A catalyst for directly preparing higher alcohols from synthesis gas

Abstract

The present application relates to the technical field of catalyst, in particular to a catalyst for directly synthesizing higher alcohols from synthesis gas, a preparation method and use thereof. The catalyst is composed of a first metal component, a second metal component, a metal additive and a carrier. The first metal component is Ru. The catalyst comprises 0.1wt%-10wt% of the first metal component, 0.1wt%-5wt% of the second metal component, 0.01wt%-3wt% of the metal additive and 72wt%-99.79wt% of the carrier, based on the mass percentage of the catalyst. The first metal component Ru in the catalyst makes the catalyst have very low water gas reaction activity, and can keep the CO2 selectivity within 3%. The second metal component can provide CO non-dissociation adsorption, so that the catalyst has the performance of directly synthesizing higher alcohols from synthesis gas, and the first metal component and the second metal component have synergistic effect. Not only the content of noble metal Ru can be effectively reduced, but also the generation of higher alcohols can be greatly promoted, so the catalyst has wide market application prospect.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, and in particular to a catalyst for the direct preparation of higher alcohols from syngas. Background Technology

[0002] With rapid social and economic development, my country's demand for energy is increasing daily, with fossil resources still dominating. In 2020, my country's dependence on imported crude oil exceeded 70%. How to achieve efficient and environmentally friendly utilization of limited energy reserves and develop other non-oil and gas resources has become an urgent problem to be solved. my country has relatively abundant reserves of coal and shale gas and coalbed methane, which are mainly composed of methane. Developing clean, efficient, and low-carbon utilization of coal and natural gas conversion technologies can effectively solve the energy shortage problem and improve the domestic environment.

[0003] Therefore, syngas (a mixture of CO and H2) can be produced from resources such as coal, natural gas, and shale gas through gasification or reforming. This syngas, then subjected to a series of catalytic reactions, can effectively transform carbon-containing resources into clean fuels and high-value-added chemicals, aligning with my country's energy structure characterized by "abundant coal, scarce oil, and limited gas." A range of high-value-added chemicals, such as alcohols, aldehydes, gasoline, and olefins, can be produced from syngas. Among these, higher carbon alcohols (C6H2O) are particularly valuable. 6+ Alcohols are an important class of chemical raw materials with broad application prospects. Currently, the preparation of higher alcohols mainly involves processes such as petroleum cracking and olefin carbonylation. Undoubtedly, the direct production of higher alcohols from syngas has advantages such as a shorter process, lower energy consumption, and avoidance of dependence on petroleum resources. However, the higher alcohol content in the products obtained from the Fischer-Tropsch reaction of syngas is generally low, and the selectivity of byproducts CH4 and CO2 is both >30%, mainly due to the lack of suitable catalysts. Therefore, the development of catalysts for the direct production of higher alcohols from syngas with high carbon efficiency and high oxygen efficiency is crucial. Summary of the Invention

[0004] In view of the shortcomings of the prior art described above, the purpose of this invention is to provide a catalyst for the direct production of higher alcohols from syngas, its preparation method, and its uses. The catalyst of this invention has a first metal component, Ru, which gives it extremely low water-gas reactivity, keeping CO2 selectivity below 3%. The second metal component allows for non-dissociative adsorption of CO, enabling the catalyst to directly produce higher alcohols from syngas. The synergistic effect between the first and second metal components not only effectively reduces the content of the precious metal Ru but also greatly promotes the formation of higher alcohols.

[0005] To achieve the above and other related objectives, the first aspect of the present invention provides a catalyst for the direct production of higher alcohols from syngas.

[0006] The catalyst comprises a first metal component, a second metal component, and a support; the first metal component is Ru; the second metal component is selected from one or more of Pt, Au, Ag, Cu, or Zn; based on the mass percentage of the catalyst, the content of the first metal component is 0.1 wt% to 10 wt%, the content of the second metal component is 0.1 wt% to 5 wt%, and the content of the support is 72 wt% to 99.79 wt%; the particle size of the catalyst is 5 to 10 nm. In a preferred embodiment, the second metal component is selected from Pt and Au.

[0007] The content of the first metal component can be 0.1–0.5 wt%, 0.5–1.0 wt%, 1.0–1.5 wt%, 1.5–2.0 wt%, 2.0–2.5 wt%, 2.5–3.0 wt%, 3.0–3.5 wt%, 3.5–4.0 wt%, 4.0–4.5 wt%, 4.5–5.0 wt%, 5.0–5.5 wt%, 5.5–6.0 wt%, 6.0–6.5 wt%, 6.5–7.0 wt%, 7.0–7.5 wt%, 7.5–8.0 wt%, 8.0–8.5 wt%, 8.5–9.0 wt%, 9.0–9.5 wt%, or 9.5–10.0 wt%.

[0008] The content of the second metal component can be 0.1–0.5 wt%, 0.5–1.0 wt%, 1.0–1.5 wt%, 1.5–2.0 wt%, 2.0–2.5 wt%, 2.5–3.0 wt%, 3.0–3.5 wt%, 3.5–4.0 wt%, 4.0–4.5 wt%, or 4.5–5.0 wt%.

[0009] The content of the carrier can be 72-80 wt%, 80-85 wt%, 85-90 wt%, 90-92.85 wt%, 92.85-94.45 wt%, 94.45-94.85 wt%, 94.85-96.47 wt%, 96.47-96.85 wt%, 96.85-97.47 wt%, 97.47-97.77 wt%, 97.77-97.85 wt%, 97.85-98.16 wt%, or 98.16-99.79 wt%.

[0010] Preferably, the catalyst further includes a metal promoter, the content of which is 0.01 wt% to 3 wt% by mass percentage of the catalyst. The metal promoter is selected from one or more of Na, K, Cs, Ca, La, Ce, Nb, or Pr. For example, the content of the metal promoter can be 0.01–0.02 wt%, 0.02–0.03 wt%, 0.03–0.04 wt%, 0.04–0.05 wt%, 0.05–0.5 wt%, 0.5–1.0 wt%, 1.0–1.5 wt%, 1.5–2.0 wt%, 2.0–2.5 wt%, or 2.5–3.0 wt%. The metal promoter provides electrons in the reaction to produce alcohols using the catalyst, promoting catalytic activity. Theoretically, any metal that can donate electrons can be used as a metal promoter. In a specific embodiment, Na is selected as the metal promoter.

[0011] Preferably, the support is selected from one or more of SiO2, TiO2, Al2O3, ZnO, MgO, or BaO. In a preferred embodiment, SiO2 is chosen as the support because of its larger specific surface area.

[0012] A second aspect of this invention discloses a method for preparing the catalyst as described above. The preparation method is selected from one or more of the first and second preparation methods.

[0013] The first preparation method includes the following steps:

[0014] a1) Weigh the corresponding soluble salts according to the proportions of the first metal component, the second metal component, and the metal auxiliary in the total mass of the catalyst, and mix the soluble salts corresponding to the first metal component, the second metal component, and the metal auxiliary in the first solvent to obtain solution A;

[0015] a2) Dissolve the competing adsorbent in water to obtain solution B;

[0016] a3) Mix the solution A and the solution B to obtain solution C. Weigh the support according to the proportion of the support in the total mass of the catalyst. Impregnate the support with solution C.

[0017] a4) Filter, dry and roast.

[0018] Preferably, in step a1), the soluble salt corresponding to the first metal component is selected from one or more of ruthenium acetylacetonate, ruthenium nitrite, and ruthenium chloride.

