Preparation method of multi-component metal framework catalyst
Multi-component metal framework catalysts were prepared by induction melting and acid-base treatment, which solved the problem of easy pulverization of traditional catalysts in high-pressure reactions and achieved a combination of high activity and wear resistance, making them suitable for industrial production.
Patent Information
- Application Number
- CN202511036044.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-25
- Publication Date
- 2025-11-28
Smart Images
Figure CN121016776A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to a preparation method of a multi-component metal skeleton catalyst, and belongs to the field of catalytic materials. BACKGROUND
[0002] With the rapid development of energy and chemical industry, the demand for catalytic conversion to prepare high-value-added chemicals is increasing. Liquid-phase hydrogen-related reactions are the core process of such conversion, and the key lies in an efficient and stable catalyst system.
[0003] Traditional catalysts (such as supported metal catalysts) face significant challenges in practical applications. Mainly, in high-pressure, high-flow-rate gas-liquid-solid three-phase continuous reactions, catalyst particles are easily pulverized and lost due to mechanical wear, leading to a decrease in activity and reactor plugging, significantly shortening the service life. For example, the hydrogenolysis of sugars to produce ethylene glycol needs to be carried out at high temperature and high pressure (> 150℃, > 5MPa). Conventional catalysts are difficult to maintain long-term stability due to their fragile structure (Chemical Research and Application, 2023, 35(03): 489-499.).
[0004] To solve the above problems, researchers have tried to improve the mechanical properties by using metal skeleton catalysts (such as Raney nickel). However, the traditional spray casting and spinning technology has limited cooling rate during the preparation process, which easily forms coarse dendritic structures, and after grinding, irregular sharp edges are formed, which aggravates the friction loss of particles in the reaction. To further improve the wear resistance, common strategies include adding high-hardness metals (such as Ti, W) to improve the strength of the substrate, coating the surface of the catalyst with a silicon carbide coating, passivating the surface of the catalyst with phosphates, and improving the structural density by spark plasma sintering, but it is still difficult to maintain the composition of the active components and the exposure degree of the catalyst active sites.
[0005] Therefore, there is an urgent need to develop a metal skeleton catalyst preparation technology that has high activity, high wear resistance, and controllable morphology, and to develop an efficient and low-cost preparation process to meet the technical requirements of large-scale catalytic conversion. SUMMARY
[0006] The purpose of the present application is to provide a preparation method of a multi-component metal skeleton catalyst, which has a spherical-like morphology and wear resistance, and the preparation process is simple and easy to operate, and easy to industrialize.
[0007] According to one aspect of the present application, a preparation method of a multi-component metal skeleton catalyst is provided. The prepared multi-component metal skeleton catalyst has excellent mechanical strength and wear resistance. Its unique spherical-like morphology and metal skeleton structure can effectively reduce particle wear during the reaction process, significantly prolong the service life of the catalyst, and is suitable for industrialized continuous production.
[0008] A method for preparing a multi-component metal framework catalyst, comprising the following steps:
[0009] S1: proportionally mixing metal elemental particles including elemental aluminum, and forming a uniform metal melt by induction melting;
[0010] S2: discharging the melt through a limiting hole, atomizing and cooling by using a high-pressure water and silicone oil mixed coolant, to obtain micron-sized spherical alloy or intermetallic compound particles;
[0011] S3: treating the alloy or intermetallic compound particles with acid and alkali to remove the surface oxide layer and activate the pore structure, to obtain the metal framework catalyst.
[0012] Optionally, in step S1, the metal element is at least one of titanium, chromium, iron, magnesium, nickel, copper, tin, zirconium, cobalt, molybdenum, niobium, tungsten, lead, manganese, silver, gold, platinum.
[0013] Preferably, in step S1, the metal element is at least three, four or five of titanium, chromium, iron, magnesium, nickel, copper, tin, zirconium, cobalt, molybdenum, niobium, tungsten, lead, manganese, silver, gold, platinum.
[0014] Optionally, the metal element is at least one of titanium, chromium, iron, magnesium, nickel, copper, tin, zirconium, cobalt, molybdenum, niobium, tungsten, lead, manganese.
