Ru-based catalyst and application of Ru-based catalyst in reaction for preparing high-carbon alcohol and co-producing olefin from synthesis gas

Abstract

The invention provides a Ru-based catalyst and application of the Ru-based catalyst in a reaction for preparing high-carbon alcohol and co-producing olefin from synthesis gas. A preparation method of the Ru-based catalyst comprises the following steps: soaking a carrier in an acid solution, washing and drying to obtain a pretreated carrier; dipping the pretreated carrier in an aqueous solution containing Ru, a metal additive and a surfactant to obtain a dipping system; and carrying out drying, roasting and water vapor treatment on the impregnation system to obtain the Ru-based catalyst. The catalyst prepared by the method shows high catalytic activity in a Fischer-Tropsch synthesis reaction, can realize high-selectivity preparation of C4 < + > high alcohols and co-production of olefins, and significantly improves the economy and industrial application potential of a synthesis gas conversion process.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, and in particular to a Ru-based catalyst and its application in the reaction of syngas to produce higher alcohols and olefins. Background Technology

[0002] Higher alcohols (usually referring to C45-4 ... 4+ Fatty alcohols (with carbon chains of 250-3500) are an important class of chemical raw materials, widely used in surfactants, detergents, lubricants, plasticizers, pharmaceutical intermediates, and other fields. They can also be used as clean fuels or fuel additives, possessing extremely high industrial application value and market prospects. Syngas (mainly composed of CO and H2) is a core intermediate for the high-value conversion of non-petroleum-based carbon resources such as coal, natural gas, and biomass. Its catalytic conversion to produce higher alcohols is one of the important ways to achieve clean and efficient utilization of carbon resources and alleviate dependence on petroleum resources, and has become a research hotspot in the field of catalysis in recent years.

[0003] The key to the synthesis of higher alcohols from syngas lies in the development of high-performance catalysts. These catalysts must simultaneously satisfy the requirements of efficient CO activation, CC coupling, and selective hydrogenation to achieve high total alcohol selectivity, higher alcohol selectivity, and good catalytic stability. Currently, catalysts for the synthesis of higher alcohols from syngas are mainly classified into four categories: Rh-based catalysts, Mo-based catalysts, modified Fischer-Tropsch synthesis (FTS) catalysts, and modified methanol synthesis (MS) catalysts. Among them, modified FTS catalysts have attracted much attention due to their controllable carbon chain growth, which makes it easier to obtain higher alcohols, and are one of the most widely studied catalysts for the synthesis of higher alcohols.

[0004] However, in existing modified Fischer-Tropsch catalytic systems, research still mainly focuses on cobalt-based and iron-based catalysts. The selectivity of alcohol products prepared by these catalytic systems is mostly concentrated in the lower alcohol category, with limited selectivity for higher alcohols (C4+) with ≥4 carbons. 4+ The selectivity is generally below 30%, and the yield is even less than 10%. Meanwhile, the selectivity for carbon dioxide and methane in the products often exceeds 20%, severely limiting the utilization efficiency of carbon atoms. Furthermore, syngas also generates olefins and alkanes with ≥2 carbon atoms during the conversion process. Under traditional catalytic systems, the products are mostly low-value-added C4 hydrocarbons. 2+ Alkanes are difficult to selectively synthesize into high-value-added olefins. Therefore, if precise catalyst design can be achieved to selectively synthesize C from syngas... 4+ Higher alcohols, in conjunction with olefin production, will significantly enhance the economics and industrial application potential of syngas reforming processes.

[0005] Ruthenium (Ru)-based catalysts are commonly used in Fischer-Tropsch synthesis, exhibiting excellent catalytic activity and extremely low selectivity for byproducts such as methane and carbon dioxide, demonstrating very high carbon utilization efficiency. However, the products are mainly saturated alkanes, making it difficult to selectively produce high-value-added chemicals such as olefins and alcohols. In recent years, ruthenium-based catalysts modified with alkali metal promoters have achieved highly selective synthesis of olefins. However, due to the limitations imposed by the interactions between the catalyst, promoter, and support, it remains difficult to achieve the co-production of enols with higher alcohols as the main product. Therefore, developing catalysts with simple preparation processes and excellent stability to achieve efficient catalytic conversion of syngas to higher alcohols and co-production of olefins has become a key technical problem urgently needing to be solved in this field. Summary of the Invention

[0006] In view of the shortcomings of the prior art described above, the purpose of this invention is to provide a Ru-based catalyst and its application in the co-production of olefins from syngas to higher alcohols, to solve the problems of low selectivity, numerous byproducts, and difficulty in co-producing high-value-added olefins in the prior art of syngas-to-higher alcohols, and to achieve C 4+ Highly efficient and selective co-production of higher alcohols and olefins.

[0007] To achieve the above and other related objectives, the present invention provides a Ru-based catalyst and its application in the reaction of syngas to produce higher alcohols and olefins.

[0008] The first aspect of the present invention provides a method for preparing a Ru-based catalyst, the method comprising: soaking, washing and drying a support in an acidic solution to obtain a pretreated support; impregnating the pretreated support in an aqueous solution containing Ru, a metal promoter and a surfactant to obtain an impregnation system; and obtaining a Ru-based catalyst after drying, calcining and steam treatment of the impregnation system.

[0009] Preferably, the carrier is any one or more selected from mesoporous SiO2, mesoporous TiO2, and mesoporous Al2O3.

[0010] If the pore size of the support is too small, intermediate or by-products will easily accumulate, leading to pore blockage and carbon buildup, slow diffusion, and impaired mass transfer, making the Fischer-Tropsch reaction impossible. If the pore size of the support is too large, the strength will be low, the specific surface area will be small, the metal dispersion will be low, and the catalyst formation will be poor.

[0011] Preferably, the Ru is obtained by dissolving a water-soluble salt of Ru in water, and the water-soluble salt of Ru is any one or more selected from ruthenium chloride, ruthenium nitrate, and ruthenium acetate.

[0012] Preferably, the metal additive is obtained by dissolving a water-soluble salt of the metal additive in water, and the water-soluble salt of the metal additive is selected from any one or more of metal chlorides, metal nitrates, metal carbonates, and metal acetates.

[0013] Preferably, the metal additive is an alkali metal and / or an alkaline earth metal.

[0014] Preferably, the metal additive is any one or more selected from Na, Mg, Cs, Li, Ba, Ca, Rb, and Sr.

[0015] Preferably, the surfactant is selected from one or more of polyvinylpyrrolidone, polyethylene glycol, and hexadecyltrimethylammonium bromide.

[0016] More preferably, the weight-average molecular weight of the polyvinylpyrrolidone is 30,000-80,000; for example, it can be 30,000, 40,000, 50,000, 60,000, 70,000, or 80,000.

[0017] More preferably, the polyvinylpyrrolidone is PVP K29-32 or PVP K30.

[0018] More preferably, the number average molecular weight of the polyethylene glycol is 1000-5000; for example, it can be 1000, 2000, 3000, 4000, or 5000.

