Combined catalyst for synthesizing alcohol-containing fuel from synthesis gas and preparation and application thereof

Abstract

The application provides a combined catalyst for synthesizing alcohol-containing fuel from synthesis gas and preparation and application thereof. The catalyst comprises two components, both of which are supported catalysts. The two components are used in combination, so that two-step reactions can be coupled in the same reactor or in series reactors. By using the series catalyst provided by the application, alcohol-containing liquid fuel can be synthesized from synthesis gas in one step. The proportion of mixed alcohol in the product is not less than 20wt%, and the proportion of alkane is not less than 60wt% (by mass).

Description

Technical Field

[0001] This invention belongs to the field of catalyst development technology, specifically relating to a co-catalyst for the production of alcohol-containing fuels from syngas, its preparation, and its application. More specifically, the catalyst comprises two components, both of which are supported catalysts. By using the catalyst provided by this invention, two different catalyst components are coupled to achieve the goal of producing alcohol-containing liquid fuels from syngas in a one-step process. Using the catalyst provided by this invention simplifies the process flow, produces products with higher added value, and achieves high economic efficiency. Background Technology

[0002] Various non-petroleum-based carbonaceous resources, such as coal, natural gas, and biomass, can be converted into syngas (a mixture of carbon monoxide and hydrogen in an adjustable ratio) using different technologies. The Fischer-Tropsch Synthesis (FTS), which uses syngas as a feedstock and employs iron-based or cobalt-based catalysts to produce clean liquid fuels, is one of the important platform technologies in the field of syngas conversion. Traditional Fischer-Tropsch synthesis reactions primarily produce straight-chain alkanes with relatively low levels of organic oxygen-containing compounds. The oxygen in the syngas is generally converted into water or carbon dioxide, resulting in significant volumes of industrial wastewater and waste gas.

[0003] With the rapid development of the syngas conversion field, new reaction processes for producing oxygen-containing compounds such as alcohols, aldehydes, and acids from syngas have attracted widespread attention from researchers in recent years. The production of oxygen-containing compounds from syngas achieves efficient utilization of oxygen and has higher atom economy, gradually becoming a research focus in C1 chemistry. Directly producing alcohol-containing fuels from syngas can retain more oxygen in the syngas, promote complete combustion of fuels, and reduce pollutant emissions.

[0004] Methanol and ethanol, when used as fuel additives, exhibit poor miscibility, low-temperature phase separation, and a degree of corrosion, although their miscibility with gasoline is slightly better. Other low-carbon alcohol-based fuel additives have significantly different carbon chains and polarities compared to diesel fuel components, resulting in poor miscibility. Alcohol-containing fuels synthesized from syngas in a one-step process contain oxygen that promotes combustion, resulting in higher energy density and significantly reducing PM2.5 and NOx emissions from diesel vehicle exhaust. x To reduce emissions, improve air quality, and meet environmental protection requirements. Summary of the Invention

[0005] The purpose of this invention is to address the shortcomings of existing technologies by developing a co-catalyst for the production of alcohol-containing fuels from syngas. The target products are a mixture of alcohols and alkanes with 2 to 18 carbon atoms, wherein the proportion of mixed alcohols in the products is not less than 20 wt%, and the proportion of alkanes is not less than 60 wt% (by mass).

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows.

[0007] A catalyst for the combined production of alcohol-containing fuels from syngas, characterized in that it comprises two components:

[0008] The first component is a supported catalyst, wherein the support is one or more of the following: silica, activated alumina, zirconium dioxide, magnesium aluminum hydrotalcite, ZSM-5 molecular sieve, activated carbon, mesoporous carbon, carbon nanotubes, carbon nanofibers, and silicon carbide (preferably one or more of the following: silica, activated alumina, magnesium aluminum hydrotalcite, activated carbon, mesoporous carbon, and silicon carbide); the active component is one or more of the following: metallic cobalt, metallic copper, cobalt carbide, cobalt-copper alloy, iron carbide, and cobalt-iron alloy (preferably one or more of the following: metallic cobalt, cobalt carbide, metallic copper, cobalt-copper alloy, and iron carbide), and the content of the active component is 5-30 wt% (preferably 7-20 wt%) of the catalyst weight. The first additive is one or more alkali metals (preferably one or more lithium, sodium, and potassium), and its content is 0.01-5 wt% (preferably 0.1-2 wt%) of the catalyst weight; the second additive is one or more alkaline earth metals (preferably one or more magnesium, calcium, and barium), and its content is 0.01-4 wt% (preferably 0.1-2 wt%) of the catalyst weight; the third additive is one or more transition metals (preferably one or more titanium, vanadium, chromium, manganese, nickel, zinc, and zirconium), and its content is 0.1-6 wt% (preferably 0.5-5 wt%) of the catalyst weight.

[0009] The second component is also a supported catalyst, with the support being one or more of activated carbon, alumina, silica, diatomaceous earth, ordered mesoporous carbon, and magnesium aluminum hydrotalcite (preferably one or more of activated carbon, alumina, silica, and magnesium aluminum hydrotalcite); the active component is one or more of nickel, copper, palladium, platinum, ruthenium, and iridium (preferably one or more of nickel, palladium, platinum, and ruthenium), and the content of the active component is 0.01 to 7 wt% (preferably 0.1 to 5 wt%) of the catalyst weight; the promoter is one or more of rare earth metals and transition metals (preferably one or more of cobalt, iron, rhenium, silver, lanthanum, and cerium), and the content of the promoter is 0.01 to 6 wt% (preferably 0.2 to 4 wt%) of the catalyst weight.

[0010] The preparation method of the above catalyst specifically includes the following steps:

[0011] (1) The first component catalyst was prepared by impregnation method, and the preparation process is as follows:

[0012] ①Immerse the carrier or deposit / precipitate it on the carrier at room temperature using an aqueous solution of one or more soluble salts of the active component, or an aqueous solution of one or more soluble salts of the first and second auxiliaries.