[0015] Preferably, the metal element is at least one of titanium, chromium, iron, nickel, copper, tin, zirconium, cobalt, tungsten, manganese, silver, gold, platinum.
[0016] Optionally, in step S1, the mass fraction of the elemental aluminum is 15% to 85%.
[0017] Optionally, the mass fraction of the elemental aluminum is independently selected from any value of 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or a range value between any two of the above values.
[0018] Optionally, in step S1, the particle size of the metal elemental particles is 1.5 to 300 mm.
[0019] Optionally, in step S1, the induction melting time is 30 to 450 min, and the induction melting temperature is 800 to 1800℃.
[0020] Optionally, inert gas is introduced during the induction melting process to prevent oxidation, and the gas flow rate is 0.01 to 5 L / min.
[0021] Optionally, the inert gas is at least one of argon, nitrogen, helium.
[0022] Preferably, argon gas is introduced during the induction melting process to prevent oxidation, with a gas flow rate of 0.05-4.5 L / min.
[0023] Optionally, in step S2, the limiting hole has a diameter of 0.5-5 mm.
[0024] Preferably, the limiting hole has a diameter of 0.5-2 mm.
[0025] Optionally, in step S2, the mixed coolant has a pressure of 2.5-60 MPa, a temperature of 5-30°C, and an atomization angle of 30-90°.
[0026] Optionally, the pressure of the mixed coolant is independently selected from any value or range between any two values of 3.5 MPa, 4.5 MPa, 7.5 MPa, 15.5 MPa, 22.5 MPa, 42 MPa, 50 MPa, and 55 MPa.
[0027] Optionally, the temperature of the mixed coolant is independently selected from any value or range between any two values of 5°C, 10°C, 15°C, 20°C, 25°C, and 30°C.
[0028] Optionally, the atomization angle of the mixed coolant is independently selected from any value or range between any two values of 30°, 40°, 50°, 60°, 70°, 80°, and 90°.
[0029] Optionally, the silicone oil is at least one of epoxy silicone oil, polysiloxane silicone oil, methyl phenyl silicone oil, dimethicone, and silicone silicone oil.
[0030] Preferably, the silicone oil is at least one of epoxy silicone oil, polysiloxane silicone oil, and methyl phenyl silicone oil.
[0031] Optionally, the mass ratio of water to silicone oil is 0.05-50:1.
[0032] Preferably, the mass ratio of water to silicone oil is 0.2-5:1.
[0033] Optionally, the mass ratio of water to silicone oil is independently selected from any value or range between any two values of 0.05:1, 0.1:1, 0.15:1, 0.2:1, 1:1, 2:1, 3:1, 4:1, 5:1, 8:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, and 50:1.
[0034] Optionally, the rate of atomization cooling is 100-50,000°C / s.
[0035] Optionally, the rate of the mixed coolant is independently selected from any value or a range between any two points of 100℃ / s, 200℃ / s, 300℃ / s, 400℃ / s, 500℃ / s, 600℃ / s, 700℃ / s, 800℃ / s, 900℃ / s, 1000℃ / s, 1500℃ / s, 2000℃ / s, 4000℃ / s, 5000℃ / s, 8000℃ / s, 10000℃ / s, 15000℃ / s, 20000℃ / s, 25000℃ / s, 30000℃ / s, 35000℃ / s, 40000℃ / s, 45000℃ / s, 50000℃ / s.
[0036] Optionally, in step S2, the particle size of the spherical alloy or intermetallic compound particles is 10-500μm, and the sphericity is ≥0.85.
[0037] Preferably, the particle size of the spherical alloy or intermetallic compound particles is 50-450μm, and the sphericity is ≥0.90.
[0038] Optionally, in step S3, the acid and alkali treatment steps are as follows:
[0039] (1) acid treatment using 0.001-2mol / L hydrochloric acid solution, solid-liquid mass ratio 1:1-2000, treatment time 0.2-24h, treatment temperature 5-40℃, and deionized water washing until the filtrate pH=6-8;
[0040] (2) alkali treatment using 0.01-6mol / L sodium hydroxide solution, solid-liquid mass ratio 1:1-2000, treatment time 0.6-72h, treatment temperature 45-100℃, deionized water washing until the filtrate pH=6-8, and drying to obtain the metal framework catalyst.
