A ruthenium-based catalyst for direct synthesis of olefins from syngas, a preparation method and applications thereof

Abstract

The application provides a ruthenium-based catalyst for directly synthesizing olefins from synthesis gas, a preparation method and application thereof, the ruthenium-based catalyst is composed of ruthenium, a metal promoter and a structural promoter, the ruthenium-based catalyst comprises 0.5wt%-10wt% of ruthenium, 0-20wt% of the metal promoter and 70wt%-99wt% of the structural promoter, according to the mass percentage of the ruthenium-based catalyst; wherein the content of the ruthenium is in terms of the mass of metallic ruthenium; the content of the metal promoter is not 0 in the ruthenium-based catalyst; and the content of the structural promoter is in terms of the mass of the corresponding oxide. The ruthenium-based catalyst with high dispersity and high stability is prepared by using a hydrothermal method, the preparation method is simple and easy to repeat, the active component of the prepared ruthenium-based catalyst is uniformly distributed on the structural promoter, the structure is stable, the utilization rate of the ruthenium metal is high, and the ruthenium-based catalyst is used in the reaction of directly synthesizing olefins from synthesis gas, and good olefin synthesis performance is shown.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of catalyst technology, in particular relates to a ruthenium-based catalyst for direct synthesis of olefins from syngas, a preparation method and application thereof. BACKGROUND

[0002] Olefins are important chemical raw materials, which are divided into low-carbon olefins (ethylene, propylene, butene) and high-carbon olefins (olefins with more than C5) according to the length of carbon chain. The low-carbon olefins with lower carbon number are mainly used for the production of plastics, synthetic textile materials, solvents, etc. The high-carbon olefins have higher added value, which can be used as comonomers to produce plastics, polyethylene elastomers, surfactants, etc., and as chemical intermediates to synthesize detergents, detergent alcohols, lubricating oils, synthetic plasticizer alcohols, etc. The traditional synthesis route of olefins is mainly prepared by catalytic cracking of petroleum. With the decrease of petroleum resources and the increase of demand for olefins, it is urgent to develop a non-petroleum synthesis route of olefins. Various carbon-containing resources are first subjected to a gasification process to obtain syngas, and then a Fischer-Tropsch synthesis reaction can obtain a variety of chemicals including olefins. Thus, a new synthesis route of olefins is provided, i.e. Fischer-Tropsch to Olefins (FTO) directly preparing olefins from syngas.

[0003] At present, the FTO catalysts are mainly iron-based and cobalt-based catalysts. Although high olefin selectivity can be obtained, the catalysts also have high water gas activity, so the selectivity of carbon dioxide in the product is high, resulting in low overall carbon efficiency of the catalyst. Noble metal catalysts are also used to synthesize efficient FTO catalysts. Since the active component is relatively expensive, how to improve the dispersion of ruthenium active sites and fully stabilize and active components becomes the key to the preparation of catalysts. The conventional noble metal catalysts are mainly prepared by impregnation method, which has the advantages of simple operation, good controllability and high utilization rate of active components in the small-scale catalyst preparation process. However, in the catalyst preparation process, the noble metal precursor solution can only diffuse locally to the surface of the carrier, so that the metal component cannot be uniformly distributed in the carrier. In the process of excessive impregnation, the metal precursor solution may be more distributed on the surface of the carrier, resulting in the aggregation and growth of the final noble metal particles. Due to the shortcomings and limitations of the impregnation method for preparing catalysts, this method is only suitable for the experimental preparation of a small amount of samples. In the large-scale industrial preparation of noble metal catalysts, in order to avoid the above problems, other catalyst preparation methods need to be developed. SUMMARY

[0004] In view of the above-mentioned disadvantages of the prior art, the purpose of the present application is to provide a ruthenium-based catalyst for direct synthesis of olefins from synthesis gas, a preparation method and application thereof, so as to solve the problem that the prior art cannot realize large-scale industrial application due to the use of impregnation method for preparing noble metal catalysts, and the problem that the noble metal precursor solution can only diffuse locally to the surface of the carrier, and the metal components are unevenly distributed on the carrier.

[0005] To achieve the above-mentioned purpose and other related purposes, the present application provides a ruthenium-based catalyst for direct synthesis of olefins from synthesis gas, which is composed of ruthenium, metal promoters and structural promoters, and contains 0.5wt%-10wt% of ruthenium, 0-20wt% of metal promoters and 70wt%-99wt% of structural promoters, in terms of mass percentage of the ruthenium-based catalyst; wherein the content of the ruthenium is in terms of mass of metallic ruthenium; the content of the metal promoters in the ruthenium-based catalyst is not 0; and the content of the structural promoters is in terms of mass of corresponding oxides.

[0006] Preferably, the metal promoters include one or more of calcium, magnesium, lithium, sodium, potassium, rubidium, cesium, cerium, barium and manganese metals.

[0007] Preferably, the structural promoters are one or more of silicon oxide, aluminum oxide, zirconium oxide and titanium oxide.

[0008] The present application also provides a preparation method of the above-mentioned ruthenium-based catalyst for direct synthesis of olefins from synthesis gas, which comprises the following steps:

[0009] S1, preparing a mixed solution A of soluble ruthenium salt according to a proportioning ratio;

[0010] S2, adding water-soluble organic matter, a salt corresponding to a first metal promoter and a precursor of a first structural promoter into the mixed solution A to obtain a mixed solution B;

[0011] S3, mixing the mixed solution B with an alkaline solution, and then loading into a reaction kettle to perform hydrothermal reaction, and after the reaction is completed, performing washing and filtering to obtain a precipitate;

[0012] S4, adding water, a salt corresponding to a second metal promoter and a precursor of a second structural promoter into the precipitate, and after ball milling and mixing, performing filtering to obtain a catalyst filter cake;

[0013] S5, drying and calcining the catalyst filter cake to obtain a ruthenium-based catalyst.

[0014] Preferably, the soluble ruthenium salt in step S1 is selected from one or more of ruthenium trichloride, ruthenium acetylacetonate, ruthenium acetate and ruthenium nitrosyl nitrate.

[0015] Preferably, the concentration of the soluble ruthenium salt in the mixed solution A in step S1 is 0.1-1.5 mol / L.

[0016] Preferably, the water-soluble organic substance in step S2 is selected from one or more of the group consisting of aqueous solutions of ethanol, ethylene glycol, sucrose, and polyethylene glycol.

[0017] Preferably, the salt of the first metal additive in step S2 and the salt of the second metal additive in step S4 are both nitrate salts of the metal additive; and the mass ratio between the salt of the first metal additive and the salt of the second metal additive is (0-1) : 1.

[0018] Preferably, the precursor of the first structural additive in step S2 and the precursor of the second structural additive in step S4 are both selected from any one of the group consisting of silica aerosol, alumina aerosol, silica sol, alumina sol, titanium dioxide, zirconium dioxide, zirconium acetylacetonate, tetraisopropyl titanate, and tetraethyl orthosilicate; and the mass ratio between the oxide corresponding to the precursor of the second structural additive and the oxide corresponding to the precursor of the first structural additive is (0-10) : 1.

[0019] Preferably, the alkaline solution in step S3 is selected from one or more of the group consisting of sodium hydroxide, sodium carbonate, sodium bicarbonate, aqueous ammonia, urea, tetrabutylammonium hydroxide, triethylamine, bicarbonate amine, ethylenediamine, and diethylamine solution, and the molar concentration of the alkaline solution is 0.1-2 mol / L.

[0020] Preferably, the temperature of the hydrothermal reaction in step S3 is 50-250℃, and the time of the hydrothermal reaction is 2-30 h.

[0021] Preferably, the drying temperature in step S5 is 40-180℃, and the drying time is 2-20 h.

[0022] Preferably, the calcination temperature in step S5 is 200-600℃, and the calcination time is 2-10 h.

[0023] Preferably, the calcination atmosphere in step S5 is selected from one of the group consisting of air, nitrogen, and reducing gas.

[0024] The application also provides a use of the above-mentioned ruthenium-based catalyst in a direct synthesis of olefins from synthesis gas.

[0025] Preferably, the ruthenium-based catalyst is activated and pretreated before the direct synthesis of olefins from synthesis gas.

[0026] Preferably, the direct synthesis of olefins from synthesis gas uses H2 and CO as the reaction gas, and the molar ratio between H2 and CO is 0.5-5.

[0027] Preferably, in the direct synthesis of olefins from synthesis gas reaction, the reaction temperature is 200-300℃, the reaction space velocity is 500-4000h -1 , and the reaction pressure is 5-20bar.

[0028] Preferably, the atmosphere of the activation pretreatment at least includes one of hydrogen and carbon monoxide.

[0029] Preferably, the temperature of the activation pretreatment is 200-450℃.

[0030] Preferably, the space velocity of the activation pretreatment is 1000-10000h -1 .

[0031] Preferably, the pressure of the activation pretreatment is 0-10bar.

[0032] Preferably, the time of the activation pretreatment is 2-10h.

[0033] As described above, the ruthenium-based catalyst for direct synthesis of olefins from synthesis gas, the preparation method and the application thereof have the following beneficial effects:

[0034] The ruthenium-based catalyst with high dispersity and high stability can be prepared on a large scale by the hydrothermal method, the preparation method is simple and easy to repeat, the active component of the prepared ruthenium-based catalyst is uniformly distributed on the structural aid, the structure is stable, the utilization rate of ruthenium metal is high, and the ruthenium-based catalyst is used in the direct synthesis of olefins from synthesis gas, and good olefin synthesis performance is shown. DETAILED DESCRIPTION

[0035] The embodiments of the present application are described below through specific concrete examples, and those skilled in the art can easily understand other advantages and effects of the present application from the disclosure. The present application can also be implemented or applied through other different specific embodiments, and various modifications or changes can be made to the details in the specification without departing from the spirit of the present application.