[0019] More preferably, the polyethylene glycol is polyethylene glycol-2000.

[0020] Preferably, the acid is selected from any one or more of hydrochloric acid, nitric acid, citric acid, oxalic acid, and hydrogen peroxide.

[0021] More preferably, the concentration of acid in the acidic solution is 0.01-2 mol / L; for example, it can be 0.1 mol / L, 0.2 mol / L, 0.5 mol / L, 0.6 mol / L, 0.8 mol / L, 1 mol / L, 1.2 mol / L, 1.5 mol / L, 1.8 mol / L, or 2 mol / L.

[0022] Preferably, the soaking temperature is 20-80℃; for example, it can be 20℃, 30℃, 40℃, 50℃, 60℃, 70℃, or 80℃.

[0023] Preferably, the soaking time is 2-12 hours; for example, it can be 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 8 hours, 10 hours, or 12 hours.

[0024] More preferably, when the acid is hydrochloric acid or nitric acid, the concentration of the acid in the acidic solution is 0.01-0.8 mol / L, the soaking temperature is 20-60℃, and the soaking time is 2-10h.

[0025] The pretreatment of the carrier in this application is to increase the surface roughness, defects and pore structure of the carrier, increase the specific surface area of ​​the carrier, and improve its heat and mass transfer.

[0026] It should be noted that this application only provides illustrative examples of acid selection, conventional soaking temperature, and time for acid treatment. In actual operation, those skilled in the art can adjust the type and concentration of acid, soaking temperature, and soaking time according to the type of carrier. For example, when Al2O3 is selected, a weak acid should be chosen for acid treatment; when SiO2 is selected, dilute hydrochloric acid, dilute nitric acid, or a weak acid can be chosen. When hydrochloric acid or nitric acid is selected, due to their strong corrosiveness, the soaking temperature needs to be lowered, and the soaking time should be shortened accordingly.

[0027] Preferably, the drying temperature is 80-120℃; for example, it can be 80℃, 90℃, 100℃, 110℃, or 120℃.

[0028] Preferably, the drying time is 4-12 hours; for example, it can be 4 hours, 5 hours, 6 hours, 8 hours, 10 hours, or 12 hours.

[0029] Preferably, based on 10g of carrier, the amount of water added to the aqueous solution is 40-200mL; for example, it can be 40mL, 50mL, 60mL, 80mL, 100mL, 120mL, 140mL, 150mL, 160mL, 180mL, or 200mL.

[0030] Preferably, the molar ratio of Ru to surfactant in the aqueous solution is 1:0.5-100; for example, it can be 1:0.5, 1:1, 1:5, 1:10, 1:20, 1:30, 1:40, 150, 1:60, 1:70, 1:80, 190, or 1:100.

[0031] Surfactants can coordinate with Ru to improve Ru dispersion. If too little surfactant is added, it cannot play a coordination role. If too much surfactant is added, it will decompose during calcination, take away the active metal, and cause Ru to agglomerate. In addition, too much surfactant cannot be completely burned during calcination, and the residue will deactivate the metal in the catalyst.

[0032] Preferably, the mass ratio of the pretreatment carrier to Ru in the aqueous solution is 2:0.01-0.1; for example, it can be 2:0.01, 2:0.02, 2:0.03, 2:0.04, 2:0.05, 2:0.06, 2:0.07, 2:0.08, 2:0.09, or 2:0.1.

[0033] Preferably, the mass ratio of the pretreatment carrier to the metal additive in the aqueous solution is 10:0.01-0.2; for example, it can be 10:0.01, 10:0.02, 10:0.03, 10:0.04, 10:0.05, 10:0.06, 10:0.07, 10:0.08, 10:0.09, 10:0.1, 10:0.12, 10:0.14, 10:0.15, 10:0.16, 10:0.18, or 10:0.2.

[0034] Preferably, the impregnation temperature is 20-60°C; for example, it can be 20°C, 30°C, 40°C, 50°C, or 60°C.

[0035] Preferably, the soaking time is 4-12 hours; for example, it can be 4 hours, 5 hours, 6 hours, 8 hours, 10 hours, or 12 hours.

[0036] Preferably, the drying temperature is 80-120℃; for example, it can be 80℃, 90℃, 100℃, 110℃, or 120℃.

[0037] Preferably, the drying time is 4-12 hours; for example, it can be 4 hours, 5 hours, 6 hours, 8 hours, 10 hours, or 12 hours.

[0038] Preferably, the roasting temperature is 300-600℃; for example, it can be 300℃, 350℃, 400℃, 450℃, 500℃, 550℃, or 600℃.

[0039] Preferably, the roasting time is 2-8 hours; for example, it can be 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, or 8 hours.

[0040] Preferably, the gas introduced during the water vapor treatment is a mixture of water vapor and inert gas, wherein the volume fraction of water vapor in the mixture is 5%-30%; for example, it can be 5%, 10%, 15%, 20%, 25%, or 30%.

[0041] More preferably, the gas introduced during the water vapor treatment is a mixture of water vapor and nitrogen.

[0042] Preferably, the temperature during the water vapor treatment is 150-400℃; for example, it can be 150℃, 200℃, 250℃, 300℃, 350℃, or 400℃.

[0043] Preferably, the water vapor treatment time is 2-8 hours; for example, it can be 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, or 8 hours.

[0044] Preferably, the pressure during water vapor treatment is 0.1-0.5 MPa; for example, it can be 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, or 0.5 MPa.

[0045] In this application, water vapor treatment can cause structural reconstruction of oxide materials, generating more surface hydroxyl groups and defect sites, which is beneficial for the dispersion of active metals, strengthening metal-support interactions, and improving the stability and catalytic performance of catalysts.

[0046] A second aspect of the present invention provides a Ru-based catalyst, wherein the catalyst is obtained by the preparation method described above; the loading of Ru is 0.5wt%-5wt% based on the mass of the support, and the loading of the metal promoter is 0.1wt%-2wt%.

[0047] Specifically, the loading of Ru can be 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, or 5wt%.

[0048] Preferably, the Ru in the catalyst has a particle size of 4~10 nm.

[0049] More preferably, the particle size of Ru in the catalyst is 5~7 nm.

[0050] Specifically, the loading of the metal additive can be 0.1wt%, 0.2wt%, 0.5wt%, 1wt%, 1.5wt%, or 2wt%.

[0051] A third aspect of the present invention provides a catalyst obtained by the above preparation method as a catalyst for the synthesis of higher alcohols from hydrogen and carbon monoxide, thereby increasing the C2O2 concentration in the Fischer-Tropsch synthesis reaction. 4+ Applications of alcohol selectivity and total alcohol-olefin selectivity.

[0052] The higher alcohols described in this invention are fatty alcohols with 4 or more carbon atoms. There is no specific upper limit on the number of carbon atoms in higher alcohols; for example, they can be C4-C. 20 C4-C 30 C4-C 40 C4-C 50 Or fatty alcohols with a higher number of carbon atoms.

