A combined catalyst for the preparation of straight-chain alcohols via syngas tandem reaction and a method for preparing straight-chain alcohols using the same.

Abstract

This application provides a combined catalyst for the tandem reaction of syngas to prepare straight-chain alcohols and a method for preparing straight-chain alcohols using the same catalyst, relating to the field of catalysis. The combined catalyst for the tandem reaction of syngas to prepare straight-chain alcohols comprises an independent first catalyst and a second catalyst. The first catalyst includes a first active component, a first promoter, and a first support. The first active component is Ru, the first promoter corresponds to the metal Na, and the first support is amorphous silica. The second catalyst includes a second active component, a second promoter, a third promoter, and a second support. The second active component is Rh, the second promoter corresponds to the metal K, the third promoter corresponds to the metal Zn and / or Fe, and the second support is an MFI-type molecular sieve composed of pure silicon. The combined catalyst provided in this application allows for efficient coupling of the two catalysts in different reactors within the same reaction apparatus, resulting in highly selective straight-chain alcohol products.

Description

Technical Field

[0001] This application relates to the field of catalysis technology, and in particular to a combinatorial catalyst for the preparation of straight-chain alcohols by a tandem reaction of syngas and a method for preparing straight-chain alcohols using the same. Background Technology

[0002] Mixed alcohols (C 2+ OH is generally defined as a straight-chain aliphatic primary alcohol containing two or more carbon atoms. Based on carbon chain length, it can be divided into low-carbon mixed alcohols (C2–C5OH) and high-carbon mixed alcohols (C2–C5OH). 6+ There are two categories: low-carbon mixed alcohols (C6-C9OH) and high-carbon alcohols (C4-C9OH). Low-carbon mixed alcohols are commonly used as organic solvents and can also replace methyl tert-butyl ether (MTBE) as a high-quality gasoline additive. High-carbon alcohols are high-value-added fine chemicals and are used in synthetic plasticizers (C6-C9OH) and detergents (C4-C9OH). 10 ~C 12 It is a key raw material for products such as OH and surfactants, and is widely used in many industrial fields such as food processing, pharmaceutical preparation, textile printing and dyeing, and papermaking.

[0003] Currently, the mainstream industrial technologies for preparing higher alcohols are the Ziegler method and the OXO method. The Ziegler method uses ethylene as a raw material, achieving carbon chain growth under triethylaluminum catalysis. Through oxidation, hydrolysis, and separation processes, C6–C6 alcohols are ultimately obtained. 16 Even-carbon straight-chain primary alcohols (FR1134907 and US3968177) are included. This method uses triethylaluminum as a catalyst, posing an extremely high explosion risk and inherent drawbacks such as high technical barriers, lengthy process flow, large catalyst consumption, and poor safety. Carbonyl synthesis, also known as hydroformylation, involves the hydroformylation reaction of olefins with syngas under a catalyst to produce aldehydes, which are then purified by hydrogenation to obtain the target alcohol. For example, in CN115999616B, CN115999629B, and CN115805102B, efficient conversion of olefins was achieved through various methods such as molecular sieve confinement, auxiliary agent regulation, and organic ligand modification. The global market demand for higher carbon alcohols has exceeded 16 million tons per year and is increasing annually. Therefore, developing new technologies for the preparation of higher carbon alcohols with simple processes, mild reaction conditions, and readily available and widely sourced raw materials has significant theoretical research value and promising industrial application prospects.

[0004] Non-petroleum-based carbonaceous feedstocks such as coal, natural gas, and biomass can be converted into syngas (CO / H2 mixture) with adjustable composition through various technologies. Fischer-Tropsch Synthesis (FTS), as the core platform technology for syngas conversion, traditional processes primarily use iron / cobalt-based catalysts to produce straight-chain alkanes, with oxygen mostly converted to H2O and CO2, resulting in low atom economy and significant industrial waste gas / wastewater emissions. In recent years, the directed conversion of syngas to produce oxygen-containing compounds such as alcohols, aldehydes, and acids has attracted considerable attention. This pathway enables efficient utilization of oxygen and improves atom economy, becoming a key focus of C1 chemistry research. Among these, the direct production of alcohol-containing fuels from syngas maximizes oxygen retention, promotes complete fuel combustion, and reduces pollutant emissions, demonstrating significant application value. Summary of the Invention

[0005] The purpose of this application is to provide a combined catalyst for the preparation of straight-chain alcohols by syngas tandem reaction and a method for preparing straight-chain alcohols using the same, in order to solve the above-mentioned problems.

[0006] To achieve the above objectives, this application adopts the following technical solution: A combined catalyst for the preparation of straight-chain alcohols via a syngas tandem reaction, the combined catalyst comprising a separate first catalyst and a second catalyst; The first catalyst includes a first active component, a first auxiliary agent, and a first support. The first active component is Ru, the metal corresponding to the first auxiliary agent is Na, and the first support is amorphous silica. The first active component and the first auxiliary agent are loaded in the form of nanoparticles inside the pores and on the surface of the first support. The second catalyst comprises a second active component, a second auxiliary agent, a third auxiliary agent, and a second support. The second active component is Rh, the metal corresponding to the second auxiliary agent is K, the metal corresponding to the third auxiliary agent is Zn and / or Fe, and the second support is an MFI-type molecular sieve composed of pure silicon. The second active component, the second auxiliary agent, and the third auxiliary agent are encapsulated in the pores of the second support in the form of sub-nano clusters or single atoms.

[0007] Preferably, the mass ratio of the first active component, the first auxiliary agent, and the first carrier is (0.5-10):(0.01-2.0):100; The mass ratio of the second active component, the second adjuvant, the third adjuvant, and the second carrier is (0.01-1.0):(0.1-2.0):(0.1-2.0):100.

[0008] Preferably, the size of the first active component is 1.2-2.5 nm; The size of the second active component is 0.6-1.2 nm.

[0009] Preferably, the preparation method of the first catalyst includes: A mixed solution is obtained by mixing a water-soluble Ru salt precursor, an auxiliary salt precursor and water, then adding the first carrier for impregnation, and after a first stirring, a first drying is performed to obtain a solid powder. The solid powder is subjected to a first calcination to obtain the first catalyst.

[0010] Preferably, the combined catalyst for the syngas tandem reaction to prepare straight-chain alcohols satisfies one or more of the following conditions: (1) The water-soluble Ru salt precursor is selected from one or more of hexaammonium trichloride, ruthenium trichloride, ruthenium nitrate, and nitrosyl ruthenium nitrate; (2) The auxiliary salt precursor is selected from one or more of sodium chloride, sodium nitrate, and sodium sulfate; (3) The first stirring speed is 300-1000 r / min, and the time is 1-3 h; (4) The temperature of the first drying is 50-120℃ and the time is 4-12h; (5) The temperature of the first roasting is 300-500℃ and the time is 3-10h.

[0011] Preferably, the method for preparing the second catalyst includes: The silicon source, template agent, second auxiliary salt and water are mixed, and after a second stirring, water-soluble Rh salt, third auxiliary salt and encapsulating agent are added. After stirring continues, a hydrothermal reaction is carried out. Solid-liquid separation, washing, and second drying are performed to obtain a solid. The solid is then calcined to obtain the second catalyst.

[0012] Preferably, the combined catalyst for the syngas tandem reaction to prepare straight-chain alcohols satisfies one or more of the following conditions: (1) The silicon source is selected from one or more of tetraethyl silicate, silica sol, and silicon dioxide; (2) The second auxiliary salt is selected from one or more of potassium chloride, potassium nitrate, and potassium hydroxide; (3) The template agent is selected from one or more of tetrapropylammonium hydroxide and tetraethylammonium hydroxide; (4) The second stirring speed is 100-1200 r / min and the time is 10-60 min; (5) The water-soluble Rh salt is selected from rhodium trichloride and / or rhodium nitrate; (6) The third auxiliary salt is selected from one or more of ferric nitrate, ferric chloride, zinc nitrate, and zinc chloride; (7) The template agent is selected from tetrapropylammonium hydroxide and / or tetraethylammonium hydroxide; (8) The stirring speed is 100-1200 r / min and the stirring time is 5-15 min; (9) The temperature of the hydrothermal reaction is 100-190℃ and the time is 12-72h; (10) The temperature of the second drying process is 60-150℃; (11) The second roasting temperature is 400-600℃ and the time is 3-12h.

[0013] This application also provides a method for preparing straight-chain alcohols using the aforementioned syngas tandem reaction combined catalyst, comprising: The first catalyst is used to catalyze the synthesis gas to carry out a first reaction to obtain straight-chain olefins; the synthesis gas includes carbon monoxide and hydrogen. The second catalyst is used to catalyze the reaction of the straight-chain olefin to obtain a second straight-chain alcohol.

