Dynamically responsive 3D-printed catalyst support models, supports, their preparation methods and applications

Abstract

This invention relates to the field of catalysts, and discloses a dynamically responsive 3D-printed catalyst support model, the support itself, its preparation method, and its applications. A 3D-printed catalyst support model is obtained by periodically arranging structural units in three-dimensional space; wherein, each structural unit comprises a porous matrix with a cavity structure and small spheres located inside the cavity structure, and the porous matrix has a structure consisting of a cube with the portion intersecting with a body-centered cubic structure removed. The dynamically responsive 3D-printed catalyst support of this invention, while leveraging the excellent mass and heat transfer properties of the porous support during catalytic reactions, also regulates the flow rate, increases the residence time of the reactant gas flow within the support, and enhances the contact frequency between the reactants and the catalyst, thereby improving the conversion rate of the reactants and the yield of the products.

Description

Technical Field

[0001] This invention relates to the field of catalysts, specifically to a dynamically responsive 3D-printed catalyst support model, the support, its preparation method, and its applications. Background Technology

[0002] Currently, catalytic reactions mostly employ fixed-bed tubular reactors or chamber-plate stacked reactors, which use granular catalysts or coated catalysts onto porous supports such as metal foam, metal fibers, and porous ceramics to meet the catalytic reaction conditions. Granular catalysts suffer from problems such as low specific surface area, high diffusion resistance, uneven reactant concentration distribution due to inconsistent particle size, and fragility during use, making recovery difficult. To improve the mass transfer performance of granular catalysts, researchers typically increase the reactant flow rate and catalyst dosage, but this leads to problems such as large reactor volume and high catalyst cost. Stacked reactors, also known as microreactors, utilize porous supports coated catalysts, which have a large specific surface area and low pressure drop, improving mass and heat transfer. However, they also have some drawbacks; their interconnected pore structure results in a short residence time of reactants within the support, especially as the reaction space velocity increases, preventing reactants from contacting the catalyst and thus reducing conversion rates. Reducing porosity can increase the contact time between reactants and catalyst; however, excessively low porosity can lead to the formation of closed pores during loading. Some scholars have attempted to improve reactor performance by modifying the internal structure of porous supports. For example, in the paper "Fabrication of porous metal by selective laser melting as catalyst support for hydrogen production microreactor," authors Jie Liu and Yu Gao designed a gradient pore structure. By increasing the probability of collisions between the gas flowing through and the catalyst supported on the support surface, and thus increasing the residence time of the reactants, this structure effectively improves the performance of methanol reforming for hydrogen production. However, this single static structure only achieves optimal improvement at a specific flow rate and lacks adaptability to different reaction flow rates. When the reaction flow rate changes significantly, its catalytic effect decreases markedly. Summary of the Invention

[0003] To overcome the problem that traditional catalysts cannot respond to inlet flow rates, this invention provides a dynamically responsive 3D-printed catalyst support model, the support itself, its preparation method, and its applications. The dynamically responsive 3D-printed catalyst support of this invention not only leverages the excellent mass and heat transfer properties of a porous support during the catalytic reaction process but also regulates the flow rate, increases the residence time of the reactant gas stream within the support, and enhances the contact frequency between the reactants and the catalyst, thereby improving the conversion rate of the reactants and the yield of the products.

[0004] To achieve the above objectives, the present invention provides a 3D printed catalyst support model, which is obtained by periodically arranging structural units in three-dimensional space; wherein, the structural unit comprises a porous matrix with a cavity structure and small spheres located inside the cavity structure, and the porous matrix has a structure in which the portion intersecting with the body-centered cubic structure is removed from the cube.

[0005] The second aspect of the present invention provides a 3D-printed catalyst support that can dynamically respond to the model described in the first aspect.

[0006] A third aspect of this invention provides a method for preparing a dynamically responsive 3D-printed catalyst support, comprising the following steps:

[0007] (1) The 3D printed catalyst support model described in the first aspect is 3D printed to obtain a 3D printed catalyst support blank.

[0008] (2) Anneal the 3D printed catalyst support blank and wire cut it to obtain the 3D printed catalyst support;

[0009] (3) Remove the support structure in the 3D printed catalyst support obtained in step (2) to obtain a dynamically responsive 3D printed catalyst support.

[0010] The fourth aspect of this invention provides the application of the dynamically responsive 3D-printed catalyst support described in the second aspect or the dynamically responsive 3D-printed catalyst support prepared by the preparation method described in the third aspect in gas-phase catalytic reactions.

[0011] The beneficial effects of the present invention through the above technical solution include:

[0012] The 3D-printed dynamic responsive catalyst support of the present invention is designed with structural units, and the pore size parameters are controllable and easy to adjust, which increases the catalytic specific surface area and improves the utilization rate of the catalyst support.

[0013] The dynamically responsive catalyst support of this invention features movable spheres designed on a porous matrix. This catalyst support combines the structural features of particulate catalysts and porous catalyst supports, allowing the porous support to perform its excellent mass and heat transfer properties during the catalytic reaction, while the spheres also regulate flow rate. Specifically, depending on the operating conditions, the spheres move randomly within the cavity structure, altering the direction of reactant gas flow. Particularly at high flow rates, the spheres can block flow holes at different locations to change the gas flow direction, increasing the contact time between reactants and catalyst, improving overall reaction efficiency, and thus increasing reactant conversion and product yield. This dynamically responsive 3D-printed catalyst support can respond to different feed rates, improving reaction efficiency at higher space velocities, thereby increasing reactant conversion and product yield. Attached Figure Description

[0014] Figure 1 This is a schematic diagram of the structure of the 3D printed catalyst support model prepared in Example 1;

[0015] Figure 2 This is a structural side view of the 3D-printed catalyst support model prepared in Example 1;

[0016] Figure 3 This is a schematic diagram of the structural unit of the 3D printed catalyst support model obtained in Example 1;

[0017] Figure 4 This is a cross-sