Catalyst for directly preparing high-carbon alcohol from synthesis gas

Abstract

The invention relates to the technical field of catalysts, in particular to a catalyst for directly preparing high-carbon alcohol from synthesis gas as well as a preparation method and application of the catalyst. The catalyst is prepared from a first metal component, a second metal component, a metal additive and a carrier, the first metal component is Ru; the catalyst is prepared from the following components in percentage by mass: 0.1 wt% to 10 wt% of the first metal component, 0.1 wt% to 5 wt% of the second metal component, 0.01 wt% to 3 wt% of the metal additive and 72 wt% to 99.79 wt% of the carrier. The first metal component Ru in the catalyst enables the catalyst to have extremely low water gas reaction activity, the CO2 selectivity can be kept within 3%, the second metal component can be used for CO non-dissociation adsorption, the catalyst has the performance of directly preparing high-carbon alcohol from synthesis gas, and the first metal component and the second metal component have a synergistic effect. The content of precious metal Ru can be effectively reduced, the generation of high alcohols can be greatly promoted, and the method has a wide market application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of catalysts, and in particular to a catalyst for directly preparing higher carbon alcohols from synthesis gas. Background Art

[0002] With the rapid development of society and economy, my country's demand for energy is increasing, among which fossil resources still occupy a dominant position. In 2020, my country's dependence on foreign crude oil has 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. In my country, coal and shale gas and coalbed methane with methane as the main component are relatively abundant. The development of clean, efficient and low-carbon utilization of coal and natural gas conversion technology can effectively solve the problem of energy shortage and improve the domestic environment.

[0003] Therefore, coal, natural gas, shale gas and other resources are gasified or reformed to produce synthesis gas, that is, a mixture of CO and H2, and then a series of catalytic reactions can effectively transform carbon-containing resources into clean fuels and high-value-added chemicals, which is in line with my country's energy structure characteristics of "rich in coal, poor in oil and lack of gas". A series of high-value-added chemicals can be prepared from synthesis gas, such as alcohols, aldehydes, gasoline and olefins, etc. Among them, high-carbon alcohols (C 6+ Alcohols are an important class of chemical raw materials with broad application prospects. At present, the preparation of high-carbon alcohols is mainly obtained through processes such as petroleum cracking and olefin carbonylation. Undoubtedly, the direct preparation of high-carbon alcohols from synthesis gas has the advantages of short process and low energy consumption, and can avoid dependence on petroleum resources. However, the content of high-carbon alcohols in the products obtained from the Fischer-Tropsch reaction of synthesis gas is generally low, and the selectivity of by-products CH4 and CO2 is both >30%, the main reason for which is the lack of suitable catalysts. Therefore, it is very important to develop a catalyst for the direct preparation of high-carbon alcohols from synthesis gas with high carbon efficiency and high oxygen efficiency. Summary of the invention

[0004] In view of the above-mentioned shortcomings of the prior art, the purpose of the present invention is to provide a catalyst for directly converting synthesis gas to high-carbon alcohols, and its preparation method and use. 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 provide non-dissociative adsorption of CO, so that the catalyst has the performance of directly converting synthesis gas to high-carbon alcohols, and the synergistic effect between the first metal component and the second metal component. It can not only effectively reduce the content of the precious metal Ru, but also greatly promote the generation of high-carbon alcohols.

[0005] To achieve the above-mentioned object and other related objects, the first aspect of the present invention provides a catalyst for directly preparing higher alcohols from synthesis gas.

[0006] 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, Ag, Cu or Zn; in terms of the mass percentage of the catalyst, the content of the first metal component is 0.1wt% to 10wt%, the content of the second metal component is 0.1wt% to 5wt%, and the content of the carrier is 72wt% to 99.79wt%; the particle size of the catalyst is 5 to 10nm. In a preferred specific embodiment, the second metal component is selected from one of Pt and Au.

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

[0008] For example, the content of the second metal component may be 0.1-0.5wt%, 0.5-1.0wt%, 1.0-1.5wt%, 1.5-2.0wt%, 2.0-2.5wt%, 2.5-3.0wt%, 3.0-3.5wt%, 3.5-4.0wt%, 4.0-4.5wt%, or 4.5-5.0wt%.

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

[0010] Preferably, the catalyst further comprises a metal promoter, and the content of the metal promoter is 0.01wt% to 3wt% in terms of the mass percentage of the catalyst, and 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 to 0.02wt%, 0.02 to 0.03wt%, 0.03 to 0.04wt%, 0.04 to 0.05wt%, 0.05 to 0.5wt%, 0.5 to 1.0wt%, 1.0 to 1.5wt%, 1.5 to 2.0wt%, 2.0 to 2.5wt%, 2.5 to 3.0wt%. The metal promoter provides electrons in the reaction of the catalyst to make alcohol, promoting catalytic activity. In theory, any metal that can provide electrons can be used as a metal promoter. In a specific embodiment, the metal promoter selects Na.

[0011] Preferably, the carrier is selected from one or more of SiO2, TiO2, Al2O3, ZnO, MgO or BaO. In a preferred embodiment, due to the large specific surface area of ​​SiO2, the carrier is selected as SiO2.

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

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

[0014] a1) weighing corresponding soluble salts according to the proportion of the first metal component, the second metal component and the metal promoter in the total mass of the catalyst, mixing and dissolving the soluble salts corresponding to the first metal component, the second metal component and the metal promoter in a first solvent to obtain a solution A;

[0015] a2) dissolving the competitive adsorbent in water to obtain solution B;

[0016] a3) mixing the solution A and the solution B to obtain a solution C, weighing a carrier according to the proportion of the carrier in the total mass of the catalyst, and impregnating the solution C on the carrier;

[0017] a4) Filter, dry and calcine.

[0018] Preferably, in step a1), the soluble salt corresponding to the first metal component is selected from one or more of ruthenium acetylacetonate, ruthenium nitrosyl nitrate 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 may be 1 mol / L, 2 mol / L, or 3 mol / L.

[0021] Preferably, in step a2), the competitive 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 competitive adsorbent to water is 1:50 to 1:100. For example, the volume ratio of the competitive 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 may be 1:10, 1:9, 1:8, 1:7, 1:6, or 1:5.

[0024] Preferably, in step a3), the immersion time is 20 to 40 minutes, such as 20 minutes, 25 minutes, or 30 minutes.

