washed, dried at 120° C. overnight, and calcined at 500° C. for 5 h, and finally the mesoporous H-USY-5-0.4M molecular sieve was obtained.

[0132] 3. Preparation steps of ruthenium (Ru) based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst:

[0133] The 3Ru-3Mn / γ-Al 2 O 3 Oxide and Mesoporous-H-USY-5-0.4M Molecular Sieve (SiO 2 / Al 2 O 3 The molar ratio = 5) was firstly tableted and ground to 40-60 mesh, and then the particles were blended at a mass ratio of 1:1 to obtain Ru = 3.0% - Mn = 3.0% / γ-Al 2 O 3 / Mesoporous-H-USY-5-0.4M bifunctional catalyst for direct production of aviation kerosene from synthesis gas by hydrogenation.

[0134] 4. Catalyst evaluation was carried out in a fixed bed microreactor, which used a stainless steel reaction tube with an inner diameter of Φ9 mm. The catalyst was first reduced with pure hydrogen at 300°C and 0.5 MPa for 3 h in the reactor, and then switched to synthesis gas (H 2 / CO / N 2 =64.7 / 32.3 / 3.0, mol%), at 260°C, 2.0MPa, 2400h -1 The reaction was carried out under the following conditions, the obtained gas phase product was detected online by gas chromatography, and the oil phase product was analyzed offline by FID chromatography. The reaction results are shown in Table 1.

[0135] Comparative Example 1

[0136] 1. Preparation of 3Ru-3Mn / SiO by step-by-step impregnation method 2 Bimetallic Oxide Steps:

[0137] Weigh 0.616 g of ruthenium chloride (RuCl 3 ) was completely dissolved in 29.6 ml of deionized water (DI), and SiO 2 10.0 g of the -380 carrier was added to a 100 ml flask and immersed for 24 h under stirring at room temperature. After filtration and washing, the filter cake was dried at 60 ° C for 12 h and calcined at 300 ° C for 5 h to obtain Ru = 3.0 wt% Ru / SiO 2 Oxide.

[0138] Weigh 1.955 g of 50% manganese nitrate (Mn(NO 3 ) 2 ) solution was completely dissolved in 29.6 ml of deionized water (DI), and the Ru / SiO 2 10.0 g of oxide was added to a 100 ml flask and immersed for 24 h under stirring at room temperature. After filtration and washing, the filter cake was dried at 60 ° C for 12 h and calcined at 300 ° C for 5 h to obtain 3Ru-3Mn / SiO with Ru = 3.0 wt% -Mn = 3.0 wt% 2 Bimetallic oxides.

[0139] 2. Preparation steps of mesoporous ZSM-5 molecular sieve:

[0140] The same steps as described in Example 1 for the mesoporous H-ZSM-5-50-0.5M molecular sieve.

[0141] 3. Preparation steps of ruthenium (Ru) based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst:

[0142] The 3Ru-3Mn / SiO 2 Oxide and Mesoporous-ZSM-5-50-0.5M Molecular Sieve (SiO 2 / Al2 O 3 The molar ratio = 50) was firstly tableted and ground to 40-60 mesh, and then the particles were blended at a mass ratio of 1:1 to obtain Ru = 3.0% - Mn = 3.0% / SiO 2 / Mesoporous-ZSM-5-50-0.5M bifunctional catalyst for direct production of aviation kerosene from synthesis gas by hydrogenation.

[0143] 4. Catalyst evaluation was carried out in a fixed bed microreactor, which used a stainless steel reaction tube with an inner diameter of Φ9 mm. The catalyst was first reduced with pure hydrogen at 300°C and 0.5 MPa for 3 h in the reactor, and then switched to synthesis gas (H 2 / CO / N 2 =64.7 / 32.3 / 3.0, mol%), at 280°C, 2.0MPa, 2400h -1 The reaction was carried out under the following conditions, the obtained gas phase product was detected online by gas chromatography, and the oil phase product was analyzed offline by FID chromatography. The reaction results are shown in Table 1.

