A CuM / SiO2|CoMn multifunctional catalyst for synthesizing high oxygen-containing compounds from synthesis gas, a preparation method and application thereof

Abstract

The present application belongs to the technical field of catalytic conversion of synthesis gas, and particularly relates to a CuM / SiO2|CoMn multifunctional catalyst for synthesis of high-level oxygen-containing compounds from synthesis gas, a preparation method and application thereof. The CuM / SiO2 catalyst (M is Ru, Rh, Pd, Ir, Pt, Au and Ag) is prepared by an excess impregnation method or an equal-volume impregnation method; the CoMn catalyst is prepared by a coprecipitation method, an impregnation method or a solid-phase grinding method; and the CuM / SiO2 catalyst and the CoMn catalyst are mixed in particles to obtain the CuM / SiO2|CoMn multifunctional catalyst. The catalyst is used for direct synthesis of high-level oxygen-containing compounds from synthesis gas, which can significantly improve the selectivity of the high-level oxygen-containing compounds, while maintaining high CO conversion rate and inhibiting the generation of C1 by-products. 2+ high-level oxygen-containing compounds, while maintaining high CO conversion rate and inhibiting the generation of C1 by-products.

Description

Technical Field

[0001] This invention belongs to the field of syngas conversion technology, specifically relating to a CuM / SiO2|CoMn multifunctional catalyst for the production of advanced oxygen-containing compounds from syngas, its preparation method, and its application. Background Technology

[0002] With the dwindling global fossil fuel resources and the increasingly severe greenhouse effect, the development of alternative petroleum-based energy routes is urgently needed. my country's energy distribution characteristics of "abundant coal, scarce oil, and limited natural gas" determine that coal dominates primary energy consumption. Fischer-Tropsch synthesis can directly produce various high-value chemicals such as advanced oxygenated hydrocarbons (ROHs), olefins, and liquid fuels from syngas, thus possessing significant potential value in industrial applications and academic research. Furthermore, syngas feedstocks are widely available, including coal, shale gas, natural gas, CO2, biomass, and municipal solid waste. Advanced oxygenated hydrocarbons (ROHs) mainly include alcohols or aldehydes. Due to their oxygen-containing functional groups, their oxygen atom utilization rate is higher, effectively reducing CO2 emissions from the products. ROHs have wide applications, with different industrial uses depending on their carbon number distribution. C2-C5 oxygenated products and their derivatives are generally used in gasoline additives, bulk chemical raw materials, pharmaceuticals, coatings, and cosmetics industries. High-carbon-number oxygenated products (C2-C5) are more widely used. 5+ ROH has higher economic and application value and is widely used in industries such as surfactants, detergents, polyolefins and lubricants.

[0003] Currently, the Fischer-Tropsch synthesis for direct production of olefins and liquid fuels has been industrialized. However, the direct production of higher oxygen-containing compounds via the Fischer-Tropsch synthesis still suffers from low selectivity due to the lack of stable and efficient catalysts. Research on this process remains in the laboratory and pilot-scale verification stages, posing significant challenges before industrial application. Meanwhile, the demand for higher oxygen-containing compounds is increasing annually both domestically and internationally. Therefore, the rational design of efficient and stable catalysts to improve the selectivity of total oxygen-containing products, particularly optimizing the proportion of high-carbon-number oxygen-containing products, has significant economic value and industrial application implications.

[0004] Currently, catalytic systems for the direct production of higher oxygen-containing compounds from syngas can be mainly classified into four categories: Rh-based catalysts, modified methanol catalysts, Mo-based catalysts, and modified Fischer-Tropsch catalysts. Among these, Rh-based catalysts are expensive, have low activity, and primarily produce ethanol. Modified methanol catalysts typically require the introduction of alkali metals or transition metals for modification, and their products are mainly methanol and a small amount of isobutanol. 2+ROH exhibits poor selectivity. Mo-based catalysts possess excellent sulfur resistance, but the reaction pressure is typically higher than 7 MPa, and CO2 selectivity is relatively high. Compared to the aforementioned catalysts, modified Fischer-Tropsch catalysts offer advantages such as low cost, mild reaction conditions, and strong carbon chain growth capability, making them the most promising candidates for catalytic systems in the production of advanced oxygenated compounds from syngas. Summary of the Invention

[0005] To address the problems of low target product selectivity, low CO conversion rate, and high C1 byproduct selectivity in the direct synthesis of advanced oxygenated compounds from syngas, this invention provides a CuM / SiO2|CoMn multifunctional catalyst for the synthesis of advanced oxygenated compounds from syngas, aiming to simultaneously improve CO conversion rate and selectivity for advanced oxygenated compounds, while effectively suppressing the formation of C1 byproducts.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows: This invention provides a method for preparing a CuM / SiO2|CoMn multifunctional catalyst for the synthesis of higher oxygen-containing compounds from syngas, comprising the following steps: Step 1: Prepare CuM / SiO2 catalyst by excess impregnation method or equal volume impregnation method, where M represents one of Ru, Rh, Pd, Ir, Pt, Au and Ag; Step 2: Prepare CoMn catalysts using co-precipitation, impregnation, or solid-phase grinding methods; Step 3: Mix CuM / SiO2 and CoMn catalyst particles to obtain the CuM / SiO2|CoMn multifunctional catalyst.

[0007] Furthermore, the specific steps for preparing the CuM / SiO2 catalyst using the excess impregnation method in step 1 include: Vaporized SiO2 powder was dispersed in deionized water to obtain a SiO2-containing suspension. A precursor solution of Cu and noble metal M was mixed uniformly and then added dropwise to the SiO2-containing suspension. The mixture was stirred at 60–90 °C until the solution evaporated to dryness. After drying at 70–120 °C for 10–18 h, the catalyst was calcined at 300–800 °C for 5–10 h to obtain the CuM / SiO2 catalyst. The loading of Cu was 8.0–12.0 wt%, and the loading of noble metal M was 0.2–1.2 wt%. The specific steps for preparing the CuM / SiO2 catalyst using the equal-volume impregnation method in step 1 include: The precursor metal salt solutions of Cu and noble metal M were mixed evenly and then added dropwise to SiO2 powder containing gas phase while stirring continuously. After the addition was completed, the mixture was aged at room temperature for 4-8 h. After drying at 70-120 °C for 10-18 h, it was calcined at 300-800 °C for 5-10 h to obtain CuM / SiO2 catalyst. The loading of Cu was 8.0-12.0 wt%, and the loading of noble metal M was 0.2-1.2 wt%.

[0008] Furthermore, the specific steps for preparing the CoMn catalyst using the co-precipitation method in step 2 include: Co and Mn precursor metal salts were dissolved in deionized water to form a metal precursor solution with a total metal ion concentration of 1.0–3.0 mol / L and an atomic molar ratio of Co / Mn of 1–4. Sodium carbonate, potassium carbonate, ammonia, or ammonium carbonate were dissolved in deionized water to form an alkaline solution with a concentration of 1.0–3.0 mol / L. The metal precursor solution and alkaline solution were added dropwise simultaneously using a co-precipitation method while maintaining continuous stirring, a pH of 8.0 ± 0.5, and a temperature of 30–70 °C. After aging for 1.0–5.0 h, the solution was washed with deionized water by centrifugation until neutral, then dried at 70–120 °C for 10–18 h, and finally calcined at 300–400 °C for 5–10 h to obtain the CoMn catalyst. The specific steps for preparing the CoMn catalyst using the impregnation method in step 2 include: Co and Mn precursor metal salts were dissolved in deionized water to form a metal precursor solution, wherein the atomic molar ratio of Co / Mn was 1-4 and the loading of Co was 10-20 wt%. The metal precursor solution was then added dropwise to activated carbon powder, stirred continuously, and aged at room temperature for 10-24 h. Subsequently, it was dried at 80-120 °C for 10-18 h and finally calcined at 300-400 °C for 5-10 h to obtain the CoMn catalyst. Alternatively, precursor metal salts of Co and Mn can be dissolved in deionized water to form a metal precursor solution, wherein the atomic molar ratio of Co / Mn is 1-4 and the Co loading is 10-20 wt%. The metal precursor solution is then added dropwise to activated carbon powder with continuous stirring. Subsequently, it is dried at 80-120 °C for 4-8 h, modified by introducing lanthanum nitrate solution, and dried further at 80-120 °C for 10-18 h, wherein the mass fraction of La is 0.2-1.0 wt%. Finally, it is calcined at 300-400 °C for 5-10 h to obtain a La-modified CoMn catalyst. The specific steps for preparing the CoMn catalyst using the solid-phase synthesis method in step 2 include: Co and Mn metal nitrate precursors were placed in a mortar and then ground and mixed for 10-30 min, wherein the atomic molar ratio of Co / Mn was 1-4; after drying at 70-120 °C for 8-12 h, they were calcined at 300-400 °C for 5-10 h to obtain the CoMn catalyst.