[0019] Preferably, in step a1), the first solvent is selected from one or more of water, ethanol, propanol and acetone.

[0020] Preferably, in step a1), the concentration of solution A is 1–3 mol / L. For example, the concentration of solution A can be 1 mol / L, 2 mol / L, or 3 mol / L.

[0021] Preferably, in step a2), the competing adsorbent is selected from one or more of hydrochloric acid, oxalic acid, and citric acid.

[0022] Preferably, in step a2), the mass ratio of the competing adsorbent to water is 1:50 to 1:100. The volume ratio of the competing adsorbent to water can be 1:50 to 1:60, 1:60 to 1:70, 1:70 to 1:80, 1:80 to 1:90, or 1:90 to 1:100.

[0023] Preferably, in step a3), the mass ratio of solution A to solution B is 1:10 to 1:5. For example, the mass ratio of solution A to solution B can be 1:10, 1:9, 1:8, 1:7, 1:6, or 1:5.

[0024] Preferably, in step a3), the soaking time is 20 to 40 minutes. For example, the soaking time can be 20 minutes, 25 minutes, or 30 minutes.

[0025] Preferably, in step a3), after the impregnation is completed, a settling step is further included, and the settling time is 10 to 20 hours. For example, the settling time can be 10 hours, 15 hours, or 20 hours.

[0026] Preferably, in step a4), the drying temperature is 70–130°C, and the drying time is 8–24 hours. For example, the drying temperature can be 70–80°C, 80–90°C, 90–100°C, 100–110°C, 110–120°C, or 120–130°C. The drying time can be 8–10 hours, 10–12 hours, 12–14 hours, 14–15 hours, 15–17 hours, 17–19 hours, 19–21 hours, or 21–24 hours.

[0027] Preferably, in step a4), the roasting atmosphere is selected from one or more of N2, He and Ar.

[0028] Preferably, in step a4), the roasting temperature is 400–500°C, and the roasting time is 2–10 hours. For example, the roasting temperature can be 400–410°C, 410–420°C, 420–430°C, 430–440°C, 440–450°C, 450–460°C, 460–470°C, 470–480°C, 480–490°C, or 490–500°C. The roasting time can be 2–3 hours, 3–4 hours, 4–5 hours, 5–6 hours, 6–7 hours, 7–8 hours, 8–9 hours, or 9–10 hours.

[0029] The second preparation method includes the following steps:

[0030] b1) Weigh the corresponding soluble salts according to the proportions of the first metal component, the second metal component, and the metal auxiliary in the total mass of the catalyst, and mix the soluble salts corresponding to the first metal component, the second metal component, and the metal auxiliary in the second solvent to obtain solution D;

[0031] b2) Weigh the support according to the proportion of the support in the total mass of the catalyst, and ultrasonically disperse the support in water to obtain solution E;

[0032] b3) Mix the solution D, the solution E, and the reducing agent;

[0033] b4) Filter and dry.

[0034] Preferably, in step b1), the soluble salt corresponding to the first metal component is selected from one or more of ruthenium acetylacetonate, ruthenium nitrite, and ruthenium chloride.

[0035] Preferably, in step b1), the second solvent is selected from one or more of water, ethanol, and acetone.

[0036] Preferably, in step b1), the volume ratio of the carrier to the second solvent is 1:100 to 1:50. For example, the volume ratio of the carrier to the second solvent can be 1:50 to 1:60, 1:60 to 1:70, 1:70 to 1:80, 1:80 to 1:90, or 1:90 to 1:100.

[0037] Preferably, in step b1), the duration of the ultrasound is 5 to 10 hours. For example, the duration of the ultrasound can be 5 to 6 hours, 6 to 7 hours, 7 to 8 hours, 8 to 9 hours, or 9 to 10 hours.

[0038] Preferably, in step b1), the concentration of solution D is 1–3 mol / L. For example, the concentration of solution D can be 1 mol / L, 2 mol / L, or 3 mol / L.

[0039] Preferably, in step b2), the duration of the ultrasound is 5 to 10 hours. For example, the duration of the ultrasound can be 5 to 6 hours, 6 to 7 hours, 7 to 8 hours, 8 to 9 hours, or 9 to 10 hours.

[0040] Preferably, in step b3), the reducing agent is selected from one or more of hydrazine hydrate solution, sodium citrate solution, and sodium borohydride solution, and the concentration of the reducing agent is 1-3 mol / L. For example, the concentration of the reducing agent can be 1 mol / L, 2 mol / L, or 3 mol / L.

[0041] Preferably, the mass ratio of solution D, solution E, and reducing agent is 1:(0.5-2):(0.5-2). For example, the mass ratio of solution E to reducing agent can be 1:0.5:0.5, 1:0.5:1, 1:0.5:2, 1:1:0.5, 1:1:1, 1:1:2, 1:2:0.5, 1:2:1, or 1:2:2.

[0042] Preferably, in step b4), the drying temperature is 100–120°C, and the drying time is 5–10 hours. For example, the drying temperature can be 100–110°C, 110–120°C, or 120–130°C. The drying time can be 3–4 hours, 4–5 hours, 5–6 hours, 6–7 hours, 7–8 hours, 8–9 hours, or 9–10 hours.

[0043] Preferably, in step b4), the drying atmosphere is selected from one or more of N2, He, and Ar.

[0044] A third aspect of the present invention discloses the use of a catalyst as described above in the direct preparation of higher alcohols from syngas.

[0045] Preferably, the catalyst is subjected to reduction treatment before being used to directly prepare higher alcohols from syngas.

[0046] Preferably, before using the catalyst to directly prepare higher alcohols from syngas, the catalyst is first compressed into tablets and sieved to 40-60 mesh.

[0047] More preferably, the gas used in the reduction process is selected from hydrogen and CO.

[0048] More preferably, the reduction treatment temperature is 300–500°C. For example, the reduction treatment temperature can be 300°C–400°C or 400°C–500°C.

[0049] More preferably, the reduction treatment time is 3 to 10 hours. For example, the reduction treatment time can be 3 to 5 hours, 5 to 7 hours, 7 to 9 hours, or 9 to 10 hours.

[0050] More preferably, the space velocity of the reduction treatment is 1000 to 10000 h⁻¹. -1 The space velocity for the reduction process described above can be 1000 h⁻¹. -1 ~2000h -1 2000h -1 ~4000h -1 4000h -1 ~6000h -1 6000h -1 ~8000h -1 8000h -1 ~10000h -1 .

[0051] More preferably, in the reaction of directly producing higher alcohols from syngas, the molar ratio of H2 to CO in the syngas is 0.5 to 5. For example, the molar ratio of H2 to CO in the syngas can be 0.5 to 1, 1 to 2, 2 to 3, 3 to 4, or 4 to 5.

[0052] More preferably, in the reaction of directly producing higher alcohols from syngas, the reaction temperature is 200–300°C. For example, the reaction temperature can be 200–250°C or 250–300°C.

[0053] More preferably, in the reaction of directly producing higher alcohols from syngas, the reaction space velocity is 3000-6000 h⁻¹. -1 The reaction space velocity, as described, can be 3000 h⁻¹. -1 4000h -1 5000h -1 6000h -1 .

[0054] More preferably, in the reaction of directly producing higher alcohols from syngas, the reaction pressure is 3 to 10 MPa. For example, the reaction pressure can be 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, or 10 MPa.

