A method for preparing a syngas-to-high alcohol catalyst with a hierarchical structure and the reaction

Abstract

This invention provides a method for preparing a syngas-to-higher alcohols catalyst with a hierarchical pore structure. The preparation method includes: loading an aqueous precursor of the active component ruthenium onto a porous oxide support, and drying it to obtain a catalyst powder precursor; mixing the catalyst powder precursor with a binder, an extrusion aid, PMMA microsphere powder, and water, and mechanically kneading it to form a plastic slurry; extruding the plastic slurry into a wet catalyst preform; drying the wet catalyst preform and calcining it to obtain a shaped Ru-based catalyst with a two-level pore structure of macropores and mesopores. The catalyst prepared by this method achieves a total alcohol selectivity of over 40% in the one-step synthesis of higher alcohols from syngas, and C... 6+ The selectivity of higher alcohols in the total alcohol products reaches over 60%, while maintaining a high CO conversion rate.

Description

Technical Field

[0001] This invention belongs to the field of industrial catalysis technology, specifically relating to a method for preparing a molded catalyst for one-step catalytic conversion of syngas (mainly composed of CO and H2) to produce higher alcohols. In particular, it relates to the preparation and application of a ruthenium (Ru)-based catalyst with mesoporous and macroporous bi-level pore structures, using polymethyl methacrylate (PMMA) microspheres as pore-forming agents. Background Technology

[0002] With the transformation of the global fossil energy structure and the increasing demand for clean liquid fuels, the catalytic conversion of syngas (CO + H2) produced from coal, natural gas, or biomass gasification into high-value-added chemicals and liquid fuels (i.e., C1 chemistry) has become a research hotspot in the energy and chemical engineering field. Among the many syngas conversion products, C... 2+ Higher alcohols (HAS) include ethanol, propanol, butanol, and longer-chain fatty alcohols (C5-). 18 Due to its unique physicochemical properties, it has great industrial application value.

[0003] Higher alcohols are not only high-performance clean fuel additives but also important basic organic chemical raw materials. As fuel additives, compared with methanol, higher alcohols have higher octane numbers, higher energy densities, lower volatility, and better miscibility with gasoline, significantly improving fuel combustion performance and reducing pollutant emissions. As chemical raw materials, higher alcohols, especially straight-chain higher alcohols, are key intermediates in the production of plasticizers, detergents, surfactants, lubricants, and various fine chemicals. Traditional preparation processes mainly rely on the hydration or carbonyl synthesis of petroleum-based olefins, which are not only highly susceptible to fluctuations in crude oil prices but also involve long processes and high energy consumption. In contrast, the one-step direct synthesis of higher alcohols from syngas, a non-petroleum resource, offers significant advantages such as a wide range of raw material sources, high atom economy, and a short process, and is hailed as one of the "holy grail" reactions in the coal chemical industry.

[0004] However, the one-step synthesis of higher alcohols from syngas is an extremely challenging and complex reaction process. This reaction involves the competition and synergy of multiple elementary steps, including CO dissociation, carbon chain growth (CC coupling), and non-dissociative CO insertion to form C-OH bonds. Mechanistically, the process is constrained by the Anderson-Schulz-Flory (ASF) statistical distribution, resulting in a wide product distribution and extremely difficult selectivity control. Thermodynamically and kinetically, the formation of thermodynamically more stable hydrocarbons (Fischer-Tropsch synthesis byproducts) and methanol typically predominates, leading to lower yields of higher alcohols.

[0005] Existing catalytic systems mainly include modified methanol synthesis catalysts (such as Cu-Zn-Al systems), modified Fischer-Tropsch synthesis catalysts (such as Fe and Co-based systems), noble metal catalysts (such as Rh-based systems), and sulfide catalysts (such as MoS2). Despite decades of research, these systems still have their respective drawbacks: Cu-based catalysts suffer from poor thermal stability, are prone to sintering and deactivation, and their main products are low-carbon alcohols; Fe / Co-based catalysts, while exhibiting strong chain growth capabilities, suffer from excessively high hydrocarbon selectivity and low alcohol yields; sulfide catalysts require harsh high-pressure conditions and a sulfur source to maintain activity. Therefore, developing a catalyst that combines high activity and high carbon content is crucial. 2+ Novel catalysts and supporting processes with high selectivity and excellent stability for alcohols are not only a challenge for the academic community, but also the key to realizing the industrial production of higher alcohols.

[0006] However, the following are the main bottlenecks in the existing technology:

[0007] Product diffusion limitations: The synthesis of higher alcohols involves the surface formation and desorption of long-chain carbon-oxygen intermediates. Traditional microporous or mesoporous catalysts have a simple pore structure, resulting in high diffusion resistance of long-chain intermediates and product molecules within the pores. This makes them prone to over-hydrogenation (forming alkanes) or secondary reactions (such as dehydration to form alkenes), thereby reducing the selectivity of higher alcohols.

[0008] Low accessibility of active sites and low mass transfer efficiency: Conventional catalyst forming process can easily lead to pore collapse or blockage, reducing the specific surface area and pore volume of the catalyst, causing some active sites to be encapsulated, and the reactants (syngas) cannot contact efficiently, thus limiting the overall activity.

[0009] Thermal management is challenging: Fischer-Tropsch synthesis and the synthesis of higher alcohols are strongly exothermic reactions. In fixed-bed reactors, local hot spots easily form within the catalyst bed, accelerating catalyst sintering and deactivation, and causing side reactions, thus affecting the long-term stability of the reactor.

[0010] The balance between catalyst pressure strength and activity: Binders added to obtain sufficient pressure strength often cover some active sites or block pores, sacrificing catalytic activity. Maximizing catalytic performance while ensuring the pressure strength of the catalyst prototyping is a key challenge.

[0011] While existing technologies have reported the use of various pore-forming agents (such as carbon powder and cellulose) to improve pore structure, these often suffer from problems such as uncontrollable pore structure and uneven distribution. Therefore, developing and applying a molded catalyst that can precisely control the catalyst pore structure, balance high strength and high activity, and optimize the mass and heat transfer characteristics of the reaction bed is of great significance for promoting the industrialization of syngas-to-high alcohols technology. Summary of the Invention

[0012] To address the shortcomings of the prior art, this invention provides a method for preparing Ru-based catalysts with hierarchical pore structures and their applications, thereby solving the problems in the prior art.

[0013] To achieve the above and other related objectives, the present invention provides a method for preparing a Ru-based catalyst with a hierarchical pore structure and its application.

[0014] The core of this invention lies in: introducing polymethyl methacrylate (PMMA) microspheres as a precise pore-forming agent, and constructing a continuous mesoporous and macroporous two-level pore structure in the shaped catalyst through unique segmented calcination; and combining optimized catalyst loading and reaction conditions to synergistically solve the problems of product diffusion limitation, low mass transfer efficiency and bed thermal management, ultimately achieving a one-step synthesis of higher alcohols from syngas with high activity, high selectivity and high stability.

[0015] The first aspect of this invention provides a method for preparing a Ru-based catalyst with a hierarchical pore structure, the method comprising the following:

[0016] Precursor preparation: The precursor solution of the active component ruthenium (abbreviated as Ru) is loaded onto a porous oxide support and dried to obtain the catalyst powder precursor; this step mainly forms the initial active phase and mesoporous structure of the catalyst.

[0017] Mixing and kneading: The catalyst powder precursor is mixed with binder, extrusion aid, polymethyl methacrylate (PMMA) microsphere powder and water, and then mechanically kneaded to form a plastic slurry.

[0018] Molding: Plastic clay is fed into a screw extruder and extruded through a mold with a specific aperture to obtain a shaped wet catalyst blank with a certain compressive strength;

[0019] Segmented calcination: After drying the shaped catalyst green body, a strictly temperature-controlled segmented calcination process is performed to obtain a shaped Ru-based catalyst with both macroporous and mesoporous pore structures. This step aims to gently and controllably remove the PMMA pore-forming agent while simultaneously completing the final shaping of the catalyst support and the immobilization of the active components.

[0020] Preferably, the ruthenium precursor solution is selected from one or both of ruthenium nitrate (abbreviated as Ru(NO)(NO3)3) or ruthenium chloride (abbreviated as RuCl3).

[0021] Preferably, the mass of ruthenium in the ruthenium precursor is 0.5% to 5% of the carrier mass, such as 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%.

[0022] Preferably, the porous oxide support is selected from one or more of SiO2, Al2O3, TiO2 or ZrO2.

[0023] Preferably, the pore size of the porous oxide support is 1.5-50 nm, such as 1.5 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, or 50 nm. More preferably, the pore size is 5-20 nm.

[0024] Preferably, the pore volume of the porous oxide support is 1~2 cm³. 3 / g, if it can be 1cm 3 / g, 1.2cm 3 / g, 1.4cm 3 / g, 1.6cm 3 / g, 1.8cm 3 / g or 2cm 3 / g.