[0025] Preferably, in the step a3), after the immersion is completed, a standing step is further included, and the standing time is 10 to 20 hours, for example, the standing 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 8h-24h. For example, the drying temperature may be 70-80°C, 80-90°C, 90-100°C, 100-110°C, 110-120°C, 120-130°C. For example, the drying time may be 8-10h, 10-12h, 12-14h, 14-15h, 15-17h, 17-19h, 19-21h, 21-24h.

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

[0028] Preferably, in the step a4), the calcination temperature is 400-500°C, and the calcination time is 2-10h. For example, the calcination temperature may 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, 490-500°C. For example, the calcination time may be 2-3h, 3-4h, 4-5h, 5-6h, 6-7h, 7-8h, 8-9h, 9-10h.

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

[0030] b1) weighing corresponding soluble salts according to the proportion of the first metal component, the second metal component and the metal promoter in the total mass of the catalyst, mixing and dissolving the soluble salts corresponding to the first metal component, the second metal component and the metal promoter in a second solvent to obtain a solution D;

[0031] b2) weighing the carrier according to the proportion of the carrier in the total mass of the catalyst, and dispersing the carrier in water by ultrasonication to obtain a solution E;

[0032] b3) mixing the solution D, the solution E and a 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 nitrosyl nitrate 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 may 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, such as 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 the solution D is 1-3 mol / L. For example, the concentration of the solution D may 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, such as 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 to 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 the solution D, the solution E and the reducing agent is 1:(0.5-2):(0.5-2). For example, the mass ratio of the solution E and the 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, 1:2:2.

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

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

[0044] The third aspect of the present invention discloses a use of the catalyst as described above in the direct preparation of higher carbon alcohols from synthesis gas.

[0045] Preferably, before using the catalyst for directly preparing higher alcohols from synthesis gas, the catalyst is first subjected to a reduction treatment.

[0046] Preferably, before the catalyst is used for directly preparing higher alcohols from synthesis gas, the catalyst is first tableted and sieved to 40-60 mesh.

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

[0048] More preferably, the temperature of the reduction treatment is 300-500°C. For example, the temperature of the reduction treatment may be 300-400°C, or 400-500°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 The space velocity of the reduction treatment can be 1000h -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 preparing higher alcohols from synthesis gas, the molar ratio of H2 to CO in the synthesis gas is 0.5 to 5. For example, the molar ratio of H2 to CO in the synthesis gas 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 preparing higher alcohols from synthesis gas, the reaction temperature is 200-300°C. For example, the reaction temperature may be 200-250°C, or 250-300°C.

[0053] More preferably, in the reaction of directly preparing higher alcohols from synthesis gas, the reaction space velocity is 3000 to 6000 h -1 As described, the reaction space velocity can be 3000h -1 , 4000h -1 , 5000h -1 、6000h -1 .

[0054] More preferably, in the reaction of directly preparing higher alcohols from synthesis gas, the reaction pressure is 3-10 MPa. For example, the reaction pressure may 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%. The second metal component can provide non-dissociative adsorption of CO, so that high-carbon alcohols can be directly prepared from synthesis gas.

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

[0058] (3) The catalyst of the present invention has relatively excellent catalytic performance, high selectivity for high-carbon alcohols in product distribution, extremely low selectivity for by-products, high yield of high-carbon 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 precious metal Ru, but also greatly promote the formation of higher carbon alcohols. DETAILED DESCRIPTION

[0060] The following is a description of the implementation of the present invention by means of specific embodiments. Those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification.

[0061] Before further describing the 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 terms used in the examples of the present invention are intended to describe specific embodiments, rather than to limit the scope of protection of the present invention. The test methods in the following examples without specifying specific conditions are generally carried out under conventional conditions or under conditions recommended by the manufacturers.

[0062] When the embodiments give numerical ranges, it should be understood that, unless otherwise specified in the present invention, both endpoints of each numerical range and any numerical value between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as those generally understood by those skilled in the art. In addition to the specific methods, equipment, and materials used in the embodiments, according to the grasp of the prior art by those skilled in the art and the record of the present invention, any methods, equipment, and materials of the prior art similar or equivalent to the methods, equipment, and materials described in the embodiments of the present invention can also be used to realize the present invention.

[0063] The reaction results of the catalyst described in the examples of the present application are 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, and the calculation formula is as follows:

[0066]

[0067] Among them, CO inlet and CO outlet represent the number of moles of CO entering / leaving the reaction system respectively.

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

[0069]

[0070] Among them, CO 2outlet Represents the number of moles of CO2 flowing out of the reaction tube.

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

[0072] Example 1

[0073] This embodiment provides a catalyst for direct production of high-carbon alcohols from synthesis gas, the catalyst comprising a first metal component, a second metal component, a metal promoter and a carrier. In terms of mass percentage of the catalyst, the catalyst comprises 3wt% of the first metal component, 0.5wt% of the second metal component, 0.03wt% of the metal promoter and 96.47wt% of the carrier. The first metal component is Ru; the second metal component is Pt, the metal promoter is Na and the carrier is SiO2.

[0074] This embodiment also provides a method for preparing a catalyst for directly preparing higher alcohols from synthesis gas, and the preparation method comprises 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 additive being 0.03wt%, ruthenium nitrosyl nitrate, chloroplatinic acid and sodium nitrate are weighed and added into deionized water to prepare a solution A with a concentration of 2 mol / L;

[0076] S2, prepare solution B by mixing hydrochloric acid and water in a mass ratio of 1:100;

[0077] S3, mixing the solution A and the solution B at a mass ratio of 1:10 to obtain a solution C, and impregnating the solution C on a SiO2 carrier for 30 minutes, wherein the mass percentage of the SiO2 carrier is 96.47wt% based on the mass percentage of the catalyst, and standing at room temperature for 15h after the impregnation;

[0078] S4, vacuum drying at 80°C for 10 hours. The dried solid was calcined in a tube furnace at 400°C in a N2 atmosphere for 3 hours to obtain the catalyst.

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

[0080] Before the direct reaction of synthesizing high-carbon alcohols from synthesis gas, the catalyst is first subjected to reduction pretreatment: the catalyst is pressed into tablets and sieved to 40-60 mesh, 1g of 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand, and the mixture is evenly mixed and loaded into a fixed bed for pretreatment reduction, the reducing atmosphere is hydrogen, and the reduction space velocity is 8000h -1 The reduction temperature is 350°C, the reduction pressure is normal pressure, the time is 5h, and the temperature is lowered to 180°C after the reduction is completed.