[0055] Compared with the prior art, the present invention has the following beneficial effects:

[0056] (1) The first metal component Ru in the catalyst of the present invention makes the catalyst have extremely low water gas reaction activity, which can keep the CO2 selectivity within 3%, and the second metal component can be used for non-dissociative adsorption of CO, which can realize the direct production of higher alcohols from syngas.

[0057] (2) In the catalyst of the present invention, the first metal component and the second metal component have a core-shell structure. Since the synthesis of alcohol requires the participation of both metal components at the same time (i.e., the synthesis of alcohol is carried out at the interface of the two metal components), the core-shell structure can be used for the synthesis of alcohol at the core-shell interface, the reaction contact area is large, and the catalytic performance is excellent.

[0058] (3) The catalyst of the present invention has superior catalytic performance, with high selectivity for higher alcohols in the product distribution, extremely low selectivity for by-products, high yield of higher alcohol products, stronger stability, and more economical product distribution.

[0059] (4) The synergistic effect between the first metal component and the second metal component in the catalyst of the present invention can not only effectively reduce the content of the noble metal Ru, but also greatly promote the generation of higher alcohols. Detailed Implementation

[0060] The following specific embodiments 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.

[0061] 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. Test methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions or as recommended by the respective manufacturers.

[0062] 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.

[0063] The reaction results of the catalyst described in the embodiments of this application were obtained by the following method:

[0064] 1) Use gas chromatography (Agilent 8860) to analyze the types and contents of various components contained in the product;

[0065] 2) The CO conversion rate is calculated based on the number of carbon atoms, using the following formula:

[0066]

[0067] CO inlet and CO outlet These represent the number of CO moles entering and exiting the reaction system, respectively.

[0068] 3) The formula for calculating carbon dioxide selectivity is:

[0069]

[0070] CO 2outlet This represents the number of moles of CO2 flowing out of the reaction tube.

[0071] 4) Methane, alcohols and C 6+ The formula for calculating alcohol selectivity is similar to that for calculating CO2 selectivity.

[0072] Example 1

[0073] This embodiment provides a catalyst for the direct production of higher alcohols from syngas. The catalyst comprises a first metal component, a second metal component, a metal promoter, and a support. By mass percentage, the catalyst includes 3 wt% of the first metal component, 0.5 wt% of the second metal component, 0.03 wt% of the metal promoter, and 96.47 wt% of the support. The first metal component is Ru; the second metal component is Pt; the metal promoter is Na; and the support is SiO2.

[0074] This embodiment also provides a method for preparing a catalyst for the direct production of higher alcohols from syngas, the preparation method comprising the following steps:

[0075] S1. According to the mass percentage of the first metal component in the catalyst being 3wt%, the mass percentage of the second metal component being 0.5wt%, and the mass percentage of the metal auxiliaries being 0.03wt%, ruthenium nitrite nitrite, chloroplatinic acid, and sodium nitrate are weighed and added to deionized water to prepare a solution A with a concentration of 2mol / L.

[0076] S2. Prepare solution B by mixing hydrochloric acid and water at a mass ratio of 1:100;

[0077] S3. Mix the solution A and the solution B in a mass ratio of 1:10 to obtain solution C. Impregnate the solution C on the SiO2 support for 30 minutes. The mass percentage of the SiO2 support is 96.47 wt% based on the mass percentage of the catalyst. After impregnation, let it stand at room temperature for 15 hours.

[0078] S4. Vacuum dry at 80℃ for 10h. Calcine the dried solid in a tube furnace at 400℃ under N2 atmosphere for 3h to obtain the catalyst.

[0079] This embodiment also provides the application of a catalyst in the direct synthesis of higher alcohols from syngas.

[0080] Before the direct synthesis of higher alcohols from syngas, the catalyst is first subjected to reduction pretreatment: the catalyst is compressed into tablets and sieved to 40-60 mesh. 1g of the 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand. After thorough mixing, the mixture is packed into a fixed bed for pretreatment reduction. The reduction atmosphere is hydrogen, and the reduction space velocity is 8000h⁻¹. -1 The reduction temperature was 350℃, the reduction pressure was atmospheric pressure, and the time was 5 hours. After the reduction was completed, the temperature was lowered to 180℃.

[0081] 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 4000 h⁻¹. -1 The reaction temperature was 200℃ and the reaction pressure was 6MPa. 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.

[0082] Example 2

[0083] This embodiment provides a catalyst for the direct production of higher alcohols from syngas. The catalyst comprises a first metal component, a second metal component, a metal promoter, and a support. By mass percentage, the catalyst comprises 2 wt% of the first metal component, 0.5 wt% of the second metal component, 0.03 wt% of the metal promoter, and 97.47 wt% of the support. The first metal component is Ru; the second metal component is Pt; the metal promoter is K; and the support is SiO2.

[0084] This embodiment also provides a method for preparing a catalyst for the direct production of higher alcohols from syngas, the preparation method comprising the following steps:

[0085] S1. According to the mass percentage of the first metal component in the catalyst being 2 wt%, the mass percentage of the second metal component being 0.5 wt%, and the mass percentage of the metal auxiliary being 0.03 wt%, ruthenium chloride, chloroplatinic acid, and potassium nitrate are weighed and added to deionized water to prepare a solution A with a concentration of 2 mol / L.

[0086] S2. Prepare solution B by mixing oxalic acid and water at a mass ratio of 1:100.

[0087] S3. Mix the solution A and the solution B in a mass ratio of 1:10 to obtain solution C. Impregnate the solution C on the SiO2 support for 30 minutes. The mass percentage of the SiO2 support is 97.47 wt% based on the mass percentage of the catalyst. After impregnation, let it stand at room temperature for 15 hours.

[0088] S4. Vacuum dry at 80℃ for 10h. Calcine the dried solid in a tube furnace at 400℃ under N2 atmosphere for 3h to obtain the catalyst.

[0089] This embodiment also provides the application of a catalyst in the direct synthesis of higher alcohols from syngas.

[0090] Before the direct synthesis of higher alcohols from syngas, the catalyst is first subjected to reduction pretreatment: the catalyst is compressed into tablets and sieved to 40-60 mesh. 1g of the 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand. After thorough mixing, the mixture is packed into a fixed bed for pretreatment reduction. The reduction atmosphere is hydrogen, and the reduction space velocity is 8000h⁻¹. -1 The reduction temperature was 350℃, the reduction pressure was atmospheric pressure, and the time was 5 hours. After the reduction was completed, the temperature was lowered to 180℃.

[0091] Then, the reaction was carried out using syngas. During the reaction, the molar ratio of H2 to CO in the syngas was 2, the reaction space velocity was 4000 h⁻¹, the reaction temperature was 200 °C, and the reaction pressure was 6 MPa. After the reaction was completed, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction were calculated accordingly. The specific results are shown in Table 1.

[0092] Example 3

[0093] This embodiment provides a catalyst for the direct production of higher alcohols from syngas. The catalyst comprises a first metal component, a second metal component, a metal promoter, and a support. By mass percentage, the catalyst includes 3 wt% of the first metal component, 0.5 wt% of the second metal component, 0.03 wt% of the metal promoter, and 96.47 wt% of the support. The first metal component is Ru; the second metal component is Au; the metal promoter is Na; and the support is SiO2.

[0094] This embodiment also provides a method for preparing a catalyst for the direct production of higher alcohols from syngas, the preparation method comprising the following steps:

[0095] S1. According to the mass percentage of the first metal component in the catalyst being 3wt%, the mass percentage of the second metal component being 0.5wt%, and the mass percentage of the metal auxiliary being 0.03wt%, ruthenium nitrite, gold chloride and sodium nitrate are weighed and added to deionized water to prepare a solution A with a concentration of 2mol / L.

