Enhanced industrial catalyst for direct alcohol synthesis from syngas and its preparation method and application

Abstract

The present application relates to the technical field of catalyst, in particular to a preparation method of an enhanced industrial catalyst for direct synthesis of alcohol from synthesis gas, the preparation method comprising: impregnating a SiO2 carrier with an impregnation solution to obtain a preliminary catalyst, and then aging, drying and calcining; the preparation method further comprises a structure enhancement treatment of the carrier and / or the preliminary catalyst, the structure enhancement treatment being selected from one or more of steps A and B; the step A comprises subjecting the carrier and / or the preliminary catalyst to superheated steam treatment; the step B comprises subjecting the carrier and / or the preliminary catalyst to hydrothermal reaction in an aqueous sol solution, the sol comprising one or more of a silicon sol, an aluminum sol and a zirconium sol. The preparation method greatly improves the mechanical strength of the catalyst under the premise of maintaining high activity of the catalyst through the structure enhancement treatment, and focuses on solving the requirement of the industrial catalyst for the mechanical strength of the catalyst.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, and in particular to an enhanced industrial catalyst for the direct production of alcohols from syngas, its preparation method, and its application. Background Technology

[0002] my country possesses abundant coal reserves, as well as rich biomass and natural gas resources. These resources can be converted into syngas through gasification processes, and then alcohols can be directly produced via the Fischer-Tropsch reaction route. This technological route successfully breaks away from the traditional synthesis process's sole reliance on petroleum resources, providing a resource-adaptable and sustainable feasible path for the industrial development of my country's alcohol industry. However, the Fischer-Tropsch route for alcohol production from syngas is a typical strongly exothermic reaction. Under industrial production conditions, even small fluctuations in reaction conditions can easily trigger the formation of local hot spots in the catalyst bed, leading to temperature differences of tens to hundreds of degrees Celsius within the initial catalyst, subjecting the catalyst to a huge heat load. Simultaneously, industrial plants typically have massive catalyst loading, with bed heights reaching tens of meters. The bottom catalyst must withstand high pressure, coupled with the continuous scouring effect of high-velocity gas flow on the reaction bed, placing stringent requirements on the structural stability of the catalyst. If the particle strength of industrial catalysts does not meet the standards for industrial applications, they are very prone to pulverization under the above-mentioned complex working conditions. This will not only cause the loss of active components and a significant decrease in catalytic reaction performance, but also cause the broken catalyst powder to enter the product tank with the material flow, increasing the difficulty of product separation. In more serious cases, the broken particles will cause complete blockage of the reaction bed, leading to a major production shutdown accident.

[0003] Therefore, it is necessary to develop a structurally stable catalyst with sufficient mechanical strength for the direct production of alcohols from syngas to resist wear and loss under industrial conditions, and to provide important support for ensuring the stable industrial operation of the direct production of alcohols via the Fischer-Tropsch reaction route. Summary of the Invention

[0004] In view of the shortcomings of the prior art described above, the purpose of this invention is to provide an enhanced industrial catalyst for direct synthesis of alcohol from syngas, its preparation method and application, in order to solve the problems in the prior art where industrial catalysts are easily pulverized under complex operating conditions, resulting in the loss of active components, a significant decrease in catalytic reaction performance, and difficulties in product separation, as well as accidents caused by broken particles clogging the reaction bed.

[0005] To achieve the above and other related objectives, the first aspect of the present invention provides a method for preparing an enhanced industrial catalyst for direct synthesis of alcohols from syngas. The method includes: impregnating a SiO2 support with an impregnation solution to obtain a preliminary catalyst, followed by aging, drying, and calcination; the impregnation solution is a mixture of Ru salt, a first metal salt, and a second metal salt; the first metal is selected from one or more of Mn, Zr, Zn, Cu, Ce, Pr, Sm, Ag, and Au; the second metal is selected from one or more of Li, Na, K, Rb, Cs, Mg, and Ca; the method further includes a structural enhancement treatment of the support and / or the preliminary catalyst, the structural enhancement treatment being selected from one or more of steps A and B; step A includes superheating the support and / or the preliminary catalyst with steam; step B includes placing the support and / or the preliminary catalyst in a sol-water solution for a hydrothermal reaction, the sol including one or more of silica sol, alumina sol, zirconium sol, and organosilanes.

[0006] In step A, superheated steam treatment, under high temperature and high pressure conditions, causes hydrolysis, dehydroxylation and recrystallization reactions on the surface of the support, eliminating structural defects of the original support and / or the preliminary catalyst, thereby adjusting its structure, specific surface area, pore size and pore volume, and improving the mechanical strength of the final industrial catalyst.

[0007] Preferably, the temperature of the superheated steam treatment in step A is 400~800℃. For example, it can be 400~450℃, 450~500℃, 500~550℃, 550~600℃, 600~650℃, 650~700℃, 700~750℃, or 750~800℃. Within the range of 400~800℃, the higher the temperature of the hot steam treatment, the greater the increase in the mechanical strength of the support and / or the preliminary catalyst. If the temperature is below 400℃, it cannot adjust the structure of the support and / or the preliminary catalyst; if the temperature is above 800℃, the structure of the support and / or the preliminary catalyst is destroyed, and the catalytic performance decreases.

[0008] Preferably, the superheated steam treatment time in step A is 2–20 h. For example, it can be 2–4 h, 4–6 h, 6–8 h, 8–10 h, 10–12 h, 12–14 h, 14–16 h, 16–18 h, or 18–20 h. If the time is less than 2 h, the structure of the support and / or the preliminary catalyst is not fully adjusted; if the time is more than 20 h, it results in resource waste.

[0009] Preferably, in step A, the water vapor used for superheated steam treatment is saturated water vapor.

[0010] Preferably, step A further includes a step of heating under an inert atmosphere before the superheated steam treatment.

[0011] More preferably, the inert gas is selected from one or more of nitrogen, argon, and helium.

[0012] In step B, the ultrafine nanoparticles in the sol are adsorbed into the pores of the support and / or the preliminary catalyst during the hydrothermal reaction. The groups on their surface then bond with the original support and / or the preliminary catalyst structure, thereby enhancing the mechanical strength of the final industrial catalyst.

[0013] Preferably, in step B, the solid content of the sol-sol solution is 0.1~10 wt%. For example, it can be 0.1~1 wt%, 1~2 wt%, 2~3 wt%, 3~4 wt%, 4~5 wt%, 5~6 wt%, 6~7 wt%, 7~8 wt%, 8~9 wt%, or 9~10 wt%. If the solid content is higher than 10 wt%, the sol-sol solution has high viscosity and poor dispersibility, making it unable to enter the pores of the support and / or the preliminary catalyst; if the solid content is lower than 0.1 wt%, the concentration is too low to improve mechanical strength. Within the range of 0.1~10 wt%, the higher the solid content, the higher the mechanical strength of the enhanced industrial catalyst.

[0014] The sol described in this application can be arbitrarily selected from sols corresponding to commonly used carriers according to actual production needs, as long as the monomer size is small enough to disperse into the pores of the carrier and / or the preliminary catalyst.

[0015] Preferably, in step B, the temperature of the hydrothermal reaction is 50~200℃. For example, it can be 50~60℃, 60~70℃, 70~80℃, 80~90℃, 90~100℃, 100~110℃, 110~120℃, 120~130℃, 130~140℃, 140~150℃, 150~160℃, 160~170℃, 170~180℃, 180~190℃, or 190~200℃. If the temperature is below 50℃, it cannot effectively adjust the structure of the support and / or the preliminary catalyst; if the temperature is above 200℃, it will damage the active components of the catalyst, resulting in a decrease in catalytic performance.