[0081] Then switch to synthesis gas for reaction. During the reaction, the molar ratio between H2 and CO in the synthesis gas is 2, and the reaction space velocity is 4000h -1 , the reaction temperature was 200°C, and the reaction pressure was 6 MPa; after the reaction, gas chromatography (Agilent 8860) was used to analyze the types and contents of various components contained in the product, 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 direct production of high-carbon alcohols from synthesis gas, the catalyst comprising a first metal component, a second metal component, a metal promoter and a carrier. In terms of mass percentage of the catalyst, the catalyst comprises 2wt% of the first metal component, 0.5wt% of the second metal component, 0.03wt% of the metal promoter and 97.47wt% of the carrier. The first metal component is Ru; the second metal component is Pt, the metal promoter is K and the carrier is SiO2.

[0084] This embodiment also provides a method for preparing a catalyst for directly preparing higher alcohols from synthesis gas, and the preparation method comprises the following steps:

[0085] 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 0.5wt%, and the mass percentage of the metal additive being 0.03wt%, ruthenium chloride, chloroplatinic acid and potassium nitrate are weighed and added into 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 in a mass ratio of 1:100;

[0087] S3, mixing the solution A and the solution B at a mass ratio of 1:10 to obtain a solution C, and impregnating the solution C on a SiO2 carrier for 30 minutes, wherein the mass percentage of the SiO2 carrier is 97.47wt% based on the mass percentage of the catalyst, and standing at room temperature for 15h after the impregnation;

[0088] S4, vacuum drying at 80°C for 10 hours. The dried solid was calcined in a tube furnace at 400°C in a N2 atmosphere for 3 hours to obtain the catalyst.

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

[0090] Before the direct reaction of synthesizing high-carbon alcohols from synthesis gas, the catalyst is first subjected to reduction pretreatment: the catalyst is pressed into tablets and sieved to 40-60 mesh, 1g of 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand, and the mixture is evenly mixed and loaded into a fixed bed for pretreatment reduction, the reducing atmosphere is hydrogen, and the reduction space velocity is 8000h -1 The reduction temperature is 350°C, the reduction pressure is normal pressure, the time is 5h, and the temperature is lowered to 180°C after the reduction is completed.

[0091] Then the reaction was switched to synthesis gas. During the reaction, the molar ratio of H2 to CO in the synthesis gas was 2, the reaction space velocity was 4000h-1, the reaction temperature was 200°C, and the reaction pressure was 6MPa. After the reaction, a gas chromatograph (Agilent 8860) was used to analyze the types and contents of various components contained in the product, 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 direct production of high-carbon alcohols from synthesis gas, the catalyst comprising a first metal component, a second metal component, a metal promoter and a carrier. In terms of mass percentage of the catalyst, the catalyst comprises 3wt% of the first metal component, 0.5wt% of the second metal component, 0.03wt% of the metal promoter and 96.47wt% of the carrier. The first metal component is Ru; the second metal component is Au, the metal promoter is Na and the carrier is SiO2.

[0094] This embodiment also provides a method for preparing a catalyst for directly preparing higher alcohols from synthesis gas, and the preparation method comprises 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 additive being 0.03wt%, ruthenium nitrosyl nitrate, auClO and sodium nitrate are weighed and added into deionized water to prepare a solution A with a concentration of 2mol / L;

[0096] S2, prepare solution B by mixing oxalic acid and water in a mass ratio of 1:100;

[0097] S3, mixing the solution A and the solution B at a mass ratio of 1:10 to obtain a solution C, and impregnating the solution C on a SiO2 carrier for 30 minutes, wherein the mass percentage of the SiO2 carrier is 96.47wt% based on the mass percentage of the catalyst, and standing at room temperature for 15h after the impregnation;

[0098] S4, vacuum drying at 100° C. for 15 h. The dried solid was calcined in a tube furnace at 450° C. in a N 2 atmosphere for 5 h to obtain the catalyst.

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

[0100] Before the direct reaction of synthesizing high-carbon alcohols from synthesis gas, the catalyst is first subjected to reduction pretreatment: the catalyst is pressed into tablets and sieved to 40-60 mesh, 1g of 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand, and the mixture is evenly mixed and loaded into a fixed bed for pretreatment reduction, the reducing atmosphere is hydrogen, and the reduction space velocity is 8000h -1 The reduction temperature is 350°C, the reduction pressure is normal pressure, the time is 5h, and the temperature is lowered to 180°C after the reduction is completed.

[0101] Then switch to synthesis gas for reaction. During the reaction, the molar ratio between H2 and CO in the synthesis gas is 2, and the reaction space velocity is 4000h -1 , the reaction temperature was 200°C, and the reaction pressure was 6 MPa; after the reaction, gas chromatography (Agilent 8860) was used to analyze the types and contents of various components contained in the product, 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 direct production of high-carbon alcohols from synthesis gas, the catalyst comprising a first metal component, a second metal component, a metal promoter and a carrier. In terms of mass percentage of the catalyst, the catalyst comprises 3wt% of the first metal component, 0.1wt% of the second metal component, 0.05wt% of the metal promoter and 96.85wt% of the carrier. The first metal component is Ru; the second metal component is Cu, the metal promoter is Na and the carrier is SiO2.

[0104] This embodiment also provides a method for preparing a catalyst for directly preparing higher alcohols from synthesis gas, and the preparation method comprises 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 additive being 0.05wt%, ruthenium nitrosyl nitrate, copper nitrate, and praseodymium nitrate are weighed and added into deionized water to prepare a solution A with a concentration of 2 mol / L;

[0106] S2, prepare solution B by mixing citric acid and water in a mass ratio of 1:100;

[0107] S3, mixing the solution A and the solution B at a mass ratio of 1:10 to obtain a solution C, and impregnating the solution C on a SiO2 carrier for 30 minutes, wherein the mass percentage of the SiO2 carrier is 96.85wt% based on the mass percentage of the catalyst, and after the impregnation, standing at room temperature for 15h;

[0108] S4, vacuum drying at 80°C for 10 hours. The dried solid was calcined in a 500°C tube furnace in a He atmosphere for 3 hours to obtain the catalyst.