[0025] Preferably, the specific surface area of ​​the porous oxide support is 200~300m². 2 / g, such as 200m 2 / g、210m 2 / g、220m 2 / g、230m 2 / g、240m 2 / g、、250m 2 / g、260m 2 / g、270m 2 / g、280m 2 / g、290m 2 / g or 300m 2 / g.

[0026] Preferably, the mass of the water is 80% to 100% of the mass of the catalyst powder precursor, such as 80%, 85%, 90%, 95% or 100%.

[0027] Preferably, the ruthenium precursor solution is loaded onto the porous oxide support by one or more of the following methods: equal-volume impregnation, initial wet impregnation, or deposition precipitation.

[0028] Preferably, the active component further includes an electronic aid and / or a structural aid precursor solution. The electronic aid and / or structural aid are used to improve the selectivity of the ruthenium-based catalyst.

[0029] More preferably, the electronic additive and / or structural additive precursor is selected from one or more of the carbonates, nitrates, chlorides, fluorides, sulfates or acetates of Fe, Co, Cu, K, Cs, La, Au, Ag, Ce, Mn, and Na.

[0030] Preferably, the mass of the metal element in the electronic additive and / or structural additive is 0.1% to 10% of the carrier mass, such as 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.

[0031] Preferably, the electronic additives and / or structural additives are co-impregnated or sequentially impregnated with the ruthenium precursor onto the carrier.

[0032] Preferably, the drying temperature during the precursor preparation process is 80~120℃, such as 80℃, 90℃, 100℃, 110℃ or 120℃.

[0033] Preferably, the drying time during the precursor preparation process is 10-20 hours, such as 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, or 20 hours.

[0034] Preferably, the adhesive is selected from one or more of boehmite, silica sol, or polyvinyl butyral (PVB).

[0035] Preferably, 25% to 30% of the aluminum sol has a particle size of 10 to 20 nm (e.g., 10 nm, 12 nm, 14 nm, 16 nm, 18 nm or 20 nm).

[0036] Preferably, the number average molecular weight of the carboxymethyl cellulose is 50,000-200,000, such as 50,000, 100,000, 150,000 or 200,000.

[0037] Furthermore, when the binder is boehmite, one or both of nitric acid or citric acid need to be added. When boehmite (AlOOH·nH2O) is used as a binder, acid must be added for sol-gel. The key is that the acid provides H⁺, which breaks up agglomeration, forms a stable sol, and forms strong Al-O-Al bonds after calcination.

[0038] Preferably, the mass of added nitric acid and / or citric acid is 0.5% to 2% of the mass of the catalyst powder precursor, such as 0.5%, 1%, 1.5%, or 2%. More preferably, the amount added is 1 wt%.

[0039] Preferably, the nitric acid and / or citric acid are added in the form of an aqueous solution of 1-5 wt% (e.g., 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt%).

[0040] Preferably, the mass of the binder is 10% to 30% of the mass of the catalyst powder precursor, such as 10%, 15%, 20%, 25% or 30%.

[0041] Preferably, the extrusion aid is guar gum powder.

[0042] Preferably, the mass of the extrusion aid is 1% to 5% of the mass of the catalyst powder precursor, such as 1%, 2%, 3%, 4% or 5%.

[0043] Preferably, the average particle size of the polymethyl methacrylate (PMMA) microspheres is 1.0 μm to 10.0 μm, such as 1.0 μm, 2.0 μm, 3.0 μm, 4.0 μm, 5.0 μm, 6.0 μm, 7.0 μm, 8.0 μm, 9.0 μm, or 10.0 μm. The PMMA microspheres serve as a template and pore-forming agent, uniformly dispersed in the slurry to form pore structures of different sizes. More preferably, the average particle size is 2.0 μm to 5.0 μm. If the particle size is too large (e.g., 10 μm), the catalyst structure will be loose; if the particle size is too small, effective hierarchical pores cannot be formed.

[0044] Preferably, the amount of PMMA microspheres added is 5wt% to 20wt% of the catalyst powder precursor, such as 5wt%, 6wt%, 8wt%, 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, or 20wt%. Adding too much will cause the catalyst to fail to form properly and become easily broken.

[0045] Preferably, the mold shape in the molding operation is one or both of the following: clover shape or cylindrical shape.

[0046] Preferably, the diameter of the shaped catalyst wet blank is 1 to 3 mm, such as 1 mm, 1.5 mm, 2 mm, 2.5 mm or 3 mm.

[0047] Preferably, the drying temperature of the molded catalyst wet blank is 20~30℃, such as 20℃, 22℃, 24℃, 26℃, 28℃ or 30℃.

[0048] Preferably, the drying time for the molded catalyst wet blank is 20 h to 30 h, such as 20 h, 22 h, 24 h, 26 h, 28 h or 30 h.

[0049] Preferably, the roasting adopts a segmented programmed heating roasting method, which includes the following three stages:

[0050] First stage: Increase the temperature to 100-150℃ (e.g., 100℃, 110℃, 120℃, 130℃, 140℃, or 150℃) at a heating rate of 0.5~2℃ / min (e.g., 0.5℃ / min, 1℃ / min, 1.5℃ / min, or 2℃ / min), and maintain this temperature for 1~3 hours (e.g., 1 hour, 2 hours, or 3 hours). This stage is the dehydration stage and is used to completely remove physically adsorbed water.

[0051] The second stage involves slowly heating the PMMA microspheres at a rate of 0.2–1.0 °C / min (e.g., 0.2 °C / min, 0.4 °C / min, 0.6 °C / min, 0.8 °C / min, or 1.0 °C / min) to 250–350 °C (e.g., 250 °C, 270 °C, 290 °C, 310 °C, 330 °C, or 350 °C), and then isothermal treatment for 2–5 hours (e.g., 2 hours, 3 hours, 4 hours, or 5 hours). This stage is the controlled decomposition and pore-forming stage of PMMA, during which the PMMA microspheres undergo thermal decomposition and vaporization. The slow heating avoids the collapse of pores or catalyst cracking caused by the instantaneous release of large amounts of gas, achieving a uniform and interconnected construction of macropores (formed by the space occupied by the PMMA microspheres), which, together with the original mesopores of the carrier, form a hierarchical pore structure.

[0052] The third stage involves heating to 400-500℃ (e.g., 400℃, 420℃, 440℃, 460℃, 480℃, or 500℃) at a rate of 2-5℃ / min (e.g., 2℃ / min, 3℃ / min, 4℃ / min, or 5℃ / min), and then isothermal treatment for 2-4 hours (e.g., 2 hours, 3 hours, or 4 hours). This stage is the shaping and activation stage, which further enhances the sintering of the binder, improves the compressive strength of the shaped catalyst, and ensures a stable bonding state between the active metal species and the support.

[0053] Preferably, the heating rate in the second stage is 0.2~1.0℃ / min; if the heating rate is too fast (e.g., 3℃ / min), the decomposition and exothermic reaction of PMMA will lead to excessively high local temperatures, causing catalyst particles to sinter, pores to collapse or catalysts to crack, resulting in a loss of specific surface area.

[0054] Preferably, the second stage involves heating to 250-350°C; if the temperature is too low (e.g., 200°C), PMMA will not decompose; if the temperature is too high (400°C), PMMA will decompose violently, which may cause the catalyst to crack.

[0055] A second aspect of the present invention provides a catalyst prepared by the above preparation method, wherein the catalyst has a two-level pore structure of macropores and mesopores.

[0056] Preferably, the macropore size of the catalyst is 1~10 μm, such as 1μm, 2μm, 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, 9μm or 10μm. The macroporous structure is generated by removing PMMA microspheres.

[0057] Preferably, the mesopore size of the catalyst is 1.5~50 nm, such as 2 nm, 5 nm, 10 nm, 20 nm, 30 nm, 40 nm or 50 nm. The mesoporous structure is composed of the inherent structure of the porous oxide support combined with a binder.

[0058] Preferably, the selectivity of the total alcohol is at least 40%. More preferably, the selectivity of the total alcohol is 40% to 65%; for example, it can be 40%, 45%, 50%, 55%, 60%, or 65%.

[0059] Preferably, C 6+ The selectivity of the alcohol is at least 60%. More preferably, C 6+ The selectivity of alcohols is 60% to 90%; for example, it can be 60%, 65%, 70%, 75%, 80%, 85% or 90%.

[0060] Preferably, the pressure strength of the catalyst is 50~100 N / cm, such as 50 N / cm, 60 N / cm, 70 N / cm, 80 N / cm, 90 N / cm or 100 N / cm. The pressure strength of the catalyst meets the requirements of industrial applications.

[0061] The present invention also discloses the use of PMMA microspheres as pore-forming agents for ruthenium-based catalysts.