[0036] The present application provides a ruthenium-based catalyst for direct synthesis of olefins from synthesis gas, which is composed of ruthenium, metal aid and structural aid, and the ruthenium-based catalyst includes 0.5wt%-10wt% of ruthenium, 0-20wt% of metal aid and 70wt%-99wt% of structural aid in terms of mass percentage of the ruthenium-based catalyst; wherein the content of ruthenium is in terms of mass of metallic ruthenium; the content of metal aid in the ruthenium-based catalyst is not 0; and the content of structural aid is in terms of mass of corresponding oxide.

[0037] Specifically, the content of ruthenium is the mass percentage of ruthenium in the ruthenium-based catalyst, including any value within the range of 0.5wt%, 1wt%, 3wt%, 5wt%, 7wt%, 9wt%, 10wt% and the like, which can be adjusted according to actual conditions; the mass percentage of the metal additive in the ruthenium-based catalyst includes any value within the range of 0.1wt%, 1wt%, 5wt%, 10wt%, 15wt%, 20wt% and the like, which can be adjusted according to actual conditions; the mass percentage of the structural additive in the ruthenium-based catalyst includes any value within the range of 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, 99wt% and the like, which can be adjusted according to actual conditions.

[0038] As an example, the metal additive includes one or more of calcium, magnesium, lithium, sodium, potassium, rubidium, cesium, cerium, barium, and manganese metal.

[0039] As an example, the structural additive is one or more of silicon oxide, aluminum oxide, zirconium oxide, and titanium oxide.

[0040] The present application also provides a preparation method of the above-mentioned ruthenium-based catalyst, which comprises the following steps:

[0041] S1, a mixed solution A of soluble ruthenium salt is prepared according to the proportion;

[0042] S2, water-soluble organic matter, a salt corresponding to the first metal additive, and a precursor of the first structural additive are added to the mixed solution A to obtain a mixed solution B;

[0043] S3, the mixed solution B is mixed with an alkaline solution, and then is loaded into a reaction kettle for hydrothermal reaction, and after the reaction is completed, the precipitate is obtained through washing and filtering;

[0044] S4, water, a salt corresponding to the second metal additive, and a precursor of the second structural additive are added to the precipitate, and after ball milling and mixing, the catalyst filter cake is obtained through filtering;

[0045] S5, the catalyst filter cake is dried and calcined to obtain the ruthenium-based catalyst.

[0046] Specifically, the specific embodiments of the present application adopt a hydrothermal reaction method to prepare the ruthenium-based catalyst, and the preparation method is simple, easy to repeat, and can be prepared on a large scale. In the process of preparing by the hydrothermal method, the active component soluble ruthenium salt and the salt corresponding to the metal additive first enter the pore channel of the carrier under high temperature conditions, and then are converted into precipitates under the chemical action of alkaline substances, and then the active component and the metal additive are stably attached to the surface of the structural additive. In the subsequent drying and calcination process, the active component and the metal additive are not easy to migrate, so that the active component is uniformly distributed on the structural additive, the structure is stable, and the utilization rate of ruthenium metal is high. In the prior art, when the conventional impregnation method is used, due to the existence of concentration gradient, the metal precursor is easy to migrate in the process of entering the carrier pore channel or when it is converted into metal oxide in the calcination process, resulting in uneven distribution of the active component.

[0047] In addition, the sum of the mass of the metal additive corresponding to the salt of the first metal additive in step S2 and the salt of the second metal additive in step S4 is within the component range of the above-mentioned ruthenium-based catalyst, that is, the mass percentage of the metal additive in the ruthenium-based catalyst is 0-20wt%, but not 0; and the sum of the mass of the oxides corresponding to the precursors of the first structural additive in step S2 and the second structural additive in step S4 is within the mass percentage of 70wt%-99wt% in the ruthenium-based catalyst.

[0048] As an example, the soluble ruthenium salt in step S1 is selected from one or more of ruthenium trichloride, ruthenium acetylacetone, ruthenium acetate, and ruthenium nitrosyl nitrate.

[0049] As an example, in the mixed solution A of step S1, the concentration of the soluble ruthenium salt is 0.1-1.5mol / L.

[0050] Specifically, in step S1, the soluble ruthenium salt is weighed according to the mass percentage of ruthenium in the ruthenium-based catalyst being 0.5wt%-10wt%, and then dissolved in water to form a mixed solution A; in the mixed solution A, the concentration of the soluble ruthenium salt can include any value within the range of 0.1mol / L, 0.3mol / L, 0.5mol / L, 0.7mol / L, 0.9mol / L, 1.2mol / L, 1.5mol / L, etc., which can be adjusted according to actual conditions.

[0051] As an example, the water-soluble organic matter in step S2 is selected from one or more of an aqueous solution of ethanol, ethylene glycol, sucrose, and polyethylene glycol.

[0052] Specifically, the water-soluble organic matter includes organic matter and water, and the organic matter is selected from one or more of ethanol, ethylene glycol, sucrose, and polyethylene glycol. The mass relationship between the organic matter and water is not excessively limited here, and needs to be determined according to the concentration of the mixed solution A.

[0053] As an example, the salt corresponding to the first metal additive in step S2 and the salt corresponding to the second metal additive in step S4 are both nitrate salts of the metal additive; and the mass ratio between the salt corresponding to the first metal additive and the salt corresponding to the second metal additive is (0-1):1.

[0054] Specifically, the first metal additive is selected from one or more of calcium, magnesium, lithium, sodium, potassium, rubidium, cesium, cerium, barium, and manganese metals, and the second metal additive is also selected from one or more of calcium, magnesium, lithium, sodium, potassium, rubidium, cesium, cerium, barium, and manganese metals.

[0055] In addition, the mass ratio between the salt corresponding to the first metal additive and the salt corresponding to the second metal additive can include any value within the range of 0, 0.2:1, 0.4:1, 0.6:1, 0.8:1, 1:1, etc. The salt of the metal additive can be added separately in step S2 and step S4, or it can be added at one time in step S4. The metal additive in step S2 is converted into a precipitate together with the active component, so that the active component is more closely combined with the active site, and the metal additive can enter the bulk phase of the active component. The metal additive added in step S4 is distributed on the surface of the active component; when added at one time, the mass ratio between the salt corresponding to the first metal additive and the salt corresponding to the second metal additive is 0.

[0056] As an example, the precursor of the first structural additive in step S2 and the precursor of the second structural additive in step S4 are both selected from any one of silicon oxide aerosol, aluminum oxide aerosol, silicon oxide sol, aluminum oxide sol, titanium dioxide, zirconium dioxide, zirconium acetylacetonate, titanium isopropylate, and tetraethyl orthosilicate; and the mass ratio between the mass of the oxide corresponding to the precursor of the second structural additive and the mass of the oxide corresponding to the precursor of the first structural additive is (0-10):1.

[0057] Specifically, the mass ratio between the mass of the oxide corresponding to the precursor of the second structural additive and the mass of the oxide corresponding to the precursor of the first structural additive can include any value within the range of 0, 1:1, 3:1, 5:1, 7:1, 9:1, 10:1, etc. In addition, the precursor of the structural additive can be added separately in step S2 and step S4, or it can be added at one time in step S2. When added at one time, the mass ratio between the mass of the oxide corresponding to the precursor of the second structural additive and the mass of the oxide corresponding to the precursor of the first structural additive is 0.

[0058] As an example, the alkaline solution in step S3 is selected from one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia, urea, tetrabutylammonium hydroxide, triethylamine, bicarbonate, ethylenediamine, and diethylamine solution, and the molar concentration of the alkaline solution is 0.1-2 mol / L.

[0059] Specifically, the molar concentration of the alkaline solution can include any value within the range of 0.1 mol / L, 0.5 mol / L, 1 mol / L, 1.5 mol / L, 1.9 mol / L, 2 mol / L, etc., and can be adjusted according to actual conditions.

[0060] As an example, the temperature of the hydrothermal reaction in step S3 is 50℃-250℃, and the time of the hydrothermal reaction is 2h-30h.

[0061] Specifically, the temperature of the hydrothermal reaction affects the crystallization process of the precursor into the corresponding precipitate, and low temperature is conducive to nucleation, and high temperature is conducive to grain growth; the temperature of the hydrothermal reaction in step S3 can include any value within the range of 50℃, 100℃, 150℃, 200℃, 250℃, etc., and can be adjusted according to actual conditions; the time of the hydrothermal reaction can include any value within the range of 2h, 5h, 10h, 15h, 20h, 25h, 30h, etc., and can be adjusted according to actual conditions.

[0062] As an example, the drying temperature in step S5 is 40℃-180℃, and the drying time is 2h-20h.

[0063] Specifically, the drying temperature in step S5 can include any value within the range of 40℃, 60℃, 80℃, 100℃, 120℃, 140℃, 160℃, 180℃, etc., and can be adjusted according to actual conditions; the drying time can include any value within the range of 2h, 5h, 10h, 15h, 18h, 20h, etc., and can be adjusted according to actual conditions.

[0064] As an example, the calcination temperature in step S5 is 200℃-600℃, and the calcination time is 2h-10h.

[0065] Specifically, the calcination temperature in step S5 can include any value within the range of 200℃, 300℃, 400℃, 500℃, 600℃, etc., and can be adjusted according to actual conditions; the calcination time can include any value within the range of 2h, 5h, 10h, 15h, 18h, 20h, etc., and can be adjusted according to actual conditions.

[0066] As an example, the calcination atmosphere in step S5 is selected from one of air, nitrogen, and a reducing gas.