[0013] The catalyst precursor prepared by impregnation method is first allowed to stand at room temperature for 4 to 12 hours (preferably 6 to 12 hours), and then dried in an air atmosphere at 45 to 120°C (preferably 50 to 80°C) for 8 to 48 hours (preferably 10 to 30 hours) to obtain a semi-dry catalyst.

[0014] The precursor prepared by the deposition-precipitation method is first centrifuged at room temperature, and then dried in an air atmosphere at 45-120°C (preferably 50-80°C) for 8-48 hours (preferably 10-30 hours) to obtain a semi-dry catalyst;

[0015] ② The prepared semi-dry catalyst is calcined in an inert atmosphere, which is one or more of nitrogen, argon, or helium. The calcination temperature is 200–430℃ (preferably 240–360℃), the pressure is 0.1–1.0 MPa (preferably 0.1–0.4 MPa), and the gas space velocity is 100–4000 h⁻¹. -1 (Preferred 1500~3000h) -1 The catalyst is calcined for 8–24 hours (preferably 6–18 hours) to obtain a dry-based catalyst.

[0016] ③ The dry-based catalyst is activated in a hydrogen-containing atmosphere, wherein the hydrogen content is 5%–100% (preferably 10%–100%), and the gases other than hydrogen in the hydrogen-containing mixture are one or more of nitrogen, argon, or helium. The activation temperature is 250–600℃ (preferably 350–500℃), the pressure is 0.1–2.0 MPa (preferably 0.1–1.0 MPa), and the gas space velocity is 300–6000 h⁻¹. -1 (Preferred 1000~4000h) -1 The catalyst is activated for 6–72 hours (preferably 8–48 hours) to obtain the activated catalyst.

[0017] ④ The catalyst needs to be pretreated with syngas (a mixture of H2 and CO) to achieve stable activity and selectivity; the molar ratio of H2 to CO in the mixture is 0.4–4.0 (preferably 1.0–3.0), the pretreatment temperature is 170–250℃ (preferably 190–220℃), the pressure is 0.1–10.0 MPa (preferably 0.5–5.0 MPa), and the space velocity is 100–10000 h⁻¹. -1 (Preferred 1000~5000h) -1 Processing time: 2–96 hours (preferably 12–56 hours);

[0018] (2) The second component catalyst was prepared by impregnation method, and the preparation process is as follows:

[0019] ①The carrier is impregnated with an aqueous solution of one or more of the soluble salts of the active component and the soluble salts of the auxiliaries at room temperature. After impregnation, the carrier is allowed to stand at room temperature for 4 to 12 hours (preferably 6 to 10 hours) and then dried in an air atmosphere at 45 to 120°C (preferably 50 to 100°C) for 8 to 24 hours (preferably 10 to 20 hours) to obtain a semi-dry-based catalyst.

[0020] ② The prepared semi-dry catalyst is calcined in an inert atmosphere, which is one or more of nitrogen, argon, or helium. The calcination temperature is 200–500℃ (preferably 240–440℃), the pressure is 0.1–1.0 MPa (preferably 0.1–0.4 MPa), and the gas space velocity is 100–4000 h⁻¹. -1 (Preferred 1500~3000h) -1 The catalyst is calcined for 8–24 hours (preferably 6–18 hours) to obtain a dry-based catalyst.

[0021] ③ The dry-based catalyst is activated in a hydrogen-containing atmosphere, wherein the hydrogen content is 5%–100% (preferably 10%–100%), and the gases other than hydrogen in the hydrogen-containing mixture are one or more of nitrogen, argon, or helium. The activation temperature is 200–500℃ (preferably 250–400℃), the pressure is 0.1–2.0 MPa (preferably 0.1–1.0 MPa), and the gas space velocity is 300–6000 h⁻¹. -1 (Preferred 1000~4000h) -1 The catalyst is activated for 6 to 24 hours (preferably 8 to 18 hours) to obtain the activated catalyst.

[0022] The soluble salt of the active component in the first component is one or more of cobalt nitrate, cobalt acetate, cobalt chloride, cobalt sulfate, ferric nitrate, ferric chloride, ferric sulfate, ferric acetate, copper nitrate, copper chloride, and copper sulfate, wherein the preferred soluble salt of the active component is one or more of cobalt nitrate, cobalt acetate, ferric nitrate, ferric chloride, copper nitrate, and copper chloride; the soluble salts of the first, second, and third auxiliaries are one or more of metal formate, acetate, oxalate, nitrate, sulfate, phosphate, citrate, malate, and chloride, wherein the preferred soluble salt of the auxiliaries is one or more of formate, acetate, nitrate, and chloride;

[0023] The soluble salt of the active component in the second component is one or more of nickel nitrate, nickel chloride, nickel sulfate, palladium nitrate, palladium chloride, palladium acetate, chloroplatinic acid, ammonium chloroplatinate, tetraammineacetate, dichlorodiammineplatinum, ruthenium chloride, ruthenium nitrate, and ruthenium acetate; the soluble salt of the auxiliary agent is one or more of metal formate, acetate, oxalate, nitrate, sulfate, phosphate, and chloride, wherein the preferred soluble salt of the auxiliary agent is one or more of acetate, nitrate, and chloride.

[0024] The above-mentioned combined catalyst is used in the synthesis of alcohol fuel from syngas. The reactor is a fixed-bed reactor. Two fixed-bed reactors can be connected in series and filled with the first component catalyst and the second component catalyst in sequence. Alternatively, the two component catalysts can be placed in series in one fixed-bed reactor, and the syngas feedstock can flow through the first component and the second component in sequence. Or, the two component catalysts can be physically mixed in one fixed-bed reactor.

[0025] Specific operating conditions: reaction temperature 170–260℃ (preferably 190–240℃), reaction pressure 0.5–8.0 MPa (preferably 1.0–6.0 MPa), gas hourly space velocity (GHSV) 500–10000 h⁻¹ -1 (Preferred 1000~8000h) -1 The H2 / CO molar ratio in the syngas is 0.5–5.0 (preferably 1.0–3.0). The feed gas (a mixture of H2 and CO) is continuously fed and reacts continuously in the catalyst bed. The gaseous and liquid products generated are continuously discharged. A hot tank is used to collect high-boiling-point heavy components, and a cold tank is used to collect low-boiling-point light components. The heating temperature of the hot tank is maintained at 100–120°C, and the temperature of the cold tank is maintained at 0–5°C.