[0041] Preferably, the concentration of the hydrochloric acid solution is 0.01-2mol / L.
[0042] Preferably, the concentration of the sodium hydroxide solution is 1-4mol / L.
[0043] Preferably, the solid-liquid mass ratio of the alkali treatment is 1:1-1500.
[0044] Preferably, the temperature of the alkali treatment is 75-100℃.
[0045] The multi-component metal framework catalyst prepared by the above preparation method has a specific surface area of 20-150m 2 / g, a porosity of 30-70%, a particle size distribution of D50=10-500μm, and a sphericity of ≥0.85.
[0046] Preferably, the particle size distribution of the multi-component metal framework catalyst is D50 = 50-450 μm, and the sphericity is ≥ 0.90.
[0047] The beneficial effects that can be produced by the present application include:
[0048] 1) The preparation method of the metal framework catalyst provided by the present application is simple and convenient, and is suitable for large-scale industrial amplification. The catalyst has a near-spherical morphology and good wear resistance in gas-liquid-solid three-phase reactions or gas-solid two-phase reactions.
[0049] 2) The metal framework catalyst provided by the present application has a catalyst composition that can be adjusted within a wide range, and can be suitable for various use scenarios.
[0050] 3) The preparation method of the metal framework catalyst provided by the present application is suitable for large-scale industrial amplification, can be realized by simple modification on the basis of existing equipment, and has good operability. BRIEF DESCRIPTION OF DRAWINGS
[0051] Figure 1 Figure 1 is a scanning electron microscope photograph of the metal framework catalyst prepared in Example 1 of the present application.
[0052] Figure 2 Figure 2 is a scanning electron microscope photograph of the metal framework catalyst prepared in Comparative Example 1 of the present application. DETAILED DESCRIPTION
[0053] The present application will be described in detail below in conjunction with examples, but the present application is not limited to these examples.
[0054] Unless otherwise specified, the raw materials in the examples of the present application are purchased through commercial channels.
[0055] Unless otherwise specified, the test methods all use conventional methods, and the instrument settings all use the recommended settings of the manufacturers.
[0056] Example 1
[0057] A mixture of 400 g of aluminum, 250 g of copper, 75 g of chromium, 95 g of nickel, and 180 g of iron particles was mixed in a quartz crucible, the entire smelting system was purged with argon, and the temperature was raised to 1100°C by induction and maintained for 45 min. The molten metal was poured through a 1.0 mm limiting hole, and then dispersed by a mixed coolant under the conditions of a pressure of 35 MPa, a temperature of 25°C, and an atomizing angle of 70°. The rate of atomization and cooling was 360°C / s, and the composition of the mixed coolant was 550 g of water and 450 g of epoxy silicone oil. The solid product was obtained by filtration and separation. 500 g of the solid product was weighed, 50000 g of a 0.05 mol / L hydrochloric acid solution was added, and stirring treatment was carried out at 25°C for 12 h. Deionized water was used for washing until the pH of the filtrate was 6.5. Then, 100000 g of a 3 mol / L sodium hydroxide solution was added, and stirring treatment was carried out at 95°C for 24 h. Deionized water was used for washing until the pH of the filtrate was 7.5. After drying, a metal framework catalyst was obtained.
[0058] The scanning electron microscope (SEM) photograph of the prepared multi-component catalyst is shown in Figure 1 The metal catalyst is in the shape of a near-sphere, and the particle size is less than 100 μm.
[0059] Examples 2-10
[0060] The preparation processes of the catalysts of Examples 2-10 were the same as those of Example 1, except that the amounts of the metals used for synthesizing the catalysts, the compositions of the mixed coolants, and the amounts of the mixed coolants were different. The specific conditions are shown in Table 1.
[0061] Table 1 Amounts of raw materials for the catalysts of Examples 2-10, compositions of mixed coolants, and amounts of mixed coolants
[0062]
[0063]
[0064] Comparative Example 1
[0065] The preparation processes of the catalysts of Examples 2-10 were the same as those of Example 1, except that the amounts of the metals used for synthesizing the catalysts, the compositions of the mixed coolants, and the amounts of the mixed coolants were different. The specific conditions are shown in Table 1.