[0067] Specifically, the reducing gas is preferably hydrogen.

[0068] The application also provides a ruthenium-based catalyst for use in a direct synthesis of olefins from synthesis gas.

[0069] As an example, the ruthenium-based catalyst is activated and pretreated before the direct synthesis of olefins from synthesis gas.

[0070] As an example, the activation pretreatment atmosphere includes at least one of hydrogen, carbon monoxide.

[0071] Specifically, the activation pretreatment atmosphere is one of H2, a mixture of H2 / N2, CO, a mixture of CO / N2, synthesis gas, a mixture of synthesis gas and N2 (synthesis gas / mixture = 20%), 10%, 20%; wherein the molar ratio of H2 in the mixture of H2 / N2 is 10%-50% (such as 10%, 20%, 30%, 40%, 50%, etc.); the molar ratio of CO in the mixture of CO / N2 is 5%-10% (such as 5%, 7%, 9%, 10%, etc.); the molar ratio of H2 / CO in the synthesis gas is 1-2; and the molar ratio of synthesis gas in the mixture of synthesis gas and N2 is 10%-20% (such as 10%, 12%, 14%, 16%, 18%, 20%, etc.).

[0072] As an example, the activation pretreatment temperature is 200-450°C.

[0073] Specifically, the activation pretreatment temperature can include any value in the range of 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, etc., and can be adjusted according to actual conditions.

[0074] As an example, the activation pretreatment space velocity is 1000-10000h -1 .

[0075] Specifically, the activation pretreatment space velocity can include any value in the range of 1000h -1 , 3000h -1 , 5000h -1 , 7000h -1 , 9000h -1 , 10000h -1 , etc., and can be adjusted according to actual conditions.

[0076] As an example, the activation pretreatment pressure is 0-10 bar.

[0077] Specifically, the activation pretreatment pressure can include any value in the range of 0 bar, 1 bar, 3 bar, 5 bar, 7 bar, 9 bar, 10 bar, etc., and can be adjusted according to actual conditions; when the pressure value is 0 bar, it is a complete vacuum state.

[0078] As an example, the activation pretreatment time is 2-10h.

[0079] Specifically, the activation pretreatment time can include any value in the range of 2h, 4h, 6h, 8h, 10h, etc., and can be adjusted according to actual conditions.

[0080] As an example, the molar ratio of H2 to CO in the syngas for the direct synthesis of olefins is 0.5-5.

[0081] Specifically, in the direct synthesis of olefins from syngas, the molar ratio of H2 to CO in the syngas can include any value within the range of 0.5, 1, 2, 3, 4, 5, etc., which can be adjusted according to actual conditions.

[0082] As an example, in the direct synthesis of olefins from syngas, the reaction temperature is 200-300°C, the reaction space velocity is 500-4000h -1 , and the reaction pressure is 5-20 bar.

[0083] Specifically, in the direct synthesis of olefins from syngas, the reaction temperature can include any value within the range of 200°C, 220°C, 240°C, 260°C, 280°C, 300°C, etc., which can be adjusted according to actual conditions; the reaction space velocity can include any value within the range of 500h -1 , 1000h -1 , 2000h -1 , 3000h -1 , 4000h -1 , etc., which can be adjusted according to actual conditions; and the reaction pressure can include any value within the range of 5 bar, 10 bar, 15 bar, 20 bar, etc., which can be adjusted according to actual conditions.

[0084] In order to better understand the ruthenium-based catalyst for the direct synthesis of olefins from syngas, the preparation method thereof, and the application thereof, the ruthenium-based catalyst for the direct synthesis of olefins from syngas, the preparation method thereof, and the application thereof will be described below with reference to specific examples, it should be noted that these examples are merely descriptive and do not limit the present application in any way.

[0085] Example 1

[0086] The present embodiment provides a ruthenium-based catalyst for the direct synthesis of olefins from syngas, which is composed of ruthenium, lithium, and a structural aid (silicon oxide), and includes 1wt% of ruthenium, 0.5wt% of lithium, and 98.5wt% of the structural aid (silicon oxide) in terms of the mass percentage of the ruthenium-based catalyst; wherein the content of ruthenium is in terms of the mass of metallic ruthenium; and the content of the structural aid is in terms of the mass of the corresponding oxide.

[0087] The present embodiment also provides a preparation method of a ruthenium-based catalyst for the direct synthesis of olefins from syngas, which includes the following steps:

[0088] S1. Based on the mass percentage of ruthenium in the ruthenium-based catalyst being 1 wt%, weigh ruthenium trichloride and add it to water to prepare a mixed solution A with a concentration of 0.5 mol / L (in mixed solution A, the concentration of ruthenium trichloride is 0.5 mol / L);

[0089] S2. Add an aqueous solution of ethanol and the precursor of the first structural aid (aerosol silica) to mixed solution A to obtain mixed solution B;

[0090] S3. Mix the mixed solution B with the alkaline solution (1 mol / L urea solution), then put it into a high-pressure reactor and carry out a hydrothermal reaction at 120°C for 20 hours. After the reaction is completed, wash and filter with deionized water to obtain the precipitate.

[0091] S4. Add water and the salt corresponding to the second metal additive (lithium nitrate) to the precipitate, mix thoroughly in a ball mill for 2 hours, wash and filter to obtain catalyst filter cake;

[0092] Specifically, the amount of salt added in step S4 corresponding to the second metal additive, based on the mass of the metal additive, is calculated as 0.5 wt% of the mass percentage of the metal additive in the ruthenium-based catalyst; the amount of precursor added in step S2 corresponding to the oxide of the structural additive, based on the mass of the oxide, is calculated as 98.5 wt% of the mass percentage of the structural additive in the ruthenium-based catalyst.

[0093] S5. The catalyst filter cake was dried at 120°C for 12 hours, and then calcined at 400°C under a nitrogen atmosphere for 5 hours to obtain a ruthenium-based catalyst.

[0094] This embodiment also provides an application of a ruthenium-based catalyst in the direct synthesis of olefins from syngas. Before the reaction, the ruthenium-based catalyst in this embodiment is first reduced and activated (the reducing atmosphere is a mixture of H2 and N2, the molar ratio of H2 in the mixture is 20%, and the reduction space velocity is 8000 h⁻¹). -1 The reduction temperature was 350℃, the reduction pressure was atmospheric pressure, and the time was 5 hours. Then, the reaction was carried out using syngas. During the reaction, the molar ratio of H2 to CO in the syngas was 2, and the reaction space velocity was 2000 h⁻¹. -1 The reaction temperature was 200℃ and the reaction pressure was 5 bar. 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 selectivity of the reaction were calculated accordingly. The specific results are shown in Table 1.

[0095] Example 2

[0096] The embodiment provides a ruthenium-based catalyst for directly synthesizing olefins from synthesis gas, the ruthenium-based catalyst is composed of ruthenium, sodium and a structural promoter (aluminum oxide), and the ruthenium-based catalyst comprises 5 wt% of ruthenium, 1.5 wt% of sodium and 93.5 wt% of the structural promoter (aluminum oxide) in percentage of mass of the ruthenium-based catalyst; wherein the content of the ruthenium is in percentage of mass of metallic ruthenium; and the content of the structural promoter is in percentage of mass of corresponding oxide.

[0097] The embodiment also provides a preparation method of the ruthenium-based catalyst for directly synthesizing olefins from synthesis gas, and the preparation method comprises the following steps:

[0098] S1, according to the percentage of mass of the ruthenium in the ruthenium-based catalyst, acetylacetone ruthenium is weighed and added into water to prepare a mixed solution A with a concentration of 1.5 mol / L (in the mixed solution A, the concentration of the acetylacetone ruthenium is 1.5 mol / L);

[0099] S2, an aqueous solution of ethanol and a precursor of a first structural promoter (aerosol aluminum oxide) are added into the mixed solution A to obtain a mixed solution B;

[0100] S3, the mixed solution B is mixed with an alkaline solution (1 mol / L sodium bicarbonate solution), and then is loaded into a high-pressure reaction kettle to perform hydrothermal reaction at 160 DEG C for 10 h; after the reaction is completed, the precipitate is obtained by washing and filtering with deionized water;

[0101] S4, water, a salt corresponding to a second metal promoter (sodium nitrate) and a precursor of a second structural promoter (aluminum oxide sol) are added into the precipitate, and after being sufficiently mixed in a ball mill for 2 h, the catalyst filter cake is obtained by washing and filtering; wherein according to the percentage of mass of the metal promoter in the ruthenium-based catalyst, the addition amount of the salt corresponding to the second metal promoter in step S4 is calculated according to 1.5 wt%.

[0102] According to the percentage of mass of the structural promoter in the ruthenium-based catalyst, the addition amount of the precursor of the first structural promoter in step S2 is calculated according to 10 wt%, and the addition amount of the precursor of the second structural promoter in step S4 is calculated according to 83.5 wt%.

[0103] S5, the catalyst filter cake is dried at 80 DEG C for 8 h, and then is calcined at 600 DEG C in an air atmosphere for 2 h to obtain the ruthenium-based catalyst.

[0104] The embodiment also provides an application of the ruthenium-based catalyst in a reaction of directly synthesizing olefins from synthesis gas, and the ruthenium-based catalyst in the embodiment is reduced and activated before the reaction (the reduction atmosphere is a mixed gas of CO and N2, the molar ratio of CO in the mixed gas is 10%, and the reduction space velocity is 5000 h-1 The reduction temperature is 200℃, the reduction pressure is normal pressure, and the time is 10h, and then the reaction is carried out by switching to synthesis gas, wherein the molar ratio between H2 and CO in the synthesis gas is 1, and the reaction space velocity is 500h-1. -1 The reaction temperature is 220℃, and the reaction pressure is 5bar; after the reaction, the types and contents of various components contained in the product are analyzed by using a gas chromatograph (Agilent 8860), and the conversion rate and selectivity of the reaction are calculated accordingly, and the specific results are shown in Table 1.