[0014] Preferably, the temperature of the first reaction is 50-300℃, the pressure is 2.5-4.5MPa, and the molar ratio of H2 to CO is 1.0-2.0:1; The temperature of the second reaction is 70-120℃, and the pressure is 2.5-4.5MPa.

[0015] Preferably, the first reaction and the second reaction are carried out in a continuous fixed bed.

[0016] Compared with the prior art, the beneficial effects of this application include: This application employs a tandem catalytic strategy, decoupling the syngas-to-alcohol process into two controllable steps through separate Ru-Na / SiO2 and Rh-K-Zn(Fe) / MFI catalyst combinations, thus revolutionizing the traditional Fischer-Tropsch synthesis pathway. Specifically, the first catalyst is responsible for the highly selective catalytic conversion of syngas into a straight-chain α-olefin intermediate; the second catalyst is dedicated to the directional conversion of this olefin intermediate into a straight-chain alcohol via hydroformylation-hydrogenation. This strategy avoids the limitations imposed by the ASF distribution pattern and the wide carbon number distribution of products in traditional processes, providing a key solution for the directional synthesis of higher alcohols. The core advantage of this design lies in stepwise optimization and synergistic effects. By spatiotemporally separating the "carbon chain growth" and "CO insertion / hydrogenation" reactions, the active sites of the two reactions can be independently optimized: Na-Ru / SiO2 focuses on the efficient generation of olefins; Rh-K-Zn(Fe) / MFI utilizes the confinement effect of molecular sieves and synergistic effects with promoters to precisely promote alcohol generation. This effectively solves the problem of competition among multiple active sites in single-catalyst systems. Ultimately, this method can significantly increase the yield of straight-chain alcohols (especially C10 ... 6+The selectivity of higher alcohols and the simple process flow open up a new path for the green and efficient preparation of high-value higher alcohols. Attached Figure Description

[0017] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation on the scope of this application.

[0018] Figure 1 This is a TEM image of heterogeneous catalyst I from Example 1 of this application; Figure 2 This is a TEM image of the heterogeneous catalyst II in Example 1 of this application; Figure 3 This is a schematic diagram of the reaction device structure of Embodiment 1 of this application. Detailed Implementation

[0019] To better illustrate the technical solution provided in this application, the technical solution will be described in its entirety before the embodiments, as follows: A combined catalyst for the preparation of straight-chain alcohols via a syngas tandem reaction, the combined catalyst comprising a separate first catalyst and a second catalyst; The first catalyst includes a first active component, a first auxiliary agent, and a first support. The first active component is Ru, the metal corresponding to the first auxiliary agent is Na, and the first support is amorphous silica. The first active component and the first auxiliary agent are loaded in the form of nanoparticles inside the pores and on the surface of the first support. The second catalyst comprises a second active component, a second auxiliary agent, a third auxiliary agent, and a second support. The second active component is Rh, the metal corresponding to the second auxiliary agent is K, the metal corresponding to the third auxiliary agent is Zn and / or Fe, and the second support is an MFI-type molecular sieve composed of pure silicon. The second active component, the second auxiliary agent, and the third auxiliary agent are encapsulated in the pores of the second support in the form of sub-nano clusters or single atoms.

[0020] It is worth noting that the traditional Fischer-Tropsch synthesis (FTS), as a classic route for hydrocarbon production from syngas, strictly follows the Anderson-Schulz-Flory (ASF) kinetics in its product carbon number distribution, exhibiting inherent thermodynamic limitations. The targeted synthesis of higher alcohols requires overcoming the limitations of the traditional FTS route, with the core being the precise coupling of the two key reactions: "carbon chain growth" and "CO insertion." A tandem catalytic strategy innovatively couples two controllable reactions—"directional preparation of long-chain α-olefins from syngas" and "hydroformylation of long-chain olefins"—providing a core solution to overcome the ASF limitations. The core advantage of this strategy is "stepwise regulation and synergistic enhancement": by spatially and temporally separating the carbon chain growth and CO insertion reactions, the active site structure and reaction conditions of the two stages can be optimized separately. This solves the active site competition problem of traditional single-catalytic systems and significantly improves the selectivity of higher alcohols through the targeted generation and conversion of olefin intermediates, opening up a new technological route for the efficient and green preparation of higher alcohols.

[0021] In one optional embodiment, the mass ratio of the first active component, the first adjuvant, and the first carrier is (0.5-10):(0.01-2.0):100; The mass ratio of the second active component, the second adjuvant, the third adjuvant, and the second carrier is (0.01-1.0):(0.1-2.0):(0.1-2.0):100.

[0022] Optionally, the mass ratio of the first active component, the first adjuvant, and the first carrier can be any value between 0.5:0.01:100, 5:1:100, 10:2:100, or (0.5-10):(0.01-2.0):100; the mass ratio of the second active component, the second adjuvant, the third adjuvant, and the second carrier can be any value between (0.01-1.0):(0.1-2.0):(0.1-2.0):100.

[0023] In one optional embodiment, the size of the first active component is 1.2-2.5 nm; The size of the second active component is 0.6-1.2 nm.

[0024] Optionally, the size of the first active component can be any value between 1.2 nm, 1.5 nm, 2.0 nm, 2.5 nm, or 1.2-2.5 nm; the size of the second active component can be any value between 0.6 nm, 1.0 nm, 1.2 nm, or 0.6-1.2 nm.

[0025] In an optional embodiment, the method for preparing the first catalyst includes: A mixed solution is obtained by mixing a water-soluble Ru salt precursor, an auxiliary salt precursor and water, then adding the first carrier for impregnation, and after a first stirring, a first drying is performed to obtain a solid powder. The solid powder is subjected to a first calcination to obtain the first catalyst.

[0026] In an optional embodiment, the combined catalyst for the syngas tandem reaction to prepare straight-chain alcohols satisfies one or more of the following conditions: (1) The water-soluble Ru salt precursor is selected from one or more of hexaammonium trichloride, ruthenium trichloride, ruthenium nitrate, and nitrosyl ruthenium nitrate; (2) The auxiliary salt precursor is selected from one or more of sodium chloride, sodium nitrate, and sodium sulfate; (3) The first stirring speed is 300-1000 r / min, and the time is 1-3 h; Optionally, the rotation speed of the first stirring can be any value between 300 r / min, 400 r / min, 500 r / min, 600 r / min, 700 r / min, 800 r / min, 900 r / min, 1000 r / min or 300-1000 r / min, and the time can be any value between 1 h, 2 h, 3 h or 1-3 h. (4) The temperature of the first drying is 50-120℃ and the time is 4-12h; Optionally, the temperature of the first drying can be any value between 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C or 50-120°C, and the time can be any value between 4h, 6h, 8h, 10h, 12h or 4-12h. (5) The temperature of the first roasting is 300-500℃ and the time is 3-10h.

[0027] Optionally, the temperature of the first roasting can be any value between 300℃, 400℃, 500℃ or 300-500℃, and the time can be any value between 3h, 5h, 8h, 10h or 3-10h.

[0028] In an optional embodiment, the method for preparing the second catalyst includes: The silicon source, template agent, second auxiliary salt and water are mixed, and after a second stirring, water-soluble Rh salt, third auxiliary salt and encapsulating agent are added. After stirring continues, a hydrothermal reaction is carried out. Solid-liquid separation, washing, and second drying are performed to obtain a solid. The solid is then calcined to obtain the second catalyst.

[0029] In an optional embodiment, the combined catalyst for the syngas tandem reaction to prepare straight-chain alcohols satisfies one or more of the following conditions: (1) The silicon source is selected from one or more of tetraethyl silicate, silica sol, and silicon dioxide; (2) The second auxiliary salt is selected from one or more of potassium chloride, potassium nitrate, and potassium hydroxide; (3) The template agent is selected from one or more of tetrapropylammonium hydroxide and tetraethylammonium hydroxide; (4) The second stirring speed is 100-1200 r / min and the time is 10-60 min; (5) The water-soluble Rh salt is selected from rhodium trichloride and / or rhodium nitrate; (6) The third auxiliary salt is selected from one or more of ferric nitrate, ferric chloride, zinc nitrate, and zinc chloride; (7) The template agent is selected from tetrapropylammonium hydroxide and / or tetraethylammonium hydroxide; (8) The stirring speed is 100-1200 r / min and the stirring time is 5-15 min; (9) The temperature of the hydrothermal reaction is 100-190℃ and the time is 12-72h; Optionally, the temperature of the hydrothermal reaction can be any value between 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃ or 100-190℃, and the time can be any value between 12h, 24h, 36h, 48h, 60h, 72h or 12-72h. (10) The temperature of the second drying process is 60-150℃; Optionally, the temperature of the second drying can be any value between 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, or 60-150°C. (11) The second roasting temperature is 400-600℃ and the time is 3-12h.