[0009] Furthermore, in step 2, when ammonia or ammonium carbonate is used as the alkaline solution in the process of preparing CoMn catalyst by coprecipitation, the process further includes grinding and mixing CoMn catalyst with K2CO3 to obtain K-modified CoMn catalyst, and the K content is 0.2~1.0 wt%.

[0010] Furthermore, in step 1, the precursor metal salt of Cu is one of copper nitrate or copper acetate, and the precursor metal salt of noble metal M is one of ruthenium chloride, rhodium nitrate, palladium nitrate, palladium chloride, iridium chloride, chloroplatinic acid, chloroauric acid, and silver nitrate; in step 2, the precursor metal salt of Co is one of cobalt nitrate, cobalt chloride, and cobalt acetate, and the soluble metal salt of Mn is one of manganese nitrate and manganese chloride.

[0011] Further, step 3 specifically includes: pressing CuM / SiO2 and CoMn catalysts into tablets, granulating and sieving them to 40~60 mesh, and then mixing the particles, with a mass ratio of 5:1 to 1:5.

[0012] In another aspect, the present invention provides a CuM / SiO2|CoMn multifunctional catalyst prepared by the method described above.

[0013] Another aspect of the present invention provides the application of the CuM / SiO2|CoMn multifunctional catalyst described above in the synthesis of advanced oxygen-containing compounds from syngas. The application includes: reducing the CuM / SiO2|CoMn catalyst and then introducing syngas (H2 / CO) for the reaction.

[0014] Further, the reduction conditions are as follows: the reducing gas is an H2 / N2 mixture with an H2 content of 10-100%, a CO / N2 mixture with a CO content of 10-100%, and a (H2+CO) / N2 mixture with a syngas content of 10-100%, the hydrogen-to-carbon ratio of the syngas (H2 / CO) is 2; the pressure is 0.1-0.5 MPa; the temperature is 280-350 °C; and the gas hourly space velocity is 6000-30000 h⁻¹. -1 The restoration time is 3~12 hours.

[0015] Furthermore, the reaction conditions are as follows: reaction temperature of 210~300 °C, pressure of 3.0~8.0 MPa, and gas hourly space velocity of 2000~10000 h⁻¹.-1 The hydrogen-to-carbon ratio (H2 / CO) of the syngas is 0.5 to 3.0.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) This invention prepares a CuM / SiO2|CoMn multifunctional catalyst based on CuM / SiO2 and CoMn catalysts modified with different noble metals. By precisely controlling the spatial distance and mass ratio between the two, high CO conversion and excellent ROH selectivity are achieved simultaneously, while significantly inhibiting the formation of CO2 and CH4. The synergistic effect of CuM / SiO2 and CoMn catalysts enhances the CH4 conversion. x O* / CO* insertion effectively promotes the formation of higher oxygen-containing compounds. The catalyst exhibits a ROH selectivity of up to 65 wt%, with C... 2+ The OH / ROH ratio can reach over 90%, C 5+ The OH / ROH ratio can reach over 60%.

[0017] (2) The catalyst preparation process of the present invention is simple, the reaction conditions are mild, the target product has high selectivity, and it can be used under various working conditions; (3) The catalyst of the present invention has excellent mechanical strength and is easy to shape during the preparation process; (4) The catalyst of the present invention has good stability and repeatability during the reaction process. Attached Figure Description

[0018] Figure 1 This is a graph showing the 150-hour reaction results of the CuRu / SiO2|CoMn multifunctional catalyst prepared in Example 1. (Reaction conditions: H2 / CO=2, T=210 °C, P=5 MPa, GHSV=2000 h) -1 。 Detailed Implementation

[0019] To facilitate understanding of the present invention, a more comprehensive description will be provided below. However, the present invention can be implemented in many different forms and is not limited to the embodiments and comparative examples described herein. Rather, these embodiments and comparative examples are provided to provide a thorough and complete understanding of the disclosure of the present invention.

[0020] Comparative Example 1 Catalyst preparation (I) Preparation of Cu / SiO2 catalyst 3 g of fumed SiO2 powder was added to 50 mL of deionized water and stirred to disperse it evenly in the liquid, forming a SiO2 suspension. 1.14 g of copper nitrate trihydrate was dissolved in 10 mL of deionized water, and then the solution was added dropwise to the SiO2 suspension. The mixture was stirred thoroughly at 80 °C until the solution evaporated to dryness. It was then dried in a 70 °C oven for 10 h and calcined in a muffle furnace at 500 °C for 5 h to obtain the Cu / SiO2 catalyst. The Cu loading was 10.0 wt%.

[0021] (II) Preparation of CoMn catalyst A solution of cobalt nitrate hexahydrate and manganese nitrate (50 wt%) was added to 150 mL of deionized water at a molar ratio of Co / Mn = 2 / 1, resulting in a total metal concentration of 2 mol / L. Simultaneously, Na₂CO₃ was dissolved in 400 mL of deionized water, and Na… + The concentration was 2 mol / L. Then, both solutions were simultaneously added dropwise to a beaker containing 100 mL of deionized water, while stirring uniformly with a magnetic stirrer. The pH of the solution was maintained at approximately 7.8, and the temperature was 30 °C. After the solution addition was complete, stirring was continued, and the mixture was aged for 2 hours. Next, the mixture was washed several times with deionized water in a centrifuge until the supernatant was neutral. The precursor was dried in an oven at 80 °C for 12 hours, and finally calcined in a muffle furnace at 330 °C for 3 hours to obtain the CoMn catalyst.

[0022] (III) Preparation of Cu / SiO2|CoMn Multifunctional Catalyst The Cu / SiO2 and CoMn catalysts prepared above were granulated and sieved to 40-60 mesh, and then the two were mixed evenly in a mass ratio of 1:1 to obtain a Cu / SiO2|CoMn multifunctional catalyst.

[0023] Catalyst Application 1.5 g of Cu / SiO2|CoMn multifunctional catalyst was mixed evenly with 3 g of quartz sand and then packed into a high-pressure stainless steel fixed-bed reactor. The catalyst was first reduced at 300 °C for 5 h under a H2 atmosphere at a pressure of 0.1 MPa. After reduction, the reactor was cooled to room temperature, then syngas (H2 / CO=2) was introduced, and the pressure was slowly increased to 5 MPa, followed by a temperature increase to 220 °C at a gas hourly space velocity (GHSV) of 4000 h⁻¹. -1 After the reaction stabilized for 24 h, the tail gas, aqueous phase, oil phase, and wax phase products were analyzed. The mass balance, carbon balance, and oxygen balance were maintained within the range of 95% to 105%. The specific performance is shown in the table below.

[0024]

[0025] Example 1 Catalyst preparation (I) Preparation of CuRu / SiO2 catalyst 3 g of fumed SiO2 support was added to 50 mL of deionized water and dispersed uniformly using magnetic stirring to form a SiO2 suspension. 1.14 g of copper nitrate trihydrate was added to 17.8 mL of ruthenium chloride solution (0.01 mol / L) and dispersed uniformly using ultrasonic treatment. The solution was then added dropwise to the SiO2 suspension at 70 °C with stirring until the solution evaporated to dryness. The solution was then dried overnight in a 70 °C oven and finally calcined in a muffle furnace at 500 °C for 5 h to obtain the CuRu / SiO2 catalyst. The loading of Cu was 10.0 wt% and the loading of Ru was 0.6 wt%.