[0053] Preferably, the catalyst has a C 4+ The alcohol selectivity is at least 40%, more preferably 40% to 60%.

[0054] Preferably, the total selectivity of the catalyst for alcohols and olefins is at least 75%, more preferably 75-90%.

[0055] The fourth aspect of this invention provides a catalyst obtained by the above preparation method for catalytically reacting hydrogen and carbon monoxide to produce C. 4+ The method of using alcohols, the method comprising the following steps:

[0056] S1. The catalyst is reduced in a reducing gas atmosphere;

[0057] S2. The reduced catalyst is loaded into the reactor, and hydrogen and carbon monoxide are introduced to carry out the catalytic reaction.

[0058] Preferably, the reducing gas is hydrogen or a mixture of hydrogen and an inert gas, wherein the volume fraction of hydrogen in the mixture is 50%-90%.

[0059] More preferably, the inert gas is any one or more selected from nitrogen, helium, neon, argon, krypton, xenon, and radon.

[0060] More preferably, the mixed gas is a mixture of hydrogen and nitrogen, or a mixture of hydrogen and argon.

[0061] Specifically, the volume fraction of hydrogen in the mixture can be 50%, 60%, 70%, 80%, or 90%.

[0062] Preferably, the space velocity of the reducing gas during the reduction process is 3000-20000 h⁻¹. -1 For example, it could be 3000h. -1 5000h -1 8000h -1 10000h -1 15000h -1 20000h -1 .

[0063] Preferably, the temperature during the reduction treatment is 300-600℃; for example, it can be 300℃, 400℃, 500℃, or 600℃.

[0064] Preferably, the pressure during the reduction process is 0.1-1 MPa; for example, it can be 0.1 MPa, 0.2 MPa, 0.5 MPa, 0.8 MPa, or 1 MPa.

[0065] Preferably, the reduction process takes 4-20 hours; for example, it can be 4 hours, 4 hours, 4 hours, 4 hours, 4 hours, 4 hours, 4 hours, 4 hours, 4 hours.

[0066] Preferably, the temperature of the catalytic reaction is 200-280℃; for example, it can be 200℃, 220℃, 240℃, 260℃, or 280℃.

[0067] Preferably, the pressure of the catalytic reaction is 4-10 MPa; for example, it can be 4 MPa, 5 MPa, 6 MPa, 8 MPa, 9 MPa, or 10 MPa.

[0068] Preferably, the molar ratio of hydrogen to carbon monoxide in the catalytic reaction is 0.5-3:1; for example, it can be 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, or 3:1.

[0069] Preferably, the space velocities of hydrogen and carbon monoxide in the catalytic reaction are 500-5000 h⁻¹. -1 For example, it could be 500h. -1 1000h -1 2000h -1 3000h -1 4000h -1 5000h -1 .

[0070] As described above, the Ru-based catalyst of the present invention and its application in the reaction of syngas to higher alcohols and olefins have the following beneficial effects:

[0071] 1. This invention provides a novel method for preparing Ru-based catalysts. The catalysts prepared by this method exhibit high catalytic activity in Fischer-Tropsch synthesis reactions, enabling highly selective preparation of C. 4+ Higher alcohols, in combination with olefins, significantly enhance the economics and industrial application potential of syngas conversion processes. Applicable to syngas generated from carbon-containing resources such as coal, natural gas, and biomass, it can achieve the co-production of two high-value-added chemicals: higher alcohols and olefins. This not only alleviates the pressure of petroleum resource shortages but also promotes the clean and efficient utilization of carbon-containing resources, reduces reaction energy consumption, and meets the development needs of energy structure transformation and the "dual-carbon" strategy, thus having broad application prospects.

[0072] 2. The preparation process of the new catalyst proposed in this invention is simple, the process is clear and highly controllable, and it is suitable for industrial-scale production. Attached Figure Description

[0073] Figure 1 The image shown is the XRD pattern of the catalyst prepared in Example 1 of this invention. Detailed Implementation

[0074] 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.

[0075] 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.

[0076] Furthermore, it should be understood that the existence of other method steps before or after the combined steps, or the insertion of other method steps between these explicitly mentioned steps, does not preclude the presence of other method steps before or after the combined steps, unless otherwise stated. It should also be understood that the combined connection relationship between one or more devices / apparatus mentioned in this invention does not preclude the existence of other devices / apparatus before or after the combined devices / apparatus, or the insertion of other devices / apparatus between these explicitly mentioned devices / apparatus. Moreover, unless otherwise stated, the numbering of each method step is merely a convenient tool for identifying each method step, and not for limiting the order of the method steps or defining 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.

[0077] Before further describing specific embodiments of the present invention, it should be understood that the scope of protection of the present invention is not limited to the specific embodiments described below; it should also be understood that the terminology used in the embodiments of the present invention is for describing specific embodiments and not for limiting the scope of protection of the present invention; in the specification and claims of the present invention, unless otherwise expressly stated in the text, the singular forms "a", "an" and "this" include the plural forms.

[0078] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in the present invention, both endpoints of each numerical range and any value between the two endpoints may be selected. 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, based on the knowledge of the prior art possessed by one of ordinary skill in the art and the description of this invention, any prior art methods, apparatus, and materials similar to or equivalent to those described, apparatus, and materials in the embodiments of this invention may be used to implement the present invention.

[0079] To address the problems of low selectivity, numerous byproducts, and difficulty in co-producing high-value-added olefins in the synthesis of higher alcohols from syngas using existing Ru-based catalysts, the applicant provides a novel method for preparing Ru-based catalysts, comprising the following steps:

[0080] S1. Carrier pretreatment: The carrier is soaked in an acid solution, washed with water, and dried to obtain the pretreated carrier.

[0081] S2, Co-impregnation: The pretreated carrier is impregnated in an aqueous solution containing Ru, metal additives and surfactants to load the metal onto the carrier, thus obtaining the impregnation system.

[0082] S3. Drying and calcination: The impregnation system is dried and then calcined to obtain the calcined catalyst.

[0083] S4. Water vapor treatment: The target catalyst is obtained after water vapor treatment of the calcined catalyst.

[0084] In some specific embodiments, the acid solution in step S1 above can be a strong acid solution such as dilute hydrochloric acid or dilute nitric acid with a concentration of 0.2-2 mol / L, or a weak acid solution such as citric acid, oxalic acid, or hydrogen peroxide with a concentration of 0.1-1 mol / L.

[0085] In some specific embodiments, the carrier in step S1 above is a mesoporous SiO2, TiO2, or Al2O3 carrier.

[0086] In some specific embodiments, the soaking temperature in step S1 above is 20-80°C.

[0087] In some specific embodiments, the soaking time in step S1 above is 2-12 hours.

[0088] In some specific embodiments, the drying temperature in step S1 above is 80-120°C.

[0089] In some specific embodiments, the drying time in step S1 above is 4-12 hours.

[0090] In some specific embodiments, the metal additive in step S2 above is any one or more selected from Na, Mg, Cs, Li, Ba, Ca, Rb, and Sr.