[0105] Embodiment 3

[0106] The embodiment provides a ruthenium-based catalyst for directly synthesizing olefins from synthesis gas, the ruthenium-based catalyst is composed of ruthenium, potassium and structural aids (titanium oxide and silicon oxide), and the ruthenium-based catalyst comprises 3wt% of ruthenium, 10wt% of potassium and 87wt% of structural aids (titanium oxide and silicon oxide) in terms of mass percentage of the ruthenium-based catalyst; wherein the content of ruthenium is in terms of mass of metallic ruthenium; and the content of the structural aids is in terms of mass of corresponding oxides.

[0107] The embodiment also provides a preparation method of the ruthenium-based catalyst for directly synthesizing olefins from synthesis gas, and the preparation method comprises the following steps:

[0108] S1, according to the mass percentage of ruthenium in the ruthenium-based catalyst being 3wt%, nitrosyl nitric ruthenium is weighed and added into water to prepare a mixed solution A with a concentration of 1mol / L (in the mixed solution A, the concentration of nitrosyl nitric ruthenium is 1mol / L);

[0109] S2, a sucrose aqueous solution and a precursor of the first structural aid (tetraisopropyl titanate) are added into the mixed solution A to obtain a mixed solution B;

[0110] S3, the mixed solution B is mixed with an alkaline solution (an aqueous solution of ethylenediamine with a concentration of 1mol / L), and then is loaded into a high-pressure reaction kettle to carry out hydrothermal reaction at 200℃ for 20h, and after the reaction, the precipitate is obtained by washing and filtering with deionized water;

[0111] S4, water, a salt corresponding to the second metal aid (potassium nitrate) and a precursor of the second structural aid (alumina sol) are added into the precipitate, and after being fully mixed in a ball mill for 2h, the catalyst filter cake is obtained by washing and filtering; wherein according to the mass percentage of the metal aid in the ruthenium-based catalyst being 10wt%, the addition amount of the salt corresponding to the second metal aid in step S4 is calculated in terms of mass of the metal aid;

[0112] The addition amount of the precursor of the first structural aid in step S2 is calculated according to the mass percentage of the structural aid in the ruthenium-based catalyst as 8.7wt%; the addition amount of the precursor of the second structural aid in step S4 is calculated according to the mass percentage of the structural aid in the ruthenium-based catalyst as 78.3wt%;

[0113] S5, drying the catalyst filter cake at 80℃ for 8h, and then calcining under an air atmosphere at 600℃ for 2h to obtain the ruthenium-based catalyst.

[0114] The ruthenium-based catalyst in the embodiment is also provided for use in a direct synthesis of olefins from synthesis gas, wherein the ruthenium-based catalyst is reduced and activated (the reduction atmosphere is 100% H2, the reduction space velocity is 1000h-1, the reduction temperature is 350℃, the reduction pressure is 5bar, and the time is 2h) before the reaction, and then the synthesis gas is used for the reaction, wherein the molar ratio between H2 and CO in the synthesis gas is 2.5, the reaction space velocity is 2000h-1, the reaction temperature is 260℃, and the reaction pressure is 5bar. -1 The types and contents of various components in the product are analyzed by using a gas chromatograph (Agilent 8860) after the reaction, and the conversion rate and the selectivity of the reaction are calculated accordingly, and the specific results are shown in Table 1. -1 The types and contents of various components in the product are analyzed by using a gas chromatograph (Agilent 8860) after the reaction, and the conversion rate and the selectivity of the reaction are calculated accordingly, and the specific results are shown in Table 1.

[0115] Embodiment 4

[0116] The embodiment provides a ruthenium-based catalyst for direct synthesis of olefins from synthesis gas, which is composed of ruthenium, rubidium and structural aids (zirconium oxide and aluminum oxide), and the ruthenium-based catalyst comprises 10wt% of ruthenium, 0.1wt% of rubidium and 89.9wt% of structural aids (zirconium oxide and aluminum oxide) according to the mass percentage of the ruthenium-based catalyst, wherein the content of ruthenium is calculated according to the mass of metallic ruthenium, and the content of the structural aid is calculated according to the mass of the corresponding oxide.

[0117] The embodiment also provides a preparation method of the ruthenium-based catalyst for direct synthesis of olefins from synthesis gas, and the preparation method comprises the following steps:

[0118] S1, according to the mass percentage of ruthenium in the ruthenium-based catalyst as 10wt%, a ruthenium acetate is weighed and added into water to prepare a mixed solution A with a concentration of 0.1mol / L (in the mixed solution A, the concentration of the ruthenium acetate is 0.1mol / L);

[0119] S2, an aqueous solution of ethylene glycol and a precursor of the first structural aid (zirconium dioxide) are added into the mixed solution A to obtain a mixed solution B;

[0120] S3, mixing the mixed solution B with an alkaline solution (1 mol / L aqueous sodium carbonate solution), and then loading into a high-pressure reaction kettle for hydrothermal reaction at 50℃ for 2h; after the reaction, washing with deionized water and filtering to obtain a precipitate;

[0121] S4, adding water, a salt corresponding to the second metal additive (rubidium nitrate) and a precursor of the second structural additive (alumina sol) into the precipitate, mixing in a ball mill for 2h, and then washing and filtering to obtain a catalyst filter cake; wherein, the amount of the salt corresponding to the second metal additive added in step S4 is calculated according to the mass percentage of the metal additive in the ruthenium-based catalyst, which is 0.1wt% based on the mass of the metal additive;

[0122] The amount of the precursor of the first structural additive added in step S2 is calculated according to the mass percentage of the structural additive in the ruthenium-based catalyst, which is 17.98wt% based on the mass of the oxide corresponding to the structural additive; and the amount of the precursor of the second structural additive added in step S4 is calculated according to the mass percentage of the structural additive in the ruthenium-based catalyst, which is 71.92wt% based on the mass of the oxide corresponding to the structural additive;

[0123] S5, drying the catalyst filter cake at 80℃ for 8h, and then calcining at 300℃ in an air atmosphere for 10h to obtain a ruthenium-based catalyst.

[0124] The ruthenium-based catalyst in this embodiment is also provided for use in a direct synthesis of olefins from synthesis gas, wherein the ruthenium-based catalyst in this embodiment is first reduced and activated (the reducing atmosphere is a mixed gas of synthesis gas (H2 / CO molar ratio is 2) and N2, the molar ratio of synthesis gas in the mixed gas is 10%, and the reduction space velocity is 10000h -1 -1), and then switched to synthesis gas for reaction; during the reaction, the molar ratio between H2 and CO in the synthesis gas is 3, the reaction space velocity is 2000h -1 -1, the reaction temperature is 280℃, and the reaction pressure is 20bar; after the reaction, the types and contents of various components contained in the product are analyzed by gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction are calculated accordingly, and the specific results are shown in Table 1.

[0125] Example 4-1

[0126] This embodiment provides a ruthenium-based catalyst for direct synthesis of olefins from synthesis gas, and the component composition and mass percentage of the catalyst are the same as those in Example 4, which will not be repeated here.

[0127] The embodiment also provides a preparation method of the ruthenium-based catalyst, which is different from the preparation method in the embodiment 4 in that the hydrothermal reaction temperature in the step S3 is 150 DEG C, and the reaction time is 10 h; other methods and steps are the same as those in the embodiment 4, and details are not described herein again.

[0128] As to the application of the ruthenium-based catalyst in the embodiment in the direct synthesis of olefins from synthesis gas, the specific reaction process is the same as that in the embodiment 4, and details are not described herein again; after the reaction is completed, the types and contents of various components contained in the product are analyzed by using a gas chromatograph (Agilent 8860), and the conversion rate and the selectivity of the reaction are calculated accordingly, and the specific results are shown in Table 1.

[0129] Embodiment 4-2

[0130] The embodiment provides a ruthenium-based catalyst for the direct synthesis of olefins from synthesis gas, which is composed of ruthenium, rubidium and structural aids (zirconium oxide and aluminum oxide), and contains 0.5wt% of ruthenium, 0.5wt% of rubidium and 94.5wt% of structural aids (zirconium oxide and aluminum oxide) in terms of the mass percentage of the ruthenium-based catalyst; wherein the content of ruthenium is in terms of the mass of metallic ruthenium; and the content of structural aids is in terms of the mass of corresponding oxides.

[0131] The embodiment also provides a preparation method of the ruthenium-based catalyst, which is different from the preparation method in the embodiment 4 in that in the step S1, the ruthenium acetate is weighed according to the mass percentage of 0.5wt% of ruthenium in the ruthenium-based catalyst, and is added into water to prepare a mixed solution A with a concentration of 0.1mol / L (in the mixed solution A, the concentration of ruthenium acetate is 0.1mol / L); other methods and steps are the same as those in the embodiment 4, and details are not described herein again, but the addition amount of the salt of the second metal aid in the step S4 is calculated according to the mass percentage of 0.5wt% of the metal aid in the ruthenium-based catalyst in terms of the mass of the metal aid; the addition amount of the precursor of the first structural aid in the step S2 is calculated according to the mass percentage of 18.9wt% of the structural aid in the ruthenium-based catalyst in terms of the mass of the corresponding oxide of the structural aid; and the addition amount of the precursor of the second structural aid in the step S4 is calculated according to the mass percentage of 75.6wt% of the structural aid in the ruthenium-based catalyst.