[0026] (II) Preparation of CoMn catalyst A solution of cobalt nitrate hexahydrate and manganese nitrate (50 wt%) was added to 150 mL of deionized water at a molar ratio of Co / Mn = 2 / 1 to form a metal precursor solution with a total metal ion concentration of 2 mol / L. Na₂CO₃ was dissolved in 400 mL of deionized water to form an alkaline solution as a precipitant, and Na₂CO₃ was added to the solution. + The concentration was 2 mol / L. The precipitant and metal precursor solution were then added dropwise to a beaker containing 100 mL of deionized water, and the mixture was continuously stirred with a stirrer, maintaining the precipitation temperature at 30 °C. The pH of the solution was monitored online using a pH meter to ensure it remained stable at approximately 8.0. After precipitation, the solution was aged for another 2 h. After several centrifugal washes with deionized water, it was dried at 80 °C for 12 h and calcined at 330 °C for 5 h to obtain fresh CoMn catalyst.

[0027] (III) Preparation of CuRu / SiO2|CoMn Multifunctional Catalyst The CoMn catalyst obtained in step (II) and the CuRu / SiO2 catalyst obtained in step (I) are mixed in a 1:1 mass ratio (40~60 mesh) to obtain a CuRu / SiO2|CoMn multifunctional catalyst.

[0028] Catalyst Application 1.5 g of CuRu / SiO2|CoMn multifunctional catalyst prepared according to the above method was mixed evenly with 3 g of quartz sand, and then loaded into a fixed-bed reactor. Reduction and reaction were carried out according to the following steps: Reduction conditions: reducing gas H2, pressure 0.1 MPa, temperature 300 ℃, gas hourly space velocity 6000 h⁻¹. -1The reduction time was 5 h. The reaction conditions were: reaction temperature 210 ℃, pressure 5.0 MPa, and gas hourly space velocity 4000 h⁻¹. -1 The hydrogen-to-carbon ratio (H2 / CO) of the syngas was 2. After stabilization for 24 h, the specific reaction performance is shown in the table below. The stability of the CuRu / SiO2|CoMn multifunctional catalyst was also evaluated; see attached figure. Figure 1 Within 160 hours of laboratory evaluation, the catalyst maintained a CO conversion rate of 10%–16%, an oxygen-containing product selectivity of 60%–65%, and CO2 and CH4 selectivities of less than 10%, indicating that the catalyst has good prospects for industrial application.

[0029] Example 2

[0030] Catalyst preparation (I) Preparation of CuRh / SiO2 catalyst 3 g of SiO2 powder was added to 50 mL of deionized water and stirred for 30 min to disperse it evenly, forming a SiO2 suspension. 1.14 g of copper nitrate trihydrate was added to 10 mL of deionized water, followed by the addition of 0.18 g of a rhodium nitrate mixed solution (10 wt%), and the mixture was sonicated for 10 min to form a metal mixed solution. This metal mixed solution was then added to the SiO2 suspension, and the mixture was stirred and heated (90 °C) until the liquid evaporated to dryness. After drying (90 °C, 10 h) and calcining (500 °C, 5 h), a CuRh / SiO2 catalyst was obtained. The loading of Cu was 10.0 wt%, and the loading of Rh was 0.6 wt%.

[0031] (II) Preparation of CoMn catalyst A solution of cobalt nitrate hexahydrate and manganese nitrate (50 wt%) was added to 150 mL of deionized water at a molar ratio of Co / Mn = 2.2 / 1 to form a metal precursor solution with a total metal ion concentration of 1.8 mol / L. Potassium carbonate was dissolved in 400 mL of deionized water to form an alkaline solution, and K... + The concentration was 1.8 mol / L. A co-precipitation method was used, with the metal precursor solution and alkaline solution added dropwise simultaneously, controlling the pH at approximately 8.3 and the precipitation temperature at 50 °C. After the addition was complete, the catalyst was aged for 2 h, centrifuged and washed (with deionized water), dried in an oven at 120 °C for 15 h, and finally calcined in a muffle furnace at 350 °C for 5 h to obtain the CoMn oxide catalyst.

[0032] (III) Preparation of CuRh / SiO2|CoMn Multifunctional Catalyst CuRh / SiO2 and CoMn catalysts were pressed into tablets, granulated, and sieved into 40-60 mesh particles, respectively. Then, the particles were mixed in a 1:1 mass ratio to obtain the CuRh / SiO2|CoMn multifunctional catalyst.

[0033] Catalyst Application 1.5 g of CuRh / SiO2|CoMn multifunctional catalyst was mixed evenly with 3 g of quartz sand (40-60 mesh) and packed into a high-pressure stainless steel fixed-bed reactor. Reduction was first carried out in a pure H2 atmosphere at 300 °C for 5 h at atmospheric pressure and a space velocity of 6000 h⁻¹. -1 After reduction, residual H2 was purged with N2. Then, syngas (H2 / CO = 2) was introduced, and the pressure and temperature were raised to 5.2 MPa and 220 °C, respectively, with a space velocity of 4000 h⁻¹. -1 After the reaction stabilized, samples were taken for analysis. The catalytic performance is shown in the table below.

[0034]

[0035] Example 3 Catalyst preparation (I) Preparation of CuPd / SiO2 catalyst 1.08 g of copper nitrate trihydrate was dissolved in 10 mL of deionized water, followed by the addition of 33.8 mL of palladium nitrate solution (0.005 mol / L) to form a metal precursor solution. 3 g of SiO2 powder was added to 50 mL of deionized water and stirred for 30 min to ensure uniform dispersion. The metal precursor solution was then added dropwise, and the mixture was stirred continuously at 80 °C until the liquid evaporated to dryness. The solution was calcined in a muffle furnace at 500 °C for 5 h to obtain a CuPd / SiO2 catalyst. The Cu loading was 9.5 wt%, and the Pd loading was 0.6 wt%.

[0036] (II) Preparation of CoMn catalyst A solution of cobalt nitrate hexahydrate and manganese nitrate (50 wt%) was added to 150 mL of deionized water at a molar ratio of Co / Mn = 2 / 1 to form a metal precursor solution with a total metal ion concentration of 2 mol / L. Ammonia (2 mol / L) was used as a precipitant. Using a co-precipitation method, the metal precursor solution and ammonia solution were added dropwise simultaneously with continuous stirring, and the pH was controlled at approximately 8.0. The precipitation temperature was 30 °C. After the addition was complete, the mixture was washed several times by centrifugation with deionized water, dried in an oven at 80 °C for 12 h, and finally calcined in a muffle furnace at 350 °C for 5 h to obtain the CoMn oxide catalyst.

[0037] (III) Preparation of CuPd / SiO2|CoMn Multifunctional Catalyst CuPd / SiO2 and CoMn catalysts were pressed into tablets, granulated, and sieved into 40-60 mesh particles, respectively. Then, the particles were mixed in a 1:1 mass ratio to obtain the CuPd / SiO2|CoMn multifunctional catalyst.

[0038] Catalyst Application 1.5 g of CuPd / SiO2|CoMn multifunctional catalyst was mixed with 3 g of quartz sand (40-60 mesh) and its performance was evaluated in a 1.5 mL fixed-bed reactor. The catalyst was first reduced at 300 °C for 5 h in a pure H2 atmosphere, with P = 0.1 MPa and a space velocity of 6000 h⁻¹. -1 After reduction, N2 was purged for 5 h. Then, syngas (H2 / CO=2) was introduced, with a reaction pressure of 5 MPa and a reaction temperature of 220 °C, and a space velocity of 4000 h⁻¹. -1 After the reaction stabilized, samples were taken for analysis, and the catalytic performance is shown in the table below.

[0039]

[0040] Example 4 Catalyst preparation (I) Preparation of CuPd / SiO2 catalyst 1.25 g of copper nitrate trihydrate was added to 16.9 mL of palladium chloride solution (0.01 mol / L), and the mixture was ultrasonically treated to form a metal mixture solution. 3 g of SiO2 powder was added to 50 mL of deionized water and stirred for 30 min to disperse it uniformly, forming a SiO2 suspension. Using an excess impregnation method, the metal mixture solution was added dropwise to the SiO2 suspension, maintaining the temperature at 80 °C, and continuously stirred with a magnetic stirrer until the liquid evaporated to dryness. The calcination conditions were: air atmosphere, 500 °C, and calcination time of 5 h, yielding a CuPd / SiO2 catalyst. The Cu loading was 11.0 wt%, and the Pd loading was 0.6 wt%.