[0091] In some specific embodiments, the surfactant in step S2 above is any one or more selected from polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), and hexadecyltrimethylammonium bromide (CTAB).

[0092] In some specific embodiments, in the impregnation system of step S2 above, based on the pretreated carrier, the loading of Ru is 0.5wt%-5wt% and the loading of metal additives is 0.3wt%-2wt%.

[0093] In some specific embodiments, in the impregnation system of step S2 above, the molar ratio of surfactant to Ru is (0.5-100):1.

[0094] In some specific embodiments, in the impregnation system of step S2 above, based on 10g of carrier, the amount of water added to the aqueous solution is 40-200mL.

[0095] In some specific embodiments, the immersion temperature in step S2 above is 20-60°C.

[0096] In some specific embodiments, the immersion time in step S2 above is 4-12 hours.

[0097] In some specific embodiments, the drying temperature in step S3 above is 80-120°C.

[0098] In some specific embodiments, the drying time in step S3 above is 4-12 hours.

[0099] In some specific embodiments, the calcination temperature in step S3 above is 300-600℃.

[0100] In some specific embodiments, the calcination time in step S3 above is 2-8 hours.

[0101] In some specific embodiments, during the water vapor treatment in step S4 above, the volume fraction of water vapor in the introduced gas is 5%-30%, and the remaining gas is nitrogen.

[0102] In some specific embodiments, the temperature during water vapor treatment in step S4 above is 150-400℃.

[0103] In some specific embodiments, the time for water vapor treatment in step S4 above is 2-8 hours.

[0104] In some specific embodiments, the pressure during water vapor treatment in step S4 above is 0.1-0.5 MPa.

[0105] This invention introduces surfactants into the catalyst system, which can effectively inhibit the agglomeration of metal active components during the preparation process, significantly improve the dispersibility of active components, and enhance the interaction between Ru metal and the support and metal promoters. This solves the technical pain points of poor dispersibility and easy deactivation of metal active components in existing Ru-based catalysts.

[0106] This invention pretreats mesoporous SiO2, TiO2, and Al2O3 supports with acid, which effectively increases the hydroxyl concentration on the support surface, enhances the interaction between the support and Ru active components, metal promoters, and surfactants, further improves the dispersibility and stability of the catalyst, and extends the catalyst's service life.

[0107] This invention modifies Ru-based catalysts using alkali metals / alkaline earth metals as metal promoters. The alkali metals / alkaline earth metals, as electronic promoters, can adjust the chemical properties of different surface sites of Ru nanoparticles, achieving a functional balance between CO dissociation and non-dissociation adsorption, and utilizing the generation of higher alcohols and olefins. At the same time, the modifying promoters and Ru active components form a synergistic effect, suppressing the occurrence of side reactions such as methanation and water-gas shift reaction, significantly improving the selectivity of higher alcohols and olefins, and breaking through the technical bottleneck of existing Ru-based catalysts that cannot achieve high selectivity for both.

[0108] The catalyst of this invention enhances the metal-support interaction and improves the stability of Ru nanoparticles by high-temperature steam treatment.

[0109] The carrier used in the following embodiments of the present invention has a central particle size in the range of 2-50 nm.

[0110] Example 1

[0111] Example 1 provides a Ru-based catalyst and its performance testing method. The specific preparation method is as follows:

[0112] S1. Pretreatment of the support: Take 15g of mesoporous SiO2 as the initial support, place it in 0.5mol / L citric acid solution, soak it at 50℃ for 6h, after soaking, wash it with deionized water until the pH of the washing solution is 7, and then dry it at 100℃ for 8h to obtain the pretreated support.

[0113] S2. Co-impregnation: Based on the total mass of 10g of the treated carrier, the Ru loading is 3.0%, the Na loading is 0.5%, and the surfactant used is PVP (PVP K30, with a molar ratio of 10 to Ru). Take 0.776g of ruthenium chloride (Ru mass 0.3g) (RuCl3·3H2O), 0.185g of sodium nitrate (Na mass 0.05g), and 1.10g of PVP, dissolve them in 50mL of deionized water to prepare a mixed impregnation solution. Add 10g of the pretreated carrier to the mixed impregnation solution and stir and impregnate at 40℃ for 8h to obtain the impregnation system.

[0114] S3. Drying and calcination: The impregnated system was dried at 100℃ for 8 hours, and then placed in a muffle furnace and heated to 450℃ at a heating rate of 5℃ / min for 4 hours to obtain the calcined catalyst.

[0115] S4. High-temperature steam treatment: The calcined catalyst is placed in a steam treatment device, and a mixture of steam and nitrogen with a steam volume fraction of 15% is introduced. The mixture is treated at 250℃ and 0.3MPa for 4 hours, and then naturally cooled to room temperature to obtain the steam-treated catalyst.

[0116] S5. Reduction Treatment: After water vapor treatment, the catalyst is placed in a reaction tube, and pure H2 gas is introduced. Reduction is carried out at 450℃ and 0.5MPa for 10 hours, with an H2 space velocity of 5000h. -1 After reduction, the catalyst was naturally cooled to room temperature to obtain the target Ru-based catalyst.

[0117] S6. Take 1.5g of the target catalyst, dilute it with 6g of silicon carbide, and pack it together in a fixed-bed reactor. Introduce syngas (H2 / CO = 2:1) and carry out the reaction under the conditions of reaction pressure 5MPa, reaction temperature 240℃ and syngas space velocity 4000 h-¹. Its performance is shown in Table 1.

[0118] Example 2

[0119] Example 2 provides a Ru-based catalyst and its performance testing method. The specific preparation method is as follows:

[0120] S1. Pretreatment of the carrier: Take 15g TiO2 as the initial carrier, place it in 0.5mol / L H2O2 solution, soak it at 20℃ for 12h. After soaking, wash it with deionized water until the pH of the washing solution is 7, and then dry it at 80℃ for 12h to obtain the pretreated carrier.

[0121] S2. Co-impregnation: Based on the total mass of 10g of the treated carrier, the loading of Ru is 0.5%, the loading of Mg is 0.1%, the loading of K is 0.2%, and the surfactant is PEG-2000 with a molar ratio of 0.5 to Ru. Take 0.142g of ruthenium nitrate (Ru: 0.05g), 0.101g of magnesium nitrate (Mg: 0.01g), 0.052g of potassium nitrate (0.02g), and 0.495g of PEG, dissolve them in 40mL of deionized water to prepare a mixed impregnation solution. Add 10g of the pretreated TiO2 carrier to the mixed impregnation solution and stir and impregnate at 25℃ for 12h to obtain the impregnation system.

[0122] S3. Drying and calcination: The impregnation system was dried at 80℃ for 12h, and then placed in a muffle furnace and heated to 300℃ at a heating rate of 2℃ / min for 8h to obtain the calcined catalyst.