[0132] As to the application of the ruthenium-based catalyst in the embodiment in the direct synthesis of olefins from synthesis gas, the specific reaction process is the same as that in the embodiment 4, and details are not described herein again; after the reaction is completed, the types and contents of various components contained in the product are analyzed by using a gas chromatograph (Agilent 8860), and the conversion rate and the selectivity of the reaction are calculated accordingly, and the specific results are shown in Table 1.

[0133] Embodiment 4-3

[0134] The embodiment provides a ruthenium-based catalyst for directly synthesizing olefins from synthesis gas, and components and mass percentages of the catalyst are the same as those in the embodiment 4, which will not be repeated here.

[0135] The embodiment also provides a preparation method of the ruthenium-based catalyst, and the preparation method is the same as that in the embodiment 4, which will not be repeated here.

[0136] Regarding application of the ruthenium-based catalyst in the embodiment in a reaction of directly synthesizing olefins from synthesis gas, a specific reaction process is the same as that in the embodiment 4, which will not be repeated here, and the reaction is directly performed without reduction treatment of the catalyst. -1 After the reaction ends, types and contents of various components contained in products are analyzed by using a gas chromatograph (Agilent 8860), and conversion rate and selectivity of the reaction are calculated accordingly, and specific results are shown in Table 1.

[0137] Embodiment 4-4

[0138] The embodiment provides a ruthenium-based catalyst for directly synthesizing olefins from synthesis gas, and components and mass percentages of the catalyst are the same as those in the embodiment 4, which will not be repeated here.

[0139] The embodiment also provides a preparation method of the ruthenium-based catalyst, and the preparation method is the same as that in the embodiment 4, which will not be repeated here.

[0140] Regarding application of the ruthenium-based catalyst in the embodiment in a reaction of directly synthesizing olefins from synthesis gas, a specific reaction process is the same as that in the embodiment 4, which will not be repeated here, and the reaction is directly performed without reduction treatment of the catalyst. -1 After the reaction ends, types and contents of various components contained in products are analyzed by using a gas chromatograph (Agilent 8860), and conversion rate and selectivity of the reaction are calculated accordingly, and specific results are shown in Table 1. -1 After the reaction ends, types and contents of various components contained in products are analyzed by using a gas chromatograph (Agilent 8860), and conversion rate and selectivity of the reaction are calculated accordingly, and specific results are shown in Table 1.

[0141] Embodiment 4-5

[0142] The embodiment provides a ruthenium-based catalyst for directly preparing olefins from synthesis gas, and components and mass percentages of the catalyst are the same as those in the embodiment 4, which will not be repeated here.

[0143] The embodiment also provides a preparation method of the ruthenium-based catalyst, and the preparation method is the same as that in the embodiment 4, which will not be repeated here.

[0144] Regarding application of the ruthenium-based catalyst in the embodiment in a reaction of directly preparing olefins from synthesis gas, a specific reaction process is different from that in the embodiment 4, and the difference lies in that a reducing atmosphere is a mixed gas of CO and N2, a molar ratio of CO in the mixed gas is 10 %, a reducing space velocity is 6000h-1, a reducing temperature is 300 DEG C, a reducing pressure is normal pressure, and a time is 10 h, and then the reaction is switched to synthesis gas, in the reaction, a molar ratio between H2 and CO in the synthesis gas is 0.5, a reaction space velocity is 2000h-1, a reaction temperature is 260 DEG C, and a reaction pressure is 15 bar. -1 -1 After the reaction ends, types and contents of various components contained in products are analyzed by using a gas chromatograph (Agilent 8860), and conversion rate and selectivity of the reaction are calculated accordingly, and specific results are shown in Table 1.

[0145] Embodiment 5

[0146] The embodiment provides a ruthenium-based catalyst for directly preparing olefins from synthesis gas, and the ruthenium-based catalyst is composed of ruthenium, magnesium and structural additives (zirconium oxide and aluminum oxide), and the ruthenium-based catalyst comprises 1wt % of ruthenium, 5wt % of magnesium and 94wt % of structural additives (zirconium oxide and aluminum oxide) according to mass percentages of the ruthenium-based catalyst, wherein the content of the ruthenium is in terms of mass of metallic ruthenium, and the content of the structural additives is in terms of mass of corresponding oxides.

[0147] The embodiment also provides a preparation method of the ruthenium-based catalyst for directly preparing olefins from synthesis gas, and the preparation method comprises the following steps.

[0148] S1, according to 1wt % of ruthenium in the ruthenium-based catalyst, acetylacetone ruthenium is weighed and added into water to prepare a mixed solution A with a concentration of 1mol / L (in the mixed solution A, the concentration of the acetylacetone ruthenium is 1mol / L);

[0149] S2, an aqueous solution of polyethylene glycol, a salt (magnesium nitrate) of the first metal additive and a precursor (acetylacetone zirconium) of the first structural additive are added into the mixed solution A to obtain a mixed solution B;

[0150] S3, the mixed solution B is mixed with an alkaline solution (an aqueous solution of 0.5mol / L ammonia), and then is loaded into a high-pressure reaction kettle to perform hydrothermal reaction at 120 DEG C for 12h, after the reaction ends, the precipitate is obtained by washing and filtering with deionized water.​

[0151] S4, adding water, a salt corresponding to the second metal promoter (magnesium nitrate) and a precursor of the second structural promoter (alumina sol) into the precipitate, mixing thoroughly in a ball mill for 2 h, washing and filtering to obtain a catalyst filter cake;

[0152] wherein the amount of the salt corresponding to the first metal promoter added in step S2 is calculated according to the mass percentage of the metal promoter in the ruthenium-based catalyst being 1.5 wt%; and the amount of the salt corresponding to the second metal promoter added in step S4 is calculated according to the mass percentage of the metal promoter in the ruthenium-based catalyst being 3.5 wt%;

[0153] wherein the amount of the precursor of the first structural promoter added in step S2 is calculated according to the mass percentage of the structural promoter in the ruthenium-based catalyst being 47 wt%; and the amount of the precursor of the second structural promoter added in step S4 is calculated according to the mass percentage of the structural promoter in the ruthenium-based catalyst being 47 wt%;

[0154] S5, drying the catalyst filter cake at 150℃ for 6 h, and then calcining at 200℃ in an air atmosphere for 10 h to obtain the ruthenium-based catalyst.

[0155] The ruthenium-based catalyst in this embodiment is also provided for use in a direct synthesis of olefins from synthesis gas, wherein the ruthenium-based catalyst in this embodiment is first reduced and activated (the reduction atmosphere is a mixed gas of synthesis gas (H2 / CO molar ratio is 1) and N2, the molar ratio of synthesis gas in the mixed gas is 20%, the reduction space velocity is 8000h-1, the reduction temperature is 350℃, the reduction pressure is normal pressure, and the time is 5h), and then switched to synthesis gas for reaction, wherein the molar ratio between H2 and CO in the synthesis gas is 0.5, the reaction space velocity is 2000h-1, the reaction temperature is 290℃, and the reaction pressure is 10 bar; after the reaction, the types and contents of various components contained in the product are analyzed by gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction are calculated accordingly, and the specific results are shown in Table 1. -1 -1 The ruthenium-based catalyst in this embodiment is also provided for use in a direct synthesis of olefins from synthesis gas, wherein the ruthenium-based catalyst in this embodiment is first reduced and activated (the reduction atmosphere is a mixed gas of synthesis gas (H2 / CO molar ratio is 1) and N2, the molar ratio of synthesis gas in the mixed gas is 20%, the reduction space velocity is 8000h-1, the reduction temperature is 350℃, the reduction pressure is normal pressure, and the time is 5h), and then switched to synthesis gas for reaction, wherein the molar ratio between H2 and CO in the synthesis gas is 0.5, the reaction space velocity is 2000h-1, the reaction temperature is 290℃, and the reaction pressure is 10 bar; after the reaction, the types and contents of various components contained in the product are analyzed by gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction are calculated accordingly, and the specific results are shown in Table 1.

[0156] Example 6

[0157] The ruthenium-based catalyst in this embodiment is also provided for use in a direct synthesis of olefins from synthesis gas, wherein the ruthenium-based catalyst in this embodiment is first reduced and activated (the reduction atmosphere is a mixed gas of synthesis gas (H2 / CO molar ratio is 1) and N2, the molar ratio of synthesis gas in the mixed gas is 20%, the reduction space velocity is 8000h-1, the reduction temperature is 350℃, the reduction pressure is normal pressure, and the time is 5h), and then switched to synthesis gas for reaction, wherein the molar ratio between H2 and CO in the synthesis gas is 0.5, the reaction space velocity is 2000h-1, the reaction temperature is 290℃, and the reaction pressure is 10 bar; after the reaction, the types and contents of various components contained in the product are analyzed by gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction are calculated accordingly, and the specific results are shown in Table 1.