[0096] S2. Prepare solution B by mixing oxalic acid and water at a mass ratio of 1:100;

[0097] S3. Mix the solution A and the solution B in a mass ratio of 1:10 to obtain solution C. Impregnate the solution C on the SiO2 support for 30 minutes. The mass percentage of the SiO2 support is 96.47 wt% based on the mass percentage of the catalyst. After impregnation, let it stand at room temperature for 15 hours.

[0098] S4. Vacuum dry at 100℃ for 15h. Calcine the dried solid in a tube furnace at 450℃ under N2 atmosphere for 5h to obtain the catalyst.

[0099] This embodiment also provides the application of a catalyst in the direct synthesis of higher alcohols from syngas.

[0100] Before the direct synthesis of higher alcohols from syngas, the catalyst is first subjected to reduction pretreatment: the catalyst is compressed into tablets and sieved to 40-60 mesh. 1g of the 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand. After thorough mixing, the mixture is packed into a fixed bed for pretreatment reduction. The reduction atmosphere is hydrogen, and the reduction space velocity is 8000h⁻¹. -1 The reduction temperature was 350℃, the reduction pressure was atmospheric pressure, and the time was 5 hours. After the reduction was completed, the temperature was lowered to 180℃.

[0101] 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 4000 h⁻¹. -1 The reaction temperature was 200℃ and the reaction pressure was 6MPa. 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.

[0102] Example 4

[0103] This embodiment provides a catalyst for the direct production of higher alcohols from syngas. The catalyst comprises a first metal component, a second metal component, a metal promoter, and a support. By mass percentage, the catalyst comprises 3 wt% of the first metal component, 0.1 wt% of the second metal component, 0.05 wt% of the metal promoter, and 96.85 wt% of the support. The first metal component is Ru; the second metal component is Cu; the metal promoter is Na; and the support is SiO2.

[0104] This embodiment also provides a method for preparing a catalyst for the direct production of higher alcohols from syngas, the preparation method comprising the following steps:

[0105] S1. According to the mass percentage of the first metal component in the catalyst being 3wt%, the mass percentage of the second metal component being 0.1wt%, and the mass percentage of the metal auxiliaries being 0.05wt%, ruthenium nitrite, copper nitrate, and praseodymium nitrate are weighed and added to deionized water to prepare a solution A with a concentration of 2mol / L.

[0106] S2. Prepare solution B by mixing citric acid and water at a mass ratio of 1:100;

[0107] S3. Mix the solution A and the solution B in a mass ratio of 1:10 to obtain solution C. Impregnate the solution C on the SiO2 support for 30 minutes. The mass percentage of the SiO2 support is 96.85 wt% based on the mass percentage of the catalyst. After impregnation, let it stand at room temperature for 15 hours.

[0108] S4. Vacuum dry at 80℃ for 10h. Calcine the dried solid in a tube furnace at 500℃ in a He atmosphere for 3h to obtain the catalyst.

[0109] This embodiment also provides the application of a catalyst in the direct synthesis of higher alcohols from syngas.

[0110] Before the direct synthesis of higher alcohols from syngas, the catalyst is first subjected to reduction pretreatment: the catalyst is compressed into tablets and sieved to 40-60 mesh. 1g of the 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand. After thorough mixing, the mixture is packed into a fixed bed for pretreatment reduction. The reduction atmosphere is hydrogen, and the reduction space velocity is 8000h⁻¹. -1 The reduction temperature was 350℃, the reduction pressure was atmospheric pressure, and the time was 5 hours. After the reduction was completed, the temperature was lowered to 180℃.

[0111] 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 4000 h⁻¹. -1The reaction temperature was 200℃ and the reaction pressure was 6MPa. 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.

[0112] Example 5

[0113] This embodiment provides a catalyst for the direct production of higher alcohols from syngas. The catalyst comprises a first metal component, a second metal component, a metal promoter, and a support. By mass percentage, the catalyst comprises 1.5 wt% of the first metal component, 0.3 wt% of the second metal component, 0.04 wt% of the metal promoter, and 98.16 wt% of the support. The first metal component is Ru; the second metal component is Zn; the metal promoter is Cs; and the support is TiO2.

[0114] This embodiment also provides a method for preparing a catalyst for the direct production of higher alcohols from syngas, the preparation method comprising the following steps:

[0115] S1. According to the mass percentage of the first metal component in the catalyst being 1.5 wt%, the mass percentage of the second metal component being 0.3 wt%, and the mass percentage of the metal auxiliaries being 0.04 wt%, ruthenium acetylacetone, zinc nitrate, and cesium nitrate are weighed and added to ethanol to prepare a solution A with a concentration of 2 mol / L.

[0116] S2. Prepare solution B by mixing hydrochloric acid and water at a mass ratio of 1:100;

[0117] S3. Mix the solution A and the solution B in a mass ratio of 1:10 to obtain solution C. Impregnate the solution C on the TiO2 support for 30 minutes. The mass percentage of the TiO2 support is 98.16 wt% based on the mass percentage of the catalyst. After impregnation, let it stand at room temperature for 20 hours.

[0118] S4. Vacuum dry at 120℃ for 10h. Calcine the dried solid in a tube furnace at 400℃ under an Ar atmosphere for 7h to obtain the catalyst.

[0119] This embodiment also provides the application of a catalyst in the direct synthesis of higher alcohols from syngas.

[0120] Before the direct synthesis of higher alcohols from syngas, the catalyst is first subjected to reduction pretreatment: the catalyst is compressed into tablets and sieved to 40-60 mesh. 1g of the 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand. After thorough mixing, the mixture is packed into a fixed bed for pretreatment reduction. The reduction atmosphere is hydrogen, and the reduction space velocity is 8000h⁻¹. -1The reduction temperature was 350℃, the reduction pressure was atmospheric pressure, and the time was 5 hours. After the reduction was completed, the temperature was lowered to 180℃.

[0121] 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 4000 h⁻¹. -1 The reaction temperature was 200℃ and the reaction pressure was 6MPa. 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.

[0122] Example 6

[0123] This embodiment provides a catalyst for the direct production of higher alcohols from syngas. The catalyst comprises a first metal component, a second metal component, a metal promoter, and a support. By mass percentage, the catalyst comprises 5 wt% of the first metal component, 0.5 wt% of the second metal component, 0.03 wt% of the metal promoter, and 94.47 wt% of the support. The first metal component is Ru; the second metal component is Pt; the metal promoter is Na; and the support is MgO.

[0124] This embodiment also provides a method for preparing a catalyst for the direct production of higher alcohols from syngas, the preparation method comprising the following steps:

[0125] S1. According to the mass percentage of the first metal component in the catalyst being 5 wt%, the mass percentage of the second metal component being 0.5 wt%, and the mass percentage of the metal auxiliaries being 0.03 wt%, ruthenium nitrite nitrite, chloroplatinic acid, and sodium nitrate are weighed and added to propanol to prepare a solution A with a concentration of 2 mol / L.

[0126] S2. Prepare solution B by mixing hydrochloric acid and water at a mass ratio of 1:100;

[0127] S3. Mix the solution A and the solution B in a mass ratio of 1:10 to obtain solution C. Impregnate the solution C on the MgO support for 30 minutes. The mass percentage of the MgO support is 94.47 wt% based on the mass percentage of the catalyst. After impregnation, let it stand at room temperature for 15 hours.