[0026] The target product is a mixture of alcohols and alkanes with 2 to 18 carbon atoms; the proportion of mixed alcohols in the product is not less than 20 wt%, and the proportion of alkanes is not less than 60 wt% (by mass).

[0027] Compared with the prior art, the present invention has the following advantages:

[0028] (1) The catalyst provided by the present invention can realize the direct production of alcohol-containing liquid fuel from syngas, and the proportion of mixed alcohol in the product is not less than 20 wt% (by mass).

[0029] (2) The tandem catalyst provided by the present invention utilizes the unique properties of the multi-component catalyst to achieve the coupling of different reactions, thereby achieving the goal of directly producing alcohol-containing liquid fuel from syngas.

[0030] (3) The catalyst provided by the present invention can be carried out in multiple reactors or in the same reactor. Detailed Implementation

[0031] The present invention will be further described below with reference to the embodiments and accompanying tables, but this does not limit the present invention in any way.

[0032] Example 1

[0033] Cat1 is prepared by a first component A and a second component B, and the specific preparation method is as follows.

[0034] Preparation of the first component:

[0035] A semi-dry catalyst was prepared by dissolving 4.4 g of cobalt nitrate hexahydrate, 0.3 g of sodium nitrate, 0.8 g of barium nitrate, and 1.2 g of nickel nitrate hexahydrate in 10 g of water. 8.7 g of purified activated carbon support was impregnated with this solution at room temperature. The carbon was dried at room temperature for 6 hours until no free-flowing moisture remained on the catalyst surface. Then, it was dried in a 70°C oven for 24 hours to obtain a semi-dry catalyst. After removal, the catalyst was calcined in nitrogen at 300°C for 20 hours to obtain a dry catalyst (pressure 0.1 MPa, gas hourly space velocity 2000 h⁻¹). -1 The dry-based catalyst was then gradually reduced in hydrogen at 400°C for 15 hours (pressure 0.1 MPa, gas hourly space velocity 2000 h⁻¹). -1 The activated catalyst was obtained. After cooling to room temperature, the catalyst was pretreated for 24 hours at 200°C with a synthesis gas volume ratio of H2 / CO = 2.0 (pressure 2.0 MPa, gas space velocity 2000 h⁻¹). -1 The first component of the catalyst, A (15Co0.5Na0.3Ba1Ni / AC), was obtained.

[0036] Preparation of the second component:

[0037] 1.5 g of nickel nitrate hexahydrate and 0.2 g of lanthanum nitrate hexahydrate were dissolved in 5.0 g of water to prepare an impregnation solution. 4.5 g of alumina support was impregnated with this solution at room temperature and dried at room temperature for 6 hours until no free-flowing moisture remained on the catalyst surface. Then, it was dried in a 50°C oven for 24 hours to obtain a semi-dry catalyst. After removal, it was calcined in nitrogen at 300°C for 10 hours to obtain a dry catalyst (pressure 0.1 MPa, gas hourly space velocity 2000 h⁻¹). -1 The dry-based catalyst was then gradually reduced in hydrogen at 400°C for 10 hours (pressure 0.1 MPa, gas space velocity 2000 h⁻¹). -1 The second component of the catalyst, B (6Ni0.4La / Al2O3), was obtained.

[0038] Catalyst evaluation methods:

[0039] Measure 1 mL of each of the two catalyst components, A and B, and sequentially add them to a fixed-bed reactor (B at the bottom, A at the top, with the syngas feedstock flowing sequentially from top to bottom through the fixed bed). Switch the syngas (volume ratio H2 / CO = 1.5), adjust the pressure to 3.0 MPa, and the gas space velocity to 4000 h⁻¹. -1 The temperature was raised to 230℃ for the reaction. After stabilizing for 12 hours, samples were taken every 24 hours to analyze the concentration of each component in the tail gas, the composition of the liquid phase product, and the yield of the liquid phase product. The results are listed in Appendix Table 1.

[0040] Example 2

[0041] Cat2 is prepared by a first component A and a second component B, and the specific preparation method is as follows.

[0042] Preparation of the first component:

[0043] A semi-dry catalyst was prepared by dissolving 4.9 g of cobalt nitrate hexahydrate, 0.2 g of potassium nitrate, 0.4 g of magnesium nitrate, and 1.0 g of zirconium nitrate tetrahydrate in 10 g of water. 7.8 g of purified ordered mesoporous carbon support was impregnated with this solution at room temperature. The support was dried at room temperature for 6 hours until no free-flowing moisture remained on the catalyst surface. Then, it was dried in a 65°C oven for 24 hours to obtain a semi-dry catalyst. After removal, the catalyst was calcined in nitrogen at 350°C for 16 hours to obtain a dry catalyst (pressure 0.2 MPa, gas hourly space velocity 3000 h⁻¹). -1 The dry-based catalyst was then gradually reduced to 440°C for 14 hours in a 10% (v / v) H2 / N2 mixture (pressure 0.2 MPa, gas space velocity 3000 h⁻¹). -1 The activated catalyst was obtained. After cooling to room temperature, the catalyst was pretreated at 205°C for 24 hours (pressure 3.0 MPa, gas space velocity 4000 h⁻¹) by switching to syngas with a volume ratio of H₂ / CO = 1.5. -1 The first component of the catalyst, A (15Co0.2K0.2Mg1Zr / OMCs), was obtained.

[0044] Preparation of the second component:

[0045] 0.7 g of chloroplatinic acid and 0.1 g of silver nitrate were dissolved in 4.0 g of water to prepare an impregnation solution. 2.5 g of silica support was impregnated with this solution at room temperature and dried for 6 hours at room temperature until no free-flowing moisture remained on the catalyst surface. Then, it was dried in a 50°C oven for 24 hours to obtain a semi-dry catalyst. After removal, it was calcined in argon gas at 300°C for 10 hours to obtain a dry catalyst (pressure 0.1 MPa, gas hourly space velocity 2000 h⁻¹). -1 The dry-based catalyst was then gradually reduced to 400°C for 10 hours in a 10% (v / v) H₂ / Ar mixture (pressure 0.1 MPa, gas hourly space velocity 2000 h⁻¹).-1 The second component of the catalyst, B (2Pt0.5Ag / SiO2), was obtained.