[0158] ​The embodiment also provides a preparation method of a ruthenium-based catalyst for direct synthesis of olefins from synthesis gas, which comprises the following steps:

[0159] S1, according to the mass percentage of ruthenium in the ruthenium-based catalyst being 1wt%, a ruthenium nitrosyl nitrate is weighed and added into water to prepare a mixed solution A with a concentration of 0.15mol / L (in the mixed solution A, the concentration of the ruthenium nitrosyl nitrate is 0.15mol / L);

[0160] S2, an aqueous solution of ethanol, a salt (calcium nitrate) corresponding to a first metal promoter and a precursor (aerosol alumina) of a first structural promoter are added into the mixed solution A to obtain a mixed solution B;

[0161] S3, the mixed solution B is mixed with an alkaline solution (an aqueous solution of sodium hydroxide with a concentration of 0.5mol / L), and then is loaded into a high-pressure reaction kettle to perform hydrothermal reaction at 80℃ for 5h, after the reaction, the precipitate is obtained by washing and filtering with deionized water;

[0162] S4, water, a salt (calcium nitrate) corresponding to a second metal promoter and a precursor (alumina sol) of a second structural promoter are added into the precipitate, and after being mixed in a ball mill for 2h, the catalyst filter cake is obtained by washing and filtering;

[0163] According to the mass percentage of the metal promoter in the ruthenium-based catalyst being 1.5wt%, the addition amount of the salt corresponding to the first metal promoter in step S2 is calculated; and according to the mass percentage of the metal promoter in the ruthenium-based catalyst being 3.5wt%, the addition amount of the salt corresponding to the second metal promoter in step S4 is calculated;

[0164] According to the mass percentage of the structural promoter in the ruthenium-based catalyst being 18.8wt%, the addition amount of the precursor of the first structural promoter in step S2 is calculated; and according to the mass percentage of the structural promoter in the ruthenium-based catalyst being 75.2wt%, the addition amount of the precursor of the second structural promoter in step S4 is calculated;

[0165] S5, the catalyst filter cake is dried at 150℃ for 6h, and then is calcined at 450℃ in an air atmosphere for 2h to obtain the ruthenium-based catalyst.

[0166] The embodiment also provides an application of the ruthenium-based catalyst in a reaction of direct synthesis of olefins from synthesis gas, and the ruthenium-based catalyst in the embodiment is reduced and activated before the reaction (the reduction atmosphere is a mixed gas of H2 and N2, the molar ratio of H2 in the mixed gas is 50%, the reduction space velocity is 8000h -1The reduction temperature is 350℃, the reduction pressure is normal pressure, the time is 5h, and then the reaction is carried out by switching to synthesis gas, wherein the molar ratio of H2 to CO in the synthesis gas is 1.5, and the reaction space velocity is 3000h-1. -1 The reaction temperature is 250℃, and the reaction pressure is 10bar; after the reaction, the types and contents of various components contained in the product are analyzed by using a gas chromatograph (Agilent 8860), and the conversion rate and selectivity of the reaction are calculated accordingly, and the specific results are shown in Table 1.

[0167] Example 7

[0168] The embodiment provides a ruthenium-based catalyst for directly synthesizing olefins from synthesis gas, the ruthenium-based catalyst is composed of ruthenium, barium and a structural promoter (silicon oxide), and the ruthenium-based catalyst comprises 0.5wt% of ruthenium, 5wt% of barium and 94.5wt% of the structural promoter (silica) in terms of mass percentage of the ruthenium-based catalyst; wherein the content of ruthenium is in terms of the mass of metallic ruthenium; and the content of the structural promoter is in terms of the mass of the corresponding oxide.

[0169] The embodiment also provides a preparation method of the ruthenium-based catalyst for directly synthesizing olefins from synthesis gas, and the preparation method comprises the following steps:

[0170] S1, according to the mass percentage of ruthenium in the ruthenium-based catalyst being 0.5wt%, a certain amount of ruthenium acetate is weighed and added into water to prepare a mixed solution A with a concentration of 0.25mol / L (in the mixed solution A, the concentration of ruthenium acetate is 0.25mol / L);

[0171] S2, a precursor of the first structural promoter (aerosol silicon oxide) is added into the mixed solution A to obtain a mixed solution B;

[0172] S3, the mixed solution B is mixed with an alkaline solution (an aqueous solution of 0.5mol / L tetrabutylammonium hydroxide), and then is loaded into a high-pressure reaction kettle to carry out a hydrothermal reaction at 160℃ for 20h; after the reaction, the precipitate is obtained by washing and filtering with deionized water;

[0173] S4, water, a salt corresponding to the second metal promoter (barium nitrate) and a precursor of the second structural promoter (silica sol) are added into the precipitate, and after being fully mixed in a ball mill for 2h, the catalyst filter cake is obtained by washing and filtering;

[0174] The addition amount of the salt corresponding to the second metal promoter in the step S4 is calculated according to the mass percentage of the metal promoter in the ruthenium-based catalyst being 5wt%;

[0175] The addition amount of the precursor of the first structural aid in step S2 is calculated according to the mass percentage of the structural aid in the ruthenium-based catalyst being 37.8wt%; the addition amount of the precursor of the second structural aid in step S4 is calculated according to the mass percentage of the structural aid in the ruthenium-based catalyst being 56.7wt%;

[0176] S5, drying the catalyst filter cake at 160℃ for 20h, and then calcining under an air atmosphere at 320℃ for 5h to obtain the ruthenium-based catalyst.

[0177] The ruthenium-based catalyst in this embodiment is also provided for use in a direct synthesis of olefins from synthesis gas, wherein the ruthenium-based catalyst is first reduced and activated (the reduction atmosphere is a mixed gas of CO and N2, the molar ratio of CO in the mixed gas is 10%, the reduction space velocity is 8000h-1, the reduction temperature is 350℃, the reduction pressure is normal pressure, and the time is 5h), and then switched to synthesis gas for reaction, wherein the molar ratio between H2 and CO in the synthesis gas is 5, the reaction space velocity is 1000h-1, the reaction temperature is 260℃, and the reaction pressure is 15bar; after the reaction, the types and contents of various components contained in the product are analyzed using a gas chromatograph (Agilent 8860), and the conversion rate and selectivity of the reaction are calculated accordingly, and the specific results are shown in Table 1. -1 -1 The ruthenium-based catalyst in this embodiment is also provided for use in a direct synthesis of olefins from synthesis gas, wherein the ruthenium-based catalyst is first reduced and activated (the reduction atmosphere is a mixed gas of CO and N2, the molar ratio of CO in the mixed gas is 10%, the reduction space velocity is 8000h-1, the reduction temperature is 350℃, the reduction pressure is normal pressure, and the time is 5h), and then switched to synthesis gas for reaction, wherein the molar ratio between H2 and CO in the synthesis gas is 5, the reaction space velocity is 1000h-1, the reaction temperature is 260℃, and the reaction pressure is 15bar; after the reaction, the types and contents of various components contained in the product are analyzed using a gas chromatograph (Agilent 8860), and the conversion rate and selectivity of the reaction are calculated accordingly, and the specific results are shown in Table 1.

[0178] Example 8

[0179] The ruthenium-based catalyst for direct synthesis of olefins from synthesis gas provided in this embodiment is composed of ruthenium, zirconium and a structural aid (aluminum oxide), and the ruthenium-based catalyst comprises 5wt% of ruthenium, 10wt% of zirconium and 85wt% of the structural aid (aluminum oxide) according to the mass percentage of the ruthenium-based catalyst; wherein the content of ruthenium is in terms of the mass of metallic ruthenium; and the content of the structural aid is in terms of the mass of the corresponding oxide.

[0180] The preparation method of the ruthenium-based catalyst for direct synthesis of olefins from synthesis gas provided in this embodiment comprises the following steps:

[0181] S1, according to the mass percentage of ruthenium in the ruthenium-based catalyst being 5wt%, a ruthenium trichloride is weighed and added into water to prepare a mixed solution A with a concentration of 1mol / L (in the mixed solution A, the concentration of the ruthenium trichloride is 1mol / L);

[0182] S2, an aqueous solution of ethylene glycol and a precursor of a first structural aid (aerosol aluminum oxide) are added into the mixed solution A to obtain a mixed solution B;

[0183] ​S3, mixing the mixed solution B with an alkaline solution (1 mol / L aqueous solution of tetrabutylammonium hydroxide), and then loading into a high-pressure reaction kettle for hydrothermal reaction at 120℃ for 10h; after the reaction, washing with deionized water and filtering to obtain a precipitate;

[0184] S4, adding water, a salt corresponding to the second metal additive (zirconium nitrate) and a precursor of the second structural additive (alumina sol) into the precipitate, mixing in a ball mill for 2h, and then washing, filtering to obtain a catalyst filter cake;

[0185] The addition amount of the salt corresponding to the second metal additive in step S4 is calculated according to the mass percentage of the metal additive in the ruthenium-based catalyst, which is 3.5wt%;

[0186] The addition amount of the precursor of the first structural additive in step S2 is calculated according to the mass percentage of the structural additive in the ruthenium-based catalyst, which is 42.5wt%, and the addition amount of the precursor of the second structural additive in step S4 is calculated according to the mass percentage of the structural additive in the ruthenium-based catalyst, which is 42.5wt%, based on the mass of the oxide corresponding to the structural additive;

[0187] S5, drying the catalyst filter cake at 80℃ for 18h, and then calcining at 300℃ in an air atmosphere for 5h to obtain a ruthenium-based catalyst.

[0188] The example also provides an application of the ruthenium-based catalyst in a direct synthesis of olefins from syngas reaction. Before the reaction, the ruthenium-based catalyst in the example is reduced and activated (the reduction atmosphere is H2, the reduction space velocity is 10000h -1 , the reduction temperature is 450℃, the reduction pressure is normal pressure, and the time is 5h), and then switched to syngas for reaction. During the reaction, the molar ratio between H2 and CO in the syngas is 3, the reaction space velocity is 4000h -1 , the reaction temperature is 270℃, and the reaction pressure is 10bar. After the reaction, the types and contents of various components contained in the product are analyzed using gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction are calculated accordingly. The specific results are shown in Table 1.

[0189] Example 9

[0190] The example provides a ruthenium-based catalyst for direct synthesis of olefins from syngas, which is composed of ruthenium, magnesium and a structural additive (silicon oxide). The ruthenium-based catalyst includes 2wt% of ruthenium, 2wt% of magnesium and 96wt% of the structural additive (alumina) in terms of mass percentage of the ruthenium-based catalyst; wherein the content of ruthenium is in terms of mass of metallic ruthenium; and the content of the structural additive is in terms of mass of the corresponding oxide.