[0128] S4. Vacuum dry at 80℃ for 10h. Calcine the dried solid in a tube furnace at 450℃ under N2 atmosphere for 3h to obtain the catalyst.

[0129] This embodiment also provides the application of a catalyst in the direct synthesis of higher alcohols from syngas.

[0130] Before the direct synthesis of higher alcohols from syngas, the catalyst is first subjected to reduction pretreatment: the catalyst is compressed into tablets and sieved to 40-60 mesh. 1g of the 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand. After thorough mixing, the mixture is packed into a fixed bed for pretreatment reduction. The reduction atmosphere is hydrogen, and the reduction space velocity is 8000h⁻¹. -1 The reduction temperature was 350℃, the reduction pressure was atmospheric pressure, and the time was 5 hours. After the reduction was completed, the temperature was lowered to 180℃.

[0131] 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 4000 h⁻¹. -1 The reaction temperature was 200℃ and the reaction pressure was 6MPa. 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.

[0132] Example 7

[0133] This embodiment provides a catalyst for the direct production of higher alcohols from syngas. The catalyst comprises a first metal component, a second metal component, a metal promoter, and a support. By mass percentage, the catalyst includes 5 wt% of the first metal component, 0.5 wt% of the second metal component, 0.05 wt% of the metal promoter, and 94.45 wt% of the support. The first metal component is Ru; the second metal component is Ag; the metal promoter is La; and the support is BaO.

[0134] This embodiment also provides a method for preparing a catalyst for the direct production of higher alcohols from syngas, the preparation method comprising the following steps:

[0135] S1. According to the mass percentage of the first metal component in the catalyst being 5 wt%, the mass percentage of the second metal component being 0.5 wt%, and the mass percentage of the metal auxiliaries being 0.05 wt%, ruthenium nitrite, silver nitrate, and lanthanum nitrate are weighed and added to depropanol to prepare a solution A with a concentration of 2 mol / L.

[0136] S2. Prepare solution B by mixing hydrochloric acid and water at a mass ratio of 1:100;

[0137] S3. Mix the solution A and the solution B in a mass ratio of 1:10 to obtain solution C. Impregnate the solution C on the BaO support for 30 minutes. The mass percentage of the BaO support is 94.45 wt% based on the mass percentage of the catalyst. After impregnation, let it stand at room temperature for 15 hours.

[0138] S4. Vacuum dry at 80℃ for 10h. Calcine the dried solid in a tube furnace at 450℃ under N2 atmosphere for 3h to obtain the catalyst.

[0139] This embodiment also provides the application of a catalyst in the direct synthesis of higher alcohols from syngas.

[0140] Before the direct synthesis of higher alcohols from syngas, the catalyst is first subjected to reduction pretreatment: the catalyst is compressed into tablets and sieved to 40-60 mesh. 1g of the 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand. After thorough mixing, the mixture is packed into a fixed bed for pretreatment reduction. The reduction atmosphere is hydrogen, and the reduction space velocity is 8000h⁻¹. -1 The reduction temperature was 350℃, the reduction pressure was atmospheric pressure, and the time was 5 hours. After the reduction was completed, the temperature was lowered to 180℃.

[0141] 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 4000 h⁻¹. -1 The reaction temperature was 200℃ and the reaction pressure was 6MPa. 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.

[0142] Example 8

[0143] This embodiment provides a catalyst for the direct production of higher alcohols from syngas. The catalyst comprises a first metal component, a second metal component, a metal promoter, and a support. By mass percentage, the catalyst comprises 2 wt% of the first metal component, 0.2 wt% of the second metal component, 0.03 wt% of the metal promoter, and 97.77 wt% of the support. The first metal component is Ru; the second metal component is Au; the metal promoter is Ce; and the support is BaO.

[0144] This embodiment also provides a method for preparing a catalyst for the direct production of higher alcohols from syngas, the preparation method comprising the following steps:

[0145] S1. According to the mass percentage of the first metal component in the catalyst being 5 wt%, the mass percentage of the second metal component being 0.5 wt%, and the mass percentage of the metal auxiliary being 0.05 wt%, ruthenium chloride, gold chloride, and cerium nitrate are weighed and added to acetone to prepare a solution A with a concentration of 2 mol / L.

[0146] S2. Prepare solution B by mixing oxalic acid and water at a mass ratio of 1:50.

[0147] S3. Mix the solution A and the solution B in a mass ratio of 1:10 to obtain solution C. Impregnate the solution C on the BaO support for 30 minutes. The mass percentage of the BaO support is 97.77 wt% based on the mass percentage of the catalyst. After impregnation, let it stand at room temperature for 15 hours.

[0148] S4. Vacuum dry at 80℃ for 10h. Calcine the dried solid in a tube furnace at 500℃ under N2 atmosphere for 3h to obtain the catalyst.

[0149] This embodiment also provides the application of a catalyst in the direct synthesis of higher alcohols from syngas.

[0150] Before the direct synthesis of higher alcohols from syngas, the catalyst is first subjected to reduction pretreatment: the catalyst is compressed into tablets and sieved to 40-60 mesh. 1g of the 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand. After thorough mixing, the mixture is packed into a fixed bed for pretreatment reduction. The reduction atmosphere is hydrogen, and the reduction space velocity is 8000h⁻¹. -1 The reduction temperature was 350℃, the reduction pressure was atmospheric pressure, and the time was 5 hours. After the reduction was completed, the temperature was lowered to 180℃.

[0151] 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 4000 h⁻¹. -1 The reaction temperature was 200℃ and the reaction pressure was 6MPa. 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.

[0152] Example 9

[0153] This embodiment provides a catalyst for the direct production of higher alcohols from syngas. The catalyst comprises a first metal component, a second metal component, a metal promoter, and a support. By mass percentage, the catalyst comprises 2 wt% of the first metal component, 0.2 wt% of the second metal component, 0.03 wt% of the metal promoter, and 97.77 wt% of the support. The first metal component is Ru; the second metal component is Au; the metal promoter is K; and the support is SiO2.

[0154] This embodiment also provides a method for preparing a catalyst for the direct production of higher alcohols from syngas, the preparation method comprising the following steps:

[0155] S1. According to the mass percentage of the first metal component in the catalyst being 2wt%, the mass percentage of the second metal component being 0.2wt%, and the mass percentage of the metal auxiliary being 0.03wt%, ruthenium chloride, gold chloride, and potassium nitrate are weighed and added to deionized water to prepare a solution D with a concentration of 2mol / L.

[0156] S2. The SiO2 support is ultrasonically dispersed in deionized water for 6 hours, with a mass ratio of SiO2 support to water of 1:50, to obtain solution E. The mass percentage of the SiO2 support is 97.77 wt% based on the mass percentage of the catalyst.

[0157] S3. Mix the solution D, the solution E and the hydrazine hydrate solution, and stir at high speed for 1 hour. The mass ratio of the solution D, the solution E and the hydrazine hydrate solution is 1:1:1, and the concentration of the hydrazine hydrate solution is 2 mol / L.

[0158] S4. Filter the solid and dry it in a tube furnace at 100°C for 10 hours under a N2 atmosphere.

[0159] This embodiment also provides the application of a catalyst in the direct synthesis of higher alcohols from syngas.

[0160] Before the direct synthesis of higher alcohols from syngas, the catalyst is first subjected to reduction pretreatment: the catalyst is compressed into tablets and sieved to 40-60 mesh. 1g of the 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand. After thorough mixing, the mixture is packed into a fixed bed for pretreatment reduction. The reduction atmosphere is hydrogen, and the reduction space velocity is 8000h⁻¹. -1 The reduction temperature was 350℃, the reduction pressure was atmospheric pressure, and the time was 5 hours. After the reduction was completed, the temperature was lowered to 180℃.

[0161] 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 4000 h⁻¹. -1 The reaction temperature was 200℃ and the reaction pressure was 6MPa. 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.

[0162] Example 10

[0163] This embodiment provides a catalyst for the direct production of higher alcohols from syngas. The catalyst comprises a first metal component, a second metal component, a metal promoter, and a support. By mass percentage, the catalyst comprises 3 wt% of the first metal component, 0.5 wt% of the second metal component, 0.05 wt% of the metal promoter, and 96.45 wt% of the support. The first metal component is Ru; the second metal component is Au; the metal promoter is Cs; and the support is SiO2.

[0164] This embodiment also provides a method for preparing a catalyst for the direct production of higher alcohols from syngas, the preparation method comprising the following steps:

[0165] S1. According to the mass percentage of the first metal component in the catalyst being 3wt%, the mass percentage of the second metal component being 0.5wt%, and the mass percentage of the metal auxiliary being 0.05wt%, ruthenium chloride, chloroauric acid, and strontium nitrate are weighed and added to deionized water to prepare a solution D with a concentration of 2mol / L.

[0166] S2. The SiO2 support is ultrasonically dispersed in deionized water for 8 hours. The mass ratio of SiO2 support to water is 1:100 to obtain solution E. The mass percentage of the SiO2 support is 96.45 wt% based on the mass percentage of the catalyst.

[0167] S3. Mix the solution D, the solution E and the sodium citrate solution, and stir at high speed for 1.5 h. The mass ratio of the solution D, the solution E and the sodium citrate solution is 1:1:1, and the concentration of the sodium citrate solution is 2 mol / L.

[0168] S4. Filter the solid and dry it in a tube furnace at 100°C for 10 hours under a N2 atmosphere.

[0169] This embodiment also provides the application of a catalyst in the direct synthesis of higher alcohols from syngas.

[0170] Before the direct synthesis of higher alcohols from syngas, the catalyst is first subjected to reduction pretreatment: the catalyst is compressed into tablets and sieved to 40-60 mesh. 1g of the 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand. After thorough mixing, the mixture is packed into a fixed bed for pretreatment reduction. The reduction atmosphere is hydrogen, and the reduction space velocity is 8000h⁻¹. -1 The reduction temperature was 350℃, the reduction pressure was atmospheric pressure, and the time was 5 hours. After the reduction was completed, the temperature was lowered to 180℃.

[0171] 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 4000 h⁻¹. -1The reaction temperature was 200℃ and the reaction pressure was 6MPa. 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.

[0172] Example 11

[0173] This embodiment provides a catalyst for the direct production of higher alcohols from syngas. The catalyst comprises a first metal component, a second metal component, a metal promoter, and a support. By mass percentage, the catalyst includes 5 wt% of the first metal component, 0.5 wt% of the second metal component, 0.05 wt% of the metal promoter, and 94.45 wt% of the support. The first metal component is Ru; the second metal component is Pt; the metal promoter is La; and the support is MgO.

[0174] This embodiment also provides a method for preparing a catalyst for the direct production of higher alcohols from syngas, the preparation method comprising the following steps:

[0175] S1. Weigh out ruthenium nitrite, chloroplatinic acid and lanthanum nitrate according to the mass percentage of the first metal component in the catalyst being 5 wt%, the mass percentage of the second metal component being 0.5 wt%, and the mass percentage of the metal auxiliaries being 0.05 wt%, and add them to deionized water to prepare a solution D with a concentration of 2 mol / L.

[0176] S2. The MgO support is ultrasonically dispersed in deionized water for 10 hours. The mass ratio of MgO support to water is 1:70 to obtain solution E. The mass percentage of the MgO support is 94.45 wt% based on the mass percentage of the catalyst.

[0177] S3. Mix the solution D, the solution E and the hydrazine hydrate solution, and stir at high speed for 2 hours. The mass ratio of the solution D, the solution E and the hydrazine hydrate solution is 1:1:1, and the concentration of the hydrazine hydrate solution is 2 mol / L.

[0178] S4. Filter the solid and dry it in a tube furnace at 120°C for 8 hours under a N2 atmosphere.

[0179] This embodiment also provides the application of a catalyst in the direct synthesis of higher alcohols from syngas.

[0180] Before the direct synthesis of higher alcohols from syngas, the catalyst is first subjected to reduction pretreatment: the catalyst is compressed into tablets and sieved to 40-60 mesh. 1g of the 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand. After thorough mixing, the mixture is packed into a fixed bed for pretreatment reduction. The reduction atmosphere is hydrogen, and the reduction space velocity is 8000h⁻¹. -1The reduction temperature was 350℃, the reduction pressure was atmospheric pressure, and the time was 5 hours. After the reduction was completed, the temperature was lowered to 180℃.

[0181] 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 4000 h⁻¹. -1 The reaction temperature was 200℃ and the reaction pressure was 6MPa. 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.

[0182] Example 12

[0183] This embodiment provides a catalyst for the direct production of higher alcohols from syngas. The catalyst comprises a first metal component, a second metal component, a metal promoter, and a support. By mass percentage, the catalyst comprises 5 wt% of the first metal component, 0.1 wt% of the second metal component, 0.05 wt% of the metal promoter, and 94.85 wt% of the support. The first metal component is Ru; the second metal component is Cu; the metal promoter is Na; and the support is MgO.

[0184] This embodiment also provides a method for preparing a catalyst for the direct production of higher alcohols from syngas, the preparation method comprising the following steps:

[0185] S1. Weigh out ruthenium nitrite, copper nitrate, and sodium nitrate and add them to deionized water to prepare a solution D with a concentration of 2 mol / L, according to the mass percentage of the first metal component in the catalyst being 2 wt%, the mass percentage of the second metal component being 0.2 wt%, and the mass percentage of the metal auxiliaries being 0.03 wt%.

[0186] S2. The MgO support is ultrasonically dispersed in deionized water for 10 hours, with a mass ratio of MgO support to water of 1:70, to obtain solution E. The mass percentage of the MgO support is 94.85 wt% based on the mass percentage of the catalyst.

[0187] S3. Mix the solution D, the solution E and the hydrazine hydrate solution, and stir at high speed for 2 hours. The mass ratio of the solution D, the solution E and the hydrazine hydrate solution is 1:1:1, and the concentration of the hydrazine hydrate solution is 2 mol / L.

[0188] S4. Filter the solid and dry it in a tube furnace at 80°C for 10 hours under a N2 atmosphere.

[0189] This embodiment also provides the application of a catalyst in the direct synthesis of higher alcohols from syngas.

[0190] Before the direct synthesis of higher alcohols from syngas, the catalyst is first subjected to reduction pretreatment: the catalyst is compressed into tablets and sieved to 40-60 mesh. 1g of the 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand. After thorough mixing, the mixture is packed into a fixed bed for pretreatment reduction. The reduction atmosphere is hydrogen, and the reduction space velocity is 8000h⁻¹. -1 The reduction temperature was 350℃, the reduction pressure was atmospheric pressure, and the time was 5 hours. After the reduction was completed, the temperature was lowered to 180℃.