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

[0110] Before the direct reaction of synthesizing high-carbon alcohols from synthesis gas, the catalyst is first subjected to reduction pretreatment: the catalyst is pressed into tablets and sieved to 40-60 mesh, 1g of 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand, and the mixture is evenly mixed and loaded into a fixed bed for pretreatment reduction, the reducing atmosphere is hydrogen, and the reduction space velocity is 8000h -1 The reduction temperature is 350°C, the reduction pressure is normal pressure, the time is 5h, and the temperature is lowered to 180°C after the reduction is completed.

[0111] Then switch to synthesis gas for reaction. During the reaction, the molar ratio between H2 and CO in the synthesis gas is 2, and the reaction space velocity is 4000h -1, the reaction temperature was 200°C, and the reaction pressure was 6 MPa; after the reaction, gas chromatography (Agilent 8860) was used to analyze the types and contents of various components contained in the product, 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 direct production of high-carbon alcohols from synthesis gas, the catalyst comprising a first metal component, a second metal component, a metal promoter and a carrier. In terms of the mass percentage of the catalyst, the catalyst comprises 1.5wt% of the first metal component, 0.3wt% of the second metal component, 0.04wt% of the metal promoter and 98.16wt% of the carrier. The first metal component is Ru; the second metal component is Zn, the metal promoter is Cs and the carrier is TiO2.

[0114] This embodiment also provides a method for preparing a catalyst for directly preparing higher alcohols from synthesis gas, and the preparation method comprises the following steps:

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

[0116] S2, prepare solution B by mixing hydrochloric acid and water in a mass ratio of 1:100;

[0117] S3, mixing the solution A and the solution B at a mass ratio of 1:10 to obtain a solution C, and impregnating the solution C on the TiO2 carrier for 30 minutes, wherein the mass percentage of the TiO2 carrier is 98.16wt% based on the mass percentage of the catalyst, and standing at room temperature for 20h after the impregnation;

[0118] S4, vacuum drying at 120° C. for 10 h. The dried solid was calcined in a tube furnace at 400° C. in an Ar atmosphere for 7 h to obtain the catalyst.

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

[0120] Before the direct reaction of synthesizing high-carbon alcohols from synthesis gas, the catalyst is first subjected to reduction pretreatment: the catalyst is pressed into tablets and sieved to 40-60 mesh, 1g of 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand, and the mixture is evenly mixed and loaded into a fixed bed for pretreatment reduction, the reducing atmosphere is hydrogen, and the reduction space velocity is 8000h -1The reduction temperature is 350°C, the reduction pressure is normal pressure, the time is 5h, and the temperature is lowered to 180°C after the reduction is completed.

[0121] Then switch to synthesis gas for reaction. During the reaction, the molar ratio between H2 and CO in the synthesis gas is 2, and the reaction space velocity is 4000h -1 , the reaction temperature was 200°C, and the reaction pressure was 6 MPa; after the reaction, gas chromatography (Agilent 8860) was used to analyze the types and contents of various components contained in the product, 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 direct production of high-carbon alcohols from synthesis gas, the catalyst comprising a first metal component, a second metal component, a metal promoter and a carrier. In terms of mass percentage of the catalyst, the catalyst comprises 5wt% of the first metal component, 0.5wt% of the second metal component, 0.03wt% of the metal promoter and 94.47wt% of the carrier. The first metal component is Ru; the second metal component is Pt, the metal promoter is Na and the carrier is MgO.

[0124] This embodiment also provides a method for preparing a catalyst for directly preparing higher alcohols from synthesis gas, and the preparation method comprises the following steps:

[0125] S1. According to the mass percentage of the first metal component in the catalyst being 5wt%, the mass percentage of the second metal component being 0.5wt%, and the mass percentage of the metal additive being 0.03wt%, ruthenium nitrosyl nitrate, 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 in a mass ratio of 1:100;

[0127] S3, mixing the solution A and the solution B at a mass ratio of 1:10 to obtain a solution C, and impregnating the solution C on the MgO carrier for 30 minutes, wherein the mass percentage of the MgO carrier is 94.47wt% based on the mass percentage of the catalyst, and after the impregnation, standing at room temperature for 15h;

[0128] S4, vacuum drying at 80°C for 10 hours. The dried solid was calcined in a tube furnace at 450°C in a N2 atmosphere for 3 hours to obtain the catalyst.

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

[0130] Before the direct reaction of synthesizing high-carbon alcohols from synthesis gas, the catalyst is first subjected to reduction pretreatment: the catalyst is pressed into tablets and sieved to 40-60 mesh, 1g of 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand, and the mixture is evenly mixed and loaded into a fixed bed for pretreatment reduction, the reducing atmosphere is hydrogen, and the reduction space velocity is 8000h -1 The reduction temperature is 350°C, the reduction pressure is normal pressure, the time is 5h, and the temperature is lowered to 180°C after the reduction is completed.

[0131] Then switch to synthesis gas for reaction. During the reaction, the molar ratio between H2 and CO in the synthesis gas is 2, and the reaction space velocity is 4000h -1 , the reaction temperature was 200°C, and the reaction pressure was 6 MPa; after the reaction, gas chromatography (Agilent 8860) was used to analyze the types and contents of various components contained in the product, 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 direct production of high-carbon alcohols from synthesis gas, the catalyst comprising a first metal component, a second metal component, a metal promoter and a carrier. In terms of the mass percentage of the catalyst, the catalyst comprises 5wt% of the first metal component, 0.5wt% of the second metal component, 0.05wt% of the metal promoter and 94.45wt% of the carrier. The first metal component is Ru; the second metal component is Ag, the metal promoter is La and the carrier is BaO.

[0134] This embodiment also provides a method for preparing a catalyst for directly preparing higher alcohols from synthesis gas, and the preparation method comprises the following steps:

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

[0136] S2, prepare solution B by mixing hydrochloric acid and water in a mass ratio of 1:100;

[0137] S3, mixing the solution A and the solution B at a mass ratio of 1:10 to obtain a solution C, and impregnating the solution C on a BaO carrier for 30 minutes, wherein the mass percentage of the BaO carrier is 94.45wt% based on the mass percentage of the catalyst, and after the impregnation, standing at room temperature for 15h;

[0138] S4, vacuum drying at 80°C for 10 hours. The dried solid was calcined in a tube furnace at 450°C in a N2 atmosphere for 3 hours to obtain the catalyst.