[0062] Preferably, in the above-mentioned applications, the PMMA microspheres have a particle size of 1.0 μm to 10.0 μm (e.g., 1.0 μm, 2.0 μm, 4.0 μm, 6.0 μm, 8.0 μm, or 10.0 μm), a number-average molecular weight of 20,000 to 60,000 (e.g., 20,000, 30,000, 40,000, 50,000, or 60,000), and a thermal decomposition temperature of 250 to 500℃ (e.g., 250℃, 300℃, 350℃, 400℃, 450℃, or 500℃).

[0063] Preferably, in the above-mentioned uses, the ruthenium-based catalyst is used in the one-step synthesis of higher alcohols from syngas.

[0064] A third aspect of the present invention provides the application of the catalyst as described above in the one-step synthesis of higher alcohols from syngas.

[0065] Preferably, the application includes three stages: filling, activation, and reaction, and the specific operations are as follows:

[0066] Loading stage: The above-mentioned catalyst, along with inert alumina microspheres and / or fused silica sand particles, is loaded into the isothermal zone of the fixed-bed reactor, and inert ceramic balls are loaded at both the top and bottom ends of the catalyst bed. This method greatly increases the bed porosity, improves the axial and radial distribution of reactants and products, enhances heat transfer within the bed, and effectively suppresses hot spot formation.

[0067] Activation stage: In the packed reactor, pure hydrogen or a hydrogen-nitrogen mixture is introduced under atmospheric to slightly positive pressure, and the temperature is programmed to rise to 180-250℃ at a rate of 0.5-2℃ / min, followed by isothermal reduction activation. After reduction, the temperature is lowered to below 50℃ under an inert atmosphere for later use. This process reduces the oxidized metal on the catalyst surface to a catalytically active metallic state.

[0068] Reaction stage: Syngas is introduced into the activated catalyst bed to initiate the reaction. Optimized reaction conditions are: temperature 180-240℃, pressure 3.0-8.0 MPa, and feed gas space velocity 500-5000 h⁻¹. -1 The H2 / CO molar ratio of the syngas is controlled at 0.5~2.0. Under these conditions, combined with the hierarchical pore structure of the catalyst itself, it can significantly promote the adsorption and activation of CO and the chain growth of long-chain alkyl / acyl intermediates. In particular, it is beneficial for long-chain oxygen-containing intermediate species (such as alcohol and aldehyde precursors) to rapidly diffuse from the active site and desorb into the final higher alcohol products, thereby inhibiting their excessive hydrogenation.

[0069] Preferably, the filling stage employs layered filling and / or dilution filling methods.

[0070] Preferably, the volume ratio of the catalyst to the inert alumina pellets and / or fused silica sand particles in the filling stage is 1:(1~3), such as 1:1, 1:1.5, 1:2, 1:2.5 or 1:3.

[0071] Preferably, the inert alumina microspheres and / or fused silica sand particles are 2-3 mm spherical particles. More preferably, they are 3 mm spherical particles.

[0072] Preferably, the hydrogen content in the hydrogen-nitrogen mixture during the activation stage is 5% to 100%, such as 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%.

[0073] Preferably, the activation stage is at atmospheric pressure to slightly positive pressure of 0.2~0.8MPa, such as 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa or 0.8MPa.

[0074] Preferably, the programmed temperature rise rate of the activation stage is 0.5~2℃ / min, such as 0.5℃ / min, 0.6℃ / min, 0.8℃ / min, 1.0℃ / min, 1.2℃ / min, 1.4℃ / min, 1.6℃ / min, 1.8℃ / min or 2.0℃ / min.

[0075] Preferably, the temperature during the activation stage is increased to 180~250℃, such as 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃ or 250℃.

[0076] Preferably, the activation stage also requires controlling the reduction space velocity to be 1000~3000 h⁻¹. -1 For example, it can be 1000 h -1 1500 h -1 2000 h -1 2500 h -1 or 3000h -1 .

[0077] Preferably, the in-situ reduction time during the activation stage is 2 to 10 hours, such as 2 hours, 4 hours, 6 hours, 8 hours, or 10 hours.

[0078] Preferably, the inert atmosphere in the activation stage refers to one or more of nitrogen, helium, or argon.

[0079] Preferably, the syngas in the reaction stage is a syngas composed of hydrogen and carbon monoxide, wherein the molar ratio of hydrogen to carbon monoxide is 0.5 to 2.0, such as 0.5, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, or 2.0. More preferably, the molar ratio is 0.8 to 1.2.

[0080] Preferably, the reaction temperature of the reaction stage is 180~240℃, such as 180℃, 190℃, 200℃, 210℃, 220℃, 230℃ or 240℃.

[0081] Preferably, the reaction pressure of the reaction stage is 3.0~8.0 MPa, such as 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa or 0.8 MPa.

[0082] Preferably, the syngas space velocity in the reaction stage is 500~5000 h⁻¹. -1 For example, it can be 500 h -1 1000 h -1 1500 h -1 2000 h -1 2500 h -13000 h -1 3500 h -1 4000 h -1 4500 h -1 or 5000 h -1 .

[0083] As described above, the beneficial effects of the present invention are as follows:

[0084] 1. A hierarchical pore system was creatively constructed: By introducing PMMA microspheres and combining them with mild segmented calcination, a continuous network of mesoporous and macroporous structures was precisely constructed within the molded catalyst. Macropores, acting as "high-speed channels," significantly reduced the diffusion resistance of long-chain product molecules; mesopores provided a large specific surface area, loading and exposing abundant active sites. The synergy of these two systems resolved the contradiction between diffusion limitations and the accessibility of active sites.

[0085] 2. Significantly Enhanced Catalytic Performance: The hierarchical pore structure optimizes mass transfer between reactants and products, making surface reactions more inclined to generate higher alcohols rather than excessively hydrogenated alkanes. Combined with optimized hydrogen-to-carbon ratio reaction conditions, the balance between surface hydrogenation and chain propagation reactions can be effectively controlled. The catalyst prepared using this invention can achieve a total alcohol selectivity of over 40%, with a C1... 6+ Higher alcohols exhibit selectivity of over 60% in total oxygen-containing products while maintaining a high CO conversion rate.

[0086] 3. Enhanced catalyst stability and bed thermal management: The molded catalyst exhibits excellent pressure resistance. The unique dilution and packing method significantly improves fluid flow and heat transfer within the fixed-bed reactor, preventing catalyst sintering and deactivation caused by localized overheating, and extending the catalyst's single-pass operating life.

[0087] 4. Controllable process and easy scale-up: The particle size and dosage of PMMA microspheres can be precisely controlled, thereby allowing for the adjustment of macropore size and porosity. The entire preparation and application process is clear, with well-defined parameters, exhibiting good repeatability and industrial scale-up potential. Attached Figure Description

[0088] Figure 1 This is a SEM image of the catalyst prepared in Example 1 of the present invention.

[0089] Figure 2 Photograph of the catalyst prepared in Example 7 of this invention. Detailed Implementation

[0090] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0091] It should be noted that the process equipment or apparatus not specifically mentioned in the following embodiments are all conventional equipment or apparatus in the art.

[0092] Furthermore, it should be understood that the one or more method steps mentioned in this invention do not preclude the existence of other method steps before or after the combined steps, or the insertion of other method steps between these explicitly mentioned steps. Unless otherwise stated, the numbering of each method step is merely a convenient tool for identifying each method step, and is not intended to limit the order of the method steps or limit the scope of the invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the invention.

[0093] Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art. In addition to the specific methods, apparatus, and materials used in the embodiments, this invention can be implemented using any prior art methods, apparatus, and materials similar to or equivalent to those described in the embodiments of this invention, based on the knowledge of the prior art possessed by one of ordinary skill in the art and the description of this invention.

[0094] In the example, extrusion molding was performed using a screw extruder (ZYDJ-40). The experimental conditions were: extrusion speed of 30~100rpm and pressure of 4-8MPa.

[0095] The reaction results of the catalyst described in the embodiments of this application were obtained by the following method:

[0096] Gas chromatography (Agilent 8860) was used to analyze the types and contents of various components contained in the product;

[0097] CO conversion rate is calculated based on the number of carbon atoms, using the following formula:

[0098] CO conversion rate = (CO 进料 -CO 出料 ) / CO 进料 ×100%

[0099] CO 进料 and CO 出料 These represent the number of CO moles entering and exiting the reaction system, respectively.

[0100] The formula for calculating carbon dioxide selectivity is:

[0101] CO2 selectivity = (CO 2出料 ) / (CO 进料 -CO 出料 ) × 100%

[0102] CO 2出料 This represents the number of moles of CO2 flowing out of the reaction tube.

[0103] Total alcohol selectivity: the molar percentage of alcohols in the total product.

[0104] Higher alcohols (C 6+ Alcohol selectivity: the percentage by mass of alcohols with 6 or more carbon atoms among all alcohol products.

[0105] Methane selectivity: the molar percentage of methane in the total compound.

[0106] C 2+ Alkane selectivity: the molar percentage of all compounds containing alkanes with 2 or more carbon atoms.

[0107] Total olefin selectivity: the molar percentage of olefins among all compounds.

[0108] Example 1

[0109] Preparation: Weigh silica (SiO2) carrier powder, load 2wt% Ru (ruthenium nitrate precursor) and 4wt% Co (cobalt nitrate precursor) using the equal volume impregnation method, and dry at 120℃ for 12 hours.

[0110] Molding: The above powder is mixed with 20% boehmite binder (by weight of powder), 2% guar gum powder, 1% dilute nitric acid, and 80% water. 10 wt% PMMA microspheres (average particle size 3.0 μm) are added, and after thorough kneading, the mixture is extruded into Φ2.5 mm cylindrical wet preforms using a screw extruder. The dilute nitric acid is added as a 3 wt% aqueous solution. The extrusion speed is 50 rpm, and the pressure is 5 MPa.

[0111] Calcination: The temperature was increased in stages: 1℃ / min to 120℃ and held for 2 hours; 0.5℃ / min to 350℃ and held for 4 hours (controlled decomposition of PMMA); 3℃ / min to 450℃ and held for 3 hours.

[0112] Loading: The catalyst is diluted with quartz sand at a 1:1 ratio and loaded into the fixed-bed reactor.

[0113] Activation and reaction: The product was packed into a fixed bed and reduced in situ at 220°C for 4 h under a pure H2 atmosphere at 0.5 MPa pressure. Reaction conditions: 210°C, 5.0 MPa, H2 / CO = 1.8, space velocity 1000 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 1.

[0114] The examination was performed using a scanning electron microscope (Sigema 300). The test conditions were: accelerating voltage 2.00 kV, working distance 6.2 mm, SE2 detector, and magnification 50x. The results are shown below. Figure 1 The image shows a cross-sectional SEM image of the catalyst. (Source: [Insert source here]) Figure 1 It can be seen that the catalyst support has a uniformly dispersed pore structure.

[0115] Comparative Example 1

[0116] This comparative example is the same as Example 1 above. The only difference from Example 1 is that PMMA microspheres were not added, and the catalyst only has the inherent mesopores of the support, without the macropores formed by the PMMA template. The remaining steps are exactly the same. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results of the reaction were calculated accordingly, as shown in Table 1.

[0117] Comparative Example 2

[0118] This comparative example is the comparative example of Example 1 above. The difference from Example 1 is that the conventional pore-forming agent carboxymethyl cellulose (CMC) is used instead of PMMA, and the amount of CMC added is 10 wt% of the powder mass. The remaining steps are exactly the same. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results of the reaction were calculated accordingly, as shown in Table 1.

[0119] Comparative Example 3

[0120] This comparative example is the comparative example of Example 1 above, except that it uses a one-time rapid roasting method.

[0121] Preparation: Weigh silica (SiO2) carrier powder, load 2wt% Ru (ruthenium nitrate precursor) and 4wt% Co (cobalt nitrate precursor) using the equal volume impregnation method, and dry at 120℃ for 12 hours.

[0122] Molding: The above powder is mixed with 20% boehmite binder (by weight of powder), 2% guar gum powder, 1% dilute nitric acid, and 80% water. 10 wt% PMMA microspheres (average particle size 3.0 μm) are added, and after thorough kneading, the mixture is extruded into Φ2.5 mm cylindrical wet preforms using a screw extruder. The dilute nitric acid is added as a 3 wt% aqueous solution. The extrusion speed is 50 rpm, and the pressure is 5 MPa.

[0123] Calcination: The temperature is increased directly from room temperature to 450°C at a rate of 5°C / min and held at that temperature for 5 hours.

[0124] Loading: The catalyst is diluted with quartz sand at a 1:1 ratio and loaded into the fixed-bed reactor.

[0125] Activation and reaction: The product was packed into a fixed bed and reduced in situ at 220°C for 4 h under a pure H2 atmosphere at 0.5 MPa pressure. Reaction conditions: 210°C, 5.0 MPa, H2 / CO = 1.0, space velocity 1000 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 1.

[0126] Comparative Example 4

[0127] This comparative example is the same as Example 1 above. The difference between Example 1 and Example 1 is that a pure catalyst bed was used for packing during the packing stage, and no quartz sand was used for dilution. The remaining steps are exactly the same. After the reaction was completed, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results of the reaction were calculated accordingly, as shown in Table 1.

[0128] Comparative Example 5

[0129] This comparative example is the comparative example of Example 1 above. The difference between Example 1 and Example 1 is that the synthesis gas used in the reaction stage is H2 / CO=2.5.

[0130] Preparation: Weigh silica (SiO2) carrier powder, load 2wt% Ru (ruthenium nitrate precursor) and 4wt% Co (cobalt nitrate precursor) using the equal volume impregnation method, and dry at 120℃ for 12 hours.

[0131] Molding: The above powder is mixed with 20% boehmite binder (by weight of powder), 2% guar gum powder, 1% dilute nitric acid, and 80% water. 10 wt% PMMA microspheres (average particle size 3.0 μm) are added, and after thorough kneading, the mixture is extruded into Φ2.5 mm cylindrical wet preforms using a screw extruder. The dilute nitric acid is added as a 3 wt% aqueous solution. The extrusion speed is 50 rpm, and the pressure is 5 MPa.

[0132] Calcination: The temperature was increased in stages: 1℃ / min to 120℃ and held for 2 hours; 0.5℃ / min to 350℃ and held for 4 hours (controlled decomposition of PMMA); 3℃ / min to 450℃ and held for 3 hours.

[0133] Loading: The catalyst is diluted with quartz sand at a 1:1 ratio and loaded into the fixed-bed reactor.

[0134] Activation and reaction: The product was packed into a fixed bed and reduced in situ at 220°C for 4 h under a pure H2 atmosphere at 0.5 MPa pressure. Reaction conditions: 210°C, 5.0 MPa, H2 / CO = 2.5, space velocity 1000 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 1.

[0135] Example 2

[0136] Preparation: Weigh silica (SiO2) carrier powder, load 2wt% Ru (ruthenium nitrate precursor) and 4wt% Co (cobalt nitrate precursor) using the equal volume impregnation method, and dry at 120℃ for 12 hours.

[0137] Molding: The above powder is mixed with 20% boehmite binder (by weight of powder), 2% guar gum powder, 1% dilute nitric acid, and 80% water. 10 wt% PMMA microspheres (average particle size 1.5 μm) are added, and after thorough kneading, the mixture is extruded into Φ2.5 mm cylindrical wet preforms using a screw extruder. The dilute nitric acid is a 3 wt% aqueous solution. The extrusion speed is 50 rpm, and the pressure is 5 MPa.

[0138] Calcination: The temperature was increased in stages: 1℃ / min to 120℃ and held for 2 hours; 0.5℃ / min to 350℃ and held for 4 hours (controlled decomposition of PMMA); 3℃ / min to 450℃ and held for 3 hours.

[0139] Loading: The catalyst is diluted with quartz sand at a 1:1 ratio and loaded into the fixed-bed reactor.

[0140] Activation and reaction: The product was packed into a fixed bed and reduced in situ at 220°C for 4 h under a pure H2 atmosphere at 0.5 MPa pressure. Reaction conditions: 210°C, 5.0 MPa, H2 / CO = 1.0, space velocity 1000 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 1.

[0141] Example 3

[0142] Preparation: Weigh silica (SiO2) carrier powder, load 2wt% Ru (ruthenium nitrate precursor) and 4wt% Co (cobalt nitrate precursor) using the equal volume impregnation method, and dry at 120℃ for 12 hours.

[0143] Molding: The above powder is mixed with 20% boehmite binder (by weight of powder), 2% guar gum powder, 1% dilute nitric acid, and 80% water. 15 wt% PMMA microspheres (average particle size 3 μm) are added, and after thorough kneading, the mixture is extruded into Φ2.5 mm cylindrical wet preforms using a screw extruder. The dilute nitric acid is added as a 3 wt% aqueous solution. The extrusion speed is 50 rpm, and the pressure is 5 MPa.

[0144] Calcination: The temperature was increased in stages: 1℃ / min to 120℃ and held for 2 hours; 0.5℃ / min to 350℃ and held for 4 hours (controlled decomposition of PMMA); 3℃ / min to 450℃ and held for 3 hours.

[0145] Loading: The catalyst is diluted with quartz sand at a 1:1 ratio and loaded into the fixed-bed reactor.

[0146] Activation and reaction: The product was packed into a fixed bed and reduced in situ at 220°C for 4 h under a pure H2 atmosphere at 0.5 MPa pressure. Reaction conditions: 210°C, 5.0 MPa, H2 / CO = 1.0, space velocity 1000 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 1.