[0123] S4. High-temperature steam treatment: The calcined catalyst is placed in a steam treatment device, and a mixture of steam and nitrogen with a steam volume fraction of 5% is introduced. The mixture is treated at 150℃ and 0.1MPa for 8 hours, and then naturally cooled to room temperature to obtain the steam-treated catalyst.

[0124] S5. Reduction Treatment: After water vapor treatment, the catalyst is placed in a reaction tube, and a mixture of H2 and Ar (H2 volume fraction 50%) is introduced. Reduction is carried out at 300℃ and 0.1MPa for 20 hours, with a mixed gas space velocity of 1000 h⁻¹. -1 After reduction, the catalyst was naturally cooled to room temperature to obtain the target Ru-based catalyst.

[0125] S6. Take 1.5g of the target catalyst, dilute it with 6g of silicon carbide, and pack it together into a fixed-bed reactor. Introduce syngas (H2 / CO molar ratio = 0.75:1) and react at a pressure of 8MPa, a temperature of 250℃, and a syngas space velocity of 500h⁻¹. -1 The reaction was carried out under certain conditions, and its performance is shown in Table 1.

[0126] Example 3

[0127] Example 3 provides a Ru-based catalyst and its performance testing method. The specific preparation method is as follows:

[0128] S1. Pretreatment of the support: Take 15g of SiO2 as the initial support and place it in a 0.2mol / L dilute hydrochloric acid solution. Soak it at 30℃ for 2h. After soaking, wash it with deionized water until the pH of the washing solution is 7. Then dry it at 120℃ for 4h to obtain the pretreated SiO2 support.

[0129] S2. Co-impregnation: Based on the total mass of 10g of the treated carrier, the loading of Ru is 5.0%, the loading of Cs is 2.0%, and the surfactant is CTAB (the molar ratio of its molar amount to Ru is 10). Take 1.371g of ruthenium acetate, 0.291g of cesium nitrate, and 18g of CTAB, dissolve them in 50mL of deionized water to prepare a mixed impregnation solution. Add 10g of the pretreated Al2O3 carrier to the mixed impregnation solution and stir and impregnate at 60℃ for 4h to obtain the impregnation system.

[0130] S3. Drying and calcination: The impregnation system was dried at 120℃ for 4 hours, and then placed in a muffle furnace and heated to 600℃ at a heating rate of 5℃ / min for 2 hours to obtain the calcined catalyst.

[0131] S4. High-temperature steam treatment: The calcined catalyst is placed in a steam treatment device, and a mixture of steam and nitrogen with a steam volume fraction of 30% is introduced. The catalyst is treated at 400℃ and 0.5MPa for 2 hours and then naturally cooled to room temperature to obtain the steam-treated catalyst.

[0132] S5. Reduction Treatment: After water vapor treatment, the catalyst is placed in a reaction tube, and pure H2 gas is introduced. Reduction is carried out at 600℃ and 1.0MPa for 4 hours, with an H2 space velocity of 20000h. -1After reduction, the catalyst was naturally cooled to room temperature to obtain the target Ru-based catalyst.

[0133] S6. Take 1.5g of the target catalyst, dilute it with 6g of silicon carbide, and pack them together in a fixed-bed reactor. Introduce syngas (H2 / CO = 3:1) and react at a pressure of 8MPa, a temperature of 200℃, and a syngas space velocity of 5000h. -1 The reaction was carried out under certain conditions, and its performance is shown in Table 1.

[0134] Example 4

[0135] Example 4 provides a Ru-based catalyst and its performance testing method. The specific preparation method is as follows:

[0136] S1. Pretreatment of the support: Take 15g of SiO2 as the initial support, place it in 0.8mol / L oxalic acid solution, soak it at 60℃ for 8h, after soaking, wash it with deionized water until the pH of the washing solution is 7, and then dry it at 110℃ for 6h to obtain the pretreated support.

[0137] S2. Co-impregnation: Based on the total mass of 10g of the treated carrier, the Ru loading is 2.5%, the Li loading is 1.0%, and the surfactant is PVP (its molar ratio to Ru is 50). Take 0.647g of ruthenium chloride (RuCl3·3H2O) (Ru: 0.25g), 0.532g of lithium carbonate (Li: 0.1g), and 13.71g of PVP (K30), dissolve them in 80mL of deionized water to prepare a mixed impregnation solution. Add 10g of the pretreated carrier to the mixed impregnation solution and stir and impregnate at 45℃ for 7h to obtain the impregnation system.

[0138] S3. Drying and calcination: The impregnation system was dried at 110℃ for 6 hours, and then placed in a muffle furnace and heated to 480℃ at a heating rate of 4℃ / min for 5 hours to obtain the calcined catalyst.

[0139] S4. High-temperature steam treatment: The calcined catalyst is placed in a steam treatment device, and a mixture of steam and nitrogen with a steam volume fraction of 20% is introduced. The mixture is treated at 300℃ and 0.3MPa for 5 hours, and then naturally cooled to room temperature to obtain the steam-treated catalyst.

[0140] S5. Reduction Treatment: After water vapor treatment, the catalyst is placed in a reaction tube, and a mixture of H2 and N2 gas (H2 volume fraction 60%) is introduced. Reduction is carried out at 450℃ and 0.1MPa for 12 hours, with a mixed gas space velocity of 10000 h⁻¹. -1 After reduction, the catalyst was naturally cooled to room temperature to obtain the target Ru-based catalyst.

[0141] S6. Take 1.5g of the target catalyst, dilute it with 6g of silicon carbide, and pack them together in a fixed-bed reactor. Introduce syngas (H2 / CO = 1.5:1) and run the reactor under the following conditions: reaction pressure 6MPa, reaction temperature 220℃, and syngas space velocity 2000 h⁻¹. - The reaction was carried out under the conditions shown in Table 1.

[0142] Example 5

[0143] Example 5 provides a Ru-based catalyst and its performance testing method. The specific preparation method is as follows:

[0144] S1. Pretreatment of the support: Take 15g of mesoporous SiO2 as the initial support, place it in a 0.5 mol / L dilute nitric acid solution, soak it at 40℃ for 10h, after soaking, wash it with deionized water until the pH of the washing solution is 7, and then dry it at 90℃ for 9h to obtain the pretreated support.

[0145] S2. Co-impregnation: Based on the total mass of 10g of the treated carrier, the loading of Ru is 3.0%, the loading of Ba is 1.5%, and the surfactant is PEG-2000 (the molar ratio of its molar amount to Ru is 10). Take 0.852g of ruthenium nitrate (Ru: 0.3g), 0.277g of barium acetate (Ru: 0.15g), and 59.4g of PEG, dissolve them in 100mL of deionized water to prepare a mixed impregnation solution. Add 10g of the pretreated SiO2 carrier to the mixed impregnation solution and stir and impregnate at 35℃ for 9h to obtain the impregnation system.

[0146] S3. Drying and calcination: The impregnation system was dried at 90°C for 9 hours, and then placed in a muffle furnace and heated to 550°C at a heating rate of 3°C / min for 3 hours to obtain the calcined catalyst.