[0041] (II) Preparation of CoMn catalyst A solution of cobalt nitrate hexahydrate and manganese nitrate (50 wt%) was added to 150 mL of deionized water at a molar ratio of Co / Mn = 1.8 / 1 to form a metal precursor solution with a total metal ion concentration of 2 mol / L. Potassium carbonate was dissolved in 400 mL of deionized water to form an alkaline solution, and K... +The concentration was 2 mol / L. A co-precipitation method was used, with the metal precursor solution and potassium carbonate solution added dropwise simultaneously, maintaining the pH at approximately 8.1, and the precipitation temperature at 60 °C. After the addition was complete, the solution was washed with deionized water by centrifugation until neutral. It was then dried in an oven at 80 °C for 12 h, and finally calcined in a muffle furnace at 350 °C in air for 5 h to obtain the CoMn oxide catalyst.

[0042] (III) Preparation of CuPd / SiO2|CoMn Multifunctional Catalyst CuPd / SiO2 and CoMn catalysts were pressed into tablets, granulated, and sieved into 40-60 mesh particles, respectively. Then, the particles were mixed at a mass ratio of 3:1 to obtain the CuPd / SiO2|CoMn multifunctional catalyst.

[0043] Catalyst Application Two g of CuPd / SiO2|CoMn multifunctional catalyst was mixed with four g of quartz sand (40-60 mesh) and its performance was evaluated in a high-pressure fixed-bed reactor. First, reduction was carried out in a pure H2 atmosphere at 300 °C for 5 h, P = 0.1 MPa, and a space velocity of 6000 h⁻¹. -1 After reduction, syngas (H2 / CO=2) was introduced, with a reaction pressure of 7 MPa and a reaction temperature of 220 °C, and a space velocity of 4000 h⁻¹. -1 After the reaction reached stability, samples were taken for analysis, and the catalytic performance is shown in the table below.

[0044]

[0045] Example 5 Catalyst preparation (I) Preparation of CuPd / SiO2 catalyst 1.03 g of copper nitrate trihydrate was dissolved in 10 mL of deionized water, followed by the addition of 22.6 mL of palladium nitrate solution (0.005 mol / L). The solution was then added dropwise to 3 g of SiO2 powder using an equal-volume impregnation method, with continuous stirring using a glass rod. After the addition was complete, the mixture was aged at room temperature for 12 h, followed by drying in an oven at 80 °C for 12 h. Finally, it was calcined in a muffle furnace at 500 °C for 5 h to obtain the CuPd / SiO2 catalyst. The Cu loading was 9.0 wt%, and the Pd loading was 0.4 wt%.

[0046] (II) Preparation of CoMn catalyst A 50 wt% solution of cobalt nitrate hexahydrate and manganese nitrate was added to 150 mL of deionized water at a molar ratio of Co / Mn = 3 / 1 to form a metal precursor solution with a total metal ion concentration of 2.1 mol / L. Sodium carbonate was dissolved in 400 mL of deionized water to form an alkaline solution, and Na... + The concentration was 2.1 mol / L. A co-precipitation method was used, with the metal solution and alkaline solution added dropwise simultaneously, while the pH of the solution was controlled at approximately 8.1, and the precipitation temperature was 30 °C. After the solution addition was complete, the mixture was aged for 2 h. It was then washed with deionized water until neutral, dried in an oven at 80 °C for 12 h, and then calcined in a muffle furnace at 330 °C for 5 h to obtain the CoMn catalyst.

[0047] (III) Preparation of CuPd / SiO2|CoMn Multifunctional Catalyst The CuPd / SiO2 and CoMn catalysts obtained above were respectively pressed, granulated, and sieved to obtain particles of 40-60 mesh. Then, they were mixed at a mass ratio of 1:3 to obtain a CuPd / SiO2|CoMn multifunctional catalyst.

[0048] Catalyst Application 3 g of CuPd / SiO2|CoMn multifunctional catalyst was mixed evenly with 6 g of quartz sand (40-60 mesh) and packed into a high-pressure fixed-bed reactor. The catalyst was first reduced at 300 °C for 5 h under a 50% H2 / N2 atmosphere, with P = 0.1 MPa and a space velocity of 8000 h⁻¹. -1 After reduction, syngas (H2 / CO=2) was introduced, the reaction pressure was 5.2 MPa, the reaction temperature was 220 °C, and the space velocity was 4000 h⁻¹. -1 After the reaction reached stability, samples were taken for analysis, and the catalytic performance is shown in the table below.

[0049]

[0050] Example 6 Catalyst preparation (I) Preparation of CuPd / SiO2 catalyst 0.84 g of copper acetate monohydrate was dissolved in 10 mL of deionized water, followed by the addition of 19.7 mL of palladium nitrate solution (0.01 mol / L). The resulting mixed metal solution was then added dropwise to a beaker containing 3 g of fumed SiO2 powder, with continuous stirring using a glass rod. The catalyst was subsequently dried in an oven at 80 °C for 15 h, and finally calcined in a muffle furnace at 700 °C for 6 h. The Cu and Pd loadings were 9.0 wt% and 0.7 wt%, respectively.

[0051] (II) Preparation of CoMn catalyst A cobalt acetate and manganese nitrate solution (50 wt%) was added to 100 mL of deionized water at a molar ratio of Co / Mn = 2.5 / 1 to form a metal precursor solution with a total metal ion concentration of 1.8 mol / L. Sodium carbonate was dissolved in 300 mL of deionized water to form an alkaline solution, and Na... + The concentration was 2.1 mol / L. A co-precipitation method was used, where the metal solution and alkaline solution were simultaneously added dropwise to a beaker, with the pH of the solution controlled at approximately 8.1 and the precipitation temperature at 60 °C. After the addition was complete, aging continued for 2 h. Subsequently, it was washed with deionized water until neutral, dried in an oven at 120 °C for 12 h, and then calcined in a muffle furnace at 330 °C for 5 h to obtain the CoMn catalyst.

[0052] (III) Preparation of CuPd / SiO2|CoMn Multifunctional Catalyst The CuPd / SiO2 and CoMn catalysts obtained above were respectively pressed, granulated, and sieved to obtain particles of 40-60 mesh. Then, they were mixed at a mass ratio of 1:1 to obtain a CuPd / SiO2|CoMn multifunctional catalyst.

[0053] Catalyst Application Two g of CuPd / SiO2|CoMn multifunctional catalyst was mixed with four g of quartz sand (40-60 mesh) and packed into a high-pressure fixed-bed reactor, with both ends secured with quartz sand. The catalyst was first subjected to a 20% CO / N2 reducing atmosphere at 300 °C, atmospheric pressure, and a space velocity of 10000 h⁻¹. -1 The reduction was carried out for 5 h. After the reduction was completed, synthesis gas (H2 / CO=2) was introduced, and then the reaction pressure and temperature were adjusted to 5 MPa and 260 °C, respectively, with a space velocity of 8000 h⁻¹. -1 After the hydrocarbon products in the exhaust gas were stabilized by chromatographic analysis, samples were taken for analysis. The catalytic performance is shown in the table below.

[0054]

[0055] Example 7 Catalyst preparation (I) Preparation of CuPd / SiO2 catalyst 1.14 g of copper nitrate trihydrate was dissolved in 10 mL of deionized water, followed by the addition of 22.6 mL of palladium chloride solution (0.01 mol / L), and the mixture was ultrasonically mixed to form a metal mixture solution. Simultaneously, 3 g of SiO2 powder was added to 50 mL of deionized water and stirred for 30 min to disperse it uniformly, forming a SiO2 suspension. The metal mixture solution was then added dropwise to the SiO2 suspension using a dropper, and the mixture was continuously stirred with a magnetic stirrer and heated (80 °C) until the solvent evaporated completely. The solution was then dried in an oven at 100 °C for 12 h, followed by calcination in a muffle furnace at 400 °C for 6 h to obtain the CuPd / SiO2 catalyst. The Cu and Pd loadings were 10 wt% and 0.8 wt%, respectively.

[0056] (II) Preparation of CoMn catalyst Cobalt nitrate hexahydrate and manganese nitrate were placed in a mortar at a molar ratio of Co / Mn = 2 / 1 and ground thoroughly for 20 min using a solid-phase grinding method to ensure uniform mixing. The ground precursor was then placed in a crucible and calcined in a muffle furnace at 350°C for 5 h to obtain the CoMn catalyst.