[0030] Optionally, the temperature of the second roasting can be any value between 400, 500, 600 or 400-600℃, and the time can be any value between 3h, 6h, 9h, 12h or 3-12h.

[0031] This application also provides a method for preparing straight-chain alcohols using the aforementioned syngas tandem reaction combined catalyst, comprising: The first catalyst is used to catalyze the synthesis gas to carry out a first reaction to obtain straight-chain olefins; the synthesis gas includes carbon monoxide and hydrogen. The second catalyst is used to catalyze the reaction of the straight-chain olefin to obtain a second straight-chain alcohol.

[0032] In one optional embodiment, the temperature of the first reaction is 50-300°C, the pressure is 2.5-4.5 MPa, and the molar ratio of H2 to CO is 1.0-2.0:1; The temperature of the second reaction is 70-120℃, and the pressure is 2.5-4.5MPa.

[0033] Optionally, the temperature of the first reaction can be any value between 50℃, 100℃, 200℃, 300℃ or 50-300℃, and the pressure can be any value between 2.5MPa, 3.0MPa, 3.5MPa, 4.0MPa, 4.5MPa or 2.5-4.5MPa. The molar ratio of H2 to CO can be any value between 1:1, 1.5:1, 2:1 or 1.0-2.0:1. The temperature of the second reaction can be any value between 70℃, 80℃, 90℃, 100℃, 110℃, 120℃ or 70-120℃, and the pressure can be any value between 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa or 2.5-4.5MPa.

[0034] In an alternative implementation, the first and second reactions are carried out in a continuous fixed bed.

[0035] The implementation schemes of this application will be described in detail below with reference to specific embodiments. However, those skilled in the art will understand that the following embodiments are only for illustrating this application and should not be regarded as limiting the scope of this application. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments used without specified manufacturers are all conventional products that can be purchased commercially.

[0036] Example 1 In this embodiment, the supported catalyst I consists of 5 wt% Ru, 0.5 wt% Na, and 94.5 wt% amorphous silica, while the encapsulated catalyst II consists of 0.3 wt% Rh, 0.8 wt% K, 0.8 wt% Zn, and 98.1 wt% MFI support. The catalyst composed of the above-mentioned supported catalyst I and encapsulated catalyst II is designated as Cat1#.

[0037] The above-mentioned supported catalyst I was prepared in the following manner: (1) Weigh 0.835g of ruthenium nitrite and 98mg of sodium nitrate, dissolve them in 11.7g of deionized water, mix and stir to obtain a mixed solution of Ru and the auxiliary agent.

[0038] (2) Add 5g of SiO2 to the above step (1), impregnate it, and stir it thoroughly for a period of time. The stirring speed is 500r / min and the stirring time is 1.5h. Then dry it at 60℃ for 10h to obtain a solid powder loaded with active components and additives.

[0039] (3) The solid powder obtained in step (2) is calcined at 400℃ for 4 hours to obtain multiphase catalyst I, which is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0040] Electron microscopy analysis showed that the average particle size of Ru was 4.7 nm.

[0041] The above-mentioned encapsulated catalyst II is prepared in the following manner: (1) Weigh 8.24 g tetraethyl silicate, 12 g deionized water, 16.24 g tetrapropylammonium hydroxide and 25 mg KOH, mix them and stir for 15 min at a speed of 500 r / min.

[0042] (2) Add 16 mg RhCl3, 34 mg ZnCl2 and 300 µL ethylenediamine to step (1) above, continue stirring for 10 min, transfer the whole thing to a 50 mL tetrafluoroethylene liner and put it into a hydrothermal reactor.

[0043] (3) The hydrothermal reactor in step (2) is subjected to hydrothermal treatment at 170°C for 24 h.

[0044] (4) After hydrothermal treatment in step (3), the solution was centrifuged, washed, and dried at 80°C for 24 h to obtain a white solid.

[0045] (5) After grinding the white solid in step (4), calcining it at 550℃ for 8 h, the multiphase catalyst II can be obtained. The catalyst is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0046] Electron microscopy analysis showed that the average particle size of Rh was 0.7 nm.

[0047] Figure 1 This is a TEM image of heterogeneous catalyst I from Example 1 of this application. Figure 2 This is a TEM image of the heterogeneous catalyst II in Example 1 of this application.

[0048] Using Cat1# as a catalyst and H2 and CO as raw materials, a series coupled reaction was carried out as follows: The performance of the catalyst in a series reaction was evaluated using a micro-fixed-bed reactor. The micro-fixed-bed reactor was modified to use two electrically heated reactors connected in series (evaluation apparatus design as follows). Figure 30.10 g of 5%Ru-0.5%Na / SiO2 catalyst (40–60 mesh) was diluted with 0.05 g of silicon carbide and loaded into the isothermal zone of the upper reactor. 0.10 g of 0.3%Rh-0.8%K-0.8%Zn@MFI catalyst (40–60 mesh) was loaded into the isothermal zone of the lower reactor. Before the catalytic reaction, the loaded catalysts underwent reduction pretreatment. The reduction process was as follows: the two catalysts were respectively subjected to H2 (40 mL) at 450 ℃ and 500 ℃. min -1 The reduction was continued for 4 hours. After the temperatures of the upper and lower reactors dropped to 260 °C and 80 °C respectively, syngas with a ratio of H2 / CO = 1 (H2 / CO / Ar = 48 / 48 / 4) was introduced in 5 mL increments. min -1 (WHSV = 3000 mL g cat. -1 h -1 The gas was injected into the reactor at a flow rate of 3.0 MPa to initiate the reaction. Argon was used as an internal standard gas for the quantitative calculation of carbon monoxide conversion and the selectivity of each product in the subsequent tail gas. The products were analyzed online by gas chromatography, and the evaluation results are shown in Table 1.

[0049] Example 2 In this embodiment, the supported catalyst I consists of 4 wt% Ru, 0.4 wt% Na, and 95.6 wt% amorphous silica, while the encapsulated catalyst II consists of 0.4 wt% Rh, 0.9 wt% K, 1.2 wt% Zn, and 97.5 wt% MFI support. The catalyst composed of the above-mentioned supported catalyst I and encapsulated catalyst II is designated as Cat2#.

[0050] The above-mentioned supported catalyst I was prepared in the following manner: (1) Weigh 0.660 g of ruthenium nitrite and 77 mg of sodium nitrate, dissolve them in 11.7 g of deionized water, mix and stir to obtain a mixed solution of Ru and the auxiliary agent.

[0051] (2) Add 5 g SiO2 to the above step (1) for impregnation, and stir thoroughly for a period of time. The stirring speed is 500 r / min and the stirring time is 1.5 h. Then dry at 60 ℃ for 10 h to obtain a solid powder loaded with active components and additives.

[0052] (3) The solid powder obtained in step (2) is calcined at 450℃ for 3h to obtain multiphase catalyst I, which is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0053] Electron microscopy analysis showed that the average particle size of Ru was 4.5 nm.

[0054] The above-mentioned encapsulated catalyst II is prepared in the following manner: (1) Weigh 8.24 g tetraethyl silicate, 12 g deionized water, 16.24 g tetrapropylammonium hydroxide and 25 mg KOH, mix them and stir for 15 min at a speed of 500 r / min.

[0055] (2) Add 21 mg RhCl3, 51 mg zinc nitrate and 300 µL ethylenediamine to step (1) above, continue stirring for 10 min, transfer the whole thing to a 50 mL tetrafluoroethylene liner and put it into a hydrothermal reactor.

[0056] (3) The hydrothermal reactor in step (2) is subjected to hydrothermal treatment at 140 °C for 48 h.

[0057] (4) After hydrothermal treatment in step (3), the solution was centrifuged, washed, and dried at 80 °C for 24 h to obtain a white solid.

[0058] (5) After grinding the white solid in step (4), calcine it at 500 °C for 12 h to obtain multiphase catalyst II. Press it into tablets, sieve it, and take 40~60 mesh samples for performance evaluation.

[0059] Electron microscopy analysis showed that the average particle size of Rh was 0.9 nm.

[0060] Using Cat2# as a catalyst and H2 and CO as raw materials, a series coupled reaction was carried out, as follows: The performance of the catalyst in a series reaction was evaluated using a micro-fixed-bed reactor. The micro-fixed-bed reactor was modified to use two electrically heated reactors connected in series (evaluation apparatus design as follows). Figure 3 0.10 g of 4%Ru-0.4%Na / SiO2 catalyst (40–60 mesh) was diluted with 0.05 g of silicon carbide and loaded into the isothermal zone of the upper reactor. 0.10 g of 0.4%Rh-0.9%K-1.2%Zn@MFI catalyst (40–60 mesh) was loaded into the isothermal zone of the lower reactor. Before the catalytic reaction, the loaded catalysts underwent reduction pretreatment. The reduction process was as follows: the two catalysts were respectively subjected to H2 (40 mL) at 450 ℃ and 500 ℃. min -1The reduction was continued for 4 hours. After the temperatures of the upper and lower reactors dropped to 280 ℃ and 90 ℃ respectively, syngas with a ratio of H2 / CO = 1 (H2 / CO / Ar = 48 / 48 / 4) was introduced in 5 mL increments. min -1 (WHSV = 3000 mL g cat. -1 h -1 The gas was injected into the reactor at a flow rate of 3.0 MPa to initiate the reaction. Argon was used as an internal standard gas for the quantitative calculation of carbon monoxide conversion and the selectivity of each product in the subsequent tail gas. The products were analyzed online by gas chromatography, and the evaluation results are shown in Table 1.

