An industrial catalyst carrier, a catalyst and their use in a synthesis gas conversion reaction

Abstract

This invention provides an industrial catalyst support, a catalyst, and its application in the conversion of syngas to higher alcohols. The catalyst support comprises silica, a colloidal solvent, and a metal salt; the metal element comprises 0.1% to 5% of the silica mass, and is selected from one or more of Na, K, Mg, Ca, Mn, La, Sm, Ce, or Zr. This support possesses excellent mechanical strength, a large specific surface area, and abundant pore structure. Furthermore, the preparation method is simple and reproducible, making it suitable for large-scale industrial production. The catalyst prepared using this support not only exhibits excellent mechanical strength and abundant pore structure but also significantly enhances the catalytic activity and selectivity of the Fischer-Tropsch synthesis catalyst in the conversion of syngas to higher alcohols, thus possessing significant application value in industrial fields.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, and relates to an industrial catalyst support, a catalyst, and its application in syngas conversion reaction. Background Technology

[0002] Fischer-Tropsch synthesis, as a key technology for converting syngas (composed of carbon monoxide and hydrogen) into liquid hydrocarbons and various chemicals, occupies a pivotal position in the energy and chemical industry. The performance of the catalyst support directly determines the overall effect and product quality of the Fischer-Tropsch synthesis reaction.

[0003] Higher alcohols, as important industrial intermediates, have extremely wide applications and are core raw materials for the preparation of various industrial products such as surfactants, plasticizers, lubricants, and detergents. Taking surfactants as an example, surfactants synthesized from higher alcohols possess excellent emulsifying, dispersing, and detergency properties, and are widely used in daily chemicals, textiles, food processing, pharmaceuticals, and other industries, becoming key components for achieving the core functions of related products. In the field of plasticizers, higher alcohol-derived ester plasticizers can effectively improve the flexibility and plasticity of plastic products, significantly broadening their application range and enhancing their performance. Furthermore, in lubricant formulations, the addition of higher alcohols can significantly enhance the anti-wear properties and lubrication effect of lubricants, reducing frictional losses during the operation of mechanical equipment, thereby extending the service life of the equipment. With the continuous improvement of performance requirements for end products across global industries, the market demand for higher alcohol quality standards and production volume is also constantly growing, making the upgrading and innovation of higher alcohol preparation technology an urgent need for industry development.

[0004] Traditional processes for preparing higher alcohols primarily rely on petroleum resources as raw materials, with core routes including olefin hydroformylation, the Ziegler process, and n-alkane oxidation. However, these traditional processes suffer from several insurmountable limitations: firstly, petroleum, as a non-renewable resource, is becoming increasingly scarce, posing a severe challenge to the stability of raw material supply for traditional processes. Furthermore, drastic fluctuations in oil prices directly impact cost control in higher alcohol production, reducing the product's market competitiveness. Secondly, traditional preparation processes typically involve complex reaction steps and require stringent reaction conditions (such as high temperature and high pressure). This not only increases equipment investment and energy consumption, raising production costs, but also generates more environmental pollutants, placing significant pressure on the ecological environment and contradicting the current trend of green chemistry.

[0005] In comparison, the Fischer-Tropsch synthesis technology for producing higher alcohols uses a variety of resources such as coal, natural gas, and biomass as raw materials. These raw material sources are more abundant, diverse, and readily available, effectively reducing over-reliance on petroleum resources and providing a new pathway for the large-scale production of higher alcohols. my country's energy structure, characterized by "abundant coal, scarce oil, and limited gas," determines that the Fischer-Tropsch synthesis technology for producing higher alcohols possesses unique resource advantages and enormous development potential in my country, and is of great significance for optimizing my country's energy utilization structure and promoting the high-quality development of the coal chemical industry.

[0006] However, the technology for preparing higher alcohols via the Fischer-Tropsch synthesis route has not yet been industrialized, and most research remains in the laboratory development stage. The main limiting factors are twofold: First, the reaction network for the Fischer-Tropsch synthesis of higher alcohols is extremely complex, with numerous side reactions, making it difficult to synthesize highly active and selective dedicated catalysts, thus failing to meet the requirements of industrial production for product yield and purity. Second, how to achieve cross-scale catalyst design, efficiently converting small-sized catalysts developed in the laboratory into particulate catalysts with industrial application performance, and solving problems such as insufficient strength and performance degradation during catalyst scale-up, faces enormous technical challenges. Summary of the Invention

[0007] In view of the shortcomings of the prior art described above, the purpose of this invention is to provide an industrial catalyst support, a catalyst, and its application in the conversion of syngas to higher alcohols, in order to solve the problems in the prior art.

[0008] To achieve the above and other related objectives, the present invention provides an industrial catalyst support, a catalyst, and its application in the conversion of syngas to higher alcohols.

[0009] The first aspect of the present invention provides an industrial catalyst support, wherein the raw material components of the support include silica, a colloidal solvent, and a metal salt.

[0010] Preferably, the metal is selected from one or more of Na, K, Mg, Ca, Mn, La, Sm, Ce, or Zr. The modified metal acts as a support modifier to improve the mechanical strength of the support, while also enhancing the catalytic activity and selectivity of the final catalyst. However, not all metals are suitable; for example, the choice of Ni can actually affect the selectivity of total oxygen-containing compounds and higher alcohols in the Fischer-Tropsch synthesis reaction.

[0011] Preferably, the mass of the metal element is 0.1% to 5% of the mass of silicon dioxide, such as 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%. The optimal amount of different metals varies and needs to be confirmed by further experiments, but within this range, they all have good catalytic effects; if the content is too high (e.g., 10%), the selectivity of the prepared catalyst will be poor.

[0012] Preferably, the metal salt is selected from one or more of carbonates, nitrates, chlorides, fluorides, sulfates, or acetates.

[0013] Preferably, the particle size of the silica is 10~20 nm, such as 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm or 20 nm.

[0014] Preferably, the diameter of the cross-section of the carrier is 1 to 3 mm, such as 1 mm, 1.5 mm, 2 mm, 2.5 mm or 3 mm.

[0015] Preferably, the length of the carrier is 5 to 10 mm, such as 5 mm, 6 mm, 7 mm, 8 mm, 9 mm or 10 mm.

[0016] Preferably, the lateral compressive strength of the carrier is at least 60 N / cm. More preferably, the lateral compressive strength of the carrier is 60~90 N / cm. For example, it can be 60 N / cm, 65 N / cm, 70 N / cm, 75 N / cm, 80 N / cm, 85 N / cm or 90 N / cm.

[0017] Preferably, the specific surface area of ​​the carrier is at least 280 μm. 2 / g. More preferably, the specific surface area of ​​the carrier is 280~300m². 2 / g. For example, it could be 280m. 2 / g、284m 2 / g、288m 2 / g、292m 2 / g、296m 2 / g or 300m 2 / g.