[0147] Example 4

[0148] Preparation: Weigh silica (SiO2) carrier powder, load 2wt% Ru (ruthenium nitrate precursor) and 4wt% Co (cobalt nitrate precursor) using the equal volume impregnation method, and dry at 120℃ for 12 hours.

[0149] Molding: The above powder is mixed with 20% boehmite binder (by weight of powder), 2% guar gum powder, 1% dilute nitric acid, and 80% water. 10 wt% PMMA microspheres (average particle size 3.0 μm) are added, and after thorough kneading, the mixture is extruded into Φ2.5 mm cylindrical wet preforms using a screw extruder. The dilute nitric acid is added as a 3 wt% aqueous solution. The extrusion speed is 50 rpm, and the pressure is 5 MPa.

[0150] Calcination: The temperature was increased in stages: 1℃ / min to 120℃ and held for 2 hours; 0.5℃ / min to 350℃ and held for 4 hours (controlled decomposition of PMMA); 3℃ / min to 450℃ and held for 3 hours.

[0151] Loading: The catalyst is diluted with quartz sand at a ratio of 1:2 and loaded into the fixed-bed reactor.

[0152] Activation and reaction: The product was packed into a fixed bed and reduced in situ at 220°C for 4 h under a pure H2 atmosphere at 0.5 MPa pressure. Reaction conditions: 210°C, 5.0 MPa, H2 / CO = 1.0, space velocity 1000 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 1.

[0153] Example 5

[0154] Preparation: Weigh silica (SiO2) carrier powder, load 2wt% Ru (ruthenium nitrate precursor) and 4wt% Co (cobalt nitrate precursor) using the equal volume impregnation method, and dry at 120℃ for 12 hours.

[0155] Molding: The above powder is mixed with 20% boehmite binder (by weight of powder), 2% guar gum powder, 1% dilute nitric acid, and 80% water. 10 wt% PMMA microspheres (average particle size 3.0 μm) are added, and after thorough kneading, the mixture is extruded into Φ2.5 mm cylindrical wet preforms using a screw extruder. The dilute nitric acid is added as a 3 wt% aqueous solution. The extrusion speed is 50 rpm, and the pressure is 5 MPa.

[0156] Calcination: The temperature was increased in stages: 1℃ / min to 120℃ and held for 2 hours; 0.5℃ / min to 350℃ and held for 4 hours (controlled decomposition of PMMA); 3℃ / min to 450℃ and held for 3 hours.

[0157] Loading: The catalyst is diluted with quartz sand at a 1:1 ratio and loaded into the fixed-bed reactor.

[0158] Activation and reaction: The product was packed into a fixed bed and reduced in situ at 220°C for 4 h under a pure H2 atmosphere at 0.5 MPa pressure. Reaction conditions: 210°C, 5.0 MPa, H2 / CO = 0.8, space velocity 1000 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 1.

[0159] Example 6

[0160] Preparation: Weigh silica (SiO2) carrier powder, load 2wt% Ru (ruthenium nitrate precursor) and 4wt% Co (cobalt nitrate precursor) using the equal volume impregnation method, and dry at 120℃ for 12 hours.

[0161] Molding: The above powder is mixed with 20% boehmite binder (by weight of powder), 2% guar gum powder, 1% dilute nitric acid, and 80% water. 15 wt% PMMA microspheres (average particle size 3.0 μm) are added, and after thorough kneading, the mixture is extruded into Φ2.5 mm cylindrical wet preforms using a screw extruder. A 3 wt% aqueous solution of dilute nitric acid is used. The extrusion speed is 50 rpm, and the pressure is 5 MPa.

[0162] Calcination: The temperature was increased in stages: 1℃ / min to 120℃ and held for 2 hours; 0.5℃ / min to 350℃ and held for 4 hours (controlled decomposition of PMMA); 3℃ / min to 450℃ and held for 3 hours.

[0163] Loading: The catalyst is diluted with quartz sand at a ratio of 1:2 and loaded into the fixed-bed reactor.

[0164] Activation and reaction: The product was packed into a fixed bed and reduced in situ at 220°C for 4 h under a pure H2 atmosphere at 0.5 MPa pressure. Reaction conditions: 210°C, 5.0 MPa, H2 / CO = 1.8, space velocity 1000 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 1.

[0165] Example 7

[0166] Preparation: Weigh alumina (Al2O3) carrier powder and load it with 1.5wt% Ru (precursor is ruthenium chloride) and 0.3wt% Ce (precursor is cerium nitrate) + 1wt% Mn (precursor is manganese nitrate) by equal volume impregnation method, and dry at 115℃ for 11 hours.

[0167] Molding: The above powder was mixed with 22 wt% boehmite binder, 2% guar gum powder, 1% dilute citric acid, and 80% water. 6 wt% PMMA microspheres (average particle size 1.5 μm) were added, and the mixture was thoroughly kneaded until homogeneous. The mixture was then extruded into 2.0 mm clover-shaped wet preforms using a screw extruder. Citric acid was added using a 3 wt% aqueous solution. The extrusion speed was 50 rpm, and the pressure was 5 MPa.

[0168] Calcination: The temperature was increased in stages: 1℃ / min to 105℃ and held for 1.5h; 0.3℃ / min to 280℃ and held for 2.5h (controlled decomposition of PMMA); 2.5℃ / min to 450℃ and held for 2.5h.

[0169] Loading: The catalyst is diluted with fused silica sand at a ratio of 1:3 and loaded into the fixed-bed reactor.

[0170] Activation and Reaction: The product was packed in a fixed bed and reduced in situ at 190°C for 4 h under a hydrogen-nitrogen mixture (H2:N2=2:1) ​​atmosphere at 0.6 MPa. Reaction conditions: 190°C, 5.0 MPa, H2 / CO=1.5, space velocity 800 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 2.

[0171] Figure 2 Photograph of the catalyst prepared in Example 7 of this invention.

[0172] Comparative Example 6

[0173] This comparative example is the comparative example of Example 7 above, except that it uses a one-time rapid roasting method.

[0174] Preparation: Weigh alumina (Al2O3) carrier powder and load it with 1.5wt% Ru (precursor is ruthenium chloride) and 0.3wt% Ce (precursor is cerium nitrate) + 1wt% Mn (precursor is manganese nitrate) by equal volume impregnation method, and dry at 115℃ for 11 hours.

[0175] Molding: The above powder was mixed with 22 wt% boehmite binder, 2% guar gum powder, 1% dilute citric acid, and 80% water. 6 wt% PMMA microspheres (average particle size 1.5 μm) were added, and the mixture was thoroughly kneaded until homogeneous. The mixture was then extruded into 2.0 mm clover-shaped wet preforms using a screw extruder. Citric acid was added using a 3 wt% aqueous solution. The extrusion speed was 50 rpm, and the pressure was 5 MPa.

[0176] Calcination: A segmented temperature program was used: the temperature was increased directly from room temperature to 450℃ at a rate of 5℃ / min and held for 2.5 hours.

[0177] Loading: The catalyst is diluted with fused silica sand at a ratio of 1:3 and loaded into the fixed-bed reactor.

[0178] Activation and Reaction: The product was packed in a fixed bed and reduced in situ at 190°C for 4 h under a hydrogen-nitrogen mixture (H2:N2=2:1) ​​atmosphere at 0.6 MPa. Reaction conditions: 190°C, 5.0 MPa, H2 / CO=1.5, space velocity 800 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 2.

[0179] Comparative Example 7

[0180] This comparative example is the same as Example 7 above. The only difference from Example 7 is that PMMA microspheres were not added, and the catalyst only has the inherent mesopores of the support, without the macropores formed by the PMMA template. The remaining steps are exactly the same. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results of the reaction were calculated accordingly, as shown in Table 2.

[0181] Example 8

[0182] Preparation: Weigh alumina (Al2O3) carrier powder, load it with 3wt% Ru (precursor is ruthenium chloride) and 0.5wt% Cs (precursor is cesium nitrate) + 3wt% Mn (precursor is manganese nitrate) by equal volume impregnation method, and dry at 130℃ for 14 hours.

[0183] Molding: The above powder is mixed with 25 wt% PVB binder, 2% guar gum powder, and 80% water. 20 wt% PMMA microspheres (average particle size 10.0 μm) are added, and the mixture is thoroughly kneaded until homogeneous. The mixture is then extruded into 3.0 mm clover-shaped wet preforms using a screw extruder. The extrusion speed is 50 rpm, and the pressure is 5 MPa.

[0184] Calcination: Segmented temperature program was used: 1℃ / min to 150℃ and hold for 3h; 1.0℃ / min to 350℃ and hold for 5h (controlled decomposition of PMMA); 5℃ / min to 500℃ and hold for 4h.