[0147] S4. High-temperature steam treatment: The calcined catalyst is placed in a steam treatment device, and a mixture of steam and nitrogen with a steam volume fraction of 25% is introduced. The mixture is treated at 350℃ and 0.4MPa for 3 hours, and then naturally cooled to room temperature to obtain the steam-treated catalyst.

[0148] S5. Reduction Treatment: The catalyst, after water vapor treatment, is placed in a reaction tube, and pure H2 gas is introduced. Reduction is carried out at 500℃ and 0.8MPa for 8 hours, with an H2 space velocity of 6000 h⁻¹. -1 After reduction, the catalyst was naturally cooled to room temperature to obtain the target Ru-based catalyst.

[0149] S6. Take 1.5g of the target catalyst, dilute it with 6g of silicon carbide, and pack them together in a fixed-bed reactor. Introduce syngas (H2 / CO = 0.5:1) and react at a pressure of 7MPa, a temperature of 260℃, and a syngas space velocity of 3000h⁻¹. -1 The reaction was carried out under certain conditions, and its performance is shown in Table 1.

[0150] Example 6

[0151] Example 6 provides a Ru-based catalyst and its performance testing method. The specific preparation method is as follows:

[0152] S1. Pretreatment of the carrier: Take 15g of mesoporous Al2O3 as the initial carrier, place it in 0.2mol / L H2O2 solution, soak it at 70℃ for 4h. After soaking, wash it with deionized water until the pH of the washing solution is 7, and then dry it at 105℃ for 7h to obtain the pretreated carrier.

[0153] S2. Co-impregnation: Based on the total mass of 10g of the treated carrier, the Ru loading is 2.0%, the Na loading is 0.8%, and the surfactant is CTAB (its molar ratio to Ru is 100). Take 0.502g of ruthenium chloride (RuCl3·3H2O) (Ru: 0.2g), 0.184g of sodium carbonate (Na 0.08g), and 71.5g of CTAB, dissolve them in 200mL of deionized water to prepare a mixed impregnation solution. Add 10g of the pretreated Al2O3 carrier to the mixed impregnation solution and stir and impregnate at 60℃ for 5h to obtain the impregnation system.

[0154] S3. Drying and calcination: The impregnated system was dried at 100℃ for 10h, and then placed in a muffle furnace and heated to 550℃ at a heating rate of 2℃ / min for calcination for 4h to obtain the calcined catalyst.

[0155] S4. High-temperature steam treatment: The calcined catalyst is placed in a steam treatment device, and a mixture of steam and nitrogen with a steam volume fraction of 20% is introduced. The mixture is treated at 320℃ and 0.4MPa for 3.5h, and then naturally cooled to room temperature to obtain the steam-treated catalyst.

[0156] S5. Reduction Treatment: The catalyst after water vapor treatment is placed in a reaction tube, and a mixed gas of H2 and Ar (H2 volume fraction 70%) is introduced. Reduction is carried out at 550℃ and 1MPa for 6 hours, with a mixed gas space velocity of 8000h. -1 After reduction, the catalyst was naturally cooled to room temperature to obtain the target Ru-based catalyst.

[0157] S6. Take 1.5g of the target catalyst, dilute it with 6g of silicon carbide, and pack them together in a fixed-bed reactor. Introduce syngas (H2 / CO = 2:1) and react at a pressure of 9MPa, a temperature of 200℃, and a syngas space velocity of 4000h⁻¹. -1 The reaction was carried out under certain conditions, and its performance is shown in Table 1.

[0158] Example 7

[0159] Example 7 provides a Ru-based catalyst and its performance testing method. The specific preparation method is as follows:

[0160] S1. Pretreatment of the carrier: Take 15g TiO2 as the initial carrier, place it in 0.6mol / L oxalic acid solution, soak it at 30℃ for 9h. After soaking, wash it with deionized water until the pH of the washing solution is 7, and then dry it at 85℃ for 10h to obtain the pretreated carrier.

[0161] S2. Co-impregnation: Based on the total mass of 10g of the treated carrier, the Ru loading is 1.5%, the Ca loading is 0.6%, and the surfactant is PVP (its molar ratio to Ru is 15). Take 0.411g of ruthenium acetate (Ru: 0.15g), 0.373g of calcium nitrate (Ca: 0.0628g), and 2.46g of PVP K30, dissolve them in 50mL of deionized water to prepare a mixed impregnation solution. Add 10g of the pretreated carrier to the mixed impregnation solution and stir and impregnate at 30℃ for 10h to obtain the impregnation system.

[0162] S3. Drying and calcination: The impregnation system was dried at 85℃ for 10h, and then placed in a muffle furnace and heated to 380℃ at a heating rate of 2.5℃ / min for 6h to obtain the calcined catalyst.

[0163] S4. High-temperature steam treatment: The calcined catalyst is placed in a steam treatment device, and a mixture of steam and nitrogen with a steam volume fraction of 12% is introduced. The mixture is treated at 220℃ and 0.2MPa for 6 hours, and then naturally cooled to room temperature to obtain the steam-treated catalyst.

[0164] S5. Reduction Treatment: The catalyst, after water vapor treatment, is placed in a reaction tube, and pure H2 gas is introduced. Reduction is carried out at 380℃ and 0.1MPa for 15 hours, with an H2 space velocity of 3000 h⁻¹. -1 After reduction, the catalyst was naturally cooled to room temperature to obtain the target Ru-based catalyst.

[0165] S6. Take 1.5g of the target catalyst, dilute it with 6g of silicon carbide, and pack them together in a fixed-bed reactor. Introduce syngas (H2 / CO molar ratio = 0.5:1) and run the reactor under the following conditions: reaction pressure 10MPa, reaction temperature 220℃, and syngas space velocity 2000 h⁻¹.-1 The reaction was carried out under certain conditions, and its performance is shown in Table 1.

[0166] Example 8

[0167] Example 8 provides a Ru-based catalyst and its performance testing method. The specific preparation method is as follows:

[0168] S1. Pretreatment of the support: Take 15g of mesoporous SiO2 as the initial support, place it in a 2mol / L H2O2 solution, soak it at 75℃ for 3h, after soaking, wash it with deionized water until the pH of the washing solution is 7, and then dry it at 115℃ for 5h to obtain the pretreated support.

[0169] S2. Co-impregnation: Based on the total mass of 10g of the treated carrier, the Ru loading is 4.0%, the Rb loading is 1.8%, and the surfactant is PEG-2000 (its molar ratio to Ru is 5). Take 1.136g of ruthenium nitrate (Ru: 0.4g), 0.311g of rubidium nitrate (Rb: 0.18g), and 39.60g of PEG, dissolve them in 100mL of deionized water to prepare a mixed impregnation solution. Add 10g of the pretreated carrier to the mixed impregnation solution and stir and impregnate at 50℃ for 6h to obtain the impregnation system.

[0170] S3. Drying and calcination: The impregnated system was dried at 120°C for 5 hours, and then placed in a muffle furnace and heated to 500°C at a heating rate of 2°C / min for 5 hours to obtain the calcined catalyst.