[0018] Preferably, the adhesive solvent is selected from one or more of silica sol, alumina sol, polyvinyl alcohol, carboxymethyl cellulose, starch, guar gum, or polyethylene glycol. The adhesive solvent is primarily a binder, used to bond the carrier particles together, which helps improve the mechanical strength of the carrier after molding. More preferably, the adhesive solvent includes starch, guar gum, and one or more selected from silica sol, alumina sol, polyvinyl alcohol, carboxymethyl cellulose, or polyethylene glycol.

[0019] Preferably, the mass ratio of silicon dioxide, starch, and guar gum powder is (70-95):(3-20):(2-10), such as 70:3:2, 80:3:2, 90:3:2, 70:10:2, 80:10:2, 90:10:2, 95:10:2, 70:20:2, 80:20:2, 90:20:2, 95:20:2, 70:3:5, 80:3:5, 90:3:5, 95:3:5, 70:10:10, 80:10:10, 90:10:10, 95:10:10, 87:10:3, 85:12:3, 70:20:10, 95:3:2, 82:15:3, 90:8:2, or 83:15:2. Guar sesame powder has water absorption and swelling capabilities, which can increase lubricity and reduce extrusion pressure. However, if the guar sesame powder content is too high, the contact between silica carriers will deteriorate, leading to a decrease in catalyst strength. Starch is used as a binder, but if too much starch is used, it may cause local overheating or residual carbon during calcination, resulting in the active sites being covered.

[0020] More preferably, the number average molecular weight of the polyvinyl alcohol is 1500~2400, such as 1500, 1600, 1700, 1800, 2000, 2200 or 2400; the degree of alcoholysis of the polyvinyl alcohol is 87%~89%, such as 87%, 88% or 89%.

[0021] More preferably, the number average molecular weight of the polyethylene glycol is 4000-6000, such as 4000, 4500, 5000, 5500 or 6000.

[0022] More preferably, the pH of the silica sol is 7.0~8.0, such as 7.0, 7.2, 7.4, 7.6, 7.8 or 8.0; the solid content is 25%~30%, such as 25%, 26%, 27%, 28%, 29% or 30%; and the particle size is 10~20nm, such as 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm or 20nm.

[0023] More preferably, the pH of the aluminum sol is 7.0~8.0, such as 7.0, 7.2, 7.4, 7.6, 7.8 or 8.0; the solid content is 15%~20%, such as 15%, 16%, 17%, 18%, 19% or 20%; and the particle size is 10~30nm, such as 10nm, 12nm, 14nm, 16nm, 18nm, 20nm, 22nm, 24nm, 26nm, 28nm or 30nm.

[0024] More preferably, the number average molecular weight of the carboxymethyl cellulose is 50,000-200,000, such as 50,000, 60,000, 70,000, 80,000, 90,000, 100,000, 120,000, 140,000, 160,000, 180,000 or 200,000.

[0025] Preferably, the amount of one or more raw materials selected from silica sol, alumina sol, polyvinyl alcohol, carboxymethyl cellulose, or polyethylene glycol is 5% to 60 wt% of the amount of silica. For example, it can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or 60%. Excessive content (80%) leads to a decrease in the specific surface area of ​​the catalyst support, blockage of internal pores, and coverage of active sites, thereby resulting in a decrease in catalytic performance; insufficient content (1%) leads to a decrease in the mechanical strength of the catalyst support.

[0026] A second aspect of the present invention provides a method for preparing an industrial catalyst support as described above. The method includes: mixing silica, starch, and guar gum powder, and ball milling the mixture to obtain a composite support powder; kneading the composite support powder with an aqueous solution of one or more selected from silica sol, alumina sol, polyvinyl alcohol, carboxymethyl cellulose, or polyethylene glycol and a metal salt to form a plastic body; processing the plastic body into a wet-formed body through an extrusion molding process; and finally obtaining a modified silica catalyst support through drying and calcination steps.

[0027] Preferably, the total mass of the aqueous solution selected from one or more of silica sol, aluminum sol, polyvinyl alcohol, carboxymethyl cellulose, or polyethylene glycol and the modified metal salt is 1.5 to 2.5 times the mass of silica, such as 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, or 2.5 times.

[0028] Preferably, the kneading time is 2 to 3 hours, such as 2 hours, 2.5 hours or 3 hours.

[0029] Preferably, the cross-sectional shape of the wet-formed article is one or both of cylindrical or clover-shaped.

[0030] Preferably, the drying process is performed in two stages.

[0031] Preferably, the first drying temperature is 20℃~30℃, such as 20℃, 22℃, 24℃, 26℃, 28℃ or 30℃.

[0032] Preferably, the first drying time is 5 h to 24 h, such as 5 h, 10 h, 15 h, 20 h or 24 h.

[0033] Preferably, the second drying temperature is 60℃~120℃, such as 60℃, 70℃, 80℃, 90℃, 100℃, 110℃ or 120℃.

[0034] Preferably, the second drying time is 2 h to 24 h, such as 2 h, 4 h, 8 h, 12 h, 16 h, 20 h or 24 h.

[0035] Preferably, the roasting temperature is 400℃~650℃, such as 400℃, 450℃, 500℃, 550℃ or 600℃.

[0036] Preferably, the roasting time is 4 h to 24 h, such as 4 h, 8 h, 12 h, 16 h, 20 h or 24 h.

[0037] A third aspect of this invention provides a catalyst for preparing the Fischer-Tropsch synthesis reaction using the aforementioned industrial catalyst support. The catalyst comprises an active metal element Ru and a metal promoter element.

[0038] Preferably, the content of the active metal Ru element is 0.1% to 10% of the industrial catalyst support. For example, it can be 0.1%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.

[0039] Preferably, the metal additive element is one or more selected from Na, K, Rb, Cs, Ca, Mg, Ba, Zr, Cu, Ag, or Mn.

[0040] Preferably, the metal element in the soluble salt of the metal additive is 0.1-5% of the industrial catalyst carrier, such as 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%.

[0041] Preferably, the lateral compressive strength of the catalyst is at least 70 N / cm. More preferably, the lateral compressive strength of the catalyst is 70~110 N / cm. For example, it can be 70 N / cm, 75 N / cm, 80 N / cm, 85 N / cm, 90 N / cm, 95 N / cm, 100 N / cm, 105 N / cm or 110 N / cm.

[0042] Preferably, the aldol selectivity of the catalyst is at least 95%. More preferably, the aldol selectivity of the catalyst is 95% to 99.9%. For example, it can be 95%, 96%, 97%, 98%, 99%, or 99.9%.

[0043] Preferably, the total oxygen-containing compound selectivity of the catalyst is at least 50%. More preferably, the total oxygen-containing compound selectivity of the catalyst is at least 50% to 75%. For example, it can be 50%, 55%, 60%, 65%, 70%, or 75%.