[0016] Preferably, in step B, the hydrothermal reaction time is 2–20 h. For example, it can be 2–4 h, 4–6 h, 6–8 h, 8–10 h, 10–12 h, 12–14 h, 14–16 h, 16–18 h, or 18–20 h. If the time is less than 2 h, the structure of the support and / or the preliminary catalyst is not fully adjusted; if the time is more than 20 h, it results in resource waste.

[0017] Preferably, step B is followed by a washing and filtering step. The washing removes unreacted sol remaining on the support and / or the surface of the preliminary catalyst.

[0018] Preferably, in step B, the organosilane is selected from one or more of tetramethylsilane, dimethyldichlorosilane, and trimethylchlorosilane.

[0019] More preferably, the washing liquid is water.

[0020] More preferably, the system after the hydrothermal reaction is cooled to 20-30°C before washing.

[0021] Preferably, based on the total mass of the enhanced industrial catalyst, the Ru content is 0.1~5 wt%, the first metal content is 0.01~20 wt%, and the second metal additive content is 0.01~10 wt%.

[0022] It should be noted that when the first metal and the second metal are different, their corresponding preferred content ranges are different.

[0023] Preferably, the impregnation solution further includes a surfactant, the amount of which is 1 to 40 times the mass of Ru in the Ru salt. The surfactant improves the dispersibility of the Ru salt in the impregnation solution, thereby enhancing the dispersibility of Ru in the catalyst.

[0024] More preferably, the amount of surfactant added is 5 to 40 times the mass of Ru in the Ru salt.

[0025] More preferably, the surfactant is selected from one or more of polyvinylpyrrolidone, polyvinyl alcohol, polysorbate, sodium dodecyl sulfate, dioctadecyl dimethyl ammonium chloride, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, hexadecyltrimethylammonium bromide, and polyethylene glycol.

[0026] The polyvinylpyrrolidone described in this application has a weight-average molecular weight of 1000~60000 g / mol, the polyvinyl alcohol has a weight-average molecular weight of 500~2000 g / mol, the polysorbate has a weight-average molecular weight of 1000~2000 g / mol, the polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer has a weight-average molecular weight of 4500~6500 g / mol, and the polyethylene glycol has a weight-average molecular weight of 400~10000 g / mol.

[0027] Preferably, the Ru salt is selected from one or more of ruthenium trichloride, ruthenium nitrite, ruthenium acetate, ruthenium acetylacetone, and ammonium hexachlororuthenate.

[0028] Preferably, the first metal salt and the second metal salt are each independently selected from one or more of nitrates, sulfates and chlorides.

[0029] Preferably, the solvent of the mixture is selected from one or more of water, ethanol, and acetone.

[0030] More preferably, the volume ratio of the solvent to the SiO2 support for equal volume adsorption is 1 to 5. For example, it can be 1 to 1.5, 1.5 to 2, 2 to 2.5, 2.5 to 3, 3 to 3.5, 3.5 to 4, 4 to 4.5, or 4.5 to 5. The equal volume adsorption refers to the volume of water that the support just fully adsorbs.

[0031] Preferably, the preparation of the impregnation solution includes stirring Ru salt, a first metal salt, and a second metal salt in water.

[0032] More preferably, the stirring time is 1 to 24 hours. For example, it can be 1 to 6 hours, 6 to 12 hours, 12 to 18 hours, or 18 to 24 hours.

[0033] More preferably, the stirring temperature is 20~90℃. For example, it can be 20~30℃, 30~40℃, 40~50℃, 50~60℃, 60~70℃, 70~80℃, or 80~90℃.

[0034] Preferably, the impregnation process further includes a step of heat-treating the carrier at a temperature of 200-400°C for 3-8 hours. This heat treatment removes water or organic matter adsorbed on the carrier. For example, the heat treatment temperature can be 200-250°C, 250-300°C, 300-350°C, or 350-400°C. The heat treatment time can be 3-4 hours, 4-5 hours, 5-6 hours, 6-7 hours, or 7-8 hours.

[0035] Preferably, the impregnation is performed in 1 to 5 stages. Multiple impregnations can control the distribution of the active component in the carrier, resulting in a more uniform distribution of the active component.

[0036] Preferably, the aging step is to allow the plant to stand for 2 to 24 hours. For example, it can be 2 to 6 hours, 6 to 12 hours, 12 to 18 hours, or 18 to 24 hours.

[0037] Preferably, the drying temperature is 30~200 ℃ and the time is 2~24 h; for example, the drying time can be 2~6 h, 6~12 h, 12~18 h, or 18~24 h. For example, the drying temperature can be 30~50 ℃, 50~100 ℃, 100~150 ℃, or 150~200 ℃.

[0038] Preferably, the roasting temperature is 200~600 ℃, and the time is 2~24 h. For example, the roasting time can be 2~6 h, 6~12 h, 12~18 h, or 18~24 h. For example, the roasting temperature can be 200~300 ℃, 300~400 ℃, 400~500 ℃, or 500~600 ℃.

[0039] A second aspect of the present invention discloses an enhanced industrial catalyst prepared by the preparation method described above.

[0040] The third aspect of this application discloses the use of the above-mentioned enhanced industrial catalyst in the direct production of alcohol from syngas in industrial applications.

[0041] The fourth aspect of this application discloses a method for the direct production of alcohols from syngas using the aforementioned enhanced industrial catalyst.

[0042] Preferably, the process further includes a step of reducing the enhanced industrial catalyst prior to the reaction.

[0043] More preferably, the atmosphere for the reduction treatment is selected from one or more of the following: a mixture of nitrogen and hydrogen, a mixture of nitrogen and carbon monoxide, a mixture of nitrogen and syngas, pure hydrogen, pure carbon monoxide, or pure syngas.

[0044] More preferably, the reduction treatment time is 2 to 20 hours. For example, it can be 2 to 6 hours, 6 to 12 hours, 12 to 18 hours, or 18 to 20 hours.

[0045] More preferably, the reduction treatment temperature is 200~450℃. For example, the calcination temperature can be 200~250℃, 250~300℃, 300~350℃, 350~400℃, or 400~450℃.

[0046] More preferably, the pressure of the reduction treatment is 0~20 bar. For example, it can be 0~5 bar, 5~10 bar, 10~15 bar, or 15~20 bar.

[0047] More preferably, the space velocity of the reduction process is 1000~10000 h⁻¹. -1 For example, it can be 1000~2000 h. -1 2000~4000 h -1 4000~6000 h-1 6000~8000 h -1 8000~10000 h -1 .

[0048] Preferably, the synthesis gas is a mixture of H2 and CO, with a volume ratio of H2 to CO of 1:(0.5~5). For example, it can be 1:0.5~1, 1:1~2, 1:2~3, 1:3~4, or 1:4~5.

[0049] Preferably, the reaction pressure is 10-80 bar. For example, it can be 10-20 bar, 20-40 bar, 40-60 bar, or 60-80 bar.

[0050] Preferably, the reaction temperature is 200~300℃. For example, it can be 200~220℃, 220~240℃, 240~260℃, or 260~300℃.

[0051] Preferably, the space velocity of the reaction is 500~10000 h⁻¹. -1 For example, it can be 500~2000 h. -1 2000~4000 h -1 4000~6000 h -1 6000~8000 h -1 8000~10000 h -1 .

[0052] Preferably, the tail gas recirculation ratio of the reaction is 1 to 5. For example, it can be 1 to 1.5, 1.5 to 2, 2 to 2.5, 2.5 to 3, 3 to 3.5, 3.5 to 4, 4 to 4.5, or 4.5 to 5.

[0053] The exhaust gas recirculation ratio mentioned in this application refers to the molar ratio of exhaust gas recirculation flow rate to fresh gas flow rate.