[0061] Example 3 In this embodiment, the supported catalyst I consists of 3.5 wt% Ru, 0.6 wt% Na, and 95.9 wt% amorphous silica, while the encapsulated catalyst II consists of 0.3 wt% Rh, 1.0 wt% K, 1.0 wt% Fe, and 97.7 wt% MFI support. The catalyst composed of the above-mentioned supported catalyst I and encapsulated catalyst II is designated as Cat3#.

[0062] The above-mentioned supported catalyst I was prepared in the following manner: (1) Weigh 0.576 g of ruthenium nitrite and 116 mg of sodium nitrate, dissolve them in 11.7 g of deionized water, mix and stir to obtain a mixed solution of Ru and the auxiliary agent.

[0063] (2) Add 5 g SiO2 to the above step (1) for impregnation, and stir thoroughly for a period of time. The stirring speed is 500 r / min and the stirring time is 1.5 h. Then dry at 60 ℃ for 10 h to obtain a solid powder loaded with active components and additives.

[0064] (3) The solid powder obtained in step (2) was calcined at 500 °C for 4 h to obtain multiphase catalyst I, which was then pressed into tablets, sieved, and 40-60 mesh samples were taken for performance evaluation.

[0065] Electron microscopy analysis showed that the average particle size of Ru was 4.3 nm.

[0066] The above-mentioned encapsulated catalyst II is prepared in the following manner: (1) Weigh 8.24 g tetraethyl silicate, 12 g deionized water, 16.24 g tetrapropylammonium hydroxide and 30 mg KOH, mix them and stir for 15 min at a speed of 500 r / min.

[0067] (2) Add 16 gRhCl3, 60 mgFeCl3 and 300 µL ethylenediamine to step (1) above, continue stirring for 10 min, transfer the whole thing to a 50 mL tetrafluoroethylene liner and put it into a hydrothermal reactor.

[0068] (3) The hydrothermal reactor in step (2) is subjected to hydrothermal treatment at 170 °C for 24 h.

[0069] (4) After hydrothermal treatment in step (3), the solution was centrifuged, washed, and dried at 80°C for 24 h to obtain a white solid.

[0070] (5) After grinding the white solid in step (4), calcining it at 500℃ for 12 h, the multiphase catalyst II can be obtained. The catalyst is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0071] Electron microscopy analysis showed that the average particle size of Rh was 0.6 nm.

[0072] Using Cat3# as a catalyst and H2 and CO as raw materials, a series coupled reaction was carried out, as follows: The performance of the catalyst in a series reaction was evaluated using a micro-fixed-bed reactor. The micro-fixed-bed reactor was modified to use two electrically heated reactors connected in series (evaluation apparatus design as follows). Figure 3 0.10 g of 3.5%Ru-0.6%Na / SiO2 catalyst (40–60 mesh) was diluted with 0.05 g of silicon carbide and loaded into the isothermal zone of the upper reactor. 0.10 g of 0.3%Rh-1.0%K-1.0%Fe@MFI catalyst (40–60 mesh) was loaded into the isothermal zone of the lower reactor. Before the catalytic reaction, the loaded catalysts underwent reduction pretreatment. The reduction process was as follows: the two catalysts were respectively subjected to H2 (40 mL) at 450 ℃ and 500 ℃. min -1 The reduction was continued for 4 hours. After the temperatures of the upper and lower reactors dropped to 260 °C and 80 °C respectively, syngas with a ratio of H2 / CO = 1 (H2 / CO / Ar = 48 / 48 / 4) was introduced in 5 mL increments. min -1 (WHSV = 3000 mL g cat. -1 h -1The gas was injected into the reactor at a flow rate of 3.0 MPa to initiate the reaction. Argon was used as an internal standard gas for the quantitative calculation of carbon monoxide conversion and selectivity of each product in the subsequent tail gas. The products were analyzed online by gas chromatography, and the evaluation results are shown in Table 1.

[0073] Example 4 In this embodiment, the supported catalyst I consists of 5 wt% Ru, 0.8 wt% Na, and 94.2 wt% amorphous silica, while the encapsulated catalyst II consists of 0.4 wt% Rh, 1.0 wt% K, 1.5 wt% Fe, and 97.1 wt% MFI support. The catalyst composed of the above-mentioned supported catalyst I and encapsulated catalyst II is designated as Cat4#.

[0074] The above-mentioned supported catalyst I was prepared in the following manner: (1) Weigh 0.837 g of ruthenium nitrite and 157 mg of sodium nitrate, dissolve them in 11.7 g of deionized water, mix and stir to obtain a mixed solution of Ru and the auxiliary agent.

[0075] (2) Add 5 g SiO2 to the above step (1) for impregnation, and stir thoroughly for a period of time. The stirring speed is 500 r / min and the stirring time is 1.5 h. Then dry at 60℃ for 10 h to obtain a solid powder loaded with active components and additives.

[0076] (3) The solid powder obtained in step (2) is calcined at 400℃ for 4 h to obtain multiphase catalyst I, which is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0077] Electron microscopy analysis showed that the average particle size of Ru was 4.8 nm.

[0078] The above-mentioned encapsulated catalyst II is prepared in the following manner: (1) Weigh 8.24 g tetraethyl silicate, 12 g deionized water, 16.24 g tetrapropylammonium hydroxide and 30 mg KOH, mix them and stir for 15 min at a speed of 500 r / min.

[0079] (2) Add 21 gRhCl3, 90 mg ferric nitrate and 300 µL ethylenediamine to step (1) above, continue stirring for 10 min, transfer the whole thing to a 50 mL tetrafluoroethylene liner and put it into a hydrothermal reactor.

[0080] (3) The hydrothermal reactor in step (2) is subjected to hydrothermal treatment at 170 °C for 24 h.

[0081] (4) After hydrothermal treatment in step (3), the solution was centrifuged, washed, and dried at 80°C for 24 h to obtain a white solid.

[0082] (5) After grinding the white solid in step (4), calcining it at 550 °C for 8 h, the multiphase catalyst II can be obtained. The catalyst is then pressed into tablets, sieved, and 40-60 mesh samples are taken for performance evaluation.

[0083] Electron microscopy analysis showed that the average particle size of Rh was 0.8 nm.

[0084] Using Cat4# as a catalyst and H2 and CO as raw materials, a series coupled reaction was carried out as follows: The performance of the catalyst in a series reaction was evaluated using a micro-fixed-bed reactor. The micro-fixed-bed reactor was modified to use two electrically heated reactors connected in series (evaluation apparatus design as follows). Figure 3 0.10 g of 3.5%Ru-0.6%Na / SiO2 catalyst (40–60 mesh) was diluted with 0.05 g of silicon carbide and loaded into the isothermal zone of the upper reactor. 0.10 g of 0.3%Rh-1.0%K-1.0%Fe@MFI catalyst (40–60 mesh) was loaded into the isothermal zone of the lower reactor. Before the catalytic reaction, the loaded catalysts underwent reduction pretreatment. The reduction process was as follows: the two catalysts were respectively subjected to H2 (40 mL) at 450 ℃ and 500 ℃. min -1 The reduction was continued for 4 hours. After the temperatures of the upper and lower reactors dropped to 270 °C and 90 °C respectively, syngas with a ratio of H2 / CO = 1 (H2 / CO / Ar = 48 / 48 / 4) was introduced in 5 mL increments. min -1 (WHSV = 3000 mL g cat. -1 h -1 The gas was injected into the reactor at a flow rate of 3.0 MPa to initiate the reaction. Argon was used as an internal standard gas for the quantitative calculation of carbon monoxide conversion and selectivity of each product in the subsequent tail gas. The products were analyzed online by gas chromatography, and the evaluation results are shown in Table 1.

[0085] Comparative Example 1 In this comparative example, supported catalyst I consisted of 0.5 wt% Na and 99.5 wt% amorphous silica, while encapsulated catalyst II consisted of 0.3 wt% Rh, 0.8 wt% K, 0.8 wt% Zn, and 98.1 wt% MFI support. The catalyst composed of the above supported catalyst I and encapsulated catalyst II is denoted as Cat1#.