[0191] 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 4000 h⁻¹. -1 The reaction temperature was 200℃ and the reaction pressure was 6MPa. 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.

[0192] Example 13

[0193] This embodiment provides a catalyst for the direct production of higher alcohols from syngas. The catalyst comprises a first metal component, a second metal component, a metal promoter, and a support. By mass percentage, the catalyst comprises 7 wt% of the first metal component, 0.1 wt% of the second metal component, 0.05 wt% of the metal promoter, and 92.85 wt% of the support. The first metal component is Ru; the second metal component is Zn; the metal promoter is Na; and the support is Al₂O₃.

[0194] This embodiment also provides a method for preparing a catalyst for the direct production of higher alcohols from syngas, the preparation method comprising the following steps:

[0195] S1. Weigh out ruthenium nitrite, zinc nitrate, and sodium nitrate and add them to deionized water to prepare a solution D with a concentration of 2 mol / L, according to the mass percentage of the first metal component in the catalyst being 7 wt%, the mass percentage of the second metal component being 0.1 wt%, and the mass percentage of the metal auxiliaries being 0.05 wt%.

[0196] S2. The Al2O3 support is ultrasonically dispersed in deionized water for 10 hours. The mass ratio of Al2O3 support to water is 1:100 to obtain solution E. The mass percentage of the Al2O3 support is 92.85 wt% based on the mass percentage of the catalyst.

[0197] S3. Mix the solution D, the solution E and the sodium borohydride solution, and stir at high speed for 1 hour. The mass ratio of the solution D, the solution E and the sodium borohydride solution is 1:1:1, and the concentration of the sodium borohydride solution is 2 mol / L.

[0198] S4. Filter the solid and dry it in a tube furnace at 80°C for 4 hours under N2 atmosphere.

[0199] This embodiment also provides the application of a catalyst in the direct synthesis of higher alcohols from syngas.

[0200] Before the direct synthesis of higher alcohols from syngas, the catalyst is first subjected to reduction pretreatment: the catalyst is compressed into tablets and sieved to 40-60 mesh. 1g of the 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand. After thorough mixing, the mixture is packed into a fixed bed for pretreatment reduction. The reduction atmosphere is hydrogen, and the reduction space velocity is 8000h⁻¹. -1 The reduction temperature was 350℃, the reduction pressure was atmospheric pressure, and the time was 5 hours. After the reduction was completed, the temperature was lowered to 180℃.

[0201] 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 4000 h⁻¹. -1 The reaction temperature was 200℃ and the reaction pressure was 6MPa. 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.

[0202] Example 14

[0203] This embodiment provides a catalyst for the direct production of higher alcohols from syngas. The catalyst comprises a first metal component, a second metal component, a metal promoter, and a support. By mass percentage, the catalyst comprises 5 wt% of the first metal component, 0.1 wt% of the second metal component, 0.05 wt% of the metal promoter, and 94.85 wt% of the support. The first metal component is Ru; the second metal component is Cu; the metal promoter is Nb; and the support is ZnO.

[0204] This embodiment also provides a method for preparing a catalyst for the direct production of higher alcohols from syngas, the preparation method comprising the following steps:

[0205] S1. Weigh out ruthenium nitrite, copper nitrate, and niobium nitrate and add them to deionized water to prepare a solution D with a concentration of 2 mol / L, according to the mass percentage of the first metal component in the catalyst being 5 wt%, the mass percentage of the second metal component being 0.1 wt%, and the mass percentage of the metal auxiliaries being 0.05 wt%.

[0206] S2. The Zn support is ultrasonically dispersed in deionized water for 10 hours. The mass ratio of ZnO support to water is 1:100 to obtain solution E. The mass percentage of the Zn support is 94.85 wt% based on the mass percentage of the catalyst.

[0207] S3. Mix the solution D, the solution E and the hydrazine hydrate solution, and stir at high speed for 2 hours. The mass ratio of the solution D, the solution E and the hydrazine hydrate solution is 1:1:1, and the concentration of the hydrazine hydrate solution is 2 mol / L.

[0208] S4. Filter the solid and dry it in a tube furnace at 80°C for 5 hours in a He atmosphere.

[0209] This embodiment also provides the application of a catalyst in the direct synthesis of higher alcohols from syngas.

[0210] Before the direct synthesis of higher alcohols from syngas, the catalyst is first subjected to reduction pretreatment: the catalyst is compressed into tablets and sieved to 40-60 mesh. 1g of the 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand. After thorough mixing, the mixture is packed into a fixed bed for pretreatment reduction. The reduction atmosphere is hydrogen, and the reduction space velocity is 8000h⁻¹. -1 The reduction temperature was 350℃, the reduction pressure was atmospheric pressure, and the time was 5 hours. After the reduction was completed, the temperature was lowered to 180℃.

[0211] Then, the reaction was carried out using syngas. During the reaction, the molar ratio of H2 to CO in the syngas was 2, the reaction space velocity was 4000 h⁻¹, the reaction temperature was 200 °C, and the reaction pressure was 6 MPa. After the reaction was completed, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction were calculated accordingly. The specific results are shown in Table 1.

[0212] Example 15

[0213] This embodiment provides a catalyst for the direct production of higher alcohols from syngas. The catalyst comprises a first metal component, a second metal component, a metal promoter, and a support. By mass percentage, the catalyst comprises 2 wt% of the first metal component, 0.1 wt% of the second metal component, 0.05 wt% of the metal promoter, and 97.85 wt% of the support. The first metal component is Ru; the second metal component is Au; the metal promoter is Ca; and the support is ZnO.

[0214] This embodiment also provides a method for preparing a catalyst for the direct production of higher alcohols from syngas, the preparation method comprising the following steps:

[0215] S1. According to the mass percentage of the first metal component in the catalyst being 2 wt%, the mass percentage of the second metal component being 0.1 wt%, and the mass percentage of the metal auxiliary being 0.05 wt%, ruthenium acetylacetone, chloroauric acid and calcium nitrate are weighed and added to deionized water to prepare a solution D with a concentration of 2 mol / L.

[0216] S2. The Zn support is ultrasonically dispersed in deionized water for 10 hours. The mass ratio of ZnO support to water is 1:100 to obtain solution E. The mass percentage of the Zn support is 97.85 wt% based on the mass percentage of the catalyst.

[0217] S3. Mix the solution D, the solution E and the hydrazine hydrate solution, and stir at high speed for 2 hours. The mass ratio of the solution D, the solution E and the hydrazine hydrate solution is 1:1:1, and the concentration of the hydrazine hydrate solution is 2 mol / L.

[0218] S4. Filter the solid and dry it in a tube furnace at 80°C for 5 hours in a He atmosphere.

[0219] This embodiment also provides the application of a catalyst in the direct synthesis of higher alcohols from syngas.

[0220] Before the direct synthesis of higher alcohols from syngas, the catalyst is first subjected to reduction pretreatment: the catalyst is compressed into tablets and sieved to 40-60 mesh. 1g of the 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand. After thorough mixing, the mixture is packed into a fixed bed for pretreatment reduction. The reduction atmosphere is hydrogen, and the reduction space velocity is 8000h⁻¹. -1 The reduction temperature was 350℃, the reduction pressure was atmospheric pressure, and the time was 5 hours. After the reduction was completed, the temperature was lowered to 180℃.

[0221] 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 4000 h⁻¹. -1 The reaction temperature was 200℃ and the reaction pressure was 6MPa. 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.