[0046] Catalyst evaluation methods:

[0047] Measure 1 mL of each of the two catalyst components, A and B, and sequentially add them to a fixed-bed reactor (B at the bottom, A at the top, with the syngas feedstock flowing sequentially from top to bottom through the fixed bed). Switch the syngas (volume ratio H2 / CO = 2.0), adjust the pressure to 3.5 MPa, and the gas space velocity to 3000 h⁻¹. -1 The temperature was raised to 220℃ for the reaction. After stabilizing for 12 hours, samples were taken every 24 hours to analyze the concentration of each component in the tail gas, the composition of the liquid phase product, and the yield of the liquid phase product. The results are listed in Appendix Table 1.

[0048] Example 3

[0049] Cat3 is prepared by a first component A and a second component B, and the specific preparation method is as follows.

[0050] Preparation of the first component:

[0051] A semi-dry catalyst was prepared by dissolving 4.6 g of ferric nitrate nonahydrate, 0.2 g of sodium nitrate, 0.6 g of calcium nitrate, and 0.5 g of a 50 wt% manganese nitrate solution in 10 g of water. 6.5 g of purified ordered mesoporous carbon support was impregnated with this solution at room temperature. The support was dried at room temperature for 6 hours until no free-flowing moisture remained on the catalyst surface. Then, it was dried in a 60°C oven for 20 hours to obtain a semi-dry catalyst. After removal, the catalyst was calcined in helium at 350°C for 16 hours to obtain a dry catalyst (pressure 0.2 MPa, gas hourly space velocity 3000 h⁻¹). -1 The dry-based catalyst was then gradually reduced in a 10% (v / v) H₂ / He mixture to 440°C for 14 hours (pressure 0.2 MPa, gas hourly space velocity 3000 h⁻¹). -1 The activated catalyst was obtained. After cooling to room temperature, the catalyst was pretreated for 24 hours at 195°C (pressure 2.5 MPa, gas space velocity 3000 h⁻¹) by switching to syngas with a volume ratio of H₂ / CO = 2.0. -1 The first component of the catalyst, A (10Fe0.1Na0.2Ca0.5Mn / OMCs), was obtained.

[0052] Preparation of the second component:

[0053] 0.7 g of chloroplatinic acid and 0.15 g of cerium nitrate hexahydrate were dissolved in 4.0 g of water to prepare an impregnation solution. 2.0 g of magnesium aluminum hydrotalcite support was impregnated with this solution at room temperature and dried for 6 hours at room temperature until no free-flowing moisture remained on the catalyst surface. Then, it was dried in a 50°C oven for 24 hours to obtain a semi-dry catalyst. After removal, it was calcined in argon gas at 300°C for 10 hours to obtain a dry catalyst (pressure 0.1 MPa, gas hourly space velocity 1500 h⁻¹). -1 The dry-based catalyst was then gradually reduced to 300°C for 10 hours in a 10% (v / v) H₂ / He mixture (pressure 0.1 MPa, gas hourly space velocity 1500 h⁻¹). -1 The catalyst third component B (2.5Pt0.3Ce / MgAl-LDHs) was obtained.

[0054] Catalyst evaluation methods:

[0055] 1 mL of each of the two catalyst components, A and B, was measured, physically mixed, and then fed into a fixed-bed reactor. The syngas was switched (volume ratio H2 / CO = 2.5), and the syngas feedstock flowed sequentially from top to bottom through the fixed bed. The pressure was adjusted to 2.5 MPa, and the gas space velocity was 3000 h⁻¹. -1 The temperature was raised to 225℃ for the reaction. After stabilizing for 12 hours, samples were taken every 24 hours to analyze the concentration of each component in the tail gas, the composition of the liquid phase product, and the yield of the liquid phase product. The results are listed in Appendix Table 1.

[0056] Example 4

[0057] Cat4 is prepared by a first component A and a second component B, and the specific preparation method is as follows.

[0058] Preparation of the first component:

[0059] 4.9 g of cobalt nitrate hexahydrate, 0.05 g of lithium nitrate, 0.3 g of magnesium nitrate, and 0.9 g of zirconium nitrate tetrahydrate were dissolved in 10 g of water to prepare an impregnation solution. 8.7 g of purified activated carbon support was impregnated with this solution at room temperature. The carbon was dried at room temperature for 6 hours until no free-flowing moisture remained on the catalyst surface. Then, it was dried in a 50°C oven for 24 hours to obtain a semi-dry catalyst. After removal, the catalyst was calcined in nitrogen at 300°C for 20 hours to obtain a dry catalyst (pressure 0.1 MPa, gas hourly space velocity 2000 h⁻¹). -1 The dry-based catalyst was then gradually reduced in hydrogen at 400°C for 15 hours (pressure 0.1 MPa, gas hourly space velocity 2000 h⁻¹). -1 The activated catalyst was obtained. After cooling to room temperature, the catalyst was pretreated for 24 hours at 200°C with a synthesis gas volume ratio of H2 / CO = 2.0 (pressure 2.0 MPa, gas space velocity 2000 h⁻¹). -1The first component of the catalyst, A (15Co0.1Li0.2Mg1Zr / AC), was obtained.

[0060] Preparation of the second component:

[0061] 0.7 g of chloroplatinic acid and 0.15 g of nickel nitrate hexahydrate were dissolved in 4.0 g of water to prepare an impregnation solution. 2.0 g of alumina support was impregnated with this solution at room temperature and dried at room temperature for 6 hours until no free-flowing moisture remained on the catalyst surface. Then, it was dried in a 50°C oven for 24 hours to obtain a semi-dry catalyst. After removal, it was calcined in argon gas at 300°C for 10 hours to obtain a dry catalyst (pressure 0.1 MPa, gas hourly space velocity 1500 h⁻¹). -1 The dry-based catalyst was then gradually reduced to 300°C for 10 hours in a 10% (v / v) H₂ / He mixture (pressure 0.1 MPa, gas hourly space velocity 1500 h⁻¹). -1 The second component of the catalyst, B (2.5Pt0.5Ni / Al2O3), was obtained.