[0066] The scanning electron microscope (SEM) photograph of the prepared multi-component catalyst is shown in Figure 2 The metal catalyst is in the shape of a near-sphere, and the particle size is less than 100 μm.
[0067] Unless otherwise specified, all the numbers appearing in the present application specification and claims, such as temperature and time, mass, speed, and the like, should not be understood as absolute precise values, and there is inevitably a certain experimental error in the measured values due to the standard deviation of the measurement technology.
[0068] The above merely describes several embodiments of the present application, and does not limit the present application in any form. Although the present application is disclosed with the preferred embodiments, it is not intended to limit the present application. Any skilled person in the art can make some changes or modifications to the disclosed technical contents without departing from the scope of the technical solutions of the present application, and the equivalent embodiments are equivalent to the equivalent embodiments, which are within the scope of the technical solutions.
Claims
1. A method for preparing a multi-component metal framework catalyst, characterized in that, Includes the following steps: S1: Mix metal elemental particles, including aluminum, in a certain proportion and then form a uniform molten metal through induction melting; S2: The molten liquid is discharged through the limiting hole and cooled by atomization using a mixture of high-pressure water and silicone oil coolant to obtain micron-sized spherical alloy or intermetallic compound particles. S3: The alloy or intermetallic compound particles are subjected to acid and alkali treatment to remove the surface oxide layer and activate the pore structure, thereby obtaining the metal framework catalyst.
2. The preparation method according to claim 1, characterized in that, In step S1, the metallic element is at least one of titanium, chromium, iron, magnesium, nickel, copper, tin, zirconium, cobalt, molybdenum, niobium, tungsten, lead, manganese, silver, gold, and platinum.
3. The preparation method according to claim 1, characterized in that, In step S1, the mass fraction of the elemental aluminum is 15% to 85%.
4. The preparation method according to claim 1, characterized in that, In step S1, the particle size of the elemental metal particles is 1.5 to 300 mm.
5. The preparation method according to claim 1, characterized in that, In step S1, the induction melting time is 30 to 450 minutes, and the induction melting temperature is 800 to 1800°C. During the induction melting process, an inert gas is introduced to protect against oxidation, and the gas flow rate is 0.01 to 5 L / min.
6. The preparation method according to claim 1, characterized in that, In step S2, the diameter of the limiting hole is 0.5 to 5 mm.
7. The preparation method according to claim 1, characterized in that, In step S2, the pressure of the mixed coolant is 2.5–60 MPa, the temperature is 5–30°C, and the atomization angle is 30–90°. The silicone oil is at least one of epoxy silicone oil, polysiloxane silicone oil, methyl phenyl silicone oil, polydimethylsiloxane, and polysiloxane silicone oil; The mass ratio of water to silicone oil is 0.05 to 50:1; The atomization cooling rate is 100–50,000 °C / s.
8. The preparation method according to claim 1, characterized in that, In step S2, the particle size of the spherical alloy or intermetallic compound particles is 10-500 μm, and the sphericity is ≥0.
85.
9. The preparation method according to claim 1, characterized in that, In step S3, the acid and alkali treatment steps are as follows: (1) Use 0.001-2 mol / L hydrochloric acid solution for acid treatment, solid-liquid mass ratio 1:1-2000, treatment time 0.2-24 h, treatment temperature 5-40℃, and wash with deionized water until the pH of the filtrate is 6-8; (2) The metal framework catalyst is obtained by alkaline treatment with 0.01-6 mol / L sodium hydroxide solution, solid-liquid mass ratio of 1:1-2000, treatment time of 0.6-72 h, treatment temperature of 45-100 °C, washing with deionized water until the pH of the filtrate is 6-8, and drying.
10. The multi-component metal framework catalyst prepared by the preparation method according to any one of claims 1 to 9, characterized in that, The specific surface area of the multi-component metal framework catalyst is 20–150 m². 2 / g, porosity 30-70%, particle size distribution D50 = 10-500μm, sphericity ≥0.85.