[0054] Compared with the prior art, the present invention has the following beneficial effects:

[0055] 1) The preparation method described in this application strengthens the structure of the support and / or the preliminary catalyst by superheated steam treatment and / or hydrothermal reaction, thereby significantly improving the mechanical strength of the catalyst while maintaining its high activity, thus addressing the requirements of industrial catalysts for mechanical strength.

[0056] 2) The preparation method described in this invention has good repeatability, low raw material price, simple and easy-to-control preparation method, and is easy to repeat to obtain products with the same quality and performance, thereby meeting the needs of large-scale stable industrial production.

[0057] 3) When the noble metal Ru content is less than 5 wt%, the total CO conversion rate of the catalyst described in this invention is >80%, the selectivity for methane and carbon dioxide is low, and the selectivity for total oxygenated compounds is as high as 60%. At the same time, the pressure strength of the catalyst is increased to 110~210 N / cm. In industrial production, it can minimize the risk of wear and loss during use, reduce the loss of active components, minimize the significant decline in catalytic reaction performance, minimize the entry of broken catalyst powder into the product tank with the material flow, and minimize the difficulty of product separation. Broken particles can cause complete blockage of the reaction bed and lead to major production shutdown accidents, thus providing the possibility for industrial application. Detailed Implementation

[0058] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification.

[0059] Before further describing specific embodiments of the present invention, it should be understood that the scope of protection of the present invention is not limited to the specific embodiments described below; it should also be understood that the terminology used in the embodiments of the present invention is for describing specific embodiments and not for limiting the scope of protection of the present invention. Test methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions or as recommended by the respective manufacturers.

[0060] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in the present invention, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art. In addition to the specific methods, apparatus, and materials used in the embodiments, based on the knowledge of the prior art possessed by one of ordinary skill in the art and the description of this invention, any prior art methods, apparatus, and materials similar to or equivalent to those described, apparatus, and materials in the embodiments of this invention may be used to implement the present invention.

[0061] This application provides an enhanced industrial catalyst for direct syngas-to-methanol production, its preparation method, and its application, addressing the problems of Ru loss and poor product distribution control in existing technologies. By precisely modifying the surface of the SiO2 support, not only is the anchoring effect of active metal Ru enhanced, but the overall performance of the catalyst is also systematically controlled, improving its industrial applicability and providing crucial support for efficient and sustainable synthetic fuel production.

[0062] The reaction results of the catalyst described in the embodiments of this application were obtained by the following method:

[0063] 1) Use gas chromatography (Agilent 8860) to analyze the types and contents of various components contained in the product;

[0064] 2) The CO conversion rate is calculated using the following formula:

[0065] CO conversion rate (wt%) = ,

[0066] CO inlet and CO outlet represents the number of moles of CO before and after the reaction, respectively.

[0067] 3) The formula for calculating the selectivity of the corresponding product is:

[0068]

[0069] 4) The test method for lateral pressure strength is as follows: The columnar granular catalyst is placed sideways on the test platform of the particle strength tester. Lateral pressure is applied to the particles. As the pressurization time increases, the pressure acting on the particles gradually increases. When the maximum pressure is reached, the particles are crushed, and then the pressure value drops sharply, ending the test. The maximum pressure value F (N) is recorded, and the column height L (cm) (length of the columnar particle) is measured. The lateral pressure strength f is obtained according to the formula f = F / L. At least 10 granular catalysts are tested to obtain the lateral pressure strength, and the average value is taken.

[0070] It should be noted that the amount of catalyst used can be adjusted according to the specific catalyst's catalytic effectiveness, reaction conditions, ease of operation and economy, and long-term operational stability. In the specific embodiments of this application below, the equipment used for catalyst performance testing is an industrial single-tube catalyst evaluation device with tail gas recirculation mode, the catalyst loading is 100ml, and the single tube size is Φ30*1200mm.

[0071] The device simulates one of the reaction tubes in a tubular reactor used in industrial production. It simulates the temperature difference of tens to hundreds of degrees Celsius inside the catalyst under industrial operating conditions, subjecting the catalyst to a huge heat load. The large packing volume and the high pressure required for the bottom catalyst, coupled with the continuous scouring effect of high-velocity gas flow on the reaction bed, necessitate a catalyst pressure measurement intensity of 110~250 N / cm.

[0072] In the following examples and comparative examples, the raw material silica carrier is an industrial clover-shaped silica carrier: 1.7 mm in diameter, 4 mm in length, and with an adsorption capacity of 1.5 mL / g.

[0073] Example 1

[0074] This embodiment provides a method for preparing an enhanced industrial catalyst for direct synthesis of alcohols from syngas, the method comprising the following steps:

[0075] 1) Based on the total mass of the enhanced industrial catalyst, weigh ammonium hexachlororuthenate, manganese nitrate, and sodium nitrate according to 2 wt% Ru, 0.1 wt% Mn, 0.3 wt% Na, and 97.6 wt% SiO2. Use polyethylene glycol (PEG, weight average molecular weight 500) as the surfactant, with an addition amount 20 times the weight of metallic Ru. Use 50 wt% ethanol aqueous solution as the solvent, with an addition amount twice the volume of adsorption of the silica support. Stir at 60°C for 10 h to form an impregnation solution.

[0076] 2) Structural reinforcement treatment of the carrier: The silica carrier was placed in a high-temperature hydrothermal reactor, and a silica sol aqueous solution with a volume 10 times that of the carrier was added. The solid content of the sol aqueous solution was 5 wt%. The temperature was then raised to 200℃ for 10 h, cooled to room temperature, washed 5 times with deionized water, filtered, dried at 50℃ for 10 h, and calcined at 600℃ for 10 h to obtain the structurally reinforced carrier.

[0077] 3) The structure-enhanced carrier obtained in step 2) was desorbed at 300℃ for 5 h, then impregnated with impregnation solution in 3 times. After each impregnation, it was allowed to stand for 10 h for aging, then dried at 50℃ for 10 h, and calcined at 400℃ for 8 h to obtain the preliminary catalyst.

[0078] 4) Preliminary catalyst structural enhancement treatment: The preliminary catalyst obtained in step 3) was placed in a tube furnace, nitrogen gas was introduced and the temperature was raised to 500°C, and then superheated steam was used for treatment for 10 h. After the treatment, the steam was turned off and the reaction tube was allowed to cool down to below 30°C. Then it was dried at 30°C for 24 h and calcined at 600°C for 10 h to obtain the enhanced industrial catalyst.

[0079] The enhanced industrial catalyst was used in the direct synthesis of alcohols from syngas. Prior to the reaction, the catalyst underwent a reduction treatment in a mixed atmosphere of H2 and N2, with H2 / N2 = 20 wt% (molar ratio), and the space velocity (SHV) was 8000 h⁻¹. -1 The reduction treatment temperature was 450 ℃, the reduction treatment pressure was 0 bar, and the time was 5 hours. After the reduction treatment was completed, the reaction was switched to syngas.

[0080] When performing the syngas-to-alcohol reaction, the molar ratio of H2 / CO in the syngas is 2, and the reaction space velocity is 2000 h⁻¹. -1The tail gas recirculation ratio was 3, the reaction temperature was 230 °C, and the reaction pressure was 60 bar. The types and contents of various components contained in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0081] Example 2

[0082] This embodiment provides a method for preparing an enhanced industrial catalyst for direct synthesis of alcohols from syngas, the method comprising the following steps:

[0083] 1) Based on the total mass of the enhanced industrial catalyst, ruthenium trichloride, zinc nitrate and potassium chloride were weighed according to 0.1 wt % Ru, 20 wt % Zn, 1.5 wt % K and 78.4 wt % SiO2. Tween was used as the surfactant and its addition amount was 15 times the weight of metallic Ru. A 50 wt % acetone aqueous solution was used as the solvent and its addition amount was 3 times the volume of adsorption of the silica support. The mixture was stirred at 60°C for 10 h to form an impregnation solution.