[0191] The embodiment also provides a preparation method of a ruthenium-based catalyst for direct synthesis of olefins from synthesis gas, which comprises the following steps:

[0192] S1, according to the mass percentage of ruthenium in the ruthenium-based catalyst being 2wt%, acetylacetone ruthenium is weighed and added into water to prepare a mixed solution A with a concentration of 0.5mol / L (in the mixed solution A, the concentration of acetylacetone ruthenium is 0.5mol / L);

[0193] S2, an aqueous solution of ethanol and a precursor of a first structural additive (aerosol silicon oxide) are added into the mixed solution A to obtain a mixed solution B;

[0194] S3, the mixed solution B is mixed with an alkaline solution (an aqueous solution of 1mol / L of bicarbonate amine), and then is loaded into a high-pressure reaction kettle to perform hydrothermal reaction at 120℃ for 20h, after the reaction, the precipitate is obtained by washing and filtering with deionized water;

[0195] S4, water, a salt corresponding to a second metal additive (magnesium nitrate) and a precursor of a second structural additive (silica sol) are added into the precipitate, and after being sufficiently mixed in a ball mill for 2h, the catalyst filter cake is obtained by washing and filtering;

[0196] The addition amount of the salt corresponding to the second metal additive in step S4 is calculated according to the mass percentage of the metal additive in the ruthenium-based catalyst being 2wt%;

[0197] According to the mass percentage of the structural additive in the ruthenium-based catalyst being 9.6wt%, the addition amount of the precursor of the first structural additive in step S2 is calculated, and according to the mass percentage of the structural additive in the ruthenium-based catalyst being 86.4wt%, the addition amount of the precursor of the second structural additive in step S4 is calculated;

[0198] S5, the catalyst filter cake is dried at 125℃ for 10h, and then is calcined at 350℃ in an air atmosphere for 5h to obtain the ruthenium-based catalyst.

[0199] The embodiment also provides an application of the ruthenium-based catalyst in a reaction of direct synthesis of olefins from synthesis gas, wherein the ruthenium-based catalyst in the embodiment is reduced and activated (the reduction atmosphere is a mixed gas of H2 and N2, the molar ratio of H2 in the mixed gas is 10%, the reduction space velocity is 3000h -1 -1, the reduction temperature is 450℃, the reduction pressure is normal pressure, and the time is 20h), and then is switched to synthesis gas to perform the reaction, wherein the molar ratio between H2 and CO in the synthesis gas is 2.5, and the reaction space velocity is 2000h -1, the reaction temperature was 260℃, and the reaction pressure was 10 bar; after the reaction was completed, the types and contents of various components contained in the product were analyzed using a gas chromatograph (Agilent 8860), and the conversion rate and selectivity of the reaction were calculated accordingly, and the specific results are shown in Table 1.

[0200] Example 10

[0201] The embodiment provides a ruthenium-based catalyst for directly synthesizing olefins from synthesis gas, the ruthenium-based catalyst is composed of ruthenium, manganese and a structural promoter (silicon oxide), and the ruthenium-based catalyst comprises 2wt% of ruthenium, 5wt% of manganese and 93wt% of the structural promoter (silicon oxide) in terms of mass percentage of the ruthenium-based catalyst; wherein the content of ruthenium is in terms of mass of metallic ruthenium; and the content of the structural promoter is in terms of mass of corresponding oxide.

[0202] The embodiment also provides a preparation method of the ruthenium-based catalyst for directly synthesizing olefins from synthesis gas, and the preparation method comprises the following steps:

[0203] S1, according to the mass percentage of ruthenium in the ruthenium-based catalyst being 2wt%, a ruthenium nitrosyl nitrate is weighed and added into water to prepare a mixed solution A with a concentration of 0.25mol / L (in the mixed solution A, the concentration of the ruthenium nitrosyl nitrate is 0.25mol / L);

[0204] S2, an aqueous solution of ethanol and a precursor of a first structural promoter (aerosol silicon dioxide) are added into the mixed solution A to obtain a mixed solution B;

[0205] S3, the mixed solution B is mixed with an alkaline solution (an aqueous solution of diethylamine with a concentration of 0.5mol / L), and then is loaded into a high-pressure reaction kettle to perform a hydrothermal reaction at 200℃ for 20h; after the reaction is completed, the precipitate is obtained by washing and filtering with deionized water;

[0206] S4, water and a salt corresponding to a second metal promoter (manganese nitrate) are added into the precipitate, and after being fully mixed in a ball mill for 2h, the catalyst filter cake is obtained by washing and filtering;

[0207] The addition amount of the salt corresponding to the second metal promoter in the step S4 is calculated according to the mass percentage of the metal promoter in the ruthenium-based catalyst being 5wt%;

[0208] The addition amount of the precursor of the first structural promoter in the step S2 is calculated according to the mass percentage of the structural promoter in the ruthenium-based catalyst being 93wt% in terms of mass of the oxide corresponding to the structural promoter;

[0209] S5, the catalyst filter cake is dried at 100℃ for 2h, and then is calcined at 400℃ under a nitrogen atmosphere for 6h to obtain the ruthenium-based catalyst.

[0210] The embodiment also provides application of the ruthenium-based catalyst in a direct synthesis gas to olefin reaction. -1 The reduction temperature is 300 DEG C, the reduction pressure is normal pressure, and the time is 5 h. Then, the synthesis gas is switched to react. During the reaction, the molar ratio between H2 and CO in the synthesis gas is 0.5, the reaction space velocity is 4000 h-1, the reaction temperature is 300 DEG C, and the reaction pressure is 10 bar. After the reaction, the types and contents of various components in the product are analyzed by using a gas chromatograph (Agilent 8860), and the conversion rate and selectivity of the reaction are calculated accordingly. The specific results are shown in Table 1. -1 The reduction temperature is 300 DEG C, the reduction pressure is normal pressure, and the time is 5 h. Then, the synthesis gas is switched to react. During the reaction, the molar ratio between H2 and CO in the synthesis gas is 0.5, the reaction space velocity is 4000 h-1, the reaction temperature is 300 DEG C, and the reaction pressure is 10 bar. After the reaction, the types and contents of various components in the product are analyzed by using a gas chromatograph (Agilent 8860), and the conversion rate and selectivity of the reaction are calculated accordingly. The specific results are shown in Table 1.

[0211] Embodiment 11

[0212] The embodiment provides a ruthenium-based catalyst for a direct synthesis gas to olefin reaction, the ruthenium-based catalyst being composed of ruthenium, iron and a structural promoter (aluminum oxide), and the ruthenium-based catalyst comprising 5wt% of ruthenium, 1wt% of iron and 94wt% of the structural promoter (aluminum oxide) in terms of the mass percentage of the ruthenium-based catalyst; wherein the content of the ruthenium is in terms of the mass of metallic ruthenium; and the content of the structural promoter is in terms of the mass of the corresponding oxide.

[0213] The embodiment also provides a preparation method of the ruthenium-based catalyst for the direct synthesis gas to olefin reaction, and the preparation method comprises the following steps:

[0214] S1, according to the mass percentage of 5wt% of ruthenium in the ruthenium-based catalyst, a ruthenium acetate is weighed and added into water to prepare a mixed solution A with a concentration of 0.5mol / L (in the mixed solution A, the concentration of the ruthenium acetate is 0.5mol / L);

[0215] S2, an ethylene glycol aqueous solution and a precursor of a first structural promoter (aerosol aluminum oxide) are added into the mixed solution A to obtain a mixed solution B;

[0216] S3, the mixed solution B is mixed with an alkaline solution (an aqueous solution of 1mol / L ammonia), and then is loaded into a high-pressure reaction kettle to perform a hydrothermal reaction at 250 DEG C for 30 h. After the reaction, the precipitate is obtained by washing and filtering with deionized water;

[0217] S4, water, a salt corresponding to a second metal promoter (ferric nitrate) and a precursor of a second structural promoter (aluminum oxide sol) are added into the precipitate, and are fully mixed in a ball mill for 2 h. Then, the catalyst filter cake is obtained by washing and filtering.

[0218] The addition amount of the salt corresponding to the second metal additive in step S4 is calculated according to the mass percentage of the metal additive in the ruthenium-based catalyst, which is 1wt%.

[0219] The addition amount of the precursor of the first structural additive in step S2 is calculated according to the mass percentage of the structural additive in the ruthenium-based catalyst, which is 47wt%; and the addition amount of the precursor of the second structural additive in step S4 is calculated according to the mass percentage of the structural additive in the ruthenium-based catalyst, which is 47wt%.

[0220] S5, drying the catalyst filter cake at 130℃ for 8h, and then calcining under an air atmosphere at 350℃ for 2h to obtain the ruthenium-based catalyst.

[0221] The ruthenium-based catalyst in the embodiment is also provided for use in a direct synthesis of olefins from synthesis gas, wherein the ruthenium-based catalyst is reduced and activated (the reduction atmosphere is a mixed gas of CO and N2, the molar ratio of CO in the mixed gas is 5%, the reduction space velocity is 5000h-1, the reduction temperature is 400℃, the reduction pressure is normal pressure, and the time is 5h) before the reaction, and then the synthesis gas is used for the reaction, wherein the molar ratio between H2 and CO in the synthesis gas is 2, the reaction space velocity is 2000h-1, the reaction temperature is 250℃, and the reaction pressure is 5bar. -1 The reaction temperature is 250℃, and the reaction pressure is 5bar; after the reaction, the types and contents of various components contained in the product are analyzed by using a gas chromatograph (Agilent 8860), and the conversion rate and selectivity of the reaction are calculated accordingly, and the specific results are shown in Table 1. -1

[0222] Embodiment 12

[0223] The embodiment provides a ruthenium-based catalyst for direct synthesis of olefins from synthesis gas, which is composed of ruthenium, cobalt and a structural additive (silicon oxide), and the ruthenium-based catalyst comprises 2wt% of ruthenium, 2wt% of cobalt and 97wt% of the structural additive (silicon oxide) according to the mass percentage of the ruthenium-based catalyst, wherein the content of the ruthenium is calculated according to the mass of metallic ruthenium, and the content of the structural additive is calculated according to the mass of the corresponding oxide.