[0185] Loading: The catalyst is diluted with quartz sand at a ratio of 1:3 and loaded into the fixed-bed reactor.

[0186] Activation and reaction: The product was packed in a fixed bed and reduced in situ at 250°C for 10 h under a hydrogen-nitrogen mixture (H2:N2=1:1) atmosphere at 0.8 MPa. Reaction conditions: 240°C, 8.0 MPa, H2 / CO=2.0, space velocity 5000 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 2.

[0187] Comparative Example 8

[0188] This comparative example is the same as Example 8 above. The only difference from Example 8 is that PMMA microspheres were not added, and the catalyst only has the inherent mesopores of the support, without the macropores formed by the PMMA template. The remaining steps are exactly the same. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results of the reaction were calculated accordingly, as shown in Table 2.

[0189] Example 9

[0190] Preparation: Weigh silica (SiO2) carrier powder, load it with 3wt% Ru (precursor is ruthenium nitrate) and 0.3wt% K (precursor is potassium nitrate) + 0.6wt% Au (precursor is chloroauric acid) by equal volume impregnation method, and dry at 120℃ for 12 hours.

[0191] Molding: The above powder was mixed with 20 wt% (silica mass equal to 20% of the precursor powder mass) of silica sol, 2% guar gum powder, and 80% water. 10 wt% PMMA microspheres (average particle size 3 μm) were added, and after thorough kneading, the mixture was extruded into Φ2.5 mm strip-shaped wet preforms using a screw extruder. The silica sol had a solid content of 30%. The extrusion speed was 50 rpm, and the pressure was 5 MPa.

[0192] Calcination: The temperature was increased in stages: 1℃ / min to 120℃ and held for 2 hours; 0.5℃ / min to 350℃ and held for 4 hours (controlled decomposition of PMMA); 3℃ / min to 450℃ and held for 5 hours.

[0193] Loading: The catalyst is diluted with quartz sand at a 1:1 ratio and loaded into the fixed-bed reactor.

[0194] Activation and reaction: The product was packed into a fixed bed and reduced in situ at 250°C for 4 hours under a pure H2 atmosphere at 0.5 MPa pressure. Reaction conditions: 230°C, 6.0 MPa, H2 / CO = 2.0, space velocity 1000 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 2.

[0195] Comparative Example 9

[0196] This comparative example is the same as Example 9 above. The only difference from Example 9 is that PMMA microspheres were not added, and the catalyst only has the inherent mesopores of the support, without the macropores formed by the PMMA template. The remaining steps are exactly the same. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results of the reaction were calculated accordingly, as shown in Table 2.

[0197] Example 10

[0198] Preparation: Weigh alumina (Al2O3) carrier powder, load it with 1wt% Ru (ruthenium chloride precursor) and 2wt% Fe (ferric nitrate precursor) by equal volume impregnation method, and dry at 110℃ for 10 hours.

[0199] Molding: The above powder is mixed with 15 wt% (silica mass is 15% of the precursor powder mass) of silica sol binder, 2% guar gum powder, and 80% water. 5 wt% PMMA microspheres (average particle size 1.0 μm) are added, and after thorough kneading, the mixture is extruded into Φ2.0 mm strips of wet preform on a screw extruder. The extrusion speed is 50 rpm and the pressure is 5 MPa.

[0200] Calcination: The temperature was increased in stages: 1℃ / min to 100℃ and held for 1 hour; 0.2℃ / min to 250℃ and held for 2 hours (controlled decomposition of PMMA); 2℃ / min to 400℃ and held for 2 hours.

[0201] Loading: The catalyst is diluted with inert alumina pellets at a ratio of 1:3 and loaded into the fixed-bed reactor.

[0202] Activation and reaction: The product was packed in a fixed bed and reduced in situ at 180°C for 2 h under a hydrogen-nitrogen mixture (H2:N2=1:1) atmosphere at 0.2 MPa. Reaction conditions: 180°C, 3.0 MPa, H2 / CO=2, space velocity 500 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 2.

[0203] Example 11

[0204] Preparation: Weigh titanium dioxide (TiO2) carrier powder, load it with 3wt% Ru (precursor is ruthenium nitrate) and 5wt% Cu (precursor is copper nitrate) + 1wt% K (precursor is potassium nitrate) by equal volume impregnation method, and dry at 130℃ for 14 hours.

[0205] Molding: The above powder is mixed with 25 wt% PVB binder, 2% guar gum powder, and 80% water. 20 wt% PMMA microspheres (average particle size 10.0 μm) are added, and the mixture is thoroughly kneaded until homogeneous. The mixture is then extruded into Φ3.0 mm strips of wet preform using a screw extruder. The extrusion speed is 50 rpm, and the pressure is 5 MPa.

[0206] Calcination: The temperature was increased in stages: 1℃ / min to 150℃ and held for 3 hours; 1.0℃ / min to 350℃ and held for 5 hours (controlled decomposition of PMMA); 5℃ / min to 500℃ and held for 4 hours.

[0207] Loading: The catalyst is diluted with fused silica sand at a ratio of 1:2 and loaded into the fixed-bed reactor.

[0208] Activation and reaction: The product was packed into a fixed bed and reduced in situ at 250°C for 10 h under a pure H2 atmosphere at 0.8 MPa pressure. Reaction conditions: 240°C, 8.0 MPa, H2 / CO = 2.0, space velocity 5000 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 2.

[0209] Example 12

[0210] Preparation: Weigh zirconium oxide (ZrO2) support powder, load it with 2wt% Ru (precursor is ruthenium nitrate) and 0.3wt% Cs (precursor is cesium nitrate) + 2wt% La (precursor is lanthanum nitrate) by equal volume impregnation method, and dry at 120℃ for 12 hours.

[0211] Molding: The above powder was mixed with 20 wt% boehmite binder, 2% guar gum powder, 1% dilute nitric acid, and 80% water. 8 wt% PMMA microspheres (average particle size 2.0 μm) were added, and the mixture was thoroughly kneaded until homogeneous. The mixture was then extruded into Φ2.5 mm strips using a screw extruder. A 3 wt% aqueous solution of dilute nitric acid was added. The extrusion speed was 50 rpm, and the pressure was 5 MPa.

[0212] Calcination: The temperature was increased in stages: 1℃ / min to 110℃ and held for 2 hours; 0.4℃ / min to 300℃ and held for 3 hours (controlled decomposition of PMMA); 3℃ / min to 420℃ and held for 3 hours.

[0213] Loading: The catalyst is diluted with quartz sand at a 1:1 ratio and loaded into the fixed-bed reactor.

[0214] Activation and Reaction: The product was packed in a fixed bed and reduced in situ at 200°C for 6 h under a hydrogen-nitrogen mixture (H2:N2=3:1) atmosphere at 0.5 MPa. Reaction conditions: 200°C, 4.0 MPa, H2 / CO=0.8, space velocity 1500 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 2.

[0215] Example 13

[0216] Preparation: Weigh silica (SiO2) carrier powder, load it with 2wt% Ru (precursor is ruthenium nitrate) and 0.4wt% Au (precursor is chloroauric acid) + 1wt% Ag (precursor is silver nitrate) by equal volume impregnation method, and dry at 120℃ for 12 hours.

[0217] Molding: The above powder was mixed with 18 wt% (silica mass equal to 18% of the precursor powder mass) of silica sol binder, 2% guar gum powder, and 80% water. 12 wt% PMMA microspheres (average particle size 5.0 μm) were added, and after thorough kneading, the mixture was extruded into Φ2.5 mm strip-shaped wet preforms on a screw extruder. The silica sol had a solid content of 30%. The extrusion speed was 50 rpm, and the pressure was 5 MPa.

[0218] Calcination: The temperature was increased in stages: 1℃ / min to 130℃ and held for 2 hours; 0.6℃ / min to 320℃ and held for 4 hours (controlled decomposition of PMMA); 4℃ / min to 460℃ and held for 3 hours.

[0219] Loading: The catalyst is diluted with inert alumina pellets at a 1:1 ratio and loaded into the fixed-bed reactor.

[0220] Activation and reaction: The product was packed into a fixed bed and reduced in situ at 210℃ for 5 h under a pure H2 atmosphere at 0.3 MPa pressure. Reaction conditions: 210℃, 6.0 MPa, H2 / CO = 1.2, space velocity 2000 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 2.

[0221] Example 14

[0222] Preparation: Weigh titanium dioxide (TiO2) carrier powder, load it with 2.5wt% Ru (precursor is ruthenium nitrate) and 1wt% Na (precursor is sodium nitrate) + 1wt% Co (precursor is cobalt nitrate) by equal volume impregnation method, and dry at 125℃ for 13 hours.

[0223] Molding: The above powder is mixed with 23 wt% PVB binder, 2% guar gum powder, and 80% water. 18 wt% PMMA microspheres (average particle size 8.0 μm) are added, and the mixture is thoroughly kneaded until homogeneous. The mixture is then extruded into Φ3.0 mm strips of wet preform using a screw extruder. The extrusion speed is 50 rpm, and the pressure is 5 MPa.