[0044] A fourth aspect of the present invention provides a method for preparing a catalyst for Fischer-Tropsch synthesis reaction as described above, the method comprising: impregnating an impregnation solution and an industrial catalyst support as described above, followed by drying, calcination, and reduction to obtain a Fischer-Tropsch synthesis catalyst, wherein the impregnation solution comprises at least the active metal Ru element.

[0045] Preferably, the impregnation is an equal-volume impregnation; the equal-volume impregnation involves uniformly spraying the impregnation liquid into a continuously tumbling catalyst until the impregnation liquid is completely and equally adsorbed into the carrier. The amount of impregnation liquid is determined based on the mass of the catalyst carrier and the water absorption rate of the carrier.

[0046] Preferably, the impregnation solution is a mixture of a soluble salt solution corresponding to the active metal Ru and a soluble salt solution corresponding to the metal auxiliary element.

[0047] Preferably, the soluble salt corresponding to the active metal Ru element is one or both of ruthenium nitrite or ruthenium chloride.

[0048] Preferably, the soluble salt corresponding to the metal auxiliary element is selected from one or more of carbonates, nitrates, chlorides, fluorides, sulfates, or acetates.

[0049] Preferably, the solvent is one or both of water and ethanol.

[0050] More preferably, when the solvent is an aqueous ethanol solution, the ethanol concentration is 0.01 vol% to 40 vol%, such as 0.01 vol%, 0.1 vol%, 1 vol%, 5 vol%, 10 vol%, 15 vol%, 20 vol%, 25 vol%, 30 vol%, 35 vol%, or 40 vol%.

[0051] Preferably, the drying temperature is 60~180℃, such as 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃ or 180℃.

[0052] Preferably, the drying time is 2 to 24 hours, such as 2 hours, 4 hours, 8 hours, 12 hours, 16 hours, 20 hours or 24 hours.

[0053] Preferably, the calcination temperature is 300-600℃, such as 300℃, 350℃, 400℃, 450℃, 500℃, 550℃ or 600℃.

[0054] Preferably, the roasting time is 2 h to 24 h, such as 2 h, 4 h, 8 h, 12 h, 16 h, 20 h or 24 h.

[0055] Preferably, the reduction is carried out in H2 or an H2 / inert gas mixture;

[0056] More preferably, the inert gas is one or more of nitrogen, argon, or helium.

[0057] More preferably, the H2 content in the H2 / inert gas is 10 vol% to 100 vol%, such as 10 vol%, 15 vol%, 20 vol%, 25 vol%, 30 vol%, 35 vol%, 40 vol%, 45 vol%, 50 vol%, 60 vol%, 70 vol%, 80 vol%, 90 vol%, or 100 vol%.

[0058] Preferably, the reduction pressure is 1 to 30 bar, such as 1 bar, 2 bar, 3 bar, 4 bar, 5 bar, 6 bar, 7 bar, 8 bar, 9 bar, 10 bar, 20 bar or 30 bar.

[0059] Preferably, the reduction temperature is 300℃~500℃, such as 300℃, 350℃, 400℃, 450℃ or 500℃.

[0060] Preferably, the space velocity for reduction is 5000~150000 h⁻¹ -1 For example, it can be 5000 h -1 6000h -1 7000h -1 8000h -1 9000h -110000h -1 11000h -1 12000h -1 13000h -1 14000h -1 Or 15000h -1 .

[0061] Preferably, the reduction time is 2h to 24h, such as 2h, 4h, 8h, 12h, 16h, 20h or 24h.

[0062] The fifth aspect of this invention provides an application of the above-mentioned Fischer-Tropsch synthesis catalyst in the direct conversion of syngas to higher alcohols via the Fischer-Tropsch reaction.

[0063] Preferably, the higher alcohol is an alcohol with 2 or more carbon atoms, such as 2, 3, 4, 5, 6, 7 or 8 carbon atoms.

[0064] Preferably, in the Fischer-Tropsch reaction, the synthesis gas is a mixture of H2 and CO, and the molar ratio of H2 to CO is 0.5 to 5, such as 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5.

[0065] Preferably, the reaction temperature in the Fischer-Tropsch reaction is 200~300℃, such as 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃ or 300℃.

[0066] Preferably, in the Fischer-Tropsch reaction, the reaction pressure is 40 to 100 bar, such as 40 bar, 50 bar, 60 bar, 70 bar, 80 bar, 90 bar or 100 bar.

[0067] Preferably, in the Fischer-Tropsch reaction, the reaction space velocity is 1000~5000 h⁻¹. -1 For example, it can be 1000 h -1 2000 h -1 3000 h -1 4000 h -1 or 5000 h -1 .

[0068] The sixth aspect of the present invention provides the use of a metal salt for improving the side pressure strength and / or specific surface area of ​​an industrial catalyst support, wherein the industrial catalyst support is a silica support.

[0069] Preferably, the metal is one or more selected from Na, K, Rb, Cs, Ca, Mg, Ba, Zr, Cu, Ag, or Mn.

[0070] Preferably, the salt corresponding to the metal element is selected from one or more of carbonates, nitrates, chlorides, fluorides, sulfates, or acetates.

[0071] Preferably, the compressive strength of the carrier modified with metal salt is increased by 35% to 75%, such as 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70% or 75%.

[0072] Preferably, the specific surface area of ​​the carrier modified with metal salt is increased by 10% to 20%, such as 10%, 12%, 14%, 16%, 18% or 20%.

[0073] As described above, the beneficial effects of the present invention are as follows:

[0074] 1. The industrial particulate catalyst support with a specific composition has a uniform surface and not only has advantages such as good mechanical strength, large specific surface area, excellent heat transfer performance and rich pore structure, but also has a simple preparation method with good reproducibility, making it suitable for large-scale industrial production.

[0075] 2. The Fischer-Tropsch synthesis catalyst for producing higher alcohols prepared using this particulate support also exhibits excellent mechanical strength and abundant pore structure. At the same time, the introduction of modifiers significantly improves the catalytic activity and selectivity of the Fischer-Tropsch synthesis catalyst in the reaction of syngas to produce higher alcohols, thus possessing significant application value in the field of industrial applications. Attached Figure Description

[0076] Figure 1 Photograph of the clover-structured catalyst support prepared in Example 1 of this invention.

[0077] Figure 2 Photograph of the clover-structured catalyst prepared in Example 1 of this invention.

[0078] Figure 3 This is a cross-sectional SEM image of the clover-structured catalyst support prepared in Example 1 of the present invention.

[0079] Figure 4 Photograph of the cylindrical catalyst support prepared in Example 3 of this invention.

[0080] Figure 5 This is a SEM image of the cylindrical catalyst support prepared in Example 3 of the present invention. Detailed Implementation

[0081] The following specific examples 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. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0082] It should be noted that the process equipment or apparatus not specifically mentioned in the following embodiments are all conventional equipment or apparatus in the art.