[0062] Catalyst evaluation methods:

[0063] Measure 1 mL of each of the two catalyst components, A and B, and sequentially add them to a fixed-bed reactor (B at the bottom, A at the top, with the syngas feedstock flowing sequentially from top to bottom through the fixed bed). Switch the syngas (volume ratio H2 / CO = 3.0), adjust the pressure to 3.0 MPa, and the gas space velocity to 2000 h⁻¹. -1 The temperature was raised to 220℃ for the reaction. After stabilizing for 12 hours, samples were taken every 24 hours to analyze the concentration of each component in the tail gas, the composition of the liquid phase product, and the yield of the liquid phase product. The results are listed in Appendix Table 1.

[0064] Example 5

[0065] Cat5 is prepared by a first component A and a second component B, and the specific preparation method is as follows.

[0066] Preparation of the first component:

[0067] A semi-dry catalyst was prepared by dissolving 2.3 g of cobalt acetate, 0.2 g of sodium nitrate, 0.6 g of calcium nitrate, and 0.7 g of chromium nitrate nonahydrate in 10 g of water. 4.6 g of purified carbon nanotube support was impregnated with this solution at room temperature and dried for 6 hours until no free-flowing moisture remained on the catalyst surface. The catalyst was then dried in a 60°C oven for 24 hours to obtain a semi-dry catalyst. After removal, the catalyst was calcined in argon gas at 320°C for 16 hours to obtain a dry catalyst (pressure 0.1 MPa, gas hourly space velocity 2000 h⁻¹). -1 The dry-based catalyst was then gradually reduced to 420°C for 16 hours in a 10% (v / v) H2 / Ar mixture (pressure 0.1 MPa, gas space velocity 2000 h⁻¹).-1 The activated catalyst was obtained. After cooling to room temperature, the catalyst was pretreated for 24 hours at 190°C with a synthesis gas volume ratio of H2 / CO = 2.0 (pressure 2.0 MPa, gas space velocity 2000 h⁻¹). -1 The first component of the catalyst, A (10Co0.1Na0.2Ca0.5Cr / CNTs), was obtained.

[0068] Preparation of the second component:

[0069] 0.7 g of chloroplatinic acid and 0.18 g of cerium nitrate hexahydrate were dissolved in 4.0 g of water to prepare an impregnation solution. 2.0 g of magnesium aluminum hydrotalcite support was impregnated with this solution at room temperature and dried at room temperature for 6 hours until no free-flowing moisture remained on the catalyst surface. Then, it was dried in a 50°C oven for 24 hours to obtain a semi-dry catalyst. After removal, it was calcined in argon gas at 300°C for 10 hours to obtain a dry catalyst (pressure 0.1 MPa, gas hourly space velocity 1500 h⁻¹). -1 The dry-based catalyst was then gradually reduced in a 10% H2 / He mixture at 300°C for 10 hours (pressure 0.1 MPa, gas space velocity 1500 h⁻¹). -1 The second component of the catalyst, B (2.5Pt0.3Ce / MgAl-LDHs), was obtained.

[0070] Catalyst evaluation methods:

[0071] 1 mL of each of the two catalyst components, A and B, was measured, physically mixed, and then fed into a fixed-bed reactor. The syngas was switched (volume ratio H2 / CO = 1.8, with the syngas feedstock flowing sequentially from top to bottom through the fixed bed). The pressure was adjusted to 3.0 MPa and the gas space velocity to 2000 h⁻¹. -1 The temperature was raised to 225℃ for the reaction. After stabilizing for 12 hours, samples were taken every 24 hours to analyze the concentration of each component in the tail gas, the composition of the liquid phase product, and the yield of the liquid phase product. The results are listed in Appendix Table 1.

[0072] Example 6

[0073] Cat6 is prepared by a first component A and a second component B, and the specific preparation method is as follows.

[0074] Preparation of the first component:

[0075] 3.1 g of cobalt nitrate hexahydrate, 0.3 g of potassium nitrate, 0.4 g of magnesium nitrate, and 0.8 g of nickel nitrate hexahydrate were dissolved in 10 g of water to prepare an impregnation solution. 7.8 g of purified ordered mesoporous carbon support was impregnated with this solution at room temperature. The support was dried at room temperature for 6 hours until no free-flowing moisture remained on the catalyst surface. Then, it was dried in a 60°C oven for 20 hours to obtain a semi-dry catalyst. After removal, the catalyst was calcined in helium at 350°C for 16 hours to obtain a dry catalyst (pressure 0.2 MPa, gas hourly space velocity 3000 h⁻¹). -1 The dry-based catalyst was then gradually reduced in a 10% H2 / He mixture at 440°C for 14 hours (pressure 0.2 MPa, gas space velocity 3000 h⁻¹). -1 The activated catalyst was obtained. After cooling to room temperature, the catalyst was pretreated at 195°C for 24 hours (pressure 2.5 MPa, gas space velocity 3000 h⁻¹) by switching to syngas with a volume ratio of H₂ / CO = 1.7. -1 The first component of the catalyst, A (10Co0.1K0.2Mg0.5Ni / OMCs), was obtained.

[0076] Preparation of the second component:

[0077] 0.9 g of chloroplatinic acid and 0.15 g of lanthanum nitrate hexahydrate were dissolved in 5.0 g of water to prepare an impregnation solution. 2.4 g of alumina support was impregnated with this solution at room temperature and dried at room temperature for 6 hours until no free-flowing moisture remained on the catalyst surface. Then, it was dried in a 50°C oven for 24 hours to obtain a semi-dry catalyst. After removal, it was calcined in nitrogen at 300°C for 10 hours to obtain a dry catalyst (pressure 0.1 MPa, gas hourly space velocity 2000 h⁻¹). -1 The dry-based catalyst was then gradually reduced in hydrogen at 400°C for 10 hours (pressure 0.1 MPa, gas space velocity 2000 h⁻¹). -1 The second component of the catalyst, B (3Pt0.5La / Al2O3), was obtained.