[0222] Table 1 Catalytic performance data of catalysts in Examples 1-15

[0223]

[0224]

[0225] As shown in Table 1, a comparison of Examples 1 to 15 shows that when the second metal component is Pt or Au, the metal auxiliary is Na, and the support is SiO2, the catalyst exhibits the highest selectivity for synthesizing higher alcohols and lower selectivity for methane and carbon dioxide. Among these, Examples 6 and 11 to 15, which use metal oxides as supports, have excessively high electron content during catalysis due to the support also providing electrons, which inhibits the catalytic reaction and results in lower selectivity for higher alcohols compared to other catalysts.

[0226] In summary, the catalyst of this invention is a novel high-carbon-efficiency catalyst that can be prepared by two methods, featuring simple preparation, easy reproducibility, and good stability. The catalyst can be used for the direct production of higher alcohols from syngas, exhibiting excellent catalytic performance in this reaction. Operating at lower temperatures and pressures, and under conditions of high single-pass CO conversion, it achieves low selectivity for byproducts methane and carbon dioxide while maintaining high selectivity for alcohols and higher alcohols. The single-pass CO conversion can reach up to 55.4%, the alcohol selectivity up to 65.8%, and the higher alcohol selectivity up to 50.1%. Compared to existing technologies where the selectivity for byproducts methane and carbon dioxide in the direct production of higher alcohols from syngas is greater than 30%, the catalyst of this application achieves a selectivity for byproducts methane and carbon dioxide as low as below 2% in this reaction.

[0227] This invention effectively overcomes the various shortcomings of the prior art and has high industrial application value.

[0228] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. Use of a catalyst for the direct production of higher alcohols from synthesis gas, characterized in that, The catalyst comprises a first metal component, a second metal component and a carrier; the first metal component is Ru; the second metal component is selected from one or more of Pt, Au and Ag; The content of the first metal component is 0.1wt%-10wt% based on the mass percentage of the catalyst, the content of the second metal component is 0.1wt%-2.5wt%, and the content of the carrier is 72wt%-99.79wt%; The particle size of the catalyst is 5-10nm; the catalyst further comprises a metal additive, and the content of the metal additive is 0.01wt%-3wt% based on the mass percentage of the catalyst, and the metal additive is selected from one or more of Na, K, Cs, Ca, La, Ce, Nb or Pr.

2. Use according to claim 1, characterized in that, The carrier is selected from one or more of SiO2, TiO2, Al2O3, ZnO, MgO or BaO; And / or, the high-carbon alcohol is an alcohol with more than or equal to 6 carbon atoms.

3. The use according to any one of claims 1 to 2, characterized in that, The preparation method of the catalyst is selected from one of a first preparation method and a second preparation method; The first preparation method comprises the following steps: a1) The first metal component, the second metal component and the metal additive are weighed according to their proportions in the total mass of the catalyst, and the corresponding soluble salts of the first metal component, the second metal component and the metal additive are mixed and dissolved in a first solvent to obtain solution A; a2) Dissolve the competitive adsorbent in water to obtain solution B; a3) Mix solution A and solution B to obtain solution C, and weigh the carrier according to its proportion in the total mass of the catalyst, and then immerse solution C in the carrier; a4) Filter and dry and calcine; The second preparation method comprises the following steps: b1) The first metal component, the second metal component and the metal additive are weighed according to their proportions in the total mass of the catalyst, and the corresponding soluble salts of the first metal component, the second metal component and the metal additive are mixed and dissolved in a second solvent to obtain solution D; b2) Weigh the carrier according to its proportion in the total mass of the catalyst, and then ultrasonically disperse the carrier in water to obtain solution E; b3) Mix solution D, solution E and a reducing agent; b4) Filter and dry.

4. Use according to claim 3, characterized in that, In step a1), the soluble salt corresponding to the first metal component is selected from one or more of ruthenium acetylacetone, ruthenium nitrosyl nitrate and ruthenium chloride; And / or, in step a1), the first solvent is selected from one or more of water, ethanol, propanol and acetone; And / or, in step a1), the concentration of solution A is 1-3mol / L; And / or, in step a2), the competitive adsorbent is selected from one or more of hydrochloric acid, oxalic acid and citric acid; And / or, in step a2), the mass ratio of the competitive adsorbent to water is 1:100-1:50; And / or, in step a3), the mass ratio of solution A to solution B is 1:10-1:5; And / or, in step a3), the immersion time is 20-40 minutes; And / or, the step a3) further comprises a standing step after the impregnation, and the standing time is 10-20h; And / or, the step a4) further comprises a drying step, and the drying temperature is 70-130℃, and the drying time is 8h-24h; And / or, the step a4) further comprises a calcination step, and the calcination atmosphere is selected from one or more of N2, He and Ar; And / or, the step a4) further comprises a calcination step, and the calcination temperature is 400-500℃, and the calcination time is 2-10h.

5. Use according to claim 3, characterized in that, The step b1) further comprises a step of dissolving the first metal component in a second solvent to obtain a solution D, and the first metal component corresponds to a soluble salt selected from one or more of ruthenium acetylacetonate, ruthenium nitrosyl nitrate and ruthenium chloride; And / or, the step b1) further comprises a step of dissolving the first metal component in a second solvent to obtain a solution D, and the second solvent is selected from one or more of water, ethanol and acetone; And / or, the step b1) further comprises a step of dissolving the first metal component in a second solvent to obtain a solution D, and the mass ratio of the carrier to the second solvent is 1:50-100; And / or, the step b1) further comprises a step of dissolving the first metal component in a second solvent to obtain a solution D, and the concentration of the solution D is 1-3mol / L; And / or, the step b2) further comprises a step of ultrasonic treatment for 5-10h; And / or, the step b3) further comprises a step of adding a reducing agent to the solution D to obtain a solution E, and the reducing agent is selected from one or more of hydrazine hydrate solution, sodium citrate solution and sodium borohydride solution, and the concentration of the reducing agent is 1-3mol / L; And / or, the step b3) further comprises a step of adding a reducing agent to the solution D to obtain a solution E, and the mass ratio of the solution D, the solution E and the reducing agent is 1:(0.5-2):(0.5-2); And / or, the step b4) further comprises a drying step, and the drying temperature is 100-120℃, and the drying time is 5h-10h; And / or, the step b4) further comprises a drying step, and the drying atmosphere is selected from one or more of N2, He and Ar.

6. Use according to claim 1, characterized in that, Before the catalyst is used for directly preparing high-carbon alcohols from synthesis gas, the catalyst is subjected to a reduction treatment.

7. Use according to claim 1, characterized in that, Before the catalyst is used for directly preparing high-carbon alcohols from synthesis gas, the catalyst is subjected to a reduction treatment.

8. Use according to claim 6, characterized in that, The gas used in the reduction treatment is selected from one or more of hydrogen and CO; And / or, the temperature of the reduction treatment is 300-500℃; And / or, the time of the reduction treatment is 3-10h; And / or, the space velocity of the reduction treatment is 1000 to 10000 h -1 .

9. The use according to claim 1, characterized in that, In the reaction of directly preparing high-carbon alcohols from synthesis gas, the molar ratio of H2 to CO in the synthesis gas is 0.5-5; And / or, in the reaction of directly preparing high-carbon alcohols from synthesis gas, the reaction temperature is 200-300℃; and / or, in the reaction of the synthesis gas to higher alcohols, the reaction space velocity is 3000 to 6000 h -1 ; And / or, in the reaction of directly preparing high-carbon alcohols from synthesis gas, the reaction pressure is 3-10MPa.

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