[0083] Furthermore, it should be understood that the one or more method steps mentioned in this invention do not preclude the existence of other method steps before or after the combined steps, or the insertion of other method steps between these explicitly mentioned steps. Unless otherwise stated, the numbering of each method step is merely a convenient tool for identifying each method step, and is not intended to limit the order of the method steps or limit the scope of the invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the invention.

[0084] 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, this invention can be implemented using any prior art methods, apparatus, and materials similar to or equivalent to those described in the embodiments of this invention, based on the knowledge of the prior art possessed by one of ordinary skill in the art and the description of this invention.

[0085] In this embodiment, the ball milling operation was carried out using an industrial horizontal ball mill (QM-500). The experimental conditions were: 5mm zirconia balls, ball milling speed of 200rpm, and ball milling time of 2h.

[0086] In this embodiment, the extrusion molding process was carried out using a single-screw extruder (ZYDJ-40). The experimental conditions were: the extrusion molding speed was 30~50 rpm.

[0087] The atmospheric pressure mentioned in the example is 1.012 bar.

[0088] The ambient temperature described in the example is 25±5℃.

[0089] Example 1

[0090] Silica, starch, and guar gum powder were mixed at a mass ratio of 87:10:3 and ball-milled to obtain a composite carrier powder. Then, neutral silica sol (30% of the mass of silica) and samarium nitrate (0.1% of the mass of silica) were weighed and prepared into a solution with a total mass 2.3 times that of silica. This solution was then thoroughly kneaded with the composite carrier powder to form a plastic body. The plastic body was processed into a 2mm clover-structure wet-formed body using an extrusion molding process. It was first dried at room temperature for 12 hours, then dried at 100℃ for 12 hours, and finally calcined at 600℃ for 5 hours to obtain the modified catalyst carrier.

[0091] Ruthenium nitrite and sodium nitrate were weighed out at 2% and 1.2% of the mass of silica, respectively, and dispersed in water to prepare an impregnation solution, wherein the amount of water added was 1.5 times the mass of the silica support. The impregnation solution was thoroughly mixed with the modified catalyst support and impregnated. The mixture was first dried at room temperature for 12 hours, then dried at 100°C for 12 hours, and finally calcined at 500°C for 5 hours to obtain the oxide-type catalyst precursor.

[0092] The catalyst was loaded into a stainless steel reactor and reduced for 5 hours at 350°C and atmospheric pressure under H2, with a reduction space velocity of 12000 h⁻¹. -1 The Fischer-Tropsch synthesis particulate catalyst obtained after reduction is the catalyst described above.

[0093] In the reactor described above, a mixture of H2 / CO with a volume ratio of 2:1 was introduced as the reactant gas, the temperature was raised to 230 °C, the reaction pressure was 60 bar, and the reaction space velocity was 3000 h⁻¹. -1 The reaction proceeded via direct conversion of syngas. After the reaction, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 1.

[0094] The cross-section of the catalyst support was examined using a scanning electron microscope (Sigema 300). The sample was directly attached to the sample stage using conductive tape. The testing conditions were: accelerating voltage 2.00 kV, working distance 6.3 mm, SE2 detector, and magnification 50x. Results are shown below. Figure 3 The SEM image shows a cross-section of the catalyst support.

[0095] Figure 1 Photograph of the clover-structured catalyst support prepared in Example 1 of this invention.

[0096] Figure 2 Photograph of the clover-structured catalyst prepared in Example 1 of this invention.

[0097] Figure 3 This is a cross-sectional SEM image of the clover-structured catalyst support prepared in Example 1 of this invention. As can be seen from the image, the catalyst support has a rich porous structure, which also endows the catalyst with excellent heat transfer performance.

[0098] Example 2

[0099] Silica, starch, and guar gum powder were mixed in a mass ratio of 70:20:10 and ball-milled to obtain a composite carrier powder. Then, neutral silica sol (30% of the silica mass) and zirconium nitrate and sodium nitrate (4.6% and 0.2% of the silica mass, respectively) were weighed and prepared into a solution with a total mass 1.6 times that of silica. This solution was then thoroughly kneaded with the composite carrier powder to form a plastic body. The plastic body was processed into a 2mm clover-structure wet-formed body using an extrusion molding process. It was first dried at room temperature for 24 hours, then dried at 120℃ for 2 hours, and finally calcined at 400℃ for 24 hours to obtain the modified catalyst carrier.

[0100] Ruthenium nitrite, rubidium nitrate, and copper nitrate were weighed out at 2%, 1.5%, and 1% of the mass of silicon dioxide, respectively, and dispersed in water to prepare an impregnation solution. The amount of water added was 1.7 times the mass of the silicon dioxide support. After thoroughly mixing and impregnating the modified catalyst support with the impregnation solution, the catalyst was first dried at room temperature for 24 hours, then dried at 180°C for 2 hours, and finally calcined at 300°C for 24 hours to obtain the oxide-type catalyst precursor.

[0101] The catalyst was loaded into a stainless steel reactor and reduced for 5 hours at 300 °C and atmospheric pressure under H2 conditions, with a reduction space velocity of 12000 h⁻¹. -1 The Fischer-Tropsch synthesis particulate catalyst obtained after reduction is the catalyst described above.

[0102] In the reactor described above, a mixture of H2 / CO with a volume ratio of 2:1 was introduced as the reactant, the temperature was raised to 230°C, the reaction pressure was 60 bar, and the reaction space velocity was 3000 h⁻¹. -1 The reaction proceeded via direct conversion of syngas. After the reaction, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 1.

[0103] Example 3

[0104] Silica, starch, and guar gum powder were mixed at a mass ratio of 95:3:2 and ball-milled to obtain a composite carrier powder. Then, neutral aluminum sol (30% of the silica mass), cerium nitrate (0.5% Ce), and calcium nitrate (1% Ca) were prepared to form a solution with a total mass 1.6 times that of silica. This solution was then thoroughly kneaded with the composite carrier powder to form a plastic body. The plastic body was processed into a cylindrical wet-formed body with a diameter of 1.5 mm using an extrusion molding process. This wet-formed body was first dried at room temperature for 12 hours, then dried at 80°C for 20 hours, and finally calcined at 500°C for 10 hours to obtain the modified catalyst carrier.

[0105] Ruthenium nitrite, potassium nitrate, and silver nitrate were weighed out at 2%, 0.5%, and 0.1% of the mass of silicon dioxide, respectively. These three components were dispersed in water to prepare an impregnation solution, wherein the amount of water added was 1.6 times the mass of the silicon dioxide support. The impregnation solution was thoroughly mixed with the modified catalyst support and impregnated. The mixture was first dried at room temperature for 24 hours, then dried at 120°C for 12 hours, and finally calcined at 500°C for 5 hours to obtain the oxide-type catalyst precursor.

[0106] The catalyst was loaded into a stainless steel reactor and reduced for 5 hours at 500 °C under H2 and atmospheric pressure, with a reduction space velocity of 12000 h⁻¹. -1 The Fischer-Tropsch synthesis particulate catalyst obtained after reduction is the catalyst described above.