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

[0140] Before the direct reaction of synthesizing high-carbon alcohols from synthesis gas, the catalyst is first subjected to reduction pretreatment: the catalyst is pressed into tablets and sieved to 40-60 mesh, 1g of 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand, and the mixture is evenly mixed and loaded into a fixed bed for pretreatment reduction, the reducing atmosphere is hydrogen, and the reduction space velocity is 8000h -1 The reduction temperature is 350°C, the reduction pressure is normal pressure, the time is 5h, and the temperature is lowered to 180°C after the reduction is completed.

[0141] Then switch to synthesis gas for reaction. During the reaction, the molar ratio between H2 and CO in the synthesis gas is 2, and the reaction space velocity is 4000h -1 , the reaction temperature was 200°C, and the reaction pressure was 6 MPa; after the reaction, gas chromatography (Agilent 8860) was used to analyze the types and contents of various components contained in the product, 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 direct production of high-carbon alcohols from synthesis gas, the catalyst comprising a first metal component, a second metal component, a metal promoter and a carrier. In terms of the mass percentage of the catalyst, the catalyst comprises 2wt% of the first metal component, 0.2wt% of the second metal component, 0.03wt% of the metal promoter and 97.77wt% of the carrier. The first metal component is Ru; the second metal component is Au, the metal promoter is Ce and the carrier is BaO.

[0144] This embodiment also provides a method for preparing a catalyst for directly preparing higher alcohols from synthesis gas, and the preparation method comprises the following steps:

[0145] S1. According to the mass percentage of the first metal component in the catalyst being 5wt%, the mass percentage of the second metal component being 0.5wt%, and the mass percentage of the metal additive being 0.05wt%, ruthenium chloride, auClO 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 in a mass ratio of 1:50;

[0147] S3, mixing the solution A and the solution B at a mass ratio of 1:10 to obtain a solution C, and impregnating the solution C on a BaO carrier for 30 minutes, wherein the mass percentage of the BaO carrier is 97.77wt% based on the mass percentage of the catalyst, and after the impregnation, standing at room temperature for 15h;

[0148] S4, vacuum drying at 80°C for 10 hours. The dried solid was calcined in a tube furnace at 500°C in a N2 atmosphere for 3 hours to obtain the catalyst.

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

[0150] Before the direct reaction of synthesizing high-carbon alcohols from synthesis gas, the catalyst is first subjected to reduction pretreatment: the catalyst is pressed into tablets and sieved to 40-60 mesh, 1g of 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand, and the mixture is evenly mixed and loaded into a fixed bed for pretreatment reduction, the reducing atmosphere is hydrogen, and the reduction space velocity is 8000h -1 The reduction temperature is 350°C, the reduction pressure is normal pressure, the time is 5h, and the temperature is lowered to 180°C after the reduction is completed.

[0151] Then switch to synthesis gas for reaction. During the reaction, the molar ratio between H2 and CO in the synthesis gas is 2, and the reaction space velocity is 4000h -1 , the reaction temperature was 200°C, and the reaction pressure was 6 MPa; after the reaction, gas chromatography (Agilent 8860) was used to analyze the types and contents of various components contained in the product, 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 direct production of high-carbon alcohols from synthesis gas, the catalyst comprising a first metal component, a second metal component, a metal promoter and a carrier. In terms of mass percentage of the catalyst, the catalyst comprises 2wt% of the first metal component, 0.2wt% of the second metal component, 0.03wt% of the metal promoter and 97.77wt% of the carrier. The first metal component is Ru; the second metal component is Au, the metal promoter is K and the carrier is SiO2.

[0154] This embodiment also provides a method for preparing a catalyst for directly preparing higher alcohols from synthesis gas, and the preparation method comprises 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 additive being 0.03wt%, ruthenium chloride, gold chloride and potassium nitrate are weighed and added into deionized water to prepare a solution D with a concentration of 2 mol / L;

[0156] S2, dispersing the SiO2 carrier in deionized water by ultrasonic for 6 hours, the mass ratio of the SiO2 carrier to water being 1:50, to obtain a solution E, in which the mass percentage of the SiO2 carrier is 97.77wt% based on the mass percentage of the catalyst;

[0157] S3, mixing the solution D, the solution E and the hydrazine hydrate solution, stirring at high speed for 1h, 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 2mol / L;

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

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

[0160] Before the direct reaction of synthesizing high-carbon alcohols from synthesis gas, the catalyst is first subjected to reduction pretreatment: the catalyst is pressed into tablets and sieved to 40-60 mesh, 1g of 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand, and the mixture is evenly mixed and loaded into a fixed bed for pretreatment reduction, the reducing atmosphere is hydrogen, and the reduction space velocity is 8000h -1 The reduction temperature is 350°C, the reduction pressure is normal pressure, the time is 5h, and the temperature is lowered to 180°C after the reduction is completed.

[0161] Then switch to synthesis gas for reaction. During the reaction, the molar ratio between H2 and CO in the synthesis gas is 2, and the reaction space velocity is 4000h -1 , the reaction temperature was 200°C, and the reaction pressure was 6 MPa; after the reaction, gas chromatography (Agilent 8860) was used to analyze the types and contents of various components contained in the product, 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 direct production of high-carbon alcohols from synthesis gas, the catalyst comprising a first metal component, a second metal component, a metal promoter and a carrier. In terms of the mass percentage of the catalyst, the catalyst comprises 3wt% of the first metal component, 0.5wt% of the second metal component, 0.05wt% of the metal promoter and 96.45wt% of the carrier. The first metal component is Ru; the second metal component is Au, the metal promoter is Cs and the carrier is SiO2.

[0164] This embodiment also provides a method for preparing a catalyst for directly preparing higher alcohols from synthesis gas, and the preparation method comprises 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 additive being 0.05wt%, ruthenium chloride, gold chloride and strontium nitrate are weighed and added into deionized water to prepare a solution D with a concentration of 2 mol / L;

[0166] S2, dispersing the SiO2 carrier in deionized water by ultrasonic for 8 h, the mass ratio of the SiO2 carrier to water being 1:100, to obtain a solution E, in which the mass percentage of the SiO2 carrier is 96.45 wt% based on the mass percentage of the catalyst;

[0167] S3, mixing the solution D, the solution E and the sodium citrate solution, and stirring at high speed for 1.5h, 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 2mol / L;

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

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

[0170] Before the direct reaction of synthesizing high-carbon alcohols from synthesis gas, the catalyst is first subjected to reduction pretreatment: the catalyst is pressed into tablets and sieved to 40-60 mesh, 1g of 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand, and the mixture is evenly mixed and loaded into a fixed bed for pretreatment reduction, the reducing atmosphere is hydrogen, and the reduction space velocity is 8000h -1 The reduction temperature is 350°C, the reduction pressure is normal pressure, the time is 5h, and the temperature is lowered to 180°C after the reduction is completed.