[0057] (III) Preparation of CuPd / SiO2|CoMn Multifunctional Catalyst The CuPd / SiO2 and CoMn catalysts obtained above were respectively pressed, granulated, and sieved to obtain particles of 40-60 mesh. Then, they were mixed at a mass ratio of 1:1 to obtain a CuPd / SiO2|CoMn multifunctional catalyst.

[0058] Catalyst Application 1.5 g of CuPd / SiO2|CoMn multifunctional catalyst was diluted with 3 g of quartz sand (40-60 mesh) and then packed into a high-pressure fixed-bed reactor. The catalyst was first subjected to a 20% (H2+CO) / N2 atmosphere at 280 °C, P=0.1 MPa, and a space velocity of 10000 h⁻¹. -1 The reduction was carried out for 5 hours. After the reduction was completed, synthesis gas (H2 / CO=0.5) was introduced, and the pressure and temperature were slowly increased to 7.0 MPa and 230 °C, respectively, with a space velocity of 3000 h⁻¹. -1 After the reaction stabilized, samples were taken for analysis, and the catalytic performance is shown in the table below.

[0059]

[0060] Example 8 Catalyst preparation (I) Preparation of CuPd / SiO2 catalyst 1.14 g of copper nitrate trihydrate was dissolved in 10 mL of deionized water, followed by the addition of 16.9 mL of palladium nitrate solution (0.01 mol / L), and the mixture was ultrasonically mixed thoroughly. The solution was then added dropwise to a beaker containing 3 g of fumed SiO2 powder, with continuous stirring using a glass rod. The mixture was then aged in a fume hood for 6 h, followed by drying in an oven at 80 °C for 16 h. Finally, it was calcined in a muffle furnace at 500 °C for 6 h. The Cu and Pd loadings were 10.0 wt% and 0.6 wt%, respectively.

[0061] (II) Preparation of CoMnK catalyst A solution of cobalt nitrate hexahydrate and manganese nitrate (50 wt%) was added to 200 mL of deionized water at a molar ratio of Co / Mn = 2 / 1 to form a metal precursor solution with a total metal ion concentration of 2 mol / L. Ammonium carbonate was dissolved in 400 mL of deionized water to form a precipitant with a carbonate concentration of 2 mol / L. The two solutions were simultaneously added dropwise using a co-precipitation method, maintaining the pH at approximately 8.2 and the temperature at 30 °C. After the addition was complete, the mixture was aged for 3 h. After washing with deionized water, it was dried in an oven at 110 °C for 12 h. Finally, it was calcined in a muffle furnace at 350 °C for 8 h to obtain CoMn precursor powder. Subsequently, 10 g of the CoMn precursor and 0.11 g of potassium carbonate powder were thoroughly ground in a mortar for 10 min to obtain a CoMnK catalyst with a K mass fraction of 0.6 wt%.

[0062] (III) Preparation of CuPd / SiO2|CoMnK Multifunctional Catalyst The CuPd / SiO2 and CoMnK catalysts obtained above were respectively pressed, granulated, and sieved to obtain particles of 40-60 mesh. Then, they were mixed at a mass ratio of 1:1 to obtain a CuPd / SiO2|CoMnK multifunctional catalyst.

[0063] Catalyst Application 1.5 g of CuPd / SiO2|CoMnK multifunctional catalyst was thoroughly mixed with 3 g of quartz sand (40-60 mesh) and packed into the isothermal zone of a fixed-bed reactor. The catalyst was first reduced with H2 at 300 °C for 5 h at a pressure of 0.1 MPa and a space velocity of 12000 h⁻¹. -1 After reduction, the temperature was lowered to 180 °C, and syngas (H2 / CO=2) was introduced. The reaction pressure was slowly increased to 5.0 MPa, followed by a temperature increase to 220 °C and a space velocity of 4000 h⁻¹. -1 After the reaction stabilized, samples were taken for analysis, and the catalytic performance is shown in the table below.

[0064]

[0065] Example 9 Catalyst preparation (I) Preparation of CuPd / SiO2 catalyst 1.08 g of copper nitrate trihydrate was dissolved in 10 mL of deionized water, followed by the addition of 19.7 mL of palladium nitrate solution (0.01 mol / L), and the mixture was ultrasonically mixed thoroughly. The solution was then added dropwise to a beaker containing 3 g of fumed SiO2 powder, with continuous stirring using a glass rod. The mixture was then aged at room temperature for 6 h in a fume hood, followed by drying in an oven at 80 °C for 15 h, and finally calcined in a muffle furnace at 500 °C for 6 h to obtain the CuPd / SiO2 catalyst. The Cu and Pd loadings were 9.5 wt% and 0.7 wt%, respectively.

[0066] (II) Preparation of CoMn catalyst A solution of cobalt nitrate hexahydrate and manganese nitrate (50 wt%) was added to 200 mL of deionized water at a molar ratio of Co / Mn = 2 / 1 to form a metal precursor solution with a total metal ion concentration of 1.8 mol / L. Ammonium carbonate was dissolved in 400 mL of deionized water to form a precipitant with a carbonate concentration of 1.8 mol / L. Using a co-precipitation method, both solutions were added dropwise simultaneously, maintaining the pH at approximately 8.1 and the precipitation temperature at 30 °C. After the addition was complete, the mixture was aged for 3 h. After washing with deionized water, it was dried in an oven at 120 °C for 10 h. Finally, it was calcined in a muffle furnace at 350 °C for 5 h to obtain the CoMn catalyst.

[0067] (III) Preparation of CuPd / SiO2|CoMn Multifunctional Catalyst The CuPd / SiO2 and CoMn catalysts obtained above were respectively pressed, granulated, and sieved to obtain particles of 40-60 mesh. Then, they were mixed at a mass ratio of 2:1 to obtain a CuPd / SiO2|CoMn multifunctional catalyst.

[0068] Catalyst Application Two g of CuPd / SiO2|CoMn multifunctional catalyst was thoroughly mixed with four g of quartz sand (40-60 mesh), and its performance was evaluated in a fixed-bed reactor. H2 was first introduced, and reduction was carried out at 300 °C for 5 h, P = 0.1 MPa, and space velocity was 20000 h⁻¹. -1 After reduction, the temperature was lowered to 150 °C, and then syngas (H2 / CO=2) was introduced. The reaction pressure and temperature were 6.0 MPa and 220 °C, respectively, and the space velocity was 4000 h⁻¹. -1After the reaction stabilized, samples were taken for analysis, and the catalytic performance is shown in the table below.

[0069]

[0070] Example 10 Catalyst preparation (I) Preparation of CuPd / SiO2 catalyst 0.98 g of copper acetate monohydrate was dissolved in 10 mL of deionized water, followed by the addition of 16.9 mL of palladium chloride solution (0.01 mol / L). Simultaneously, 3 g of SiO2 powder was added to 50 mL of deionized water and stirred for 30 min to ensure uniform dispersion. The metal mixture was then added dropwise to the SiO2 suspension using a dropper, with continuous stirring and heating (80 °C) using a magnetic stirrer until the solvent evaporated completely. The mixture was then dried in an oven at 80 °C for 12 h, and finally calcined in a muffle furnace at 500 °C for 5 h to obtain the CuPd / SiO2 catalyst. The Cu and Pd loadings were 10.5 wt% and 0.6 wt%, respectively.

[0071] (II) Preparation of CoMnK catalyst A solution of cobalt nitrate hexahydrate and manganese nitrate (50 wt%) was added to 200 mL of deionized water at a molar ratio of Co / Mn = 2 / 1 to form a metal precursor solution with a total metal ion concentration of 2.5 mol / L. Ammonium carbonate was dissolved in 400 mL of deionized water to form a precipitant with a carbonate concentration of 2.5 mol / L. Using a co-precipitation method, the two solutions were simultaneously added dropwise to a beaker containing 200 mL of deionized water using a peristaltic pump, maintaining the pH at approximately 8.4 and the precipitation temperature at 30 °C. After the addition was complete, the mixture was allowed to age for 2 h, followed by washing with deionized water and drying in an oven at 80 °C for 12 h. Finally, it was calcined at 350 °C for 5 h to obtain CoMn precursor powder. Subsequently, 10 g of the CoMn precursor and 0.18 g of potassium carbonate powder were thoroughly ground in a mortar for 10 min to obtain a CoMnK catalyst with a K mass fraction of 1.0 wt%.