[0107] In the reactor described above, a mixture of H2 / CO with a volume ratio of 2:1 was introduced as the reactant, the temperature was raised to 230°C, the reaction pressure was 60 bar, and the reaction space velocity was 3000 h⁻¹. -1 The reaction proceeded via direct conversion of syngas. After the reaction, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 1.

[0108] The analysis was performed using a scanning electron microscope (Sigema 300). The sample was directly attached to the sample stage using conductive tape. The testing conditions were: accelerating voltage 2.00 kV, working distance 6.5 mm, SE2 detector, and magnification 50x. Results were obtained as follows: Figure 5 The SEM image shows a cross-section of the catalyst support.

[0109] Figure 4 Photograph of the cylindrical catalyst support prepared in Example 3 of this invention.

[0110] Figure 5This is a SEM image of the cylindrical catalyst support prepared in Example 3 of this invention. As can be seen from the image, the sample consists of irregularly shaped blocky particles that are tightly packed together, and the catalyst support has a rich porous structure. These pores also give the catalyst excellent heat transfer performance.

[0111] Example 4

[0112] Silica, starch, and guar gum powder were mixed in a mass ratio of 82:15:3 and ball-milled to obtain a composite carrier powder. Then, polyethylene glycol (equivalent to 20% of the mass of silica) and potassium nitrate (equivalent to 1% of the mass of silica) were weighed and prepared into a solution with a total mass 1.6 times that of silica. This solution was then thoroughly kneaded with the composite carrier powder to form a plastic body. Using an extrusion molding process, the plastic body was processed into a 3mm clover-structured wet-molded body, dried at room temperature for 24 hours, then dried at 120℃ for 24 hours, and finally calcined at 650℃ for 8 hours to obtain the modified catalyst carrier.

[0113] Ruthenium chloride, cesium nitrate, and zirconium nitrate were weighed out at 2%, 0.5%, and 4% of the mass of silicon dioxide, respectively, and dispersed in water to prepare an impregnation solution. The amount of water added was 2.0 times the mass of the silicon dioxide support. After thoroughly mixing and impregnating the modified catalyst support with the impregnation solution, the catalyst was first dried at room temperature for 24 hours, then dried at 120°C for 24 hours, and finally calcined at 450°C for 20 hours to obtain the oxide-type catalyst precursor.

[0114] The catalyst was loaded into a stainless steel reactor and reduced for 5 hours at 350°C and atmospheric pressure under H2, with a reduction space velocity of 12000 h⁻¹. -1 The Fischer-Tropsch synthesis particulate catalyst obtained after reduction is the catalyst described above.

[0115] In the reactor described above, a mixture of H2 / CO with a volume ratio of 2:1 was introduced as the reactant, the temperature was raised to 230°C, the reaction pressure was 60 bar, and the reaction space velocity was 3000 h⁻¹. -1 The reaction proceeded via direct conversion of syngas. After the reaction, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 1.

[0116] Example 5

[0117] Silica, starch, and guar gum powder were mixed in a mass ratio of 90:8:2 and ball-milled to obtain a composite carrier powder. Then, polyvinyl alcohol (equivalent to 20% of the mass of silica) and a manganese nitrate aqueous solution (50% Mn concentration) containing 5% Mn of silica were weighed and prepared into a solution with a total mass 1.5 times that of silica. This solution was then thoroughly kneaded with the composite carrier powder to form a plastic body. The plastic body was processed into a cylindrical wet-formed body with a diameter of 1.5 mm using an extrusion molding process. It was first dried at room temperature for 24 hours, then dried at 120°C for 24 hours, and finally calcined at 450°C for 12 hours to obtain the modified catalyst carrier.

[0118] Ruthenium chloride, sodium nitrate, and barium nitrate were weighed out at 2%, 0.5%, and 0.5% of the mass of silicon dioxide, respectively. These three components were dispersed in water to prepare an impregnation solution, wherein the amount of water added was 2.2 times the mass of the silicon dioxide support. The impregnation solution was thoroughly mixed with the modified catalyst support and impregnated. The mixture was first dried at room temperature for 24 hours, then dried at 120°C for 18 hours, and finally calcined at 450°C for 20 hours to obtain the oxide-type catalyst precursor.

[0119] The catalyst was loaded into a stainless steel reactor and reduced for 5 hours at 50% H2 / N2, 400°C, and atmospheric pressure, with a reduction space velocity of 12000 h⁻¹. -1 The Fischer-Tropsch synthesis particulate catalyst obtained after reduction is the catalyst described above.

[0120] In the reactor described above, a mixture of H2 / CO with a volume ratio of 2:1 was introduced as the reactant, the temperature was raised to 230°C, the reaction pressure was 60 bar, and the reaction space velocity was 3000 h⁻¹. -1 The reaction proceeded via direct conversion of syngas. After the reaction, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 1.

[0121] Example 6

[0122] Silica, starch, and guar gum powder were mixed in a mass ratio of 87:10:3 and ball-milled to obtain a composite carrier powder. Then, carboxymethyl cellulose (equivalent to 10% of the mass of silica) and magnesium nitrate (equivalent to 1% of the mass of silica) were weighed and prepared into a solution with a total mass 2.3 times that of silica. This solution was then thoroughly kneaded with the composite carrier powder to form a plastic body. The plastic body was processed into a cylindrical wet-formed body with a diameter of 1.5 mm using an extrusion molding process. It was first dried at room temperature for 12 hours, then dried at 100°C for 12 hours, and finally calcined at 600°C for 5 hours to obtain the modified catalyst carrier.

[0123] Ruthenium nitrite, sodium nitrate, and magnesium nitrate were weighed out at 2%, 0.5%, and 0.1% of the mass of silicon dioxide, respectively. These three components were dispersed in water to prepare an impregnation solution, wherein the amount of water added was 1.5 times the mass of the silicon dioxide support. The impregnation solution was thoroughly mixed with the modified catalyst support and impregnated. The mixture was first dried at room temperature for 12 hours, then dried at 100°C for 12 hours, and finally calcined at 500°C for 5 hours to obtain the oxide-type catalyst precursor.

[0124] The catalyst was loaded into a stainless steel reactor and reduced for 5 hours under H2, 350°C, and atmospheric pressure, with a reduction space velocity of 12000 h⁻¹. -1 The Fischer-Tropsch synthesis particulate catalyst obtained after reduction is the catalyst described above.

[0125] In the reactor described above, a mixture of H2 / CO with a volume ratio of 2:1 was introduced as the reactant, the temperature was raised to 230°C, the reaction pressure was 60 bar, and the reaction space velocity was 3000 h⁻¹. -1 The reaction proceeded via direct conversion of syngas. After the reaction, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 1.