[0086] The above-mentioned supported catalyst I was prepared in the following manner: (1) Weigh 98 mg of sodium nitrate and dissolve it in 11.7 g of deionized water. Mix and stir to obtain a metal precursor solution.

[0087] (2) Add 5g of SiO2 to the above step (1), impregnate it, and stir it thoroughly for a period of time. The stirring speed is 500r / min and the stirring time is 1.5h. Then dry it at 60℃ for 10h to obtain a solid powder loaded with active components and additives.

[0088] (3) The solid powder obtained in step (2) is calcined at 400℃ for 4 hours to obtain multiphase catalyst I, which is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0089] The above-mentioned encapsulated catalyst II is prepared in the following manner: (1) Weigh 8.24 g tetraethyl silicate, 12 g deionized water, 16.24 g tetrapropylammonium hydroxide and 25 mg KOH, mix them and stir for 15 min at a speed of 500 r / min.

[0090] (2) Add 16 mg RhCl3, 34 mg ZnCl2 and 300 µL ethylenediamine to step (1) above, continue stirring for 10 min, transfer the whole thing to a 50 mL tetrafluoroethylene liner and put it into a hydrothermal reactor.

[0091] (3) The hydrothermal reactor in step (2) is subjected to hydrothermal treatment at 170°C for 24 h.

[0092] (4) After hydrothermal treatment in step (3), the solution was centrifuged, washed, and dried at 80°C for 24 h to obtain a white solid.

[0093] (5) After grinding the white solid in step (4), calcining it at 550℃ for 8 h, the multiphase catalyst II can be obtained. The catalyst is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0094] Using Cat1# as a catalyst and H2 and CO as raw materials, a series coupled reaction was carried out as follows: The performance of the catalyst in a series reaction was evaluated using a micro-fixed-bed reactor. The micro-fixed-bed reactor was modified to use two electrically heated reactors connected in series (evaluation apparatus design as follows). Figure 3 0.10 g of 0.5% Na / SiO2 catalyst (40–60 mesh) was diluted with 0.05 g of silicon carbide and loaded into the isothermal zone of the upper reactor. 0.10 g of 0.3% Rh-0.8% K-0.8% Zn@MFI catalyst (40–60 mesh) for hydroformylation was loaded into the isothermal zone of the lower reactor. Before the catalytic reaction, the loaded catalysts underwent reduction pretreatment. The reduction process was as follows: the two catalysts were respectively subjected to H2 (40 mL) at 450 ℃ and 500 ℃. min -1 The reduction was continued for 4 hours. After the temperatures of the upper and lower reactors dropped to 260 °C and 80 °C respectively, syngas with a ratio of H2 / CO = 1 (H2 / CO / Ar = 48 / 48 / 4) was introduced in 5 mL increments. min -1 (WHSV = 3000 mL g cat. -1 h -1 The gas was injected into the reactor at a flow rate of 3.0 MPa to initiate the reaction. Argon was used as an internal standard gas for the quantitative calculation of carbon monoxide conversion and the selectivity of each product in the subsequent tail gas. The products were analyzed online by gas chromatography, and the evaluation results are shown in Table 1.

[0095] Comparative Example 2 In this comparative example, supported catalyst I consisted of 5 wt% Ru and 95 wt% amorphous silica, while encapsulated catalyst II consisted of 0.3 wt% Rh, 0.8 wt% K, 0.8 wt% Zn, and 98.1 wt% MFI support. The catalyst composed of the above supported catalyst I and encapsulated catalyst II is denoted as Cat2#.

[0096] The above-mentioned supported catalyst I was prepared in the following manner: (1) Weigh 0.835g of ruthenium nitrite and dissolve it in 11.7g of deionized water. Mix and stir to obtain a metal precursor solution.

[0097] (2) Add 5g of SiO2 to the above step (1), impregnate it, and stir it thoroughly for a period of time. The stirring speed is 500r / min and the stirring time is 1.5h. Then dry it at 60℃ for 10h to obtain a solid powder loaded with active components and additives.

[0098] (3) The solid powder obtained in step (2) is calcined at 400℃ for 4 hours to obtain multiphase catalyst I, which is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0099] The above-mentioned encapsulated catalyst II is prepared in the following manner: (1) Weigh 8.24 g tetraethyl silicate, 12 g deionized water, 16.24 g tetrapropylammonium hydroxide and 25 mg KOH, mix them and stir for 15 min at a speed of 500 r / min.

[0100] (2) Add 16 mg RhCl3, 34 mg ZnCl2 and 300 µL ethylenediamine to step (1) above, continue stirring for 10 min, transfer the whole thing to a 50 mL tetrafluoroethylene liner and put it into a hydrothermal reactor.

[0101] (3) The hydrothermal reactor in step (2) is subjected to hydrothermal treatment at 170°C for 24 h.

[0102] (4) After hydrothermal treatment in step (3), the solution was centrifuged, washed, and dried at 80°C for 24 h to obtain a white solid.

[0103] (5) After grinding the white solid in step (4), calcining it at 550℃ for 8 h, the multiphase catalyst II can be obtained. The catalyst is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0104] Using Cat2# as a catalyst and H2 and CO as raw materials, a series coupled reaction was carried out, as follows: The performance of the catalyst in a series reaction was evaluated using a micro-fixed-bed reactor. The micro-fixed-bed reactor was modified to use two electrically heated reactors connected in series (evaluation apparatus design as follows). Figure 3 0.10 g of 5% Ru / SiO2 catalyst (40–60 mesh) was diluted with 0.05 g of silicon carbide and loaded into the isothermal zone of the upper reactor. 0.10 g of 0.3% Rh-0.8% K-0.8% Zn@MFI catalyst (40–60 mesh) for hydroformylation was loaded into the isothermal zone of the lower reactor. Before the catalytic reaction, the loaded catalysts underwent reduction pretreatment. The reduction process was as follows: the two catalysts were respectively treated with H2 (40 mL) at 450 ℃ and 500 ℃. min -1 The reduction was continued for 4 hours. After the temperatures of the upper and lower reactors dropped to 260 °C and 80 °C respectively, syngas with a ratio of H2 / CO = 1 (H2 / CO / Ar = 48 / 48 / 4) was introduced in 5 mL increments. min -1(WHSV = 3000 mL g cat. -1 h -1 The gas was injected into the reactor at a flow rate of 3.0 MPa to initiate the reaction. Argon was used as an internal standard gas for the quantitative calculation of carbon monoxide conversion and selectivity of each product in the subsequent tail gas. The products were analyzed online by gas chromatography, and the evaluation results are shown in Table 1.

[0105] Unlike Example 1, supported catalyst I does not contain Na.

[0106] Comparative Example 3 In this comparative example, supported catalyst I consisted of 5 wt% Ru, 0.5 wt% Na, and 94.5 wt% titanium dioxide, while encapsulated catalyst II consisted of 0.3 wt% Rh, 0.8 wt% K, 0.8 wt% Zn, and 98.1 wt% MFI support. The catalyst composed of the above supported catalyst I and encapsulated catalyst II is designated Cat3#.

[0107] The above-mentioned supported catalyst I was prepared in the following manner: (1) Weigh 0.835g of ruthenium nitrite and 98mg of sodium nitrate, dissolve them in 11.7g of deionized water, mix and stir to obtain a mixed solution of Ru and the auxiliary agent.

[0108] (2) Add 5g TiO2 to the above step (1) for impregnation, and stir thoroughly for a period of time. The stirring speed is 500r / min and the stirring time is 1.5h. Then dry at 60℃ for 10h to obtain a solid powder loaded with active components and additives.

[0109] (3) The solid powder obtained in step (2) is calcined at 400℃ for 4 hours to obtain multiphase catalyst I, which is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0110] The above-mentioned encapsulated catalyst II is prepared in the following manner: (1) Weigh 8.24 g tetraethyl silicate, 12 g deionized water, 16.24 g tetrapropylammonium hydroxide and 25 mg KOH, mix them and stir for 15 min at a speed of 500 r / min.

[0111] (2) Add 16 mg RhCl3, 34 mg ZnCl2 and 300 µL ethylenediamine to step (1) above, continue stirring for 10 min, transfer the whole thing to a 50 mL tetrafluoroethylene liner and put it into a hydrothermal reactor.

[0112] (3) The hydrothermal reactor in step (2) is subjected to hydrothermal treatment at 170°C for 24 h.

[0113] (4) After hydrothermal treatment in step (3), the solution was centrifuged, washed, and dried at 80°C for 24 h to obtain a white solid.