[0084] 2) Structural enhancement treatment of the carrier: The carrier was placed in a tube furnace, argon gas was introduced, and the temperature was raised to 600℃. Then, superheated steam was used for treatment for 2 hours. After the treatment was completed, the steam was turned off, and the carrier was removed after the reaction tube cooled down to below 30℃ to obtain structurally enhanced carrier particles.

[0085] 3) The carrier particles obtained in step 2) were desorbed at 300℃ for 5 h, then impregnated with impregnation solution in 3 times. After each impregnation, they were allowed to stand for 10 h for aging, then dried at 50℃ for 10 h, and calcined at 400℃ for 6 h to obtain a preliminary catalyst with active components.

[0086] 4) Structural enhancement treatment of the preliminary catalyst: The preliminary catalyst obtained in step 3) was placed in a high-temperature hydrothermal reactor, and a tetramethylsilane sol-water solution with a volume 10 times that of the support was added. The solid content of the sol-water solution was 10 wt%. The mixture was then heated to 150°C for 20 h, cooled to room temperature, washed five times with deionized water, filtered, dried at 200°C for 2 h, and calcined at 500°C for 24 h to obtain the enhanced industrial catalyst.

[0087] This catalyst is used for the direct synthesis of alcohols from syngas. Prior to the reaction, the catalyst undergoes reduction activation. The reducing atmosphere is a mixture of H2 and N2, with H2 / mixture = 20 wt% (molar ratio), and the reduction space velocity is 8000 h⁻¹. -1 The reduction temperature was 350℃, the reduction pressure was 0 bar, and the time was 5 hours. After the reduction was completed, the reaction was switched to syngas.

[0088] The synthesis of alcohols from syngas is carried out with a H2 / CO molar ratio of 2 and a space velocity of 1000 h⁻¹. -1 The tail gas recirculation ratio was 5, the reaction temperature was 280 ℃, and the reaction pressure was 50 bar. The types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0089] Example 3

[0090] This embodiment provides a method for preparing an enhanced industrial catalyst for direct synthesis of alcohols from syngas, the method comprising the following steps:

[0091] 1) Based on the total mass of the enhanced industrial catalyst, weigh ruthenium nitrite, zirconium sulfate, sodium hydroxide, and surfactant polyvinylpyrrolidone (weight average molecular weight 8000 g / mol) according to 2 wt% Ru, 5 wt% Zr, 0.5 wt% Na, and 92.5 wt% Al2O3. The amount of added surfactant is 20 times the weight of metallic Ru. Water is used as the solvent, and the amount of added solvent is twice the volume of adsorption of the support. Stir at 30°C for 10 h to form an impregnation solution.

[0092] 2) The support was desorbed at 300℃ for 5 h, then impregnated twice with impregnation solution. After each impregnation, it was allowed to stand for 2 h for aging, then dried at 150℃ for 10 h, and calcined at 800℃ for 5 h to obtain a preliminary catalyst with active components.

[0093] 3) Structural enhancement treatment of the preliminary catalyst: The preliminary catalyst obtained in step 2) is placed in a tube furnace, nitrogen gas is introduced, and the temperature is raised to 800°C. Then, it is treated with superheated steam for 2 hours. After the treatment, the steam is turned off, and the reaction tube is allowed to cool down to below 30°C. Then, it is dried at 30°C for 24 hours and calcined at 600°C for 10 hours to obtain the enhanced industrial catalyst.

[0094] This catalyst is used for the direct synthesis of alcohols from syngas. Prior to the reaction, the catalyst undergoes reduction activation under a 100 wt% H₂ atmosphere and a reduction space velocity of 1000 h⁻¹. -1 The reduction temperature was 350 ℃, the reduction pressure was 5 bar, and the time was 2 hours. After the reduction was completed, the reaction was switched to syngas.

[0095] This catalyst is used for the direct synthesis of alcohols from syngas, with an H2 / CO molar ratio of 2.5 in the syngas and a reaction space velocity of 2000 h⁻¹. -1The tail gas recirculation ratio was 1, the reaction temperature was 220 °C, and the reaction pressure was 40 bar. The types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0096] Example 4

[0097] This embodiment provides a method for preparing an enhanced industrial catalyst for direct synthesis of alcohols from syngas, the method comprising the following steps:

[0098] 1) Based on the total mass of the enhanced industrial catalyst, ruthenium acetate, copper chloride, and rubidium nitrate were weighed according to the following formula: 5 wt% Ru, 1 wt% Cu, 10 wt% Rb, and 84 wt% TiO2. Polyvinylpyrrolidone (weight average molecular weight 58000 g / mol) was used as the surfactant and added at a rate 20 times the weight of metallic Ru. Water was used as the solvent and added at a rate 5 times the volume of adsorption capacity of the TiO2 support. The mixture was stirred at 40°C for 24 h to form an impregnation solution.

[0099] 2) Structural enhancement treatment of the carrier: The carrier was placed in a tube furnace, helium gas was introduced and the temperature was raised to 500℃, and the treatment was switched to 20 h. After the treatment was completed, the steam was turned off, and the carrier was removed after the reaction tube cooled to below 30℃, thus obtaining steam-treated carrier particles.

[0100] 3) The carrier particles obtained in step 2) were desorbed at 300°C for 5 h, then impregnated with impregnation solution 5 times. After each impregnation, they were allowed to stand for 10 h for aging, then dried at 200°C for 2 h, and calcined at 600°C for 2 h to obtain the enhanced industrial catalyst.

[0101] This catalyst is used for the direct synthesis of alcohols from syngas. Prior to the reaction, the catalyst undergoes reduction activation. The reducing atmosphere is a mixture of syngas (H2 / CO=2) and N2, with a syngas / mixed gas ratio of 10 wt% (molar ratio), and a reduction space velocity of 10000 h⁻¹. -1 The reduction temperature was 450 ℃, the reduction pressure was 0 bar, and the time was 5 hours. After the reduction was completed, the reaction was switched to syngas.

[0102] When performing a direct synthesis of alcohols from syngas, the molar ratio of H2 to CO in the syngas is 0.5, and the reaction space velocity is 5000 h⁻¹. -1 The tail gas recirculation ratio was 1, the reaction temperature was 200 ℃, and the reaction pressure was 10 bar. The types and contents of various components contained in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0103] Example 5

[0104] This embodiment provides a method for preparing an enhanced industrial catalyst for direct synthesis of alcohols from syngas, the method comprising the following steps:

[0105] 1) Based on the total mass of the enhanced industrial catalyst, ruthenium acetate, cerium nitrate, and potassium carbonate were weighed according to 5 wt% Ru, 1 wt% Ce, 10 wt% K, and 84 wt% TiO2. The surfactant used was hexadecyltrimethylammonium bromide (CTAB), which was added at 30 times the weight of metallic Ru. The solvent used was 50 wt% aqueous ethanol solution, which was added at 3 times the volume of adsorption capacity of the TiO2 support. The mixture was stirred at 40°C for 24 h to form an impregnation solution.

[0106] 2) Structural enhancement treatment of the carrier: The carrier was placed in a high-temperature hydrothermal reactor, and a zirconium sol aqueous solution with a volume of 10 times that of the carrier was added. The solid content of the sol aqueous solution was 5 wt%. The temperature was then raised to 120℃ for 20 h, cooled to room temperature, washed 5 times with deionized water, filtered, dried at 50℃ for 10 h, and calcined at 600℃ for 10 h to obtain the enhanced carrier.

[0107] 3) The support obtained in step 2) was desorbed at 300℃ for 5 h, then impregnated with impregnation solution in 3 times. After each impregnation, it was allowed to stand for 10 h for aging, then dried at 50℃ for 10 h, and calcined at 450℃ for 6 h to obtain the preliminary catalyst.