[0144] Comparative Example 2

[0145] 1. Preparation of 3Ru-3Mn / SiO by step-by-step impregnation method 2 Bimetallic Oxide Steps:

[0146] The same as the 3Ru-3Mn / SiO 2 Double Metal Oxide Step.

[0147] 2. Preparation steps of mesoporous ZSM-5 molecular sieve:

[0148] The same steps as described in Example 1 for the mesoporous H-ZSM-5-50-0.5M molecular sieve.

[0149] 3. Preparation steps of ruthenium (Ru) based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst:

[0150] The 3Ru-3Mn / SiO 2 Oxide and Mesoporous-ZSM-5-50-0.5M Molecular Sieve (SiO 2 / Al 2 O 3 The powders were first blended at a mass ratio of 1:1, ground for 10 min, and then tableted and crushed to 40-60 mesh to obtain Ru = 3.0% - Mn = 3.0% / SiO 2 / Mesoporous-ZSM-5-50-0.5M bifunctional catalyst for synthesis gas to aviation kerosene reaction.

[0151] 4. Catalyst evaluation was carried out in a fixed bed microreactor, which used a stainless steel reaction tube with an inner diameter of Φ9 mm. The catalyst was first reduced with pure hydrogen at 300°C and 0.5 MPa for 3 h in the reactor, and then switched to synthesis gas (H 2 / CO / N 2 =64.7 / 32.3 / 3.0, mol%), at 260°C, 2.0 MPa, 2600 h -1 The reaction was carried out under the following conditions, the obtained gas phase product was detected online by gas chromatography, and the oil phase product was analyzed offline by FID chromatography. The reaction results are shown in Table 1.

[0152] Table 1 Activity of Ru-based bimetallic oxide / mesoporous molecular sieve catalysts for synthesis gas to aviation kerosene

[0153]

[0154]

[0155] In summary, when the ruthenium (Ru)-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst of the present invention is used to produce aviation kerosene from synthesis gas, the carbon monoxide conversion rate reaches 50.5%, and CH 4 Selectivity 6.7%, C 5 + Selectivity reached 76.4%, among which C 8 ~C 16 The fraction selectivity reaches 53.5%, and the isomerization ratio is 3.3, which is applicable to the needs of the process of preparing aviation kerosene from synthesis gas. Therefore, the present invention effectively overcomes various disadvantages in the prior art and also has high industrial utilization value.

[0156] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst, characterized in that: It includes Ru-M ruthenium-based bimetallic oxide and mesoporous molecular sieve, the mass ratio of the Ru-M ruthenium-based bimetallic oxide and the mesoporous molecular sieve is (4:1) to (1:4), the metal M in the Ru-M ruthenium-based bimetallic oxide is selected from one or more transition metals or rare earth metals; the carrier in the Ru-M ruthenium-based bimetallic oxide is selected from one or more of SiO2, Al2O3, TiO2, and the mesoporous molecular sieve is selected from one or more of mesoporous-ZSM-5, mesoporous-Y, and mesoporous-Beta.

2. The ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst according to claim 1, characterized in that: Also includes one or more of the following characteristics: A1) the transition metal is selected from one or more of Mn, Zn and Zr; the rare earth metal is selected from one or more of La and Ce; A2) the mass ratio of metal Ru / M in the Ru-M ruthenium-based bimetallic oxide is (1-6):3; A3) the mass ratio of the total mass of the ruthenium source and the metal M source to the carrier is (4-11):10; A4) the particle size of the Ru-M ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst is 20 to 120 meshes; A5) the Ru-M ruthenium-based bimetallic oxide is prepared by a co-impregnation method; A6) the mesoporous molecule is selected from mesoporous-ZSM-5; A7) The mass ratio of the Ru-M ruthenium-based bimetallic oxide to the mesoporous molecular sieve is (2:1) to (1:1).