[0114] (5) After grinding the white solid in step (4), calcining it at 550℃ for 8 h, the multiphase catalyst II can be obtained. The catalyst is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0115] Using Cat3# as a catalyst and H2 and CO as raw materials, a series coupled reaction was carried out, as follows: The performance of the catalyst in a series reaction was evaluated using a micro-fixed-bed reactor. The micro-fixed-bed reactor was modified to use two electrically heated reactors connected in series (evaluation apparatus design as follows). Figure 3 0.10 g of 5%Ru-0.5%Na / TiO2 catalyst (40–60 mesh) was diluted with 0.05 g of silicon carbide and loaded into the isothermal zone of the upper reactor. 0.10 g of 0.3%Rh-0.8%K-0.8%Zn@MFI catalyst (40–60 mesh) for hydroformylation was loaded into the isothermal zone of the lower reactor. Before the catalytic reaction, the loaded catalysts underwent reduction pretreatment. The reduction process was as follows: the two catalysts were respectively subjected to H2 (40 mL) at 450 ℃ and 500 ℃. min -1 The reduction was continued for 4 hours. After the temperatures of the upper and lower reactors dropped to 260 °C and 80 °C respectively, syngas with a ratio of H2 / CO = 1 (H2 / CO / Ar = 48 / 48 / 4) was introduced in 5 mL increments. min -1 (WHSV = 3000 mL g cat. -1 h -1 The gas was injected into the reactor at a flow rate of 3.0 MPa to initiate the reaction. Argon was used as an internal standard gas for the quantitative calculation of carbon monoxide conversion and the selectivity of each product in the subsequent tail gas. The products were analyzed online by gas chromatography, and the evaluation results are shown in Table 1.

[0116] Comparative Example 4 In this comparative example, supported catalyst I consisted of 5 wt% Ru, 0.5 wt% Na, and 94.5 wt% amorphous silica, while encapsulated catalyst II consisted of 0.8 wt% K, 0.8 wt% Zn, and 98.4 wt% MFI support. The catalyst composed of the above supported catalyst I and encapsulated catalyst II is designated Cat4#.

[0117] The above-mentioned supported catalyst I was prepared in the following manner: (1) Weigh 0.835g of ruthenium nitrite and 98mg of sodium nitrate, dissolve them in 11.7g of deionized water, mix and stir to obtain a mixed solution of Ru and the auxiliary agent.

[0118] (2) Add 5g of SiO2 to the above step (1), impregnate it, and stir it thoroughly for a period of time. The stirring speed is 500r / min and the stirring time is 1.5h. Then dry it at 60℃ for 10h to obtain a solid powder loaded with active components and additives.

[0119] (3) The solid powder obtained in step (2) is calcined at 400℃ for 4 hours to obtain multiphase catalyst I, which is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0120] The above-mentioned encapsulated catalyst II is prepared in the following manner: (1) Weigh 8.24 g tetraethyl silicate, 12 g deionized water, 16.24 g tetrapropylammonium hydroxide and 25 mg KOH, mix them and stir for 15 min at a speed of 500 r / min.

[0121] (2) Add 34 mg ZnCl2 and 300 µL ethylenediamine to step (1) above, continue stirring for 10 min, transfer the whole thing to a 50 mL tetrafluoroethylene liner, and put it into a hydrothermal reactor.

[0122] (3) The hydrothermal reactor in step (2) is subjected to hydrothermal treatment at 170°C for 24 h.

[0123] (4) After hydrothermal treatment in step (3), the solution was centrifuged, washed, and dried at 80°C for 24 h to obtain a white solid.

[0124] (5) After grinding the white solid in step (4), calcining it at 550℃ for 8 h, the multiphase catalyst II can be obtained. The catalyst is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0125] Using Cat4# as a catalyst and H2 and CO as raw materials, a series coupled reaction was carried out as follows: The performance of the catalyst in a series reaction was evaluated using a micro-fixed-bed reactor. The micro-fixed-bed reactor was modified to use two electrically heated reactors connected in series (evaluation apparatus design as follows). Figure 3 0.10 g of 5%Ru-0.5%Na / SiO2 catalyst (40–60 mesh) was diluted with 0.05 g of silicon carbide and loaded into the isothermal zone of the upper reactor. 0.10 g of 0.8%K-0.8%Zn@MFI hydroformylation catalyst (40–60 mesh) was loaded into the isothermal zone of the lower reactor. Before the catalytic reaction, the loaded catalysts underwent reduction pretreatment. The reduction process was as follows: the two catalysts were respectively treated with H2 (40 mL) at 450 ℃ and 500 ℃. min -1 The reduction was continued for 4 hours. After the temperatures of the upper and lower reactors dropped to 260 °C and 80 °C respectively, syngas with a ratio of H2 / CO = 1 (H2 / CO / Ar = 48 / 48 / 4) was introduced in 5 mL increments. min -1 (WHSV = 3000 mL g cat. -1 h -1 The gas was injected into the reactor at a flow rate of 3.0 MPa to initiate the reaction. Argon was used as an internal standard gas for the quantitative calculation of carbon monoxide conversion and selectivity of each product in the subsequent tail gas. The products were analyzed online by gas chromatography, and the evaluation results are shown in Table 1.

[0126] Comparative Example 5 In this comparative example, supported catalyst I consisted of 5 wt% Ru, 0.5 wt% Na, and 94.5 wt% amorphous silica, while encapsulated catalyst II consisted of 0.3 wt% Rh, 0.8 wt% K, and 98.1 wt% MFI support. The catalyst composed of the above supported catalyst I and encapsulated catalyst II is designated Cat5#.

[0127] The above-mentioned supported catalyst I was prepared in the following manner: (1) Weigh 0.835g of ruthenium nitrite and 98mg of sodium nitrate, dissolve them in 11.7g of deionized water, mix and stir to obtain a mixed solution of Ru and the auxiliary agent.

[0128] (2) Add 5g of SiO2 to the above step (1), impregnate it, and stir it thoroughly for a period of time. The stirring speed is 500r / min and the stirring time is 1.5h. Then dry it at 60℃ for 10h to obtain a solid powder loaded with active components and additives.

[0129] (3) The solid powder obtained in step (2) is calcined at 400℃ for 4 hours to obtain multiphase catalyst I, which is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0130] The above-mentioned encapsulated catalyst II is prepared in the following manner: (1) Weigh 8.24 g tetraethyl silicate, 12 g deionized water, 16.24 g tetrapropylammonium hydroxide and 25 mg KOH, mix them and stir for 15 min at a speed of 500 r / min.

[0131] (2) Add 16 mg RhCl3 and 300 µL ethylenediamine to step (1) above, continue stirring for 10 min, transfer the whole mixture to a 50 mL tetrafluoroethylene liner, and put it into a hydrothermal reactor.

[0132] (3) The hydrothermal reactor in step (2) is subjected to hydrothermal treatment at 170°C for 24 h.

[0133] (4) After hydrothermal treatment in step (3), the solution was centrifuged, washed, and dried at 80°C for 24 h to obtain a white solid.

[0134] (5) After grinding the white solid in step (4), calcining it at 550℃ for 8 h, the multiphase catalyst II can be obtained. The catalyst is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0135] Using Cat5# as a catalyst and H2 and CO as raw materials, a series coupled reaction was carried out, as follows: The performance of the catalyst in a series reaction was evaluated using a micro-fixed-bed reactor. The micro-fixed-bed reactor was modified to use two electrically heated reactors connected in series (evaluation apparatus design as follows). Figure 3 0.10 g of 5%Ru-0.5%Na / SiO2 catalyst (40–60 mesh) was diluted with 0.05 g of silicon carbide and loaded into the isothermal zone of the upper reactor. 0.10 g of 0.3%Rh-0.8%K@MFI hydroformylation catalyst (40–60 mesh) was loaded into the isothermal zone of the lower reactor. Before the catalytic reaction, the loaded catalysts underwent reduction pretreatment. The reduction process was as follows: the two catalysts were respectively treated with H2 (40 mL) at 450 ℃ and 500 ℃. min -1 The reduction was continued for 4 hours. After the temperatures of the upper and lower reactors dropped to 260 °C and 80 °C respectively, syngas with a ratio of H2 / CO = 1 (H2 / CO / Ar = 48 / 48 / 4) was introduced in 5 mL increments. min -1 (WHSV = 3000 mL g cat. -1 h -1 The gas was injected into the reactor at a flow rate of 3.0 MPa to initiate the reaction. Argon was used as an internal standard gas for the quantitative calculation of carbon monoxide conversion and selectivity of each product in the subsequent tail gas. The products were analyzed online by gas chromatography, and the evaluation results are shown in Table 1.

[0136] Comparative Example 6 In this comparative example, supported catalyst I consisted of 5 wt% Ru, 0.5 wt% Na, and 94.5 wt% amorphous silica, while encapsulated catalyst II consisted of 0.3 wt% Rh, 0.8 wt% Zn, and 98.9 wt% MFI support. The catalyst composed of the above supported catalyst I and encapsulated catalyst II is designated Cat6#.