[0171] Then switch to synthesis gas for reaction. During the reaction, the molar ratio between H2 and CO in the synthesis gas is 2, and the reaction space velocity is 4000h -1, the reaction temperature was 200°C, and the reaction pressure was 6 MPa; after the reaction, gas chromatography (Agilent 8860) was used to analyze the types and contents of various components contained in the product, and the conversion rate and selectivity of the reaction were calculated accordingly. The specific results are shown in Table 1.

[0172] Embodiment 11

[0173] This embodiment provides a catalyst for direct production of high-carbon alcohols from synthesis gas, the catalyst comprising a first metal component, a second metal component, a metal promoter and a carrier. In terms of mass percentage of the catalyst, the catalyst comprises 5wt% of the first metal component, 0.5wt% of the second metal component, 0.05wt% of the metal promoter and 94.45wt% of the carrier. The first metal component is Ru; the second metal component is Pt, the metal promoter is La and the carrier is MgO.

[0174] This embodiment also provides a method for preparing a catalyst for directly preparing higher alcohols from synthesis gas, and the preparation method comprises the following steps:

[0175] S1. According to the mass percentage of the first metal component in the catalyst being 5wt%, the mass percentage of the second metal component being 0.5wt%, and the mass percentage of the metal additive being 0.05wt%, ruthenium nitrosyl nitrate, chloroplatinic acid and lanthanum nitrate are weighed and added into deionized water to prepare a solution D with a concentration of 2 mol / L;

[0176] S2, dispersing the MgO carrier in deionized water by ultrasonic for 10 hours, wherein the mass ratio of the MgO carrier to water is 1:70, to obtain a solution E, wherein the mass percentage of the MgO carrier is 94.45 wt % based on the mass percentage of the catalyst;

[0177] S3, the solution D, the solution E and the hydrazine hydrate solution are mixed and stirred at high speed for 2h, the mass ratio of the solution D, the solution E and the hydrazine hydrate is 1:1:1, and the concentration of the hydrazine hydrate solution is 2mol / L;

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

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

[0180] Before the direct reaction of synthesizing high-carbon alcohols from synthesis gas, the catalyst is first subjected to reduction pretreatment: the catalyst is pressed into tablets and sieved to 40-60 mesh, 1g of 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand, and the mixture is evenly mixed and loaded into a fixed bed for pretreatment reduction, the reducing atmosphere is hydrogen, and the reduction space velocity is 8000h -1The reduction temperature is 350°C, the reduction pressure is normal pressure, the time is 5h, and the temperature is lowered to 180°C after the reduction is completed.

[0181] Then switch to synthesis gas for reaction. During the reaction, the molar ratio between H2 and CO in the synthesis gas is 2, and the reaction space velocity is 4000h -1 , the reaction temperature was 200°C, and the reaction pressure was 6 MPa; after the reaction, gas chromatography (Agilent 8860) was used to analyze the types and contents of various components contained in the product, 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 direct production of high-carbon alcohols from synthesis gas, the catalyst comprising a first metal component, a second metal component, a metal promoter and a carrier. In terms of the mass percentage of the catalyst, the catalyst comprises 5wt% of the first metal component, 0.1wt% of the second metal component, 0.05wt% of the metal promoter and 94.85wt% of the carrier. The first metal component is Ru; the second metal component is Cu, the metal promoter is Na and the carrier is MgO.

[0184] This embodiment also provides a method for preparing a catalyst for directly preparing higher alcohols from synthesis gas, and the preparation method comprises the following steps:

[0185] 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 additive being 0.03wt%, ruthenium nitrosyl nitrate, copper nitrate and sodium nitrate are weighed and added into deionized water to prepare a solution D with a concentration of 2 mol / L;

[0186] S2, dispersing the MgO carrier in deionized water by ultrasonic for 10 hours, wherein the mass ratio of the MgO carrier to water is 1:70, to obtain a solution E, wherein the mass percentage of the MgO carrier is 94.85 wt % based on the mass percentage of the catalyst;

[0187] S3, the solution D, the solution E and the hydrazine hydrate solution are mixed and stirred at high speed for 2h, 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 2mol / L;

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

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

[0190] Before the direct reaction of synthesizing high-carbon alcohols from synthesis gas, the catalyst is first subjected to reduction pretreatment: the catalyst is pressed into tablets and sieved to 40-60 mesh, 1g of 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand, and the mixture is evenly mixed and loaded into a fixed bed for pretreatment reduction, the reducing atmosphere is hydrogen, and the reduction space velocity is 8000h -1 The reduction temperature is 350°C, the reduction pressure is normal pressure, the time is 5h, and the temperature is lowered to 180°C after the reduction is completed.

[0191] Then switch to synthesis gas for reaction. During the reaction, the molar ratio between H2 and CO in the synthesis gas is 2, and the reaction space velocity is 4000h -1 , the reaction temperature was 200°C, and the reaction pressure was 6 MPa; after the reaction, gas chromatography (Agilent 8860) was used to analyze the types and contents of various components contained in the product, 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 direct production of high-carbon alcohols from synthesis gas, the catalyst comprising a first metal component, a second metal component, a metal promoter and a carrier. In terms of mass percentage of the catalyst, the catalyst comprises 7wt% of the first metal component, 0.1wt% of the second metal component, 0.05wt% of the metal promoter and 92.85wt% of the carrier. The first metal component is Ru; the second metal component is Zn, the metal promoter is Na and the carrier is Al2O3.