[0126] Example 7

[0127] Silica, starch, and guar gum powder were mixed in a mass ratio of 87:10:3 and ball-milled to obtain a composite carrier powder. Then, neutral silica sol (30% of the mass of silica) and sodium nitrate (0.2% of the mass of silica) were weighed and prepared into a solution with a total mass 1.8 times that of silica. This solution was then thoroughly kneaded with the composite carrier powder to form a plastic body. The plastic body was processed into a cylindrical wet-formed body with a diameter of 2 mm using an extrusion molding process. It was first dried at room temperature for 24 hours, then dried at 120°C for 24 hours, and finally calcined at 650°C for 4 hours to obtain the modified catalyst carrier.

[0128] Ruthenium nitrite, potassium nitrate, and silver nitrate were weighed out at 2%, 0.5%, and 0.1% of the mass of silicon dioxide, respectively, and dispersed in water to prepare an impregnation solution. The amount of water added was 1.9 times the mass of the silicon dioxide support. After thoroughly mixing and impregnating the modified catalyst support with the impregnation solution, the catalyst was first dried at room temperature for 24 hours, then dried at 120°C for 24 hours, and finally calcined at 450°C for 20 hours to obtain the oxide-type catalyst precursor.

[0129] The catalyst was loaded into a stainless steel reactor and reduced for 5 hours at 10% H2 / Ar, 500°C, and atmospheric pressure, with a reduction space velocity of 12000 h⁻¹. -1The Fischer-Tropsch synthesis particulate catalyst obtained after reduction is the catalyst described above.

[0130] In the reactor described above, a mixture of H2 / CO with a volume ratio of 2:1 was introduced as the reactant, the temperature was raised to 230°C, the reaction pressure was 60 bar, and the reaction space velocity was 3000 h⁻¹. -1 The reaction proceeded via direct conversion of syngas. After the reaction, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 1.

[0131] Example 8

[0132] Silica, starch, and guar gum powder were mixed in a mass ratio of 87:10:3 and ball-milled to obtain a composite carrier powder. Then, neutral silica sol (equivalent to 15% of the silica mass) and samarium nitrate (with a Sm content of 0.05% of the silica mass) were weighed and prepared into a solution with a total mass 1.8 times that of silica. This solution was then thoroughly kneaded with the composite carrier powder to form a plastic body. The plastic body was processed into a 2mm clover-structure wet-formed body using an extrusion molding process. It was first dried at room temperature for 24 hours, then dried at 120℃ for 24 hours, and finally calcined at 550℃ for 5 hours to obtain the modified catalyst carrier.

[0133] Ruthenium nitrite, sodium nitrate, copper nitrate, and silver nitrate were weighed out at 2%, 0.5%, 0.1%, and 0.1% of the mass of silicon dioxide, respectively, and dispersed in water to prepare an impregnation solution. The amount of water added was 1.8 times the mass of the silicon dioxide support. After thoroughly mixing and impregnating the modified catalyst support with the impregnation solution, the catalyst was first dried at room temperature for 24 hours, then dried at 120°C for 24 hours, and finally calcined at 550°C for 15 hours to obtain the oxide-type catalyst precursor.

[0134] The catalyst was loaded into a stainless steel reactor and reduced for 5 hours at 400°C and 10 bar under H2 conditions, with a reduction space velocity of 12000 h⁻¹. -1 The Fischer-Tropsch synthesis particulate catalyst obtained after reduction is the catalyst described above.

[0135] In the reactor described above, a mixture of H2 / CO with a volume ratio of 2:1 was introduced as the reactant, the temperature was raised to 230°C, the reaction pressure was 60 bar, and the reaction space velocity was 3000 h⁻¹. -1 The reaction proceeded via direct conversion of syngas. After the reaction, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 1.

[0136] Example 9

[0137] Silica, starch, and guar gum powder were mixed at a mass ratio of 83:15:2 and ball-milled to obtain a composite carrier powder. Then, neutral silica sol (equivalent to 10% of the silica mass) and samarium nitrate (with a Sm content of 0.2% of the silica mass) were weighed and prepared into a solution with a total mass 2.0 times that of silica. This solution was then thoroughly kneaded with the composite carrier powder to form a plastic body. The plastic body was processed into a 2mm clover-structure wet-formed body using an extrusion molding process. It was first dried at room temperature for 24 hours, then dried at 120℃ for 24 hours, and finally calcined at 600℃ for 5 hours to obtain the modified catalyst carrier.

[0138] Ruthenium nitrite, sodium nitrate, and silver nitrate were weighed out at 2%, 0.5%, and 0.1% of the mass of silicon dioxide, respectively, and dispersed in water to prepare an impregnation solution. The amount of water added was 1.9 times the mass of the silicon dioxide support. After thoroughly mixing and impregnating the modified catalyst support with the impregnation solution, the catalyst was first dried at room temperature for 24 hours, then dried at 120°C for 24 hours, and finally calcined at 450°C for 20 hours to obtain the oxide-type catalyst precursor.

[0139] The catalyst was loaded into a stainless steel reactor and reduced for 5 hours under H2, 450°C, and atmospheric pressure, with a reduction space velocity of 12000 h⁻¹. -1 The Fischer-Tropsch synthesis particulate catalyst obtained after reduction is the catalyst described above.

[0140] In the reactor described above, a mixture of H2 / CO with a volume ratio of 2:1 was introduced as the reactant, the temperature was raised to 230°C, the reaction pressure was 60 bar, and the reaction space velocity was 3000 h⁻¹. -1 The reaction proceeded via direct conversion of syngas. After the reaction, the types and contents of various components in the product were analyzed using gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results were calculated accordingly, as shown in Table 1.

[0141] Comparative Example 1

[0142] Silica, starch, and guar gum powder were mixed in a ratio of 87:10:3 and ball-milled. Then, a neutral aluminum sol, equivalent to 30% of the silica mass, was weighed and prepared into a solution with a total mass 2.3 times that of silica. This solution was then thoroughly kneaded with the composite carrier powder to form a plastic body. The plastic body was processed into clover-shaped wet-formed bodies with a diameter of 1.5 mm using an extrusion molding process. These wet-formed bodies were dried at room temperature for 12 hours, then dried at 100°C for 12 hours and calcined at 600°C for 5 hours to finally obtain a strip-shaped silica catalyst carrier.

[0143] Ruthenium nitrite and sodium nitrate were weighed out at 2% and 0.5% of the mass of silicon dioxide, respectively, and dispersed in water to prepare an impregnation solution. The amount of water added was 1.5 times the mass of the silicon dioxide support. After stirring for 2 hours, the solution was impregnated onto the support in equal volumes, dried at room temperature for 12 hours, dried at 100°C for 12 hours, and calcined at 500°C for 5 hours to finally obtain the Fischer-Tropsch synthesis catalyst.

[0144] The catalyst was reduced in H2 at 350°C and atmospheric pressure for 5 h, with a reduction space velocity of 12000 h⁻¹. -1 After the reduction is complete, the temperature is lowered to 180℃.