3. The ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst according to claim 2, characterized in that: Also includes one or more of the following characteristics: A21) based on the carrier mass, the mass ratio of metal Ru / M in the Ru-M ruthenium-based bimetallic oxide is (1-3):3; A41) the Ru-M ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst has a particle size of 20 to 40 meshes; A42) the particle size of the Ru-M ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst is 40 to 60 meshes; A43) The particle size of the Ru-M ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst is 60 to 80 meshes; A44) the particle size of the Ru-M ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst is 80 to 120 meshes; A61) The SiO2 / Al2O3 molar ratio in the mesoporous ZSM-5 molecular sieve is 25 to 300, preferably 25 to 50.

4. The method for preparing the ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst according to any one of claims 1 to 3, characterized in that: The method comprises the steps of: grinding and blending Ru-M ruthenium-based bimetallic oxide and mesoporous molecular sieve respectively to obtain the Ru-M ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst.

5. The method for preparing the ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst according to claim 4, characterized in that: The mass ratio of the Ru-M ruthenium-based bimetallic oxide to the mesoporous molecular sieve is (4:1) to (1:4); And / or, the grinding is grinding to 40-60 mesh.

6. The method for preparing the ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst according to claim 4, characterized in that: The preparation method of the Ru-M ruthenium-based bimetallic oxide comprises: dissolving a ruthenium source and a metal M source in a solvent to form a mixed solution A, placing a carrier in a round-bottom flask, slowly dripping the mixed solution A into the carrier, stirring and co-impregnating, washing, drying, and calcining to obtain the Ru-M ruthenium-based bimetallic oxide.

7. The method for preparing the ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst according to claim 6, characterized in that: Also includes one or more of the following characteristics: B1) the ruthenium source is selected from one or more of ruthenium nitrosyl nitrate, ruthenium chloride, and ruthenium acetylacetonate; B2) the metal M source is selected from one or more of nitrates, chlorides or acetates of M; B3) the solvent is deionized water; B4) the co-impregnation temperature is 25 to 40°C; B5) the co-impregnation time is 24 to 48 hours; B6) the drying temperature is 60-80°C; B7) The drying time is 12 to 24 hours; B8) the calcination temperature is 200-400°C; B9) The calcination time is 4 to 6 hours.

8. The method for preparing the ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst according to claim 4, characterized in that: The pretreatment of the mesoporous molecular sieve before grinding includes: treating the mesoporous molecular sieve with an alkaline solution, then washing, drying, and calcining, then performing proton exchange treatment with an NH4NO3 solution, and then washing, drying, and calcining again for standby use.

9. The method for preparing the ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst according to claim 8, characterized in that: Also includes one or more of the following characteristics: C1) the alkaline solution is a NaOH solution; C2) the concentration of the alkaline solution is 0.2-1.0 mol / L; C3) the temperature of the alkali treatment is 60 to 80°C; C4) the drying temperature is 100-120°C; C5) the calcination temperature is 400-500°C; C6) the calcination time is 4 to 6 hours; C7) The proton exchange treatment time is 1 to 3 hours.

10. Use of the ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst according to any one of claims 1 to 3 in direct production of aviation kerosene by hydrogenation of synthesis gas.

11. A method for directly producing aviation kerosene by hydrogenating synthesis gas, characterized in that: The ruthenium-based bimetallic oxide / mesoporous molecular sieve bifunctional catalyst described in any one of claims 1 to 3 is reduced, and then a mixed gas of H2 / CO / N2 is introduced for reaction to prepare aviation kerosene.

12. The method for directly producing aviation kerosene by hydrogenating synthesis gas according to claim 11, characterized in that: Also includes one or more of the following characteristics: D1) the reduction is carried out at 260-320° C. and 0.1-0.5 MPa; D2) the reduction is carried out under pure H2 conditions; D3) the molar percentage of H2, CO, and N2 in the H2 / CO / N2 mixed gas (64.7-72.8): (24.2-32.3): 3.0; D4) the temperature at which the synthesis gas is reacted is 220-300°C; D5) the pressure of the synthesis gas for reaction is 1.0-3.0 MPa; D6) The flow rate of the synthesis gas for reaction is 2000~3000h -1 .

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