[0171] S4. High-temperature steam treatment: The calcined catalyst is placed in a steam treatment device, and a mixture of steam and nitrogen with a steam volume fraction of 5% is introduced. The mixture is treated at 350℃ and 0.1MPa for 3 hours, and then naturally cooled to room temperature to obtain the steam-treated catalyst.

[0172] S5. Reduction Treatment: After water vapor treatment, the catalyst is placed in a reaction tube, and a mixture of H2 and N2 gas (H2 volume fraction 80%) is introduced. Reduction is carried out at 450℃ and 0.2MPa for 5 hours, with a mixed gas space velocity of 5000 h⁻¹. -1 After reduction, the catalyst was naturally cooled to room temperature to obtain the target Ru-based catalyst.

[0173] S6. Take 1.5g of the target catalyst, dilute it with 6g of silicon carbide, and pack them together in a fixed-bed reactor. Introduce syngas (H2 / CO=2:1) ​​and react at a pressure of 4 MPa, a temperature of 250℃, and a syngas space velocity of 5000 h⁻¹. -1 The reaction was carried out under certain conditions, and its performance is shown in Table 1.

[0174] Example 9

[0175] Example 9 provides a Ru-based catalyst and its performance testing method. The specific preparation method is as follows:

[0176] S1. Pretreatment of the support: Take 15g of mesoporous SiO2 as the initial support, place it in 0.3mol / L citric acid solution, soak it at 25℃ for 11h, after soaking, wash it with deionized water until the pH of the washing solution is 7, and then dry it at 120℃ for 11h to obtain the pretreated support.

[0177] S2. Co-impregnation: Based on the total mass of 10g modified carrier, the loading of Ru is 0.8%, the loading of Sr is 0.3%, and the loading of Na is 0.3%. The surfactant used is CTAB (the molar ratio of its molar amount to Ru is 10). Take 0.201g of ruthenium chloride (RuCl3·3H2O) (Ru: 0.08g), 0.0797g of strontium chloride (Sr: 0.03g), 0.11g of sodium nitrate (Na: 0.03g), and 28.5g of CTAB, dissolve them in 100mL of deionized water to prepare a mixed impregnation solution. Add 10g of pretreated carrier to the mixed impregnation solution and stir and impregnate at 28℃ for 11h to obtain the impregnation system.

[0178] S3. Drying and calcination: The impregnation system was dried at 100℃ for 12h, and then placed in a muffle furnace and heated to 300℃ at a heating rate of 2℃ / min for 8h to obtain the calcined catalyst.

[0179] S4. High-temperature steam treatment: The calcined catalyst is placed in a steam treatment device, and a mixture of steam and nitrogen with a steam volume fraction of 5% is introduced. The mixture is treated at 150℃ and 0.1MPa for 7 hours, and then naturally cooled to room temperature to obtain the steam-treated catalyst.

[0180] S5. Reduction Treatment: The catalyst, after water vapor treatment, is placed in a reaction tube, and pure H2 gas is introduced. Reduction is carried out at 320℃ and 0.1MPa for 18 hours, with an H2 space velocity of 8000 h⁻¹. -1 After reduction, the catalyst was naturally cooled to room temperature to obtain the target Ru-based catalyst.

[0181] S6. Take 1.5g of the target catalyst, dilute it with 6g of silicon carbide, and pack them together in a fixed-bed reactor. Introduce syngas (H2 / CO = 1:1) and run the reactor under the following conditions: reaction pressure 8MPa, reaction temperature 210℃, and syngas space velocity 1000 h⁻¹. -1 The reaction was carried out under certain conditions, and its performance is shown in Table 1.

[0182] Example 10

[0183] Example 10 provides a Ru-based catalyst and its performance testing method. The specific preparation method is as follows:

[0184] S1. Pretreatment of the support: Take 15g of SiO2 as the initial support and place it in a 0.8mol / L dilute hydrochloric acid solution. Soak it at 60℃ for 2 h. After soaking, wash it with deionized water until the pH of the washing solution is 7. Then dry it at 120℃ for 10 h to obtain the pretreated support.

[0185] S2. Co-impregnation: Based on the total mass of 10g modified carrier, the loading of Ru is 4%, the total loading of Cs and Mg dual-modifying agents (mass ratio 1:1) is 2%, and the surfactant selected is PVP (K29-32, its molar ratio to Ru is 40); take 1.1g ruthenium acetate (Ru: 0.4g), 0.147g cesium nitrate (CS: 0.1g), 1.05g magnesium nitrate (Mg: 0.1g), and 17.57g PVP, dissolve them in 60mL of deionized water to prepare a mixed impregnation solution; add the pretreated 10g carrier to the mixed impregnation solution, stir and impregnate at 50℃ for 4.5h to obtain the impregnation system.

[0186] S3. Drying and calcination: The impregnated system was dried at 120℃ for 8 hours, and then placed in a muffle furnace and heated to 600℃ at a heating rate of 2℃ / min for 2 hours to obtain the calcined catalyst.

[0187] S4. High-temperature steam treatment: The calcined catalyst is placed in a steam treatment device, and a mixture of steam and nitrogen with a volume fraction of 10% is introduced. The mixture is treated at 350℃ and 0.5MPa for 2 hours, and then naturally cooled to room temperature to obtain the steam-treated catalyst.

[0188] S5. Reduction Treatment: The catalyst after water vapor treatment is placed in a reaction tube, and a mixed gas of H2 and Ar (H2 volume fraction 65%) is introduced. Reduction is carried out at 400℃ and 1MPa for 5 hours, with a mixed gas space velocity of 7000h. -1 After reduction, the catalyst was naturally cooled to room temperature to obtain the target Ru-based catalyst.

[0189] S6. Take 1.5g of the target catalyst, dilute it with 6g of silicon carbide, and pack them together in a fixed-bed reactor. Introduce syngas (H2 / CO = 1.9:1) and run the reaction at a pressure of 7MPa, a temperature of 230℃, and a syngas space velocity of 3000h⁻¹. -1 The reaction was carried out under certain conditions, and its performance is shown in Table 1.

[0190] Comparative Example 1

[0191] Comparative Example 1 is a comparative example of Example 1. The only difference between Comparative Example 1 and Example 1 is that the high-temperature steam treatment is not performed, and the calcined catalyst is directly reduced. The other preparation methods and performance tests are the same as those in Example 1.

[0192] Comparative Example 2

[0193] Comparative Example 2 is a comparative example of Example 3. The only difference between Comparative Example 2 and Example 3 is that no metal additive cesium nitrate is added during the impregnation process. All other preparation methods and performance tests are the same as those in Example 3.

[0194] Comparative Example 3

[0195] Comparative Example 3 is a comparative example of Example 1. The only difference between Comparative Example 3 and Example 1 is that no carrier pretreatment is performed, and the untreated carrier is directly co-impregnated. The other preparation methods and performance tests are the same as those in Example 1.