[0078] Catalyst evaluation methods:

[0079] Measure 1 mL of each of the two catalyst components, A and B, and sequentially add them to a fixed-bed reactor (B at the bottom, A at the top, with the syngas feedstock flowing sequentially from top to bottom through the fixed bed). Switch the syngas (volume ratio H2 / CO = 3.0), adjust the pressure to 3.0 MPa, and the gas space velocity to 2000 h⁻¹. -1 The temperature was raised to 220℃ for the reaction. After stabilizing for 12 hours, samples were taken every 24 hours to analyze the concentration of each component in the tail gas, the composition of the liquid phase product, and the yield of the liquid phase product. The results are listed in Appendix Table 1.

[0080] Example 7

[0081] Cat7 is prepared by a first component A and a second component, and the specific preparation method is as follows.

[0082] Preparation of the first component:

[0083] A semi-dry catalyst was prepared by dissolving 6.6 g of ferric nitrate nonahydrate, 0.4 g of sodium nitrate, 0.4 g of magnesium nitrate, and 1.8 g of chromium nitrate nonahydrate in 10 g of water. 6.5 g of purified activated carbon support was impregnated with this impregnation solution at room temperature. The carbon was then dried at room temperature for 6 hours until no free-flowing moisture remained on the catalyst surface. Finally, it was dried in a 60°C oven for 20 hours to obtain a semi-dry catalyst. After removal, the catalyst was calcined in nitrogen at 350°C for 18 hours to obtain a dry catalyst (pressure 0.1 MPa, gas hourly space velocity 3000 h⁻¹). -1 The dry-based catalyst was then gradually reduced in hydrogen at 440°C for 18 hours (pressure 0.1 MPa, gas hourly space velocity 3000 h⁻¹). -1 The activated catalyst was obtained. After cooling to room temperature, the catalyst was pretreated for 24 hours at 200°C with a synthesis gas volume ratio of H2 / CO = 1.7 (pressure 3.0 MPa, gas space velocity 2500 h⁻¹). -1 The first component of the catalyst, A (15Fe0.3Na0.2Mg2Cr / AC), was obtained.

[0084] Preparation of the second component:

[0085] 0.6 g of palladium chloride and 0.18 g of cerium nitrate hexahydrate were dissolved in 4.0 g of water to prepare an impregnation solution. 2.0 g of alumina support was impregnated with this solution at room temperature and dried at room temperature for 6 hours until no free-flowing moisture remained on the catalyst surface. Then, it was dried in a 50°C oven for 24 hours to obtain a semi-dry catalyst. After removal, it was calcined in argon gas at 300°C for 10 hours to obtain a dry catalyst (pressure 0.1 MPa, gas hourly space velocity 1500 h⁻¹). -1 The dry-based catalyst was then gradually reduced in hydrogen at 300°C for 10 hours (pressure 0.1 MPa, gas space velocity 2500 h⁻¹). -1 The second component of the catalyst, B (2.5Pd0.5Ce / Al2O3), was obtained.

[0086] Catalyst evaluation methods:

[0087] Measure 1 mL of each of the two catalyst components, A and B, and sequentially add them to a fixed-bed reactor (B at the bottom, A at the top, with the syngas feedstock flowing through the fixed bed from top to bottom). Switch the syngas (volume ratio H2 / CO = 1.7), adjust the pressure to 3.0 MPa, and the gas space velocity to 2000 h⁻¹. -1The temperature was raised to 230℃ for the reaction. After stabilizing for 12 hours, samples were taken every 24 hours to analyze the concentration of each component in the tail gas, the composition of the liquid phase product, and the yield of the liquid phase product. The results are listed in Appendix Table 1.

[0088] Comparative Example 1

[0089] Cat8 is prepared by a first component A and a second component, and the specific preparation method is as follows.

[0090] Preparation of the first component:

[0091] 4.9 g of cobalt nitrate hexahydrate and 0.9 g of zirconium nitrate tetrahydrate were dissolved in 10 g of water to prepare an impregnation solution. 8.7 g of titanium dioxide support was impregnated with this solution at room temperature and dried for 3 hours at room temperature until no free-flowing moisture remained on the catalyst surface. Then, it was dried in an oven at 130 °C for 6 hours to obtain a semi-dry catalyst. After removal, it was calcined in nitrogen at 450 °C for 48 hours to obtain a dry catalyst (pressure 1.0 MPa, gas hourly space velocity 2000 h⁻¹). -1 The dry-based catalyst was then gradually reduced in hydrogen at 600°C for 48 hours (pressure 0.1 MPa, gas hourly space velocity 2000 h⁻¹). -1 The activated catalyst was obtained. After cooling to room temperature, the catalyst was pretreated at 260°C for 48 hours (pressure 2.0 MPa, gas space velocity 2000 h⁻¹) by switching to syngas with a volume ratio of H₂ / CO = 5.0. -1 The first component of the catalyst, A (15Co1Zr / TiO2), was obtained.

[0092] Preparation of the second component:

[0093] 1.5 g of nickel nitrate hexahydrate and 0.15 g of lanthanum nitrate hexahydrate were dissolved in 5.0 g of water to prepare an impregnation solution. 4.5 g of titanium dioxide support was impregnated with this solution at room temperature and dried for 6 hours at room temperature until no free-flowing moisture remained on the catalyst surface. Then, it was dried in a 50°C oven for 24 hours to obtain a semi-dry catalyst. After removal, it was calcined in nitrogen at 150°C for 10 hours to obtain a dry catalyst (pressure 0.1 MPa, gas hourly space velocity 2000 h⁻¹). -1 The dry-based catalyst was then gradually reduced in hydrogen at 200°C for 10 hours (pressure 0.1 MPa, gas space velocity 2000 h⁻¹). -1 The second component of the catalyst, B(2Ni0.3La / TiO2), was obtained.