[0145] A mixture of H2 / CO with a volume ratio of 2:1 was introduced as the reactant, the temperature was raised to 230 °C, the reaction pressure was 60 bar, and the reaction space velocity was 3000 h⁻¹. -1 The reaction was carried out by direct conversion of syngas to olefins. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results of the reaction were calculated accordingly, as shown in Table 1.

[0146] Comparative Example 2

[0147] Silica, starch, and guar gum powder were mixed in a ratio of 87:10:3 and ball-milled. Then, carboxymethyl cellulose, equivalent to 10% of the mass of silica, was weighed and prepared into a solution with a total mass 2.3 times that of silica. This solution was then thoroughly kneaded with the aforementioned composite carrier powder to form a plastic body. The plastic body was processed into cylindrical wet-formed bodies with a diameter of 1.5 mm using an extrusion molding process. These wet-formed bodies were dried at room temperature for 12 hours, then dried at 100°C for 12 hours and calcined at 600°C for 5 hours to finally obtain a strip-shaped silica catalyst carrier.

[0148] Ruthenium nitrite, sodium nitrate, and magnesium nitrate were weighed out at 2%, 0.5%, and 0.1% of the mass of silicon dioxide, respectively, and dispersed in water to prepare an impregnation solution. The amount of water added was 1.5 times the mass of the silicon dioxide support. After stirring for 2 hours, the solution was impregnated onto the support in equal volumes, dried at room temperature for 12 hours, dried at 100°C for 12 hours, and calcined at 500°C for 5 hours to finally obtain the Fischer-Tropsch synthesis catalyst.

[0149] The catalyst was reduced in H2 at 350°C and atmospheric pressure for 5 h, with a reduction space velocity of 12000 h⁻¹. -1 After the reduction is complete, the temperature is lowered to 180 ℃.

[0150] A mixture of H2 / CO with a volume ratio of 2:1 was introduced as the reactant, the temperature was raised to 230℃, the reaction pressure was 60 bar, and the reaction space velocity was 3000 h⁻¹. -1The reaction was carried out by direct conversion of syngas to olefins. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results of the reaction were calculated accordingly, as shown in Table 1.

[0151] Comparative Example 3

[0152] Silica, starch, and guar gum powder were mixed in a ratio of 85:12:3 and ball-milled. Then, neutral silica sol (30% by weight of silica) and samarium nitrate (0.1% by weight of silica) were weighed and prepared into a solution with a total mass 1.8 times that of silica. This solution was then thoroughly kneaded with the composite carrier powder to form a plastic body. The plastic body was processed into clover-shaped wet-formed bodies with a diameter of 2 mm using an extrusion molding process. After drying at room temperature for 5 hours, it was further dried at 60°C for 24 hours and calcined at 600°C for 4 hours to finally obtain a strip-shaped silica catalyst carrier.

[0153] Ruthenium nitrite and sodium nitrate were weighed out at 2% and 0.2% of the mass of silicon dioxide, respectively, and dispersed in water to prepare an impregnation solution. The amount of water added was 1.5 times the mass of the silicon dioxide support. After stirring for 2 hours, the solution was impregnated onto the support in equal volumes, dried at room temperature for 12 hours, dried at 60°C for 24 hours, and calcined at 600°C for 2 hours to finally obtain the Fischer-Tropsch synthesis catalyst.

[0154] The catalyst was reduced in H2 at 450°C and atmospheric pressure for 5 h, with a reduction space velocity of 12000 h⁻¹. -1 After the reduction is complete, the temperature is lowered to 180 ℃.

[0155] A mixture of H2 / CO with a volume ratio of 2:1 was introduced as the reactant, the temperature was raised to 230℃, the reaction pressure was 60 bar, and the reaction space velocity was 3000 h⁻¹. -1 The reaction was carried out by direct conversion of syngas to olefins. After the reaction, the types and contents of various components in the product were analyzed by gas chromatography (Agilent 8860), and the conversion rate and selective catalysis results of the reaction were calculated accordingly, as shown in Table 1.

[0156] The lateral compressive strength and specific surface area of ​​the catalyst supports prepared in Examples 1-9 and Comparative Examples 1-3 were tested, and the test results are shown in Table 1. The test methods are as follows.

[0157] Lateral pressure strength: The formed cylindrical granular catalyst is placed on the test platform of the particle strength tester (KQ-3) and 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. Subsequently, the pressure value drops sharply, and the test process ends.

[0158] Record the maximum pressure value F (N), measure the column height L (cm) of the cylindrical particle, and obtain the lateral pressure intensity f according to the calculation formula: f = F / L.

[0159] The side pressure strength of at least 30 particulate catalysts was obtained and the average value was taken.

[0160] Specific surface area testing method: In a vacuum environment, impurities (such as water vapor and organic matter) on the sample surface are removed by heating (100-300℃) to ensure surface cleanliness. Nitrogen is selected as the adsorbate, and the amount of gas adsorbed (V, converted to standard state volume) corresponding to different relative pressures (P / P0, range of 0.05-0.3) is measured at liquid nitrogen temperature (77K). Based on the relationship between adsorption amount and relative pressure, the saturated adsorption amount of the monolayer is calculated using the BET formula, and then the specific surface area is determined.

[0161] BET equation:

[0162] V: Adsorption capacity under equilibrium pressure P; V m : Monolayer saturated adsorption capacity; P0: Saturated vapor pressure; C: Constant related to the heat of adsorption.

[0163] Specific surface area calculation:

[0164] N A σ is Avogadro's constant, σ is the cross-sectional area of ​​the N2 molecule (0.162 nm²), and m is the sample mass.

[0165] By right Plot a straight line and calculate V from the slope and intercept. m Substituting this into the above formula yields the specific surface area.

[0166] Table 1: Side pressure strength and catalytic performance data of catalysts in Examples 1-9 and Comparative Examples 1-3

[0167]

[0168] a C 2+ OH: Oxygen-containing compounds with 2 or more carbon atoms; this part usually represents higher alcohols.

[0169] b ROH: Total oxygenated compounds.

[0170] In Table 1, the CO conversion rate is calculated based on the number of carbon atoms, using the following formula:

[0171] CO conversion rate = (CO 进料 -CO 出料 ) / CO进料 ×100%

[0172] CO 进料 and CO 出料 These represent the number of CO moles entering and exiting the reaction system, respectively.

[0173] The formula for calculating carbon dioxide selectivity is:

[0174] CO2 selectivity = (CO 2出料 ) / (CO 进料 -CO 出料 ) × 100%

[0175] CO 出料 This represents the number of moles of CO2 flowing out of the reaction tube.

[0176] The formula for calculating the selectivity of methane and total oxygenated compounds is as follows:

[0177]

[0178] Among them, S i The carbon number selectivity of product i; N i The molar content of product i; n i This represents the number of carbons in product i.