[0108] 4) Preliminary catalyst structural enhancement treatment: The preliminary catalyst obtained in step 3) was placed in a tube furnace, argon gas was introduced, and the temperature was raised to 450°C. Then, superheated steam treatment was applied for 10 hours. After the treatment, the steam was turned off, and the reaction tube was allowed to cool down to below 30°C. Subsequently, it was dried at 30°C for 24 hours and calcined at 600°C for 10 hours to obtain the enhanced industrial catalyst.

[0109] This catalyst is used for the direct synthesis of alcohols from syngas. Prior to the reaction, the catalyst undergoes reduction activation. The reducing atmosphere is a mixture of syngas (H2 / CO=2) and N2, with a syngas / mixed gas ratio of 10 wt% (molar ratio), and a reduction space velocity of 10000 h⁻¹. -1 The reduction temperature was 450 ℃, the reduction pressure was 0 bar, and the time was 5 hours. After the reduction was completed, the reaction was switched to syngas.

[0110] When performing the syngas-to-alcohol reaction, the molar ratio of H2 / CO in the syngas is 4, and the reaction space velocity is 1000 h⁻¹. -1The reaction temperature was 230 °C and the reaction pressure was 80 bar. The types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0111] Example 6

[0112] This embodiment provides a method for preparing an enhanced industrial catalyst for direct synthesis of alcohols from syngas, the method comprising the following steps:

[0113] 1) Based on the total mass of the enhanced industrial catalyst, ruthenium trichloride, praseodymium chloride, and calcium hydroxide were weighed according to 1 wt% Ru, 0.5 wt% Pr, 0.5 wt% K, and 98 wt% Al2O3. Polyethylene glycol (PEG, weight average molecular weight 2000 g / mol) was used as the surfactant and added at 40 times the weight of metallic Ru. A 50 wt% acetone aqueous solution was used as the solvent and added at twice the volume of the Al2O3 support. The mixture was stirred at 60°C for 10 h to form an impregnation solution.

[0114] 2) Structural enhancement treatment of the carrier: The carrier was placed in a high-temperature hydrothermal reactor, and an aluminum sol aqueous solution with a volume of 10 times that of the carrier was added. The solid content of the sol aqueous solution was 10 wt%. The temperature was then raised to 200℃ for 5 h, cooled to room temperature, washed 5 times with deionized water, filtered, dried at 50℃ for 10 h, and calcined at 600℃ for 5 h to obtain the enhanced carrier.

[0115] 3) The support obtained in step 2) was desorbed at 300℃ for 5 h, then impregnated with impregnation solution in 3 times. After each impregnation, it was allowed to stand for 10 h for aging, then dried at 50℃ for 10 h, and calcined at 450℃ for 6 h to obtain the preliminary catalyst.

[0116] 4) Preliminary catalyst structural enhancement treatment: The preliminary catalyst obtained in step 3) was placed in a tube furnace, nitrogen gas was introduced, and the temperature was raised to 400°C. Then, superheated steam treatment was applied for 10 hours. After the treatment, the steam was turned off, and the reaction tube was allowed to cool down to below 30°C. The catalyst was then removed, dried at 30°C for 24 hours, and calcined at 450°C for 2 hours to obtain the enhanced industrial catalyst.

[0117] This catalyst is used for the direct synthesis of alcohols from syngas. Prior to the reaction, the catalyst undergoes reduction activation. The reducing atmosphere is a mixture of H2 and N2, with H2 / mixture = 20 wt% (molar ratio), and the reduction space velocity is 2000 h⁻¹. -1 The exhaust gas recirculation ratio is 2, the reduction temperature is 300 ℃, the reduction pressure is 0 bar, and the time is 5 hours. After the reduction is completed, the reaction is switched to syngas.

[0118] When performing the syngas-to-alcohol reaction, the molar ratio of H2 / CO in the syngas is 1, the tail gas recycle ratio is 4, and the reaction space velocity is 10000 h⁻¹. -1 The reaction temperature was 300 ℃, and the reaction pressure was 70 bar. Gas chromatography (Agilent 8860) was used to analyze the types and contents of various components in the product, and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0119] Example 7

[0120] This embodiment provides a method for preparing an enhanced industrial catalyst for direct synthesis of alcohols from syngas, the method comprising the following steps:

[0121] 1) Based on the total mass of the enhanced industrial catalyst, ruthenium trichloride, samarium nitrate, and calcium hydroxide were weighed according to 1 wt% Ru, 2 wt% Sm, 0.5 wt% K, and 96.5 wt% Al2O3. The surfactant used was dioctadecyl dimethyl ammonium chloride, and the amount added was 30 times the weight of metallic Ru. The solvent used was 50 wt% acetone aqueous solution, and the amount of solvent added was equal to the volume adsorption amount of Al2O3 support. The mixture was stirred at 60°C for 10 h to form an impregnation solution.

[0122] 2) Structural enhancement treatment of the carrier: The carrier was placed in a high-temperature hydrothermal reactor, and a silica sol aqueous solution with a volume of 10 times that of the carrier was added. The solid content of the sol aqueous solution was 2 wt%. The temperature was then raised to 180℃ for 20 h, cooled to room temperature, washed 5 times with deionized water, filtered, dried at 50℃ for 10 h, and calcined at 600℃ for 5 h to obtain the enhanced carrier.

[0123] 3) The support obtained in step 2) was desorbed at 300℃ for 5 h, then impregnated once with impregnation solution. After each impregnation, it was allowed to stand for 10 h for aging, then dried at 50℃ for 10 h, and calcined at 450℃ for 6 h to obtain the preliminary catalyst.

[0124] 4) Preliminary catalyst structural enhancement treatment: The preliminary catalyst obtained in step 3) was placed in a tube furnace, argon gas was introduced, and the temperature was raised to 400℃. Then, superheated steam was used for treatment for 20 h. After treatment, the steam was turned off, and the reaction tube was allowed to cool to below 30℃. The catalyst was then removed, dried at 30℃ for 24 h, and calcined at 450℃ for 2 h. The enhanced industrial catalyst was obtained.

[0125] This catalyst is used for the direct synthesis of alcohols from syngas. Prior to the reaction, the catalyst undergoes reduction activation. The reducing atmosphere is a mixture of H2 and N2, with H2 / mixture = 20 wt% (molar ratio), and the reduction space velocity is 8000 h⁻¹. -1The reduction temperature was 350℃, the reduction pressure was 0 bar, and the time was 5 hours. After the reduction was completed, the reaction was switched to syngas.

[0126] When performing the syngas-to-alcohol reaction, the molar ratio of H2 / CO in the syngas is 1, the tail gas recycle ratio is 4, and the reaction space velocity is 500 h⁻¹. -1 The reaction temperature was 250 °C and the reaction pressure was 50 bar. The types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0127] Example 8

[0128] This embodiment provides a method for preparing an enhanced industrial catalyst for direct synthesis of alcohols from syngas, the method comprising the following steps:

[0129] 1) Based on the total mass of the enhanced industrial catalyst, weigh ruthenium acetylacetone, silver nitrate, and magnesium nitrate according to 3wt%Ru, 0.1wt%Ag, 5wt%Mg, and 91.9wt%ZrO2. Use polyvinyl alcohol (weight average molecular weight 1000 g / mol) as the surfactant, with an addition amount 10 times the weight of metallic Ru. Use 50wt% ethanol aqueous solution as the solvent, with an addition amount 1.5 times the volume of ZrO2 carrier adsorption. Stir at 40℃ for 24 h to form an impregnation solution.

[0130] 2) The carrier was desorbed at 300℃ for 5 h, then impregnated with impregnation solution in 3 times. After each impregnation, it was allowed to stand for 10 h for aging, then dried at 70℃ for 2 h, and calcined at 500℃ for 5 h to obtain the preliminary catalyst.