[0224] Calcination: The temperature was increased in stages: 1℃ / min to 140℃ and held for 2.5h; 0.8℃ / min to 340℃ and held for 4.5h (controlled decomposition of PMMA); 4.5℃ / min to 480℃ and held for 3.5h.

[0225] Loading: The catalyst is diluted with quartz sand at a ratio of 1:2 and loaded into the fixed-bed reactor.

[0226] Activation and reaction: The product was packed into a fixed bed and reduced in situ at 230°C for 8 h under a pure H2 atmosphere at 0.7 MPa pressure. Reaction conditions: 230°C, 7.0 MPa, H2 / CO = 1.8, space velocity 4000 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 2.

[0227] Example 15

[0228] Preparation: Weigh zirconium oxide (ZrO2) carrier powder, load it with 2wt% Ru (precursor is ruthenium nitrate) and 2wt% Fe (precursor is ferric nitrate) + 3wt% Cu (precursor is copper nitrate) by equal volume impregnation method, and dry at 120℃ for 12 hours.

[0229] Molding: The above powder was mixed with 20 wt% (silica mass equal to 20% of the precursor powder mass) of silica sol binder, 2% guar gum powder, and 80% water. 10 wt% PMMA microspheres (average particle size 3.5 μm) were added, and after thorough kneading, the mixture was extruded into Φ2.5 mm strip-shaped wet preforms on a screw extruder. The silica sol had a solid content of 30%. The extrusion speed was 50 rpm, and the pressure was 5 MPa.

[0230] Calcination: The temperature was increased in stages: 1℃ / min to 120℃ and held for 2 hours; 0.5℃ / min to 310℃ and held for 3 hours (controlled decomposition of PMMA); 3℃ / min to 440℃ and held for 3 hours.

[0231] Loading: The catalyst is diluted with inert alumina pellets at a 1:1 ratio and loaded into the fixed-bed reactor.

[0232] Activation and Reaction: The product was packed in a fixed bed and reduced in situ at 220°C for 7 h under a hydrogen-nitrogen mixture (H2:N2=4:1) atmosphere at 0.4 MPa. Reaction conditions: 220°C, 5.5 MPa, H2 / CO=1.0, space velocity 2500 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 2.

[0233] Example 16

[0234] Preparation: Weigh silica (SiO2) carrier powder, load it with 1wt% Ru (precursor is ruthenium nitrate) and 0.8wt% K (precursor is potassium nitrate) + 2wt% Ce (precursor is cerium nitrate) by equal volume impregnation method, and dry at 110℃ for 10 hours.

[0235] Molding: The above powder was mixed with 16 wt% boehmite binder, 2% guar gum powder, 1% dilute nitric acid, and 80% water. 5 wt% PMMA microspheres (average particle size 1.0 μm) were added, and the mixture was thoroughly kneaded until homogeneous. The mixture was then extruded into Φ2.0 mm strips using a screw extruder. A 3 wt% aqueous solution of dilute nitric acid was added. The extrusion speed was 50 rpm, and the pressure was 5 MPa.

[0236] Calcination: The temperature was increased in stages: 1℃ / min to 100℃ and held for 1 hour; 0.2℃ / min to 250℃ and held for 2 hours (controlled decomposition of PMMA); 2℃ / min to 400℃ and held for 2 hours.

[0237] Loading: The catalyst is diluted with fused silica sand at a 1:1 ratio and loaded into the fixed-bed reactor.

[0238] Activation and reaction: The product was packed into a fixed bed and reduced in situ at 180°C for 2 h under a pure H2 atmosphere at 0.2 MPa pressure. Reaction conditions: 180°C, 3.0 MPa, H2 / CO = 0.5, space velocity 500 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 2.

[0239] Example 17

[0240] Preparation: Weigh titanium dioxide (TiO2) carrier powder, load it with 2wt% Ru (precursor is ruthenium nitrate) and 2wt% La (precursor is lanthanum nitrate) + 2wt% Co (precursor is cobalt nitrate) by equal volume impregnation method, and dry at 120℃ for 12 hours.

[0241] Molding: The above powder was mixed with 19 wt% (silica mass equal to 19% of the precursor powder mass) of silica sol binder, 2% guar gum powder, and 80% water. 15 wt% PMMA microspheres (average particle size 6.0 μm) were added, and after thorough kneading, the mixture was extruded into Φ2.5 mm strip-shaped wet preforms on a screw extruder. The silica sol had a solid content of 30%. The extrusion speed was 50 rpm, and the pressure was 5 MPa.

[0242] Calcination: The temperature was increased in stages: 1℃ / min to 125℃ and held for 2 hours; 0.7℃ / min to 330℃ and held for 3.5 hours (controlled decomposition of PMMA); 3.5℃ / min to 470℃ and held for 3 hours.

[0243] Loading: The catalyst is diluted with inert alumina pellets at a ratio of 1:2 and loaded into the fixed-bed reactor.

[0244] Activation and reaction: The product was packed into a fixed bed and reduced in situ at 210℃ for 6 h under a pure H2 atmosphere at 0.5 MPa pressure. Reaction conditions: 205℃, 4.5 MPa, H2 / CO = 0.9, space velocity 1800 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 2.

[0245] Example 18

[0246] Preparation: Weigh zirconium oxide (ZrO2) carrier powder, load it with 2wt% Ru (precursor is ruthenium nitrate) and 3wt% Ag (precursor is silver nitrate) + 1wt% Na (precursor is sodium nitrate) by equal volume impregnation method, and dry at 120℃ for 12 hours.

[0247] Molding: The above powder was mixed with 21 wt% boehmite binder, 2% guar gum powder, 1% dilute nitric acid, and 80% water. 10 wt% PMMA microspheres (average particle size 4.0 μm) were added, and the mixture was thoroughly kneaded until homogeneous. The mixture was then extruded into Φ2.5 mm strips using a screw extruder. A 3 wt% aqueous solution of dilute nitric acid was added. The extrusion speed was 50 rpm, and the pressure was 5 MPa.

[0248] Calcination: The temperature was increased in stages: 1℃ / min to 115℃ and held for 2 hours; 0.5℃ / min to 300℃ and held for 3 hours (controlled decomposition of PMMA); 3℃ / min to 430℃ and held for 3 hours.

[0249] Loading: The catalyst is diluted with fused silica sand at a 1:1 ratio and loaded into the fixed-bed reactor.

[0250] Activation and reaction: The product was packed in a fixed bed and reduced in situ at 200℃ for 5 h under a hydrogen-nitrogen mixture (H2:N2=3:1) atmosphere at 0.5 MPa. Reaction conditions: 215℃, 6.5 MPa, H2 / CO=1.1, space velocity 3000 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 2.

[0251] Example 19

[0252] Preparation: Weigh silica (SiO2) carrier powder and load it with 2wt% Ru (precursor is ruthenium nitrate) and 1wt% Co (precursor is cobalt nitrate) + 2wt% Cu (precursor is copper nitrate) by equal volume impregnation method, and dry at 120℃ for 12 hours.

[0253] Molding: The above powder was mixed with 20 wt% boehmite binder, 2% guar gum powder, 1% dilute nitric acid, and 80% water. 7 wt% PMMA microspheres (average particle size 2.5 μm) were added, and the mixture was thoroughly kneaded until homogeneous. The mixture was then extruded into Φ2.5 mm strips using a screw extruder. A 3 wt% aqueous solution of dilute nitric acid was added. The extrusion speed was 50 rpm, and the pressure was 5 MPa.

[0254] Calcination: The temperature was increased in stages: 1℃ / min to 120℃ and held for 2 hours; 0.6℃ / min to 320℃ and held for 4 hours (controlled decomposition of PMMA); 3℃ / min to 450℃ and held for 3 hours.

[0255] Loading: The catalyst is diluted with quartz sand at a 1:1 ratio and loaded into the fixed-bed reactor.

[0256] Activation and reaction: The product was packed into a fixed bed and reduced in situ at 220°C for 4 hours under a pure H2 atmosphere at 0.5 MPa pressure. Reaction conditions: 210°C, 5.0 MPa, H2 / CO = 1.0, space velocity 1000 h⁻¹. After the reaction, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 2.

[0257] Table 1: Catalytic performance data of catalysts in Examples 1-6 and Comparative Examples 1-5

[0258]

[0259] As shown in Table 1, in both Example 1 and Comparison 1, the addition of PMMA doubled the total alcohol selectivity (from 27.2% to 50.1%), especially for C. 6+ The selectivity of alcohols was significantly improved (from 40% to 70.2%).