[0179] Higher alcohol selectivity (alcohol-aldehyde selectivity): C 2+ OH / ROH: The percentage by mass of oxygen-containing compounds with 2 or more carbon atoms in the total oxygen-containing products.

[0180] Table 1 shows the data. Comparative Example 1 is the comparative example of Example 1, and Comparative Example 2 is the comparative example of Example 6. As can be seen from Table 1, the catalyst support and catalyst prepared with the added modifier have better mechanical strength. In the syngas to higher alcohols reaction, the CO single-pass conversion rate is increased by at least 20%, the total oxygen-containing compound selectivity is increased by nearly 30%, and the methane selectivity (<3%) and carbon dioxide selectivity (<3%) remain at a low level. Different support metals have different degrees of improvement on reaction performance and mechanical strength. Specifically, samarium metal has a more significant improvement in selectivity, while magnesium metal has a more significant improvement in mechanical strength. Comparative Example 3 shows that adding nickel metal to the support improves the mechanical strength of both the support and the catalyst, but the total oxygen-containing compound selectivity of the reaction decreases significantly, dropping to 5.5%.

[0181] As can be clearly seen from the data in Table 1, the particulate catalyst support and corresponding particulate catalyst prepared in this invention possess excellent overall mechanical strength (lateral compressive strength >79 N / cm). In the syngas-to-higher alcohols reaction, it exhibits high CO single-pass conversion, low methane (<3%) and carbon dioxide (<3%) selectivity, and significantly improved total alcohol and higher alcohol (C2+OH) selectivity (>50%). This particulate catalyst has stable performance and can be directly used as an industrial-grade catalyst, suitable for industrial plants with scales from kilograms to tons / year and above.

[0182] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any form or substance. It should be noted that those skilled in the art can make various improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention. Any modifications, alterations, and equivalent changes made by those skilled in the art based on the above-disclosed technical content without departing from the spirit and scope of the present invention are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and evolutions made to the above embodiments based on the essential technology of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A support for an industrial catalyst, characterized in that, The carrier raw material components include silicon dioxide, a colloidal solvent, and a metal salt; the mass of the metal element is 0.1% to 5% of the mass of silicon dioxide, and the metal is one or more selected from Na, K, Mg, Ca, Mn, La, Sm, Ce, or Zr.

2. The support for the industrial catalyst according to claim 1, characterized in that, The adhesive solvent is selected from one or more of silica sol, aluminum sol, polyvinyl alcohol, carboxymethyl cellulose, starch, guar gum powder, or polyethylene glycol; and / or, the metal salt is selected from one or more of carbonate, nitrate, chloride, fluoride, sulfate, or acetate. And / or, the particle size of the silica is 10~20nm; And / or, the diameter of the cross-section of the carrier is 1~3mm, and the length of the carrier is 5~10mm.

3. The support for the industrial catalyst according to claim 2, characterized in that, Includes one or more of the following features: The number average molecular weight of polyvinyl alcohol is 1500~2400, and the degree of alcoholysis of polyvinyl alcohol is 87%~89%. The number average molecular weight of polyethylene glycol is 4000~6000; The silica sol has a pH of 7.0~8.0, a solid content of 25%~30%, and a particle size of 10~20nm; The aluminum sol has a pH of 7.0~8.0, a solid content of 15%~20%, and a particle size of 10~30nm; The number-average molecular weight of carboxymethyl cellulose is 50,000-200,000; The colloidal solvent includes starch, guar gum powder, and one or more selected from silica sol, aluminum sol, polyvinyl alcohol, carboxymethyl cellulose, or polyethylene glycol.

4. The support for the industrial catalyst according to claim 3, characterized in that, Includes one or more of the following features: the mass ratio of silicon dioxide, starch and guar gum powder is (70-95):(3-20):(2-10); The amount of raw materials selected from one or more of silica sol, aluminum sol, polyvinyl alcohol, carboxymethyl cellulose, or polyethylene glycol is 5% to 60 wt% of the amount of silica.

5. A method for preparing a support for an industrial catalyst as described in any one of claims 1 to 4, characterized in that, The preparation method includes: mixing silica, starch and guar gum powder, and ball milling to obtain composite carrier powder; kneading an aqueous solution of one or more of silica sol, alumina sol, polyvinyl alcohol, carboxymethyl cellulose, or polyethylene glycol and a metal salt with the composite carrier powder to form a plastic body; processing the plastic body into a wet-formed body through an extrusion molding process, and then drying and calcining to obtain a modified silica catalyst carrier.

6. The preparation method according to claim 5, characterized in that, The drying process is performed in two stages. The first drying temperature is 20-30℃, and the second drying temperature is 60-120℃. And / or, the calcination temperature is 400~650℃; And / or, the total mass of the aqueous solution selected from one or more of silica sol, aluminum sol, polyvinyl alcohol, carboxymethyl cellulose, or polyethylene glycol and modified metal salt is 1.5 to 2.5 times the mass of silica.

7. A catalyst for Fischer-Tropsch synthesis using the industrial catalyst support according to any one of claims 1 to 4, characterized in that, The catalyst comprises an active metal Ru and a metal promoter element, wherein the content of the active metal Ru is 0.1-10 wt% of the industrial catalyst support, and the content of the metal promoter element is 0.1-5 wt% of the industrial catalyst support; the metal promoter element is one or more selected from Na, K, Rb, Cs, Ca, Mg, Ba, Zr, Cu, Ag or Mn.

8. A method for preparing the catalyst for Fischer-Tropsch synthesis as described in claim 7, characterized in that, The preparation method includes: impregnating an impregnation solution with any industrial catalyst support as described in claims 1 to 4, followed by drying, calcination, and reduction to obtain a Fischer-Tropsch synthesis catalyst, wherein the impregnation solution includes at least the active metal Ru element.

9. The preparation method according to claim 8, characterized in that, The impregnation solution is a mixture of a soluble salt solution corresponding to the active metal Ru and a soluble salt solution corresponding to a metal auxiliary element; preferably, the soluble salt corresponding to the active metal Ru is one or two of ruthenium nitrite or ruthenium chloride; preferably, the soluble salt corresponding to the metal auxiliary element is selected from one or more of carbonates, nitrates, chlorides, fluorides, sulfates or acetates; And / or, the drying temperature is 60~180℃; And / or, the calcination temperature is 300-600℃; And / or, the reduction is carried out in H2 or an H2 / inert gas mixture at 0.1~1.0 MPa, 300~500 °C, and a space velocity of 1000~20000 h⁻¹. -1 Under the given conditions, reduction is performed.

10. An application of the catalyst for Fischer-Tropsch synthesis as described in any one of claims 1 to 4, and claim 7, in the direct conversion of syngas into higher alcohols via the Fischer-Tropsch reaction.

11. Use of metal salts to improve the side pressure strength and / or specific surface area of ​​an industrial catalyst support, wherein the industrial catalyst support is a silica support.

Images