[0131] 3) Structural enhancement treatment of the preliminary catalyst: The preliminary catalyst obtained in step 2) is placed in a tube furnace, nitrogen gas is introduced, and the temperature is raised to 800°C. Then, it is treated with superheated steam for 20 hours. After the treatment, the steam is turned off, and the reaction tube is allowed to cool down to below 30°C. Then, it is dried at 30°C for 24 hours and calcined at 600°C for 10 hours to obtain the enhanced industrial catalyst.

[0132] This catalyst is used for the direct synthesis of alcohols from syngas. Prior to the reaction, the catalyst undergoes reduction activation. The reducing atmosphere is a mixture of syngas (H2 / CO=1) and N2, with a syngas / mixed gas ratio of 20 wt% (molar ratio), and a reduction space velocity of 8000 h⁻¹. -1 The reduction temperature was 350 ℃, the reduction pressure was 0 bar, and the time was 5 hours. After the reduction was completed, the reaction was switched to syngas.

[0133] When performing the direct synthesis of alcohols from syngas, the molar ratio of H2 to CO in the syngas is 0.5, and the reaction space velocity is 2000 h⁻¹. -1 The tail gas recirculation ratio was 1, the reaction temperature was 270 °C, and the reaction pressure was 40 bar. The types and contents of various components contained in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0134] Example 9

[0135] This embodiment provides a method for preparing an enhanced industrial catalyst for direct synthesis of alcohols from syngas, the method comprising the following steps:

[0136] 1) Based on the total mass of the enhanced industrial catalyst, ruthenium trichloride, chloroauric acid, and magnesium chloride were weighed according to 1 wt% Ru, 0.1 wt% Au, 0.5 wt% Mg, and 98.4 wt% Al2O3. N-methylpyrrolidone was used as the surfactant and its addition amount was 10 times the weight of metallic Ru. 50 wt% acetone aqueous solution was used as the solvent and its addition amount was twice the volume of adsorption of the Al2O3 support. The mixture was stirred at 60°C for 10 h to form an impregnation solution.

[0137] 2) Structural enhancement treatment of the carrier: The carrier was placed in a high-temperature hydrothermal reactor, and a silica sol aqueous solution with a volume of 10 times that of the carrier was added. The solid content of the sol aqueous solution was 0.1 wt%. The temperature was then raised to 50℃ for 20 h, cooled to room temperature, washed 5 times with deionized water, filtered, dried at 50℃ for 10 h, and calcined at 600℃ for 2 h to obtain the enhanced carrier.

[0138] 3) The support obtained in step 2) was desorbed at 300℃ for 5 h, then impregnated with impregnation solution in 3 times. After each impregnation, it was allowed to stand for 10 h for aging, then dried at 30℃ for 24 h, and calcined at 450℃ for 8 h to obtain the preliminary catalyst.

[0139] 4) Preliminary catalyst structural enhancement treatment: The preliminary catalyst obtained in step 3) is placed in a tube furnace, nitrogen gas is introduced, and the temperature is raised to 600°C. Then, it is treated with superheated steam for 10 hours. After the treatment, the steam is turned off, and the reaction tube is allowed to cool down to below 30°C. Then, it is dried at 30°C for 24 hours and calcined at 600°C for 10 hours to obtain the enhanced industrial catalyst.

[0140] This catalyst is used for the direct synthesis of alcohols from syngas. Prior to the reaction, the catalyst undergoes reduction activation. The reducing atmosphere is a mixture of H2 and N2, with H2 / mixture = 50 wt% (molar ratio), and the reduction space velocity is 8000 h⁻¹. -1The reduction temperature was 350℃, the reduction pressure was 0 bar, and the time was 5 hours. After the reduction was completed, the reaction was switched to syngas.

[0141] When performing the direct synthesis of alcohols from syngas, the molar ratio of H2 to CO in the syngas is 1.5, and the reaction space velocity is 1000 h⁻¹. -1 The tail gas recirculation ratio was 3, the reaction temperature was 240 ℃, and the reaction pressure was 60 bar. The types and contents of various components contained in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0142] Example 10

[0143] This embodiment provides a method for preparing an enhanced industrial catalyst for direct synthesis of alcohols from syngas, the method comprising the following steps:

[0144] 1) Based on the total mass of the enhanced industrial catalyst, weigh ruthenium nitrite, manganese chloride, and calcium chloride according to 0.5wt%Ru, 0.5wt%Mn, 1wt%Ca, and 98wt%SiO2. Use N,N-dimethylacetamide as the surfactant, with an addition amount of 15 times the weight of metallic Ru. Use 50wt% ethanol aqueous solution as the solvent, with an addition amount of 3 times the volume of adsorption of the silica support. Stir at 80°C for 10 h to form an impregnation solution.

[0145] 2) The support was desorbed at 300℃ for 5 h, then impregnated with impregnation solution in 3 times. After each impregnation, it was allowed to stand for 10 h for aging, then dried at 50℃ for 10 h, and calcined at 400℃ for 5 h to obtain the preliminary catalyst.

[0146] 3) Preliminary catalyst structural enhancement treatment: The preliminary catalyst obtained in step 3) is placed in a tube furnace, nitrogen gas is introduced, and the temperature is raised to 500°C. Then, it is treated with superheated steam for 10 hours. After the treatment, the steam is turned off, and the reaction tube is allowed to cool down to below 30°C. Then, it is dried at 30°C for 24 hours and calcined at 600°C for 10 hours to obtain the enhanced industrial catalyst.

[0147] This catalyst is used for the direct synthesis of alcohols from syngas. Prior to the reaction, the catalyst undergoes reduction activation. The reduction atmosphere is a mixture of CO and N2, with CO / N2 = 10 wt% (molar ratio), and the reduction space velocity is 8000 h⁻¹. -1 The reduction temperature was 350 ℃, the reduction pressure was 0 bar, and the time was 5 hours. After the reduction was completed, the reaction was switched to syngas.

[0148] When performing the syngas-to-alcohol reaction, the molar ratio of H2 / CO in the syngas is 5, and the reaction space velocity is 1000 h⁻¹.-1 The tail gas recirculation ratio was 3, the reaction temperature was 250 °C, and the reaction pressure was 60 bar. The types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0149] Example 11

[0150] This embodiment provides a method for preparing an enhanced industrial catalyst for direct synthesis of alcohols from syngas, the method comprising the following steps:

[0151] 1) Based on the total mass of the enhanced industrial catalyst, ruthenium acetate, silver nitrate, and potassium hydroxide were weighed according to 5wt%Ru, 0.1wt%Ag, 5wt%K, and 89.9wt%SiO2. Polyvinyl alcohol (PEG, weight average molecular weight 1000 g / mol) was used as the surfactant and added at 5 times the weight of metallic Ru. 50wt% ethanol aqueous solution was used as the solvent and added at 2 times the volume of adsorption capacity of the silica support. The mixture was stirred at 80°C for 10 h to form an impregnation solution.

[0152] 2) Structural enhancement treatment of the carrier: The silica carrier was placed in a tube furnace, nitrogen gas was introduced, and then the temperature was raised to 400℃. The process was then switched to superheated steam treatment for 10 h. After the treatment was completed, the steam was turned off, and the carrier was removed after the reaction tube cooled to below 30℃, yielding steam-treated carrier particles.

[0153] 3) The carrier particles obtained in step 2) were desorbed at 300℃ for 5 h, then impregnated twice with impregnation solution. After each impregnation, they were allowed to stand for 10 h for aging, then dried at 80℃ for 10 h, and calcined at 400℃ for 5 h to obtain the preliminary catalyst.