[0196] Comparative Example 4

[0197] Comparative Example 4 is a comparative example of Example 1. The only difference between it and Example 1 is that no surfactant is added during the impregnation treatment. All other preparation methods and performance tests are the same as those in Example 1.

[0198] The catalyst performance test results of Examples 1-10 and Comparative Examples 1-4 are shown in Table 1.

[0199] Table 1. Catalyst performance test results for Examples 1-10 and Comparative Examples 1-4

[0200]

[0201] According to the catalyst performance test results in Table 1, when the catalysts prepared using the methods in Examples 1-10 are used for syngas reforming catalytic reactions, C 4+ The selectivity of alcohols was >40%, and the total selectivity of alcohols and alkenes was >75%. The selectivity of CH4 and CO2 was <3%, exhibiting high activity and high C content. 4+ Alcohol selectivity, high total alcohol and olefin selectivity, and low CH4 and CO2 selectivity.

[0202] Compared to Example 1, Comparative Example 1 did not involve steam treatment, and the catalyst prepared in Comparative Example 1 underwent a catalytic reaction with C1. 4+ Both the selectivity for alcohols and the overall selectivity for alcohols and alkenes were significantly reduced; compared with Example 3, no metal promoter was added in Comparative Example 2, resulting in a lower C1 ratio during the catalytic reaction of the prepared catalyst. 4+ Both the selectivity for alcohols and the overall selectivity for alcohols and alkenes were significantly reduced; compared to Example 9, Comparative Example 3 did not undergo a support soaking pretreatment, resulting in a lower C1 ratio during the catalytic reaction. 4+Both the selectivity for alcohols and the overall selectivity for alcohols and olefins were significantly reduced; compared to Example 1, no surfactant was added during the impregnation treatment in Comparative Example 4, resulting in a lower C1 ratio during the catalytic reaction of the prepared catalyst. 4+ Both the selectivity for alcohols and the overall selectivity for alcohols and alkenes decreased significantly. This indicates that the steps in the preparation method of this catalyst are synergistically coordinated, and the Ru-based catalyst prepared has high C60 content. 4+ Alcohol selectivity and total alcohol-olefin selectivity.

[0203] Figure 1 The XRD pattern of the catalyst prepared in Example 1 shows that only the signal peaks of SiO2 and Ru are displayed, while the absorption peak of the metal promoter Na is not shown, which proves that Na is highly dispersed in the catalyst and therefore no diffraction peak appears. Furthermore, the particle size of Ru was calculated to be 6.4 nm using the Scherrer equation, which is within the optimal particle size range for the Fischer-Tropsch reaction.

[0204] Therefore, this invention creatively proposes a novel method for preparing a Fischer-Tropsch synthesis catalyst, the prepared catalyst being capable of achieving highly selective production of C from syngas. 4+ Higher alcohols, in conjunction with olefin production, significantly enhance the economics and industrial application potential of syngas reforming processes.

[0205] 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 Ru-based catalyst, characterized in that, The preparation method includes: soaking, washing, and drying a support in an acidic solution to obtain a pretreated support; impregnating the pretreated support in an aqueous solution containing Ru, a metal additive, and a surfactant to obtain an impregnation system; and obtaining a Ru-based catalyst after drying, calcining, and steam treatment of the impregnation system.

2. The preparation method according to claim 1, characterized in that, The carrier is selected from any one or more of mesoporous SiO2, mesoporous TiO2, and mesoporous Al2O3; And / or, the metal additive is an alkali metal and / or an alkaline earth metal; And / or, the surfactant is any one or more selected from polyvinylpyrrolidone, polyethylene glycol, and hexadecyltrimethylammonium bromide.

3. The preparation method according to claim 1, characterized in that, The acid is selected from any one or more of hydrochloric acid, nitric acid, citric acid, oxalic acid, and hydrogen peroxide; And / or, the soaking temperature is 20-80℃; And / or, the soaking time is 2-12 hours; And / or, the drying temperature is 80-120°C; And / or, the drying time is 4-12 hours.

4. The preparation method according to claim 1, characterized in that, Based on 10g of carrier, the amount of water added to the aqueous solution is 40-200mL; And / or, the molar ratio of Ru to surfactant in the aqueous solution is 1:0.5-100; And / or, the mass ratio of the pretreated carrier to Ru in the aqueous solution is 2:0.01-0.1; And / or, the mass ratio of the pretreatment carrier to the metal additive in the aqueous solution is 10:0.01-0.2; And / or, the impregnation temperature is 20-60°C; And / or, the immersion time is 4-12 hours.

5. The preparation method according to claim 1, characterized in that, The drying temperature is 80-120℃; And / or, the drying time is 4-12 hours; And / or, the calcination temperature is 300-600℃; And / or, the calcination time is 2-8 hours.

6. The preparation method according to claim 1, characterized in that, The gas introduced during the water vapor treatment is a mixture of water vapor and inert gas, wherein the volume fraction of water vapor in the mixture is 5%-30%. And / or, the temperature during the steam treatment is 150-400℃; And / or, the time for the water vapor treatment is 2-8 hours; And / or, the pressure during the water vapor treatment is 0.1-0.5 MPa.

7. A Ru-based catalyst, characterized in that, The catalyst is obtained by any one of the preparation methods described in claims 1-6; based on the mass of the support, the loading of Ru is 0.5wt%-5wt%, and the loading of the metal additive is 0.1wt%-2wt%.

8. The catalyst obtained by any one of the preparation methods of claims 1-6, or the catalyst of claim 7, as a catalyst for the synthesis of higher alcohols from hydrogen and carbon monoxide, increases the C4 concentration in the Fischer-Tropsch synthesis reaction. 4+ Applications of alcohol selectivity and total alcohol-olefin selectivity.

9. A catalyst obtained by any one of the preparation methods of claims 1-6, or, as described in claim 7, a catalyst for catalyzing the reaction of hydrogen and carbon monoxide to produce C. 4+ The method using alcohols, characterized in that, The method includes the following steps: S1. The catalyst is reduced in a reducing gas atmosphere; S2. The reduced catalyst is loaded into the reactor, and hydrogen and carbon monoxide are introduced to carry out the catalytic reaction.

10. The method according to claim 9, characterized in that, The reducing gas is hydrogen or a mixture of hydrogen and an inert gas, wherein the volume fraction of hydrogen in the mixture is 50%-90%. And / or, the space velocity of the reducing gas during the reduction process is 3000-20000 h⁻¹. -1 ; And / or, the temperature during the reduction treatment is 300-600℃; And / or, the pressure during the reduction treatment is 0.1-1 MPa; And / or, the reduction process takes 4-20 hours; And / or, the temperature of the catalytic reaction is 200-280°C; And / or, the pressure of the catalytic reaction is 4-10 MPa; And / or, the molar ratio of hydrogen to carbon monoxide in the catalytic reaction is 0.5-3:1; And / or, the space velocities of hydrogen and carbon monoxide in the catalytic reaction are 500-5000 h⁻¹. -1 .

Images