[0094] Measure 1 mL of each of the two catalyst components, A and B, and sequentially add them to a fixed-bed reactor (B at the bottom, A at the top, with the syngas feedstock flowing sequentially from top to bottom through the fixed bed). Switch the syngas (volume ratio H2 / CO = 1.0), adjust the pressure to 3.0 MPa, and the gas space velocity to 4000 h⁻¹.-1 The temperature was raised to 230℃ for the reaction. After stabilizing for 12 hours, samples were taken every 24 hours to analyze the concentration of each component in the tail gas, the composition of the liquid phase product, and the yield of the liquid phase product. The results are listed in Appendix Table 1.

[0095] Appendix 1

[0096] Comparison of the performance of syngas to alcohol-containing fuels on different catalysts

[0097]

[0098] Among them, C 2+ Alkanes are straight-chain alkanes with 2 to 18 carbon atoms, while alcohols are straight-chain or branched monohydric alcohols with 2 to 18 carbon atoms.

[0099] The comparison results show that the tandem catalyst provided by this patent can realize the one-step preparation of alcohol-containing fuel from syngas, which can better utilize the oxygen element in syngas and has higher product added value and economy.

[0100] Unless otherwise specified, the raw materials and equipment used in this invention are all commonly used in the field; unless otherwise specified, the methods used in this invention are all conventional methods in the field.

[0101] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, alterations, and equivalent transformations made to the above embodiments based on the technical essence of the present invention shall still fall within the protection scope of the present invention.

Claims

1. The application of a co-catalyst for the production of alcohol-containing fuels from syngas, characterized in that, It contains two components: The first component is a supported catalyst, with the support being one of activated carbon, mesoporous carbon, or carbon nanotubes; the active component is metallic cobalt, and its content is 5-30 wt% of the catalyst weight; the first promoter is one of lithium, sodium, or potassium, and its content is 0.01-5 wt% of the catalyst weight; the second promoter is one of magnesium, calcium, or barium, and its content is 0.01-4 wt% of the catalyst weight; the third promoter is one of chromium, manganese, nickel, or zirconium, and its content is 0.1-6 wt% of the catalyst weight. The second component is also a supported catalyst, with the support being one of alumina, silica, magnesium aluminum, and hydrotalcite; the active component is one of nickel, palladium, and platinum, with the content of the active component being 0.01~7 wt% of the catalyst weight; the promoter is one of silver, lanthanum, and cerium, with the content of the promoter being 0.01~6 wt% of the catalyst weight. The target products are a mixture of alcohols and alkanes with 2 to 18 carbon atoms; The proportion of mixed alcohols in the product is not less than 20 wt% by mass; The proportion of alkanes, expressed by mass, shall not be less than 60 wt%; The reactor is a fixed-bed reactor, consisting of two fixed-bed reactors connected in series, which are sequentially filled with a first component catalyst and a second component catalyst, or two component catalysts are placed in series in a single fixed-bed reactor, with the syngas feedstock flowing sequentially through the first and second components; or the two component catalysts are physically mixed in a single fixed-bed reactor. The synthesis gas is a mixture of H2 and CO.

2. The application according to claim 1, characterized in that, It contains two components: The first component is a supported catalyst, with the support being one of activated carbon, mesoporous carbon, or carbon nanotubes; the active component is metallic cobalt, and its content is 7-20 wt% of the catalyst weight; the first promoter is one of lithium, sodium, or potassium, and its content is 0.1-2 wt% of the catalyst weight; the second promoter is one of magnesium, calcium, or barium, and its content is 0.1-2 wt% of the catalyst weight; the third promoter is one of chromium, manganese, nickel, or zirconium, and its content is 0.5-5 wt% of the catalyst weight. The second component is also a supported catalyst, with the support being one of alumina, silica, magnesium aluminum hydrotalcite, or double hydroxide; the active component is one of nickel, palladium, or platinum, with the content of the active component being 0.1 to 5 wt% of the catalyst weight; and the promoter is one of silver, lanthanum, or cerium, with the content of the promoter being 0.2 to 4 wt% of the catalyst weight.

3. The application according to claim 1, characterized in that, The reaction temperature is 170~260 ℃, the reaction pressure is 0.5~8.0 MPa, and the gas hourly space velocity is 500~10000 h⁻¹. -1 The H2 / CO molar ratio in the syngas is 0.5~5.

0.

4. The application according to claim 3, characterized in that, The reaction temperature is 190~240 ℃, the reaction pressure is 1.0~6.0 MPa, and the gas hourly space velocity is 1000~8000 h⁻¹. -1 The H2 / CO molar ratio in the syngas is 1.0~3.

0.

5. The application according to claim 3, characterized in that, The H2 and CO mixture is fed continuously, and the reaction takes place continuously in the catalyst bed. The gaseous and liquid products generated by the reaction are discharged continuously. A hot tank is used to collect the high-boiling-point heavy components, and a cold tank is used to collect the low-boiling-point light components. The heating temperature of the hot tank is maintained at 100~120 ℃, and the temperature of the cold tank is maintained at 0~5 ℃.