[0154] 4) Preliminary catalyst structural enhancement treatment: The preliminary catalyst obtained in step 3) was placed in a high-temperature hydrothermal reactor, and a silica sol aqueous solution with a volume 10 times that of the support was added. The solid content of the sol aqueous solution was 0.1 wt%. The mixture was then heated to 150°C for 10 h, cooled to room temperature, washed 5 times with deionized water, filtered, dried at 80°C for 2 h, and calcined at 500°C for 2 h to obtain the enhanced industrial catalyst.

[0155] This catalyst is used in the direct synthesis of alcohols from syngas. Prior to the reaction, the catalyst undergoes reduction activation under a H2 atmosphere and a reduction space velocity of 10,000 h⁻¹. -1 The reduction temperature was 450 °C, the reduction pressure was 5 bar, and the time was 5 hours. After the reduction was completed, the reaction was switched to syngas.

[0156] When performing the syngas-to-alcohol reaction, the molar ratio of H2 / CO in the syngas is 3, and the reaction space velocity is 4000 h⁻¹. -1 The tail gas recirculation ratio was 5, the reaction temperature was 240 °C, and the reaction pressure was 80 bar. The types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0157] Example 12

[0158] This embodiment provides a method for preparing an enhanced industrial catalyst for direct synthesis of alcohols from syngas, the method comprising the following steps:

[0159] 1) Based on the total mass of the enhanced industrial catalyst, weigh ruthenium acetate, manganese chloride, and potassium hydroxide according to 1.5 wt% Ru, 1 wt% Mn, 1 wt% K, and 96.5 wt% SiO2. The surfactant is a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer (weight average molecular weight 5800 g / mol), and the amount added is 10 times the weight of metallic Ru. The solvent is a 50 wt% aqueous ethanol solution, and the amount of solvent added is 3 times the volume of adsorption of the silica support.

[0160] 2) Structural enhancement treatment of the carrier: The silica carrier was placed in a tube furnace, nitrogen gas was introduced, and the temperature was raised to 500°C. Then, superheated steam treatment was switched on for 10 hours. After the treatment was completed, the steam was turned off, and the carrier was removed after the reaction tube cooled to below 30°C to obtain steam-treated carrier particles.

[0161] 3) The carrier particles obtained in step 2) were desorbed at 300℃ for 5 h, then impregnated with impregnation solution in 3 times. After each impregnation, they were allowed to stand for 10 h for aging, then dried at 60℃ for 24 h, and calcined at 450℃ for 8 h to obtain the preliminary catalyst.

[0162] 4) Preliminary catalyst structural enhancement treatment: The preliminary catalyst obtained in step 3) was placed in a tube furnace, and nitrogen gas was introduced at a rate of 1 L / min. The temperature was then increased to 800°C at a rate of 2 °C / min, and superheated steam was introduced at a rate of 0.5 L / min for 8 h. After treatment, the steam was turned off, and the reaction tube was allowed to cool to below 30°C. It was then dried at 30°C for 24 h and calcined at 600°C for 10 h to obtain the enhanced industrial catalyst.

[0163] This catalyst is used for the direct synthesis of alcohols from syngas. Prior to the reaction, the catalyst undergoes reduction activation. The reducing atmosphere is a mixture of H2 and N2, with H2 / mixture = 10 wt% (molar ratio), and the reduction space velocity is 3000 h⁻¹. -1The reduction temperature was 450℃, the reduction pressure was 0 bar, and the time was 20 hours. After the reduction was completed, the reaction was switched to syngas.

[0164] When preparing alcohols from syngas, the molar ratio of H2 to CO in the syngas is 2.5, and the reaction space velocity is 1000 h⁻¹. -1 The tail gas recirculation ratio was 3, the reaction temperature was 220 °C, and the reaction pressure was 50 bar. The types and contents of various components contained in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0165] Example 13

[0166] This embodiment provides a method for preparing an enhanced industrial catalyst for direct synthesis of alcohols from syngas, the method comprising the following steps:

[0167] 1) Based on the total mass of the enhanced industrial catalyst, weigh ruthenium acetylacetone, copper nitrate, and magnesium nitrate according to 3wt%Ru, 5wt%Cu, 10wt%Mg, and 82wt%SiO2. Use N,N-dimethylformamide as the surfactant, with an addition amount of 40 times the weight of metallic Ru. Use 50wt% ethanol aqueous solution as the solvent, with the amount of solvent added consistent with the volumetric adsorption amount of the silica support.

[0168] 2) Structural enhancement treatment of the carrier: The silica carrier was placed in a high-temperature hydrothermal reactor, and a zirconium sol aqueous solution with a volume of 10 times that of the carrier was added. The solid content of the sol aqueous solution was 5 wt%. The temperature was then raised to 120℃ for 20 h, cooled to room temperature, washed 5 times with deionized water, filtered, dried at 50℃ for 10 h, and calcined at 600℃ for 10 h to obtain the enhanced carrier.

[0169] 3) The support obtained in step 2) was desorbed at 300℃ for 5 h, then impregnated once with impregnation solution. After impregnation, it was allowed to stand for 10 h, then dried at 50℃ for 10 h, and calcined at 400℃ for 8 h to obtain the preliminary catalyst.

[0170] 4) Preliminary catalyst structural enhancement treatment: The catalyst obtained in step 3) was placed in a tube furnace, nitrogen gas was introduced and the temperature was raised to 400°C, and then switched to superheated steam treatment for 10 h. After the treatment was completed, the steam was turned off, and after the reaction tube cooled to below 30°C, the support was removed to obtain the enhanced industrial catalyst.

[0171] This catalyst is used for the direct synthesis of alcohols from syngas. Prior to the reaction, the catalyst undergoes reduction activation. The reducing atmosphere is a mixture of H2 and N2, with H2 / mixture = 20 wt% (molar ratio), and the reduction space velocity is 8000 h⁻¹. -1The reduction temperature was 300℃, the reduction pressure was 0 bar, and the time was 5 hours. After the reduction was completed, the reaction was switched to syngas.

[0172] When performing the syngas-to-alcohol reaction, the molar ratio of H2 / CO in the syngas is 0.5, and the reaction space velocity is 1500 h⁻¹. -1 The tail gas recirculation ratio was 2, the reaction temperature was 230 °C, and the reaction pressure was 60 bar. The types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0173] Comparative Example 1

[0174] This comparative example provides a method for preparing a catalyst for the direct production of alcohols from syngas. The difference between this method and Example 1 is that it does not include steps 2) and 4).

[0175] This catalyst is used for the direct synthesis of alcohols from syngas. Before the reaction, the catalyst is first reduced and activated, and the reduction conditions are the same as in Example 1.

[0176] When the reaction to prepare alcohol from syngas was carried out, the reaction conditions were the same as in Example 1, and the reaction results are shown in Table 1.

[0177] Comparative Example 2

[0178] This comparative example provides a method for preparing a catalyst for direct synthesis of alcohols from syngas. The difference between this method and Example 8 is that it does not include steps 2) and 4).

[0179] This catalyst is used for the direct synthesis of alcohols from syngas. Before the reaction, the catalyst is first reduced and activated, and the reduction conditions are the same as in Example 8.

[0180] When the reaction to prepare alcohol from syngas was carried out, the reaction conditions were the same as in Example 8, and the reaction results are shown in Table 1.

[0181] Comparative Example 3

[0182] This comparative example provides a method for preparing a catalyst for direct synthesis of alcohols from syngas. The difference between this preparation method and Example 6 is that, in step 4), the superheated steam treatment temperature is 900°C.

[0183] This catalyst is used for the direct synthesis of alcohols from syngas. Before the reaction, the catalyst is first reduced and activated, and the reduction conditions are the same as in Example 6.

[0184] When the reaction to prepare alcohol from syngas was carried out, the reaction conditions were the same as in Example 6, and the reaction results are shown in Table 1.