[0072] (III) Preparation of CuPd / SiO2|CoMnK Multifunctional Catalyst The CuPd / SiO2 and K-modified CoMn catalysts obtained above were respectively pressed, granulated, and sieved to obtain 40-60 mesh particles. Then, they were mixed at a mass ratio of 1:1 to obtain the CuPd / SiO2|CoMnK multifunctional catalyst.

[0073] Catalyst Application 1.5 g of CuPd / SiO2|CoMnK catalyst was thoroughly mixed with 3 g of quartz sand (40-60 mesh) and placed in a fixed-bed reactor for reaction evaluation. Initially, 50% H2 / N2 was introduced, and reduction was carried out at 300 °C for 5 h, P = 0.1 MPa, and space velocity was 18000 h⁻¹. -1 After reduction, synthesis gas (H2 / CO=2) is introduced to carry out the reaction under the following conditions: P=6.0 MPa, T=220 °C, GHSV=4000 h. -1 After the reaction stabilized, samples were taken for analysis, and the catalytic performance is shown in the table below.

[0074]

[0075] Example 11 Catalyst preparation (I) Preparation of CuIr / SiO2 catalyst 1.14 g of copper nitrate trihydrate was dissolved in 10 mL of deionized water, and 9.37 mL of iridium chloride solution (0.01 mol / L) was added simultaneously. The mixture was then sonicated until homogeneous. 3 g of fumed SiO2 powder was thoroughly dispersed in 50 mL of deionized water, and the above metal mixture was then added dropwise. The mixture was stirred for 30 min and heated to 80 °C until the solvent was evaporated. The solution was then dried in a 100 °C oven for 12 h and finally calcined at 500 °C for 5 h to obtain the CuIr / SiO2 catalyst. The loading of Cu was 10.0 wt%, and the loading of Ir was 0.6 wt%.

[0076] (II) Preparation of CoMn catalyst A solution of cobalt nitrate hexahydrate and manganese nitrate (50 wt%) was added to 200 mL of deionized water at a molar ratio of Co / Mn = 2 / 1 to form a metal precursor solution with a total metal ion concentration of 2 mol / L. Sodium carbonate was dissolved in 350 mL of deionized water to form an alkaline solution, and Na... + The concentration was 2 mol / L. The solution was simultaneously added dropwise to a beaker using a peristaltic pump, with the pH precisely controlled at approximately 8.0 and the precipitation temperature at 40 °C. After aging for 2 h, it was washed with deionized water until neutral, then dried in an oven at 80 °C for 12 h, and finally calcined at 350 °C for 5 h to obtain the CoMn catalyst.

[0077] (III) Preparation of CuIr / SiO2|CoMn Multifunctional Catalyst The CuIr / SiO2 and CoMn catalysts obtained above were respectively pressed, granulated, and sieved to obtain particles of 40-60 mesh. Then, they were mixed at a mass ratio of 1:1 to obtain a CuIr / SiO2|CoMn multifunctional catalyst.

[0078] Catalyst Application 1.5 g of CuIr / SiO2|CoMn multifunctional catalyst was thoroughly mixed with 3 g of quartz sand and packed into a fixed-bed reactor for reaction evaluation. First, pure H2 was introduced, and reduction was carried out at 300 °C for 5 h (P = 0.1 MPa). After cooling to room temperature, syngas (H2 / CO = 3) was introduced for further reaction. The reaction pressure and temperature were 6.0 MPa and 240 °C, respectively, with a GHSV of 6000 h⁻¹. -1 After the reaction stabilized, samples were taken for analysis, and the catalytic performance is shown in the table below.

[0079]

[0080] Example 12 Catalyst preparation (I) Preparation of CuAu / SiO2 catalyst 1.14 g of copper nitrate trihydrate was dissolved in 15 mL of deionized water, and 9.0 mL of chloroauric acid solution (0.01 mol / L) was added and the mixture was ultrasonically mixed until homogeneous. 3 g of fumed SiO2 powder was thoroughly dispersed in 50 mL of deionized water and stirred for 30 min to ensure uniform dispersion. The above metal mixture was then added dropwise, and the mixture was stirred at 80 °C until the solvent evaporated. The mixture was then dried in an oven at 100 °C for 15 h, followed by calcination in a muffle furnace at 600 °C for 8 h to obtain the CuAu / SiO2 catalyst. The loading of Cu was 10.0 wt%, and the loading of Au was 0.6 wt%.

[0081] (II) Preparation of CoMn catalyst Cobalt chloride and manganese chloride were dissolved in 180 mL of deionized water at a molar ratio of Co / Mn = 2 / 1 to form a metal precursor solution with a total metal ion concentration of 2 mol / L. Sodium carbonate was dissolved in 400 mL of deionized water to form an alkaline solution, and Na... + The concentration was 2 mol / L. The metal precursor solution and alkaline solution were simultaneously added dropwise to a beaker using a peristaltic pump, with the pH precisely controlled at approximately 8.1 and the precipitation temperature at 50 °C. After aging for 2 h, the solution was washed with deionized water until neutral, then dried in an oven at 80 °C for 12 h, and finally calcined at 380 °C for 5 h to obtain the CoMn catalyst.

[0082] (III) Preparation of CuAu / SiO2|CoMn Multifunctional Catalyst The CuAu / SiO2 and CoMn catalysts obtained above were respectively pressed, granulated, and sieved to obtain particles of 40-60 mesh. Then, they were mixed at a mass ratio of 2:1 to obtain a CuAu / SiO2|CoMn multifunctional catalyst.

[0083] Catalyst Application 1.5 g of CuAu / SiO2|CoMn multifunctional catalyst was thoroughly mixed with 3 g of quartz sand and then packed into the isothermal zone of a fixed-bed reactor. First, a 20% (H2+CO) / N2 mixed gas was introduced, and reduction was carried out at 350 °C for 5 h at P = 0.1 MPa. After cooling to room temperature, synthesis gas (H2 / CO = 1.5) was introduced to proceed with the reaction. Reaction conditions: P = 6.0 MPa, T = 250 °C, GHSV = 8000 h. -1 After the reaction stabilized, samples were taken for analysis, and the catalytic performance is shown in the table below.

[0084]

[0085] Example 13 Catalyst preparation (I) Preparation of CuPt / SiO2 catalyst 1.14 g of copper nitrate trihydrate was dissolved in 10 mL of deionized water, and 9.2 mL of chloroplatinic acid solution (0.01 mol / L) was added and ultrasonically mixed until homogeneous. 3 g of fumed SiO2 powder was thoroughly dispersed in 50 mL of deionized water and stirred for 30 min to ensure uniform dispersion. The above metal mixture was then added dropwise using a dropper, and the mixture was stirred continuously at 80 °C until it evaporated to dryness. The mixture was then dried in an oven at 110 °C for 12 h, followed by calcination in a muffle furnace at 550 °C for 6 h to obtain the CuPt / SiO2 catalyst. The Cu loading was 10.0 wt%, and the Pt loading was 0.6 wt%.

[0086] (II) Preparation of CoMn / AC catalyst A solution of cobalt nitrate hexahydrate and manganese nitrate (50 wt%) was added to 10 mL of deionized water at a molar ratio of Co / Mn = 2 / 1 and mixed thoroughly by ultrasonication. Then, it was added dropwise to 5 g of coconut shell charcoal (AC) powder with continuous stirring using a glass rod and aged at room temperature for 12 h. Subsequently, it was dried at 80 °C for 10 h and calcined in a muffle furnace at 350 °C for 5 h to obtain a CoMn / AC catalyst with a Co loading of 15 wt%.

[0087] (III) Preparation of CuPt / SiO2|CoMn / AC Multifunctional Catalyst The CuPt / SiO2 and CoMn / AC catalysts obtained above were respectively pressed, granulated, and sieved to obtain particles of 40-60 mesh. Then, they were mixed at a mass ratio of 1:1 to obtain a CuPt / SiO2|CoMn / AC multifunctional catalyst.

[0088] Catalyst Application 1.5 g of a CuPt / SiO2|CoMn / AC multifunctional catalyst was mixed with 3 g of quartz sand and packed into a fixed-bed reactor for performance evaluation. Initially, 50% H2 / N2 was introduced for reduction at 300 °C for 6 h under atmospheric pressure. After cooling to room temperature, the gas was switched to syngas (H2 / CO=2) for reaction under the following conditions: P=5.0 MPa, T=220 °C, GHSV=4000 h. -1 After the reaction stabilized, samples were taken for analysis, and the catalytic performance is shown in the table below.