6. The application according to claim 1, characterized in that, The preparation method of the catalyst specifically includes the following steps: (1) The first component catalyst was prepared by impregnation method, and the preparation process is as follows: ①Immerse the carrier or deposit / precipitate on the carrier at room temperature using an aqueous solution of one of the soluble salts of the active component, the first auxiliary agent, the second auxiliary agent, and the third auxiliary agent; The catalyst precursor prepared by the impregnation method is first allowed to stand at room temperature for 4 to 12 hours, and then dried in an air atmosphere at 45 to 120 °C for 8 to 48 hours to obtain a semi-dry catalyst. The precursor prepared by the deposition-precipitation method was first centrifuged at room temperature and then dried in an air atmosphere at 45~120 °C for 8~48 hours to obtain a semi-dry-based catalyst. ② The prepared semi-dry catalyst is calcined in an inert atmosphere, which is one or more of nitrogen, argon, or helium. The calcination temperature is 200~430 ℃, the pressure is 0.1~1.0 MPa, and the gas space velocity is 100~4000 h⁻¹. -1 The catalyst was calcined for 8-24 hours to obtain a dry-based catalyst. ③ Activate the dry-based catalyst in a hydrogen-containing atmosphere with a hydrogen content of 5% to 100%. The hydrogen-containing mixture contains one or more of nitrogen, argon, or helium, excluding hydrogen. The activation temperature is 250 to 600 °C, the pressure is 0.1 to 2.0 MPa, and the gas space velocity is 300 to 6000 h⁻¹. -1 The activated catalyst was obtained by activating it for 6-72 hours. ④ The catalyst needs to be pretreated with syngas to achieve stable activity and selectivity; the molar ratio of H2 to CO in the mixed gas is 0.4~4.0, the pretreatment temperature is 170~250 ℃, the pressure is 0.1~10.0 MPa, and the space velocity is 100~10000 h⁻¹. -1 Processing time: 2-96 hours; (2) The second component catalyst was prepared by impregnation method, and the preparation process is as follows: ①The carrier is impregnated with an aqueous solution of one or more of the soluble salts of the active component and the soluble salts of the auxiliary agent at room temperature. After impregnation, the carrier is allowed to stand at room temperature for 4 to 12 hours, and then dried in an air atmosphere at 45 to 120 °C for 8 to 24 hours to obtain a semi-dry catalyst. ② The prepared semi-dry catalyst is calcined in an inert atmosphere, which is one or more of nitrogen, argon, or helium. The calcination temperature is 200~500 ℃, the pressure is 0.1~1.0 MPa, and the gas space velocity is 100~4000 h⁻¹. -1 The catalyst was calcined for 8-24 hours to obtain a dry-based catalyst. ③ Activate the dry-based catalyst in a hydrogen-containing atmosphere with a hydrogen content of 5% to 100%. The hydrogen-containing mixture contains one or more of nitrogen, argon, or helium, excluding hydrogen. The activation temperature is 200 to 500 °C, the pressure is 0.1 to 2.0 MPa, and the gas space velocity is 300 to 6000 h⁻¹. -1 The activated catalyst was obtained by activating it for 6 to 24 hours.

7. The application according to claim 6, characterized in that, The preparation method of the catalyst specifically includes the following steps: (1) The first component catalyst was prepared by impregnation method, and the preparation process is as follows: ①Immerse the carrier or deposit / precipitate on the carrier at room temperature using an aqueous solution of one of the soluble salts of the active component, the first auxiliary agent, the second auxiliary agent, and the third auxiliary agent; The catalyst precursor prepared by the impregnation method is first allowed to stand at room temperature for 6 to 12 hours, and then dried in an air atmosphere at 50 to 80°C for 10 to 30 hours to obtain a semi-dry catalyst. The precursor prepared by the deposition-precipitation method was first centrifuged at room temperature and then dried in an air atmosphere at 50-80 °C for 10-30 hours to obtain a semi-dry catalyst. ② The prepared semi-dry catalyst is calcined in an inert atmosphere, which is one or more of nitrogen, argon, or helium. The calcination temperature is 240~360 ℃, the pressure is 0.1~0.4 MPa, and the gas space velocity is 1500~3000 h⁻¹. -1 The catalyst was calcined for 6 to 18 hours to obtain a dry-based catalyst. ③ Activate the dry-based catalyst in a hydrogen-containing atmosphere with a hydrogen content of 10% to 100%. The hydrogen-containing mixture contains one or more of nitrogen, argon, or helium, excluding hydrogen. The activation temperature is 350 to 500 °C, the pressure is 0.1 to 1.0 MPa, and the gas space velocity is 1000 to 4000 h⁻¹. -1 The activated catalyst was obtained by activating it for 8-48 hours. ④ The catalyst needs to be pretreated with syngas to achieve stable activity and selectivity; the molar ratio of H2 to CO in the mixed gas is 1.0~3.0, the pretreatment temperature is 190~220 ℃, the pressure is 0.5~5.0 MPa, and the space velocity is 1000~5000 h⁻¹. -1 Processing time is 12-56 hours; (2) The second component catalyst was prepared by impregnation method, and the preparation process is as follows: ①The carrier is impregnated with an aqueous solution of one or more of the soluble salts of the active component and the soluble salts of the auxiliaries at room temperature. After impregnation, the carrier is allowed to stand at room temperature for 6 to 10 hours, and then dried in an air atmosphere at 50 to 100 °C for 10 to 20 hours to obtain a semi-dry catalyst. ② The prepared semi-dry catalyst is calcined in an inert atmosphere, which is one or more of nitrogen, argon, or helium. The calcination temperature is 240~440 ℃, the pressure is 0.1~0.4 MPa, and the gas space velocity is 1500~3000 h⁻¹. -1 The catalyst was calcined for 6 to 18 hours to obtain a dry-based catalyst. ③ Activate the dry-based catalyst in a hydrogen-containing atmosphere with a hydrogen content of 10% to 100%. The hydrogen-containing mixture contains one or more of nitrogen, argon, or helium, excluding hydrogen. The activation temperature is 250 to 400 °C, the pressure is 0.1 to 1.0 MPa, and the gas space velocity is 1000 to 4000 h⁻¹. -1 The activated catalyst was obtained by activating it for 8-18 hours.

8. The application according to claim 6, characterized in that: The soluble salt of the active component in the first component is one or more of cobalt nitrate, cobalt acetate, cobalt chloride, and cobalt sulfate; the soluble salts of the first, second, and third auxiliaries are one or more of metal formate, acetate, oxalate, nitrate, sulfate, phosphate, citrate, malate, and chloride. The soluble salt of the active component in the second component is one or more of nickel nitrate, nickel chloride, nickel sulfate, palladium nitrate, palladium chloride, palladium acetate, chloroplatinic acid, ammonium chloroplatinate, tetraammineacetate, and dichlorodiammineplatinum; the soluble salt of the auxiliaries is one or more of metal formate, acetate, oxalate, nitrate, sulfate, phosphate, and chloride.

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