[0185] Comparative Example 4

[0186] This comparative example provides a method for preparing a catalyst for direct synthesis of alcohols from syngas. The difference between this method and Example 11 is that, in step 4) structural enhancement treatment, the solid content of the sol-sol aqueous solution used is 30 wt%.

[0187] This catalyst is used for the direct synthesis of alcohols from syngas. Before the reaction, the catalyst is first reduced and activated, and the reduction conditions are the same as in Example 11.

[0188] When the reaction to prepare alcohol from syngas was carried out, the reaction conditions were the same as in Example 11, and the reaction results are shown in Table 1.

[0189] Table 1. Catalyst reaction results of Examples 1-13 and Comparative Examples 1-4

[0190]

[0191]

[0192] The results above show that, compared to the catalysts in Comparative Examples 1-4, the enhanced industrial catalyst described in this application exhibits higher activity, higher alcohol selectivity, higher mechanical strength, and higher structural stability under the same reaction conditions. Specifically, the enhanced industrial catalysts described in Examples 1-13 of this application, when the noble metal Ru content is less than 5 wt%, can achieve a total CO conversion rate of 72.2% to 96.9%, with lower methane and carbon dioxide selectivity, and a maximum alcohol selectivity of 62.2%.

[0193] Furthermore, compared with Comparative Examples 1-2, the pressure measurement intensity of the enhanced industrial catalysts described in Examples 1-13 of this application is significantly enhanced, increasing from 42-50 N / cm before enhancement to 110-210 N / cm. This can minimize the risk of wear and loss during use, reduce the loss of active components, minimize the significant decline in catalytic reaction performance, minimize the entry of broken catalyst powder into the product tank with the material flow, and minimize the difficulty of product separation. Broken particles can cause complete blockage of the reaction bed, leading to major production shutdown accidents.

[0194] Compared to Comparative Example 3, in Example 6, under the same catalyst composition and reaction conditions, the selectivity for methane and carbon dioxide was significantly reduced, while the selectivity for alcohols was significantly increased. This is because the excessively high temperature of the superheated steam treatment led to a reduction in the specific surface area of ​​the catalyst, resulting in the growth of active nanoparticles and a decline in performance. Although the mechanical properties increased significantly, the catalytic performance decreased.

[0195] Compared to Comparative Example 4, in Example 11, under the same catalyst composition and reaction conditions, the selectivity for methane and carbon dioxide was significantly reduced, while the selectivity for alcohols and the pressure intensity were significantly improved. This is because when the silica sol concentration is too high, the solution viscosity is too high, preventing it from fully penetrating the pores of the catalyst, thus diminishing the enhancing effect. After calcination, the catalyst is encapsulated by a dense oxide layer, affecting the diffusion behavior of reactants and products, thereby reducing catalyst performance.

[0196] This invention effectively overcomes the various shortcomings of the prior art and has high industrial application value.

[0197] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A method for preparing an enhanced industrial catalyst for direct syngas-to-methanol production, characterized in that, The preparation method includes: impregnating a SiO2 support with an impregnation solution to obtain a preliminary catalyst, followed by aging, drying and calcining; The impregnation solution is a mixture of Ru salt, a first metal salt, and a second metal salt; the first metal is selected from one or more of Mn, Zr, Zn, Cu, Ce, Pr, Sm, Ag, and Au; the second metal is selected from one or more of Li, Na, K, Rb, Cs, Mg, and Ca. The preparation method further includes structural enhancement treatment of the support and / or the preliminary catalyst, wherein the structural enhancement treatment is selected from one or more of steps A and B; Step A includes subjecting the support and / or the preliminary catalyst to superheated steam treatment; Step B includes placing the support and / or the preliminary catalyst in a sol-water solution for a hydrothermal reaction, wherein the sol includes one or more of silica sol, aluminum sol, zirconium sol, and organosilane sol.

2. The preparation method according to claim 1, characterized in that, The temperature of the superheated steam treatment in step A is 400~800℃; And / or, the superheated steam treatment time in step A is 2~20 h; And / or, in step A, the water vapor used for superheated steam treatment is saturated water vapor; And / or, in step A, the superheated steam treatment is further preceded by a step of heating in an inert atmosphere; And / or, in step B, the solid content of the sol-sol aqueous solution is 0.1~10 wt%; And / or, in step B, the temperature of the hydrothermal reaction is 50~200℃; And / or, in step B, the hydrothermal reaction time is 2~20 h; And / or, step B may be followed by a washing and filtering step; And / or, in step B, the organosilane is selected from one or more of tetramethylsilane, dimethyldichlorosilane, and trimethylchlorosilane.

3. The preparation method according to claim 2, characterized in that, The inert gas is selected from one or more of nitrogen, argon, and helium; And / or, the washing liquid is water; And / or, the system after the hydrothermal reaction is cooled to 20-30°C before washing.

4. The preparation method according to claim 1, characterized in that, Based on the total mass of the enhanced industrial catalyst, the Ru content is 0.1~5 wt%, the first metal content is 0.01~20 wt%, and the second metal promoter content is 0.01~10 wt%. And / or, the impregnation solution further includes a surfactant, wherein the amount of the surfactant added is 1 to 40 times the mass of Ru in the Ru salt; And / or, the Ru salt is selected from one or more of ruthenium trichloride, ruthenium nitrite, ruthenium acetate, ruthenium acetylacetone, and ammonium hexachlororuthenate; And / or, the first metal salt and the second metal salt are each independently selected from one or more of nitrates, sulfates and chlorides; And / or, the solvent of the mixture is selected from one or more of water, ethanol, and acetone; And / or, the preparation of the impregnation solution includes stirring Ru salt, a first metal salt, and a second metal salt in water; And / or, the impregnation process further includes a step of heat-treating the carrier, wherein the heat treatment temperature is 200~400℃ and the time is 3~8 h; And / or, the impregnation is performed in 1 to 5 stages; And / or, the aging step is to let it stand for 2 to 24 hours; And / or, the drying temperature is 30~200 ℃, and the time is 2~24 h; And / or, the calcination temperature is 200~600 ℃, and the time is 2~24 h.

5. The preparation method according to claim 4, characterized in that, The surfactant is selected from one or more of the following: polyvinylpyrrolidone, polyvinyl alcohol, polysorbate, sodium dodecyl sulfate, dioctadecyl dimethyl ammonium chloride, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, hexadecyltrimethylammonium bromide, and polyethylene glycol. And / or, the stirring time is 1~24 h; And / or, the stirring temperature is 20~90℃; And / or, the volume ratio of the solvent to the SiO2 support adsorbed at equal volumes is 1 to 5.

6. An enhanced industrial catalyst prepared by the preparation method according to any one of claims 1 to 5.

7. Use of the enhanced industrial catalyst as described in claim 6 in industrial direct syngas to alcohol production.

8. A method for the direct production of alcohols from syngas using the enhanced industrial catalyst as described in claim 6.

9. The method according to claim 8, characterized in that, The reaction process also includes a step of reducing the enhanced industrial catalyst. And / or, the synthesis gas is a mixture of H2 and CO, with a volume ratio of H2 to CO of 1:0.5~5; And / or, the pressure of the reaction is 10~80 bar; And / or, the temperature of the reaction is 200~300℃; And / or, the space velocity of the reaction is 500~10000 h⁻¹ -1 ; And / or, the tail gas recycle ratio of the reaction is 1 to 5.

10. The method according to claim 9, characterized in that, The reduction process takes 2 to 20 hours. And / or, the temperature of the reduction treatment is 200~450℃; And / or, the apparent pressure of the reduction treatment is 0~20 bar; And / or, the space velocity of the reduction process is 1000~10000 h⁻¹ -1 .

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