[0260] As can be seen from Example 1 and Comparative Example 2, compared with traditional pore-forming agents, PMMA improves the CO conversion rate of the prepared catalyst by 12%, the total alcohol selectivity by 56%, and the C... 6+ Alcohol selectivity increased by 35%.

[0261] As can be seen from Example 1 and Comparative Example 3, although PMMA was added in Comparative Example 2, the CO conversion rate was only 28%, showing a significant deactivation effect. Furthermore, the selectivity of total alcohols and higher alcohols was also low, indicating that rapid heating caused PMMA to deflagrate, and local high temperature caused Ru particles to grow and sinter, resulting in a loss of specific surface area. This demonstrates the key importance of the "segmented calcination" method in this invention.

[0262] As can be seen from Example 1 and Comparative Example 4, during the reaction stage, without dilution of the catalyst with inert particles, the initial activity is slightly higher, but the bed temperature rises significantly, and the final C 6+ The selectivity of alcohols drops below 40%, and the stability is poor.

[0263] As can be seen from Example 1 and Comparative Example 5, when the H2 / CO ratio in the mixed gas is too high during the reaction stage, the H2 content is too high, the conversion rate increases, but the product has a stronger tendency to alkane and the alcohol selectivity decreases.

[0264] Data from Examples 1-6 show that, within the scope described in this application, optimization of the hydrogen-to-carbon ratio reaction conditions, the particle size and amount of PMMA microspheres, and the packing method effectively controlled the balance between surface hydrogenation and chain growth reactions. Ultimately, under comprehensively optimized conditions, the reaction achieved a CO conversion rate of 45%, a total alcohol selectivity of 58%, and a C... 6 + Alcohol selectivity: 79%.

[0265] Table 2: Catalytic performance data of catalysts in Examples 7-19 and Comparative Examples 6-9

[0266]

[0267] As can be seen from Tables 2, Examples 7-9 and Comparative Examples 6-9, this method introduces PMMA microspheres as a precise pore-forming agent. Compared with the corresponding comparative examples without added PMMA, the CO conversion rate, total alcohol selectivity, and C content of this invention are significantly improved. 6 + The selectivity of alcohols was improved to varying degrees.

[0268] As can be seen from Examples 7-19 in Table 2, this method introduces PMMA microspheres as a precise pore-forming agent. Through unique segmented calcination, a two-level pore structure of interconnected macropores and mesopores is constructed in the shaped catalyst. Combined with optimized catalyst loading and reaction conditions, it synergistically solves the problems of product diffusion limitation, low mass transfer efficiency, and bed thermal management, ultimately achieving a total alcohol selectivity of over 40% and a C60% or higher. 6+ Alcohol selectivity.

[0269] Meanwhile, the catalyst prepared in this application has a lateral compressive strength of 60~90 N / cm and does not break during the above reaction and other normal reaction processes, thus meeting the requirements for industrial applications.

[0270] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any form or substance. It should be noted that those skilled in the art can make various improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention. Any modifications, alterations, and equivalent changes made by those skilled in the art based on the above-disclosed technical content without departing from the spirit and scope of the present invention are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and evolutions made to the above embodiments based on the essential technology of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A method for preparing a syngas-to-higher alcohols catalyst with a hierarchical pore structure, characterized in that, Preparation methods include: An aqueous precursor of the active component ruthenium was loaded onto a porous oxide support and dried to obtain a catalyst powder precursor. The catalyst powder precursor is mixed with binder, extrusion aid, PMMA microsphere powder and water, and formed into plastic mud by mechanical kneading. The plastic mud is then extruded to obtain a shaped catalyst wet blank. After drying the wet catalyst blank, it is calcined to obtain a shaped Ru-based catalyst with a hierarchical pore structure of macropores and mesopores.

2. The preparation method according to claim 1, characterized in that, The average particle size of the PMMA microsphere powder is 1.0 μm to 10.0 μm; And / or, the ruthenium precursor is selected from one or both of RuCl3 or Ru(NO)(NO3)3; And / or, the porous oxide support is selected from one or more of SiO2, Al2O3, TiO2 or ZrO2; And / or, the porous oxide support has a pore size of 1.5~50 nm and a pore volume of 1~2 cm³. 3 / g, specific surface area of ​​200~300m² 2 / g; And / or, the precursor solution is loaded onto the porous oxide support by one or more of the following methods: equal volume impregnation, initial wet impregnation, or deposition precipitation. And / or, the active component further includes a precursor solution of electronic auxiliaries and / or structural auxiliaries; And / or, the binder is selected from one or more of boehmite, silica sol, or PVB; And / or, the extrusion aid is selected from guar gum powder; And / or, the mass of ruthenium in the ruthenium precursor is 0.5-5% of the carrier mass; And / or, the amount of PMMA microspheres added is 5 wt% to 20 wt% of the catalyst powder precursor; And / or, the mass of the binder is 10% to 30% of the mass of the catalyst powder precursor; And / or, the mass of the extrusion aid is 1% to 5% of the mass of the catalyst powder precursor; And / or, the mass of the water is 80% to 100% of the mass of the catalyst powder precursor.

3. The preparation method according to claim 2, characterized in that, When the binder is boehmite, 0.5% to 2% of nitric acid and / or citric acid by weight of the catalyst powder precursor also needs to be added; the nitric acid and / or citric acid are added in the form of a 1 to 5 wt% aqueous solution. And / or, the electronic additive and / or structural additive precursor is selected from one or more of the carbonates, nitrates, chlorides, fluorides, sulfates or acetates of Fe, Co, Cu, K, Cs, La, Au, Ag, Ce, Mn, and Na; And / or, the mass of the metal element in the electronic additive and / or structural additive is 0.1 to 10% of the mass of the carrier.

4. The preparation method according to claim 1, characterized in that, The drying temperature during the preparation of the catalyst powder precursor is 80~120℃; And / or, the drying temperature of the molded catalyst wet blank is 20~30℃.

5. The preparation method according to claim 1, characterized in that, The roasting process employs a segmented, programmed heating method, which includes the following three stages: First stage: Increase the temperature to 100-150℃ at a heating rate of 0.5-2℃ / min, and maintain the temperature for 1-3 hours; Second stage: Increase the temperature to 250~350℃ at a heating rate of 0.2~1.0℃ / min, and maintain the temperature for 2~5 hours; The third stage: the temperature is increased to 400-500℃ at a rate of 2-5℃ / min, and then kept at a constant temperature for 2-4 hours.

6. A catalyst prepared by the preparation method according to any one of claims 1 to 5, characterized in that, The catalyst includes one or more of the following features: it has a macroporous and mesoporous hierarchical pore structure; The selectivity of the total alcohol is at least 40%; C 6+ The selectivity of the alcohol is at least 60%; The lateral compressive strength of the catalyst is 50~100 N / cm; The catalyst has a macropore size of 1~10 μm; The catalyst has a mesopore size of 1.5~50 nm.

7. Use of PMMA microspheres as pore-forming agents for ruthenium-based catalysts.

8. The application of the catalyst as described in claim 6 in the one-step synthesis of higher alcohols from syngas.

9. The application according to claim 8, characterized in that, The application includes three stages: loading, activation, and reaction, and the specific operations are as follows: Filling stage: The catalyst as described in any one of claims 6 to 7, along with inert alumina microspheres and / or fused silica sand particles, are filled into the constant temperature zone of the fixed bed reactor, and inert ceramic balls are filled at both the upper and lower ends of the catalyst bed. Activation stage: Under normal pressure to slightly positive pressure, pure hydrogen or hydrogen-nitrogen mixture is introduced and the temperature is raised to 180-250℃ at a rate of 0.5-2℃ / min for in-situ reduction activation. Then, the temperature is lowered to below 50℃ in an inert atmosphere for later use. Reaction stage: Synthesis gas is introduced to carry out the reaction.

10. The application according to claim 9, characterized in that, During the filling stage, the inert alumina spheres or fused silica sand particles are 2-3 mm spherical particles; And / or, the volume ratio of catalyst to inert alumina pellets and / or fused silica sand particles in the filling stage is 1:(1~3); And / or, the hydrogen content in the hydrogen-nitrogen mixture during the activation phase is 5-100%; And / or, the activation phase is performed at a pressure of 0.2 to 0.8 MPa from ambient pressure to slightly positive pressure; And / or, the activation stage also requires controlling the space velocity of in-situ reduction to 1000-3000 h⁻¹. -1 ; And / or, the inert atmosphere in the activation phase refers to one or more of nitrogen, helium or argon; And / or, the syngas in the reaction stage is a syngas composed of hydrogen and carbon monoxide, wherein the molar ratio of hydrogen to carbon monoxide is 0.5 to 2.0; And / or, the reaction temperature of the reaction stage is 180-240°C; And / or, the reaction pressure of the reaction stage is 3.0-8.0 MPa; And / or, the space velocity of the reaction stage is 500-5000 h⁻¹.

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