[0194] This embodiment also provides a method for preparing a catalyst for directly preparing higher alcohols from synthesis gas, and the preparation method comprises the following steps:

[0195] S1. According to the mass percentage of the first metal component in the catalyst being 7wt%, the mass percentage of the second metal component being 0.1wt%, and the mass percentage of the metal additive being 0.05wt%, ruthenium nitrosyl nitrate, zinc nitrate and sodium nitrate are weighed and added into deionized water to prepare a solution D with a concentration of 2 mol / L;

[0196] S2, dispersing the Al2O3 carrier in deionized water by ultrasonic for 10 h, wherein the mass ratio of the Al2O3 carrier to water is 1:100, to obtain a solution E, wherein the mass percentage of the Al2O3 carrier is 92.85 wt% based on the mass percentage of the catalyst;

[0197] S3, mixing the solution D, the solution E and the sodium borohydride solution, and stirring at high speed for 1 hour, wherein 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 and dry the filtered solid in a tube furnace under N2 atmosphere at 80°C for 4 h.

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

[0200] Before the direct reaction of synthesizing high-carbon alcohols from synthesis gas, the catalyst is first subjected to reduction pretreatment: the catalyst is pressed into tablets and sieved to 40-60 mesh, 1g of 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand, and the mixture is evenly mixed and loaded into a fixed bed for pretreatment reduction, the reducing atmosphere is hydrogen, and the reduction space velocity is 8000h -1 The reduction temperature is 350°C, the reduction pressure is normal pressure, the time is 5h, and the temperature is lowered to 180°C after the reduction is completed.

[0201] Then switch to synthesis gas for reaction. During the reaction, the molar ratio between H2 and CO in the synthesis gas is 2, and the reaction space velocity is 4000h -1 , the reaction temperature was 200°C, and the reaction pressure was 6 MPa; after the reaction, gas chromatography (Agilent 8860) was used to analyze the types and contents of various components contained in the product, and the conversion rate and selectivity of the reaction were calculated accordingly. The specific results are shown in Table 1.

[0202] Embodiment 14

[0203] This embodiment provides a catalyst for direct production of high-carbon alcohols from synthesis gas, the catalyst comprising a first metal component, a second metal component, a metal promoter and a carrier. In terms of the mass percentage of the catalyst, the catalyst comprises 5wt% of the first metal component, 0.1wt% of the second metal component, 0.05wt% of the metal promoter and 94.85wt% of the carrier. The first metal component is Ru; the second metal component is Cu, the metal promoter is Nb and the carrier is ZnO.

[0204] This embodiment also provides a method for preparing a catalyst for directly preparing higher alcohols from synthesis gas, and the preparation method comprises the following steps:

[0205] S1. According to the mass percentage of the first metal component in the catalyst being 5wt%, the mass percentage of the second metal component being 0.1wt%, and the mass percentage of the metal additive being 0.05wt%, ruthenium nitrosyl nitrate, copper nitrate, and niobium nitrate are weighed and added into deionized water to prepare a solution D with a concentration of 2 mol / L;

[0206] S2, dispersing the Zn carrier in deionized water by ultrasonic for 10 h, the mass ratio of the ZnO carrier to water being 1:100, to obtain a solution E, wherein the mass percentage of the Zn carrier is 94.85 wt % based on the mass percentage of the catalyst;

[0207] S3, the solution D, the solution E and the hydrazine hydrate solution are mixed and stirred at high speed for 2h, 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 2mol / L;

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

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

[0210] Before the direct reaction of synthesizing high-carbon alcohols from synthesis gas, the catalyst is first subjected to reduction pretreatment: the catalyst is pressed into tablets and sieved to 40-60 mesh, 1g of 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand, and the mixture is evenly mixed and loaded into a fixed bed for pretreatment reduction, the reducing atmosphere is hydrogen, and the reduction space velocity is 8000h -1 The reduction temperature is 350°C, the reduction pressure is normal pressure, the time is 5h, and the temperature is lowered to 180°C after the reduction is completed.

[0211] Then the reaction was switched to synthesis gas. During the reaction, the molar ratio of H2 to CO in the synthesis gas was 2, the reaction space velocity was 4000h-1, the reaction temperature was 200°C, and the reaction pressure was 6MPa. After the reaction, a gas chromatograph (Agilent 8860) was used to analyze the types and contents of various components contained in the product, and the conversion rate and selectivity of the reaction were calculated accordingly. The specific results are shown in Table 1.

[0212] Embodiment 15

[0213] This embodiment provides a catalyst for direct production of high-carbon alcohols from synthesis gas, the catalyst comprising a first metal component, a second metal component, a metal promoter and a carrier. In terms of mass percentage of the catalyst, the catalyst comprises 2wt% of the first metal component, 0.1wt% of the second metal component, 0.05wt% of the metal promoter and 97.85wt% of the carrier. The first metal component is Ru; the second metal component is Au, the metal promoter is Ca and the carrier is ZnO.

[0214] This embodiment also provides a method for preparing a catalyst for directly preparing higher alcohols from synthesis gas, and the preparation method comprises the following steps:

[0215] 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 0.1wt%, and the mass percentage of the metal additive being 0.05wt%, ruthenium acetylacetonate, auClO and calcium nitrate are weighed and added into deionized water to prepare a solution D with a concentration of 2 mol / L;

[0216] S2, dispersing the Zn carrier in deionized water by ultrasonic for 10 h, the mass ratio of the ZnO carrier to water being 1:100, to obtain a solution E, wherein the mass percentage of the Zn carrier is 97.85 wt % based on the mass percentage of the catalyst;

[0217] S3, the solution D, the solution E and the hydrazine hydrate solution are mixed and stirred at high speed for 2h, 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 2mol / L;

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

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

[0220] Before the direct reaction of synthesizing high-carbon alcohols from synthesis gas, the catalyst is first subjected to reduction pretreatment: the catalyst is pressed into tablets and sieved to 40-60 mesh, 1g of 40-60 mesh catalyst is weighed and mixed with 2g of quartz sand, and the mixture is evenly mixed and loaded into a fixed bed for pretreatment reduction, the reducing atmosphere is hydrogen, and the reduction space velocity is 8000h -1 The reduction temperature is 350°C, the reduction pressure is normal pressure, the time is 5h, and the temperature is lowered to 180°C after the reduction is completed.

[0221] Then switch to synthesis gas for reaction. During the reaction, the molar ratio between H2 and CO in the synthesis gas is 2, and the reaction space velocity is 4000h -1 , the reaction temperature was 200°C, and the reaction pressure was 6 MPa; after the reaction, gas chromatography (Agilent 8860) was used to analyze the types and contents of various components contained in the product, and the conversion rate and selectivity of the reaction were calculated accordingly. The specific results are shown in Table 1.