[0089]

[0090] Example 14 Catalyst preparation (I) Preparation of CuAg / SiO2 catalyst 1.14 g of copper nitrate trihydrate was dissolved in 10 mL of deionized water, and 16.7 mL of silver nitrate solution (0.01 mol / L) was added and the mixture was ultrasonically mixed until homogeneous. This mixture was then added dropwise to 3 g of fumed SiO2 powder and continuously stirred with a glass rod. The mixture was allowed to stand at room temperature for 6 h, then dried in an oven at 80 °C for 10 h, and finally calcined in a muffle furnace at 600 °C for 5 h to obtain the CuAg / SiO2 catalyst. The loading of Cu was 10.0 wt%, and the loading of Ag was 0.6 wt%.

[0091] (II) Preparation of CoMnLa / AC catalyst A solution of cobalt nitrate hexahydrate and manganese nitrate (50 wt%) was added to 10 mL of deionized water at a molar ratio of Co / Mn = 2 / 1 and mixed thoroughly by ultrasonication. Then, 5 g of coconut shell charcoal (AC) powder was added dropwise while continuously stirred with a glass rod. The mixture was then dried at 80 °C for 6 h. Further modification was carried out by adding 10.8 mL of lanthanum nitrate solution (0.02 mol / L) dropwise while continuously stirring with a glass rod, followed by drying at 80 °C for 10 h. Finally, the mixture was calcined in a muffle furnace at 330 °C for 5 h to obtain the CoMnLa / AC catalyst. The Co loading was 15 wt%, and the La loading was 0.6 wt%.

[0092] (III) Preparation of CuAg / SiO2|CoMnLa / AC Multifunctional Catalyst The CuAg / SiO2 and CoMnLa / AC catalysts obtained above were respectively pressed, granulated, and sieved to obtain particles of 40-60 mesh. Then, they were mixed at a mass ratio of 1:1 to obtain a CuAg / SiO2|CoMnLa / AC multifunctional catalyst.

[0093] Catalyst Application Two g of a CuAg / SiO2|CoMnLa / AC multifunctional catalyst (40-60 mesh) was mixed with four g of quartz sand (40-60 mesh) and packed into a fixed-bed reactor for CO hydrogenation performance evaluation. First, 50% CO / N2 was introduced for reduction at 280 °C for 4 h at a pressure of 0.1 MPa. After cooling to 150 °C, the gas was switched to syngas (H2 / CO=3) for reaction. Reaction conditions: P=3.0 MPa, T=240 °C, GHSV=4000 h. -1 After the reaction stabilized, samples were taken for analysis, and the catalytic performance is shown in the table below.

[0094]

[0095] Example 15 Catalyst preparation (I) Preparation of CuPd / SiO2 catalyst 1.37 g of copper nitrate trihydrate was dissolved in 10 mL of deionized water, followed by the addition of 28.2 mL of palladium nitrate solution (0.01 mol / L) to form a metal precursor solution. 3 g of SiO2 powder was added to 50 mL of deionized water and stirred for 30 min to ensure uniform dispersion. The aforementioned metal mixture was then added to the solution, and the mixture was stirred continuously and evaporated to dryness at 80 °C. The solution was then dried in an oven at 80 °C for 10 h, and finally calcined in a muffle furnace at 500 °C for 5 h to obtain the CuPd / SiO2 catalyst. The loadings of Cu and Pd were 12.0 wt% and 1.0 wt%, respectively.

[0096] (II) Preparation of CoMnLa / AC catalyst A solution of cobalt nitrate hexahydrate and manganese nitrate (50 wt%) was added to 15 mL of deionized water at a molar ratio of Co / Mn = 2 / 1 and mixed thoroughly by ultrasonication. Then, 5 g of coconut shell charcoal (AC) powder was added dropwise while continuously stirring with a glass rod, and the mixture was dried at 80°C for 5 h. Next, 18 mL of lanthanum nitrate solution (0.02 mol / L) was added dropwise for modification, and the mixture was dried in an oven at 80°C for 10 h. Finally, the mixture was calcined in a muffle furnace at 330°C for 5 h to obtain the CoMnLa / AC catalyst. The Co loading was 20 wt%, and the La loading was 1.0 wt%.

[0097] (III) Preparation of CuPd / SiO2|CoMnLa / AC Multifunctional Catalyst The CuPd / SiO2 and CoMnLa / AC catalysts obtained above were respectively pressed, granulated, and sieved to obtain particles of 40-60 mesh. Then, they were mixed at a mass ratio of 1:1 to obtain a CuPd / SiO2|CoMnLa / AC multifunctional catalyst.

[0098] Catalyst Application 1.5 g of a CuPd / SiO2|CoMnLa / AC multifunctional catalyst was mixed with 3 g of silica sand and then packed into a fixed-bed reactor. H2 was first introduced for reduction at 300 °C for 5 h at P = 0.1 MPa. After cooling to room temperature, syngas (H2 / CO = 2) was introduced for the reaction. The reaction conditions were 4.0 MPa, 230 °C, and a space velocity of 4000 h⁻¹. -1 After the reaction stabilized, samples were taken for analysis, and the catalytic performance is shown in the table below.

[0099] Example 16 Catalyst preparation (I) Preparation of CuPd / SiO2 catalyst 1.25 g of copper nitrate trihydrate was dissolved in 10 mL of deionized water, followed by the addition of 4.5 mL of palladium nitrate solution (0.05 mol / L) to form a metal precursor solution. 3 g of fumed silica was placed in a beaker, and the above metal mixture was added dropwise while continuously stirring with a glass rod. The mixture was then dried in an oven at 80 °C for 12 h and calcined in a muffle furnace at 450 °C for 8 h to obtain a CuPd / SiO2 catalyst. The loadings of Cu and Pd were 11.0 wt% and 0.8 wt%, respectively.

[0100] (II) Preparation of CoMn / AC catalyst A solution of cobalt nitrate hexahydrate and manganese nitrate (50 wt%) was added to 10 mL of deionized water at a Co / Mn molar ratio of 2 / 1 and mixed thoroughly by ultrasonication. Then, it was added dropwise to 5 g of coconut shell charcoal (AC) powder while continuously stirring with a glass rod. After the addition was complete, the mixture was aged at room temperature for 24 h. It was then dried at 110 °C for 12 h and finally calcined in a muffle furnace at 330 °C for 5 h to obtain the CoMn / AC catalyst. The Co loading was 18 wt%.

[0101] (III) Preparation of CuPd / SiO2|CoMn / AC Multifunctional Catalyst The CuPd / SiO2 and CoMn / AC catalysts obtained above were respectively pressed, granulated, and sieved to obtain particles of 40-60 mesh. Then, they were mixed at a mass ratio of 1:1 to obtain a CuPd / SiO2|CoMn / AC multifunctional catalyst.

[0102] Catalyst Application 1.5 g of a CuPd / SiO2|CoMn / AC multifunctional catalyst was diluted with 3 g of silica sand and evaluated in a fixed-bed reactor. Reduction conditions: 30% H2 / N2, 300 °C for 5 h, and P = 0.1 MPa. Reaction conditions: Syngas (H2 / CO = 0.5), 5.0 MPa, 260 °C, and space velocity 4000 h⁻¹. -1 After the reaction stabilized, samples were taken for analysis, and the catalytic performance is shown in the table below.

[0103] Example 17 Catalyst preparation (I) Preparation of CuPd / SiO2 catalyst 1.37 g of copper nitrate trihydrate was dissolved in 10 mL of deionized water, followed by the addition of 6.8 mL of palladium nitrate solution (0.05 mol / L) to form a metal precursor solution. 3 g of fumed silica was placed in a beaker, and the above metal mixture was added dropwise while continuously stirring with a glass rod. The mixture was then dried in an oven at 80 °C for 12 h and calcined in a muffle furnace at 600 °C for 8 h to obtain a CuPd / SiO2 catalyst. The loadings of Cu and Pd were 12.0 wt% and 1.2 wt%, respectively.