[0137] The above-mentioned supported catalyst I was prepared in the following manner: (1) Weigh 0.835g of ruthenium nitrite and 98mg of sodium nitrate, dissolve them in 11.7g of deionized water, mix and stir to obtain a mixed solution of Ru and the auxiliary agent.

[0138] (2) Add 5g of SiO2 to the above step (1), impregnate it, and stir it thoroughly for a period of time. The stirring speed is 500r / min and the stirring time is 1.5h. Then dry it at 60℃ for 10h to obtain a solid powder loaded with active components and additives.

[0139] (3) The solid powder obtained in step (2) is calcined at 400℃ for 4 hours to obtain multiphase catalyst I, which is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0140] The above-mentioned encapsulated catalyst II is prepared in the following manner: (1) Weigh 8.24 g tetraethyl silicate, 12 g deionized water and 16.24 g tetrapropylammonium hydroxide, mix them and stir for 15 min at a speed of 500 r / min.

[0141] (2) Add 16 mg RhCl3, 34 mg ZnCl2 and 300 µL ethylenediamine to step (1) above, continue stirring for 10 min, transfer the whole thing to a 50 mL tetrafluoroethylene liner and put it into a hydrothermal reactor.

[0142] (3) The hydrothermal reactor in step (2) is subjected to hydrothermal treatment at 170°C for 24 h.

[0143] (4) After hydrothermal treatment in step (3), the solution was centrifuged, washed, and dried at 80°C for 24 h to obtain a white solid.

[0144] (5) After grinding the white solid in step (4), calcining it at 550℃ for 8 h, the multiphase catalyst II can be obtained. The catalyst is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0145] Using Cat6# as a catalyst and H2 and CO as raw materials, a series coupled reaction was carried out, as follows: The performance of the catalyst in a series reaction was evaluated using a micro-fixed-bed reactor. The micro-fixed-bed reactor was modified to use two electrically heated reactors connected in series (evaluation apparatus design as follows). Figure 3 0.10 g of 5%Ru-0.5%Na / SiO2 catalyst (40–60 mesh) was diluted with 0.05 g of silicon carbide and loaded into the isothermal zone of the upper reactor. 0.10 g of 0.3%Rh-0.8%Zn@MFI hydroformylation catalyst (40–60 mesh) was loaded into the isothermal zone of the lower reactor. Before the catalytic reaction, the loaded catalysts underwent reduction pretreatment. The reduction process was as follows: the two catalysts were respectively subjected to H2 (40 mL) at 450 ℃ and 500 ℃. min -1 The reduction was continued for 4 hours. After the temperatures of the upper and lower reactors dropped to 260 °C and 80 °C respectively, syngas with a ratio of H2 / CO = 1 (H2 / CO / Ar = 48 / 48 / 4) was introduced in 5 mL increments. min -1 (WHSV = 3000 mL g cat. -1 h -1 The gas was injected into the reactor at a flow rate of 3.0 MPa to initiate the reaction. Argon was used as an internal standard gas for the quantitative calculation of carbon monoxide conversion and selectivity of each product in the subsequent tail gas. The products were analyzed online by gas chromatography, and the evaluation results are shown in Table 1.

[0146] Comparative Example 7 In this comparative example, supported catalyst I consisted of 5 wt% Ru, 0.5 wt% Na, and 94.5 wt% amorphous silica, while encapsulated catalyst II consisted of 0.3 wt% Rh, 0.8 wt% K, 0.8 wt% Zn, and 98.1 wt% MEL support. The catalyst composed of the above supported catalyst I and encapsulated catalyst II is designated Cat7#.

[0147] The above-mentioned supported catalyst I was prepared in the following manner: (1) Weigh 0.835g of ruthenium nitrite and 98mg of sodium nitrate, dissolve them in 11.7g of deionized water, mix and stir to obtain a mixed solution of Ru and the auxiliary agent.

[0148] (2) Add 5g of SiO2 to the above step (1), impregnate it, and stir it thoroughly for a period of time. The stirring speed is 500r / min and the stirring time is 1.5h. Then dry it at 60℃ for 10h to obtain a solid powder loaded with active components and additives.

[0149] (3) The solid powder obtained in step (2) is calcined at 400℃ for 4 hours to obtain multiphase catalyst I, which is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0150] The above-mentioned encapsulated catalyst II is prepared in the following manner: (1) Weigh 8.24 g tetraethyl silicate, 12 g deionized water, 7.76 g tetrabutylammonium hydroxide and 25 mg KOH, mix them and stir for 15 min at a speed of 500 r / min.

[0151] (2) Add 16 mg RhCl3, 34 mg ZnCl2 and 300 µL ethylenediamine to step (1) above, continue stirring for 10 min, transfer the whole thing to a 50 mL tetrafluoroethylene liner and put it into a hydrothermal reactor.

[0152] (3) The hydrothermal reactor in step (2) is subjected to hydrothermal treatment at 170°C for 24 h.

[0153] (4) After hydrothermal treatment in step (3), the solution was centrifuged, washed, and dried at 80°C for 24 h to obtain a white solid.

[0154] (5) After grinding the white solid in step (4), calcining it at 550℃ for 8 h, the multiphase catalyst II can be obtained. The catalyst is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0155] Using Cat7# as a catalyst and H2 and CO as raw materials, a series coupled reaction was carried out, as follows: The performance of the catalyst in a series reaction was evaluated using a micro-fixed-bed reactor. The micro-fixed-bed reactor was modified to use two electrically heated reactors connected in series (evaluation apparatus design as follows). Figure 30.10 g of 5%Ru-0.5%Na / SiO2 catalyst (40–60 mesh) was diluted with 0.05 g of silicon carbide and loaded into the isothermal zone of the upper reactor. 0.10 g of 0.3%Rh-0.8%K-0.8%Zn@MFI catalyst (40–60 mesh) was loaded into the isothermal zone of the lower reactor. Before the catalytic reaction, the loaded catalysts underwent reduction pretreatment. The reduction process was as follows: the two catalysts were respectively subjected to H2 (40 mL) at 450 ℃ and 500 ℃. min -1 The reduction was continued for 4 hours. After the temperatures of the upper and lower reactors dropped to 260 °C and 80 °C respectively, syngas with a ratio of H2 / CO = 1 (H2 / CO / Ar = 48 / 48 / 4) was introduced in 5 mL increments. min -1 (WHSV = 3000 mL g cat. -1 h -1 The gas was injected into the reactor at a flow rate of 3.0 MPa to initiate the reaction. Argon was used as an internal standard gas for the quantitative calculation of carbon monoxide conversion and the selectivity of each product in the subsequent tail gas. The products were analyzed online by gas chromatography, and the evaluation results are shown in Table 1.

[0156] Comparative Example 8 In this comparative example, catalysts I and II each consisted of 5 wt% Ru, 0.5 wt% Na, and 94.5 wt% amorphous silica. The catalyst composed of the above supported catalysts I and II is designated Cat8#.

[0157] Both of the above supported catalysts I and II were prepared according to the following method: (1) Weigh 0.835g of ruthenium nitrite and 98mg of sodium nitrate, dissolve them in 11.7g of deionized water, mix and stir to obtain a mixed solution of Ru and the auxiliary agent.

[0158] (2) Add 5g of SiO2 to the above step (1), impregnate it, and stir it thoroughly for a period of time. The stirring speed is 500r / min and the stirring time is 1.5h. Then dry it at 60℃ for 10h to obtain a solid powder loaded with active components and additives.

[0159] (3) The solid powder obtained in step (2) is calcined at 400℃ for 4 hours to obtain multiphase catalyst I, which is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0160] Using Cat8# as a catalyst and H2 and CO as raw materials, a series coupled reaction was carried out, as follows: The performance of the catalyst in a series reaction was evaluated using a micro-fixed-bed reactor. The micro-fixed-bed reactor was modified to use two electrically heated reactors connected in series (evaluation apparatus design as follows). Figure 3 0.10 g of 5%Ru-0.5%Na / SiO2 catalyst with a particle size of 40–60 mesh was diluted with 0.05 g of silicon carbide and loaded into the isothermal zone of the upper reactor. The same catalyst composition was then loaded into the isothermal zone of the lower reactor. Before the catalytic reaction, the loaded catalyst underwent a reduction pretreatment. The reduction process was as follows: the catalyst was heated at 450 °C with 40 mL of H2. min -1 The reduction was continued for 4 hours. After the temperatures of the upper and lower reactors dropped to 260 °C and 80 °C respectively, syngas with a ratio of H2 / CO = 1 (H2 / CO / Ar = 48 / 48 / 4) was introduced in 5 mL increments. min -1 (WHSV = 3000 mL g cat. -1 h -1 The gas was injected into the reactor at a flow rate of 3.0 MPa to initiate the reaction. Argon was used as an internal standard gas for the quantitative calculation of carbon monoxide conversion and selectivity of each product in the subsequent tail gas. The products were analyzed online by gas chromatography, and the evaluation results are shown in Table 1.