[0224] The embodiment also provides a preparation method of the ruthenium-based catalyst for direct synthesis of olefins from synthesis gas, and the preparation method comprises the following steps:

[0225] S1, according to the mass percentage of the ruthenium in the ruthenium-based catalyst, which is 2wt%, a ruthenium trichloride is weighed and added into water to prepare a mixed solution A with a concentration of 0.25mol / L (in the mixed solution A, the concentration of the ruthenium trichloride is 0.25mol / L);

[0226] ​S2, adding an ethanol aqueous solution and a precursor of a first structure aid (aerosol silica) into the mixed solution A to obtain a mixed solution B;

[0227] S3, mixing the mixed solution B with an alkaline solution (a 1 mol / L aqueous solution of triethylamine), and then loading into a high-pressure reaction kettle to perform hydrothermal reaction at 220°C for 25h, after the reaction, washing with deionized water and filtering to obtain a precipitate;

[0228] S4, adding water and a salt corresponding to a second metal aid (cobalt nitrate) into the precipitate, and mixing in a ball mill for 2h, and then washing, filtering to obtain a catalyst filter cake;

[0229] The addition amount of the salt corresponding to the second metal aid in step S4 is calculated according to the mass percentage of the metal aid in the ruthenium-based catalyst, which is 2wt%;

[0230] The addition amount of the precursor of the first structure aid in step S2 is calculated according to the mass percentage of the structure aid in the ruthenium-based catalyst, which is 97wt%, based on the mass of the oxide corresponding to the structure aid;

[0231] S5, drying the catalyst filter cake at 140℃ for 5h, and then calcining at 360℃ under a nitrogen atmosphere for 6h to obtain a ruthenium-based catalyst.

[0232] The example also provides an application of the ruthenium-based catalyst in a direct synthesis of olefins from synthesis gas, before the reaction, the ruthenium-based catalyst in the example is reduced and activated (the reducing atmosphere is a mixed gas of H2 and N2, the molar ratio of H2 in the mixed gas is 20%, the reduction space velocity is 3000h -1 -1, the reduction temperature is 300℃, the reduction pressure is normal pressure, and the time is 5h), and then switching to synthesis gas for reaction, during the reaction, the molar ratio between H2 and CO in the synthesis gas is 1, the reaction space velocity is 3000h -1 -1, the reaction temperature is 250℃, and the reaction pressure is 10bar; after the reaction, the types and contents of various components contained in the product are analyzed using a gas chromatograph (Agilent 8860), and the conversion rate and selectivity of the reaction are calculated accordingly, and the specific results are shown in Table 1.

[0233] Table 1, the results of the ruthenium-based catalyst prepared in examples 1-12 in the direct synthesis of olefins from synthesis gas

[0234]

[0235] As shown in Table 1, the ruthenium-based catalysts prepared in Examples 1-12 exhibit good catalytic performance in the direct synthesis of olefins from synthesis gas, the CO conversion in Example 4 is as high as 82.8%, the methane selectivity in Example 1 is only 1.3%, the selectivity to carbon dioxide in each example is less than 10%, and the lowest is only 1.6%; the olefin selectivity in the total product of Example 1 is as high as 86.2%.

[0236] In summary, the ruthenium-based catalyst with high dispersity and stability can be prepared by the hydrothermal method on a large scale, the preparation method is simple and easy to repeat, the active component of the prepared ruthenium-based catalyst is uniformly distributed on the structural additive, the structure is stable, the utilization rate of ruthenium metal is high, and the ruthenium-based catalyst is used in the direct synthesis of olefins from synthesis gas, and exhibits good olefin synthesis performance. Therefore, the present application effectively overcomes the various shortcomings in the prior art and has high industrial utilization value.

[0237] The above examples only exemplarily illustrate the principles and effects of the present application, and are not used to limit the present application. Any person skilled in the art can modify or change the above examples without departing from the spirit and scope of the present application. Therefore, all equivalent modifications or changes completed by those skilled in the art without departing from the spirit and technical thought disclosed by the present application should be covered by the claims of the present application.

Claims

1. A process for the preparation of a ruthenium-based catalyst for the direct synthesis of olefins from synthesis gas, characterized in that: The ruthenium-based catalyst is composed of ruthenium, a metal promoter and a structure promoter, and contains 0.5wt%-10wt% of ruthenium, 0-20wt% of the metal promoter and 70wt%-99wt% of the structure promoter in terms of mass percentage of the ruthenium-based catalyst; wherein the content of the ruthenium is in terms of mass of metallic ruthenium; the content of the metal promoter in the ruthenium-based catalyst is not 0; the content of the structure promoter is in terms of mass of corresponding oxide; and the preparation method comprises the following steps: S1, preparing a mixed solution A of soluble ruthenium salt according to a proportioning; S2, adding water-soluble organic matter, a salt corresponding to a first metal promoter and a precursor of a first structure promoter into the mixed solution A to obtain a mixed solution B; S3, mixing the mixed solution B with an alkaline solution, then loading into a reaction kettle to perform hydrothermal reaction, and after the reaction, performing washing and filtering to obtain a precipitate; the hydrothermal reaction is performed at a temperature of 50-250°C for a time of 2-30h; S4, adding water, a salt corresponding to a second metal promoter and a precursor of a second structure promoter into the precipitate, then performing ball milling, filtering to obtain a catalyst filter cake; S5, drying and calcining the catalyst filter cake to obtain a ruthenium-based catalyst.

2. The process for the preparation of a ruthenium-based catalyst for the direct synthesis of olefins from synthesis gas according to claim 1, characterized in that: One or more of the following conditions are included: The metal promoter comprises one or more of calcium, magnesium, lithium, sodium, potassium, rubidium, cesium, cerium, barium and manganese metal; The structure promoter is one or more of silicon oxide, aluminum oxide, zirconium oxide and titanium oxide.

3. The method for preparing a ruthenium-based catalyst for direct synthesis gas to olefins according to claim 1, characterized by: One or more of the following conditions are included: The soluble ruthenium salt in step S1 is selected from one or more of ruthenium trichloride, ruthenium acetylacetonate, ruthenium acetate and ruthenium nitrosyl nitrate; In the mixed solution A in step S1, the concentration of the soluble ruthenium salt is 0.1-1.5mol / L.

4. The method for preparing a ruthenium-based catalyst for direct synthesis of olefins from syngas according to claim 1, characterized in that: One or more of the following conditions are included: The water-soluble organic matter in step S2 is selected from one or more of aqueous solution of ethanol, ethylene glycol, sucrose and polyethylene glycol; The salt corresponding to the first metal promoter in step S2 and the salt corresponding to the second metal promoter in step S4 are both nitrate salt corresponding to the metal promoter; and the mass ratio between the salt corresponding to the first metal promoter and the salt corresponding to the second metal promoter is (0-1):1, and the mass of the salt corresponding to the first metal promoter is not 0; The precursor of the first structure promoter in step S2 and the precursor of the second structure promoter in step S4 are both selected from any one of silicon oxide aerosol, aluminum oxide aerosol, silicon oxide sol, aluminum oxide sol, titanium dioxide, zirconium dioxide, zirconium acetylacetonate, titanium isopropylate and tetraethyl orthosilicate; and the mass ratio between the oxide corresponding to the precursor of the second structure promoter and the oxide corresponding to the precursor of the first structure promoter is (0-10):1, and the mass of the oxide corresponding to the precursor of the second structure promoter is not 0.

5. The process for the preparation of a ruthenium-based catalyst for the direct synthesis of olefins from synthesis gas according to claim 1, characterized in that: One or more of the following conditions are included: The basic solution in step S3 is selected from one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, aqueous ammonia, tetrabutylammonium hydroxide, triethylamine, ammonium bicarbonate, ethylenediamine, diethylamine solution, and the molar concentration of the basic solution is 0.1-2 mol / L.

6. The process for the preparation of a ruthenium-based catalyst for the direct synthesis of olefins from synthesis gas according to claim 1, characterized in that: One or more of the following conditions are included: The drying temperature in step S5 is 40-180°C, and the drying time is 2-20 h; The calcination temperature in step S5 is 200-600°C, and the calcination time is 2-10 h; The calcination atmosphere in step S5 is selected from one of air, nitrogen, and a reducing gas.

7. Use of a ruthenium-based catalyst prepared by the method of claim 1 or 2 in a direct synthesis of olefins from syngas reaction.

8. Use according to claim 7, characterized in that: One or more of the following conditions are included: The ruthenium-based catalyst is activated and pretreated before the direct synthesis of olefins from syngas reaction; The direct synthesis of olefins from syngas reaction uses H2 and CO as the reaction gas, and the molar ratio between H2 and CO is 0.5-5; In the direct synthesis gas to olefin reaction, the reaction temperature is 200-300°C, the reaction space velocity is 500-4000 h -1 , and the reaction pressure is 5-20 bar.

9. Use according to claim 8, characterized in that: The step of activation and pretreatment includes one or more of the following conditions: The activation and pretreatment atmosphere includes at least one of hydrogen and carbon monoxide; The activation and pretreatment temperature is 200-450°C; The space velocity of the activation pretreatment is 1000-10000 h -1 ; The activation and pretreatment pressure is 1-10 bar; The activation and pretreatment time is 2-10 h.

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