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

[0223]

[0224]

[0225] As shown in Table 1, by comparing Examples 1 to 15, it can be seen that when the second metal component is Pt or Au, the metal additive is Na, and the carrier is SiO2, the catalyst has the highest selectivity for high-carbon alcohols and lower selectivity for methane and carbon dioxide; among them, in Examples 6 and 11 to 15 using metal oxides as carriers, since the carrier also provides electrons, the electron content is too high during catalysis, which inhibits the catalytic reaction, and the selectivity for high-carbon alcohols is lower than that of other catalysts.

[0226] In summary, the catalyst of the present invention is a novel high-carbon-efficiency catalyst, which can be prepared by two methods, and has the characteristics of simple preparation, easy repetition, and good stability; the catalyst can be used for direct synthesis of high-carbon alcohols from synthesis gas, and shows excellent catalytic performance in the direct synthesis of high-carbon alcohols from synthesis gas. It operates at a lower temperature and pressure, and under the condition of a higher single-pass CO conversion rate, it achieves lower byproduct methane and carbon dioxide selectivity and higher alcohol and high-carbon alcohol selectivity, and the single-pass CO conversion rate can be as high as 55.4%, the alcohol selectivity can be as high as 65.8%, and the high-carbon alcohol selectivity can be as high as 50.1%. Compared with the prior art in which the selectivity of byproduct methane and carbon dioxide from synthesis gas to high-carbon alcohols is greater than 30%, the selectivity of byproduct methane and carbon dioxide in the catalyst of the present application for the direct synthesis of high-carbon alcohols from synthesis gas can be as low as 2% or less.

[0227] The present invention effectively overcomes various shortcomings of the prior art and has high industrial utilization value.

[0228] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may 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 a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A catalyst for directly preparing 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, Ag, Cu or Zn; In terms of 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 carrier is 72 wt% to 99.79 wt%; The particle size of the catalyst is 5 to 10 nm.

2. The catalyst according to claim 1, characterized in that The catalyst further comprises a metal additive, wherein the content of the metal additive is 0.01wt% to 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; And / or, the carrier is selected from one or more of SiO2, TiO2, Al2O3, ZnO, MgO or BaO; And or, the higher carbon alcohol is an alcohol having 6 or more carbon atoms.

3. The method for preparing a catalyst according to any one of claims 1 to 2, characterized in that: The preparation method is selected from one of the first preparation method and the second preparation method; The first preparation method comprises the following steps: a1) weighing corresponding soluble salts according to the proportion of the first metal component, the second metal component and the metal promoter in the total mass of the catalyst, mixing and dissolving the soluble salts corresponding to the first metal component, the second metal component and the metal promoter in a first solvent to obtain a solution A; a2) dissolving the competitive adsorbent in water to obtain solution B; a3) mixing the solution A and the solution B to obtain a solution C, weighing a carrier according to the proportion of the carrier in the total mass of the catalyst, and impregnating the solution C on the carrier; a4) filtering, drying and calcining; The second preparation method comprises the following steps: b1) weighing corresponding soluble salts according to the proportion of the first metal component, the second metal component and the metal promoter in the total mass of the catalyst, mixing and dissolving the soluble salts corresponding to the first metal component, the second metal component and the metal promoter in a second solvent to obtain a solution D; b2) weighing a carrier according to the proportion of the carrier in the total mass of the catalyst, and ultrasonically dispersing the carrier in water to obtain a solution E; b3) mixing the solution D, the solution E and a reducing agent; b4) Filter and dry.

4. The preparation method according to claim 3, characterized in that: In the step a1), the soluble salt corresponding to the first metal component is selected from one or more of ruthenium acetylacetonate, 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 to 3 mol / 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 to 1:50; And / or, in the step a3), the mass ratio of the solution A to the solution B is 1:10 to 1:5; And / or, in step a3), the immersion time is 20 to 40 minutes; And / or, in the step a3), after the immersion is completed, a standing step is further included, and the standing time is 10 to 20 hours; And / or, in the step a4), the drying temperature is 70 to 130° C., and the drying time is 8 to 24 hours; And / or, in the step a4), the calcination atmosphere is selected from one or more of N2, He and Ar; And / or, in the step a4), the calcination temperature is 400-500° C., and the calcination time is 2-10 hours.

5. The preparation method according to claim 3, characterized in that: In the step b1), the soluble salt corresponding to the first metal component is selected from one or more of ruthenium acetylacetonate, ruthenium nitrosyl nitrate and ruthenium chloride; And / or, in step b1), the second solvent is selected from one or more of water, ethanol and acetone; And / or, in the step b1), the mass ratio of the carrier to the second solvent is 1:50-100; And / or, in step b1), the concentration of the solution D is 1 to 3 mol / L; And / or, in the step b2), the duration of the ultrasound is 5 to 10 hours; And / or, 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 to 3 mol / L. And / or, in the step b3), the mass ratio of the solution D, the solution E and the reducing agent is 1:(0.5-2):(0.5-2); And / or, in the step b4), the drying temperature is 100-120° C., and the drying time is 5 h to 10 h; And / or, in step b4), the dry atmosphere is selected from one or more of N2, He and Ar.

6. Use of the catalyst according to any one of claims 1 to 2 in the direct preparation of higher alcohols from synthesis gas.

7. The use according to claim 6, characterized in that Before the catalyst is used for directly preparing higher alcohols from synthesis gas, the catalyst is firstly subjected to reduction treatment.

8. The use according to claim 6, characterized in that Before the catalyst is used for directly preparing higher alcohols from synthesis gas, the catalyst is firstly pressed into tablets and sieved to 40-60 meshes.

9. The use according to claim 6, characterized in that: The gas used in the reduction treatment is selected from one of hydrogen and CO; And / or, the temperature of the reduction treatment is 300-500°C; And / or, the reduction treatment time is 3 to 10 hours; And / or, the space velocity of the reduction treatment is 1000~10000h -1 .

10. The use according to claim 6, characterized in that In the reaction of directly preparing higher alcohols from synthesis gas, the molar ratio of H2 to CO in the synthesis gas is 0.5 to 5; And / or, in the reaction of directly preparing higher alcohols from synthesis gas, the reaction temperature is 200-300° C.; And / or, in the reaction of directly preparing higher alcohols from synthesis gas, the reaction space velocity is 3000-6000h -1 ; And / or, in the reaction of directly preparing higher alcohols from synthesis gas, the reaction pressure is 3-10 MPa.

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