[0161] Comparative Example 9 In this comparative example, catalysts I and II both consist of 0.3 wt% Rh, 0.8 wt% K, 0.8 wt% Zn, and 98.1 wt% MFI support. The catalyst composed of the above-mentioned encapsulated catalysts I and II is designated Cat9#.

[0162] Both of the above-mentioned encapsulated catalysts I and II were prepared according to the following method: (1) Weigh 8.24 g tetraethyl silicate, 12 g deionized water, 16.24 g tetrapropylammonium hydroxide and 25 mg KOH, mix them and stir for 15 min at a speed of 500 r / min.

[0163] (2) Add 16 mg RhCl3, 34 mg ZnCl2 and 300 µL ethylenediamine to step (1) above, continue stirring for 10 min, transfer the whole thing to a 50 mL tetrafluoroethylene liner and put it into a hydrothermal reactor.

[0164] (3) The hydrothermal reactor in step (2) is subjected to hydrothermal treatment at 170°C for 24 h.

[0165] (4) After hydrothermal treatment in step (3), the solution was centrifuged, washed, and dried at 80°C for 24 h to obtain a white solid.

[0166] (5) After grinding the white solid in step (4), calcining it at 550℃ for 8 h, the multiphase catalyst II can be obtained. The catalyst is then pressed into tablets, sieved, and 40~60 mesh samples are taken for performance evaluation.

[0167] Using Cat9# as a catalyst and H2 and CO as raw materials, a series coupled reaction was carried out, as follows: The performance of the catalyst in a series reaction was evaluated using a micro-fixed-bed reactor. The micro-fixed-bed reactor was modified to use two electrically heated reactors connected in series (evaluation apparatus design as follows). Figure 3 Two identical 0.10 g portions of hydroformylation catalyst (0.3% Rh-0.8% K-0.8% Zn@MFI) with a particle size of 40–60 mesh were respectively loaded into the isothermal zones of the upper and lower reactors. Before the catalytic reaction, the loaded catalyst underwent a reduction pretreatment process: at 500 °C, it was treated with H2 (40 mL) min -1 The reduction was continued for 4 hours. After the temperatures of the upper and lower reactors dropped to 260 °C and 80 °C respectively, syngas with a ratio of H2 / CO = 1 (H2 / CO / Ar = 48 / 48 / 4) was introduced in 5 mL increments. min -1 (WHSV = 3000 mL) g cat. -1 h -1 The gas was injected into the reactor at a flow rate of 3.0 MPa to initiate the reaction. Argon was used as an internal standard gas for the quantitative calculation of carbon monoxide conversion and selectivity of each product in the subsequent tail gas. The products were analyzed online by gas chromatography, and the evaluation results are shown in Table 1.

[0168] Table 1 Results of various catalysts in the production of straight-chain alcohols via syngas tandem reaction. As shown in the table above, the "Ru-Na / SiO2|Rh-K-Zn(Fe) / MFI" tandem catalytic system provided by the invention achieves the directed synthesis of higher alcohols through tandem catalysis. Experiments show that this system achieves a CO conversion rate of 30%-42%, a straight-chain alcohol selectivity of 22%-38%, and a high C content in the products. 6+The alcohol content is as high as 56%-75%. Systematic comparative studies confirmed the indispensable core components in the catalytic system, demonstrating that the "spatial tandem" strategy is fundamental to overcoming the limitations of traditional single catalysts and achieving efficient synthesis. This approach provides a highly efficient new route for the preparation of high-value-added straight-chain alcohols and has significant industrial application value.

[0169] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

Claims

1. A combined catalyst for the preparation of straight-chain alcohols via a syngas tandem reaction, characterized in that, The combined catalyst includes a separate first catalyst and a second catalyst; The first catalyst includes a first active component, a first auxiliary agent, and a first support. The first active component is Ru, the metal corresponding to the first auxiliary agent is Na, and the first support is amorphous silica. The first active component and the first auxiliary agent are loaded in the form of nanoparticles inside the pores and on the surface of the first support. The second catalyst comprises a second active component, a second auxiliary agent, a third auxiliary agent, and a second support. The second active component is Rh, the metal corresponding to the second auxiliary agent is K, the metal corresponding to the third auxiliary agent is Zn and / or Fe, and the second support is an MFI-type molecular sieve composed of pure silicon. The second active component, the second auxiliary agent, and the third auxiliary agent are encapsulated in the pores of the second support in the form of sub-nano clusters or single atoms.

2. The combined catalyst for the syngas tandem reaction to prepare straight-chain alcohols according to claim 1, characterized in that, The mass ratio of the first active component, the first auxiliary agent, and the first carrier is (0.5-10):(0.01-2.0):100; The mass ratio of the second active component, the second auxiliary agent, the third auxiliary agent, and the second carrier is (0.01-1.0):(0.1-2.0):(0.1-2.0):

100.

3. The combined catalyst for the preparation of straight-chain alcohols via syngas tandem reaction according to claim 1, characterized in that, The size of the first active component is 1.2-2.5 nm; The size of the second active component is 0.6-1.2 nm.

4. The combined catalyst for the preparation of straight-chain alcohols via syngas tandem reaction according to claim 1, characterized in that, The preparation method of the first catalyst includes: A mixed solution is obtained by mixing a water-soluble Ru salt precursor, an auxiliary salt precursor and water, then adding the first carrier for impregnation, and after a first stirring, a first drying is performed to obtain a solid powder. The solid powder is subjected to a first calcination to obtain the first catalyst.

5. The combined catalyst for the preparation of straight-chain alcohols via syngas tandem reaction according to claim 4, characterized in that, One or more of the following conditions must be met: (1) The water-soluble Ru salt precursor is selected from one or more of hexaammonium trichloride, ruthenium trichloride, ruthenium nitrate, and nitrosyl ruthenium nitrate; (2) The auxiliary salt precursor is selected from one or more of sodium chloride, sodium nitrate, and sodium sulfate; (3) The first stirring speed is 300-1000 r / min, and the time is 1-3 h; (4) The temperature of the first drying is 50-120℃ and the time is 4-12h; (5) The temperature of the first roasting is 300-500℃ and the time is 3-10h.

6. The combined catalyst for the preparation of straight-chain alcohols via syngas tandem reaction according to any one of claims 1-5, characterized in that, The preparation method of the second catalyst includes: The silicon source, template agent, second auxiliary salt and water are mixed, and after a second stirring, water-soluble Rh salt, third auxiliary salt and encapsulating agent are added. After stirring continues, a hydrothermal reaction is carried out. Solid-liquid separation, washing, and second drying are performed to obtain a solid. The solid is then calcined to obtain the second catalyst.

7. The combined catalyst for the preparation of straight-chain alcohols via syngas tandem reaction according to claim 6, characterized in that, One or more of the following conditions must be met: (1) The silicon source is selected from one or more of tetraethyl silicate, silica sol, and silicon dioxide; (2) The second auxiliary salt is selected from one or more of potassium chloride, potassium nitrate, and potassium hydroxide; (3) The template agent is selected from one or more of tetrapropylammonium hydroxide and tetraethylammonium hydroxide; (4) The second stirring speed is 100-1200 r / min and the time is 10-60 min; (5) The water-soluble Rh salt is selected from rhodium trichloride and / or rhodium nitrate; (6) The third auxiliary salt is selected from one or more of ferric nitrate, ferric chloride, zinc nitrate, and zinc chloride; (7) The template agent is selected from tetrapropylammonium hydroxide and / or tetraethylammonium hydroxide; (8) The stirring speed is 100-1200 r / min and the stirring time is 5-15 min; (9) The temperature of the hydrothermal reaction is 100-190℃ and the time is 12-72h; (10) The temperature of the second drying process is 60-150℃; (11) The second roasting temperature is 400-600℃ and the time is 3-12h.

8. A method for preparing straight-chain alcohols using a combined catalyst for syngas tandem reaction according to any one of claims 1-7, characterized in that, include: The first catalyst is used to catalyze the synthesis gas to carry out a first reaction to obtain straight-chain olefins; the synthesis gas includes carbon monoxide and hydrogen. The second catalyst is used to catalyze the reaction of the straight-chain olefin to obtain a second straight-chain alcohol.

9. The method according to claim 8, characterized in that, The temperature of the first reaction is 50-300℃, the pressure is 2.5-4.5MPa, and the molar ratio of H2 to CO is 1.0-2.0:1; The temperature of the second reaction is 70-120℃, and the pressure is 2.5-4.5MPa.

10. The method according to claim 8 or 9, characterized in that, The first reaction and the second reaction are carried out in a continuous fixed bed.

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