[0104] (II) Preparation of CoMnLa / AC catalyst A solution of cobalt nitrate hexahydrate and manganese nitrate (50 wt%) was added to 10 mL of deionized water at a Co / Mn molar ratio of 2 / 1 and mixed thoroughly by ultrasonication. This mixture was then added dropwise to 5 g of coconut shell charcoal (AC) powder with continuous stirring using a glass rod. The mixture was subsequently dried at 80 °C for 6 h, followed by the dropwise addition of 7.2 mL of lanthanum nitrate solution (0.02 mol / L) for modification. The mixture was then dried at 100 °C for 12 h and finally calcined in a muffle furnace at 300 °C for 5 h to obtain the CoMnLa / AC catalyst. The atomic molar ratio of Co / Mn was 2, with a Co loading of 12 wt% and a La loading of 0.4 wt%.

[0105] (III) Preparation of CuPd / SiO2|CoMnLa / AC Multifunctional Catalyst The CuPd / SiO2 and CoMnLa / AC catalysts were pressed into tablets, granulated, and sieved into 40-60 mesh particles, respectively. They were then mixed uniformly at a mass ratio of 1:1 to obtain the CuPd / SiO2|CoMnLa / AC multifunctional catalyst.

[0106] Catalyst Application 1.5 g of a CuPd / SiO2|CoMnLa / AC multifunctional catalyst was diluted with 3 g of silica sand and evaluated in a fixed-bed reactor. The catalyst was first reduced for 5 h at 300 °C and 0.1 MPa in a 20% CO / N2 atmosphere. Subsequently, syngas (H2 / CO = 1) was introduced, and the reaction conditions were 7.0 MPa, 260 °C, and a space velocity of 4000 h⁻¹. -1 After the reaction stabilized, samples were taken for analysis, and the catalytic performance is shown in the table below.

[0107] The above description is only for better explaining the embodiments and comparative examples of the present invention, and is not intended to limit the present invention.

Claims

1. A method for preparing a CuM / SiO2|CoMn multifunctional catalyst for the synthesis of higher oxygen-containing compounds from syngas, characterized in that, Includes the following steps: Step 1: Prepare CuM / SiO2 catalyst by excess impregnation method or equal volume impregnation method, where M represents one of Ru, Rh, Pd, Ir, Pt, Au and Ag; Step 2: Prepare CoMn catalysts using co-precipitation, impregnation, or solid-phase grinding methods; Step 3: Mix CuM / SiO2 and CoMn catalyst particles to obtain the CuM / SiO2|CoMn multifunctional catalyst.

2. The preparation method according to claim 1, characterized in that, The specific steps for preparing the CuM / SiO2 catalyst using the excess impregnation method in step 1 include: Vaporized SiO2 powder was dispersed in deionized water to obtain a SiO2-containing suspension. A precursor solution of Cu and noble metal M was mixed uniformly and then added dropwise to the SiO2-containing suspension. The mixture was stirred at 60–90 °C until the solution evaporated to dryness. After drying at 70–120 °C for 10–18 h, the catalyst was calcined at 300–800 °C for 5–10 h to obtain the CuM / SiO2 catalyst. The loading of Cu was 8.0–12.0 wt%, and the loading of noble metal M was 0.2–1.2 wt%. The specific steps for preparing the CuM / SiO2 catalyst using the equal-volume impregnation method in step 1 include: The precursor metal salt solutions of Cu and noble metal M were mixed evenly and then added dropwise to SiO2 powder containing gas phase while stirring continuously. After the addition was completed, the mixture was aged at room temperature for 4-8 h. After drying at 70-120 °C for 10-18 h, it was calcined at 300-800 °C for 5-10 h to obtain CuM / SiO2 catalyst. The loading of Cu was 8.0-12.0 wt%, and the loading of noble metal M was 0.2-1.2 wt%.

3. The preparation method according to claim 1, characterized in that, The specific steps for preparing the CoMn catalyst using the co-precipitation method in step 2 include: Co and Mn precursor metal salts were dissolved in deionized water to form a metal precursor solution with a total metal ion concentration of 1.0–3.0 mol / L and an atomic molar ratio of Co / Mn of 1–4. Sodium carbonate, potassium carbonate, ammonia, or ammonium carbonate were dissolved in deionized water to form an alkaline solution with a concentration of 1.0–3.0 mol / L. The metal precursor solution and alkaline solution were added dropwise simultaneously using a co-precipitation method while maintaining continuous stirring, a pH of 8.0 ± 0.5, and a temperature of 30–70 °C. After aging for 1.0–5.0 h, the solution was washed with deionized water by centrifugation until neutral, then dried at 70–120 °C for 10–18 h, and finally calcined at 300–400 °C for 5–10 h to obtain the CoMn catalyst. The specific steps for preparing the CoMn catalyst using the impregnation method in step 2 include: Co and Mn precursor metal salts were dissolved in deionized water to form a metal precursor solution, wherein the atomic molar ratio of Co / Mn was 1-4 and the loading of Co was 10-20 wt%. The metal precursor solution was then added dropwise to activated carbon powder, stirred continuously, and aged at room temperature for 10-24 h. Subsequently, it was dried at 80-120 °C for 10-18 h and finally calcined at 300-400 °C for 5-10 h to obtain the CoMn catalyst. Alternatively, precursor metal salts of Co and Mn can be dissolved in deionized water to form a metal precursor solution, wherein the atomic molar ratio of Co / Mn is 1-4 and the Co loading is 10-20 wt%. The metal precursor solution is then added dropwise to activated carbon powder with continuous stirring. Subsequently, it is dried at 80-120 °C for 4-8 h, modified by introducing lanthanum nitrate solution, and dried further at 80-120 °C for 10-18 h, wherein the mass fraction of La is 0.2-1.0 wt%. Finally, it is calcined at 300-400 °C for 5-10 h to obtain a La-modified CoMn catalyst. The specific steps for preparing the CoMn catalyst using the solid-phase synthesis method in step 2 include: Co and Mn metal nitrate precursors were placed in a mortar and then ground and mixed for 10-30 min, wherein the atomic molar ratio of Co / Mn was 1-4; after drying at 70-120 °C for 8-12 h, they were calcined at 300-400 °C for 5-10 h to obtain the CoMn catalyst.

4. The preparation method according to claim 3, characterized in that, In step 2, when ammonia or ammonium carbonate is used as the alkaline solution in the process of preparing CoMn catalyst by coprecipitation, the process also includes grinding and mixing CoMn catalyst with K2CO3 to obtain K-modified CoMn catalyst, and the K content is 0.2~1.0 wt%.

5. The preparation method according to claim 2 or 3, characterized in that, In step 1, the precursor metal salt of Cu is one of copper nitrate or copper acetate, and the precursor metal salt of noble metal M is one of ruthenium chloride, rhodium nitrate, palladium nitrate, palladium chloride, iridium chloride, chloroplatinic acid, chloroauric acid, and silver nitrate; in step 2, the precursor metal salt of Co is one of cobalt nitrate, cobalt chloride, and cobalt acetate, and the soluble metal salt of Mn is one of manganese nitrate and manganese chloride.

6. The preparation method according to claim 1, characterized in that, Step 3 specifically includes: pressing CuM / SiO2 and CoMn catalysts into tablets, granulating and sieving them to 40~60 mesh, and then mixing the particles, with a mass ratio of 5:1 to 1:

5.

7. A CuM / SiO2|CoMn multifunctional catalyst prepared by the preparation method according to any one of claims 1 to 6.

8. The application of the CuM / SiO2|CoMn multifunctional catalyst according to claim 7 in the synthesis gas to higher oxygen-containing compounds reaction, characterized in that, After reduction, the CuM / SiO2|CoMn catalyst is introduced into the synthesis gas H2 / CO for reaction.

9. The application according to claim 8, characterized in that, The reduction conditions are as follows: the reducing gas is an H2 / N2 mixture with an H2 content of 10-100%, a CO / N2 mixture with a CO content of 10-100%, and a (H2+CO) / N2 mixture with a syngas content of 10-100%, the hydrogen-to-carbon ratio (H2 / CO) of the syngas is 2; the pressure is 0.1-0.5 MPa; the temperature is 280-350 °C; and the gas hourly space velocity is 6000-30000 h⁻¹. -1 The restoration time is 3~12 hours.

10. The application according to claim 8, characterized in that, The reaction conditions are as follows: reaction temperature 210~300°C, pressure 3.0~8.0 MPa, and gas hourly space velocity 2000~10000 h⁻¹. -1 The hydrogen-to-carbon ratio (H2 / CO) of the syngas is 0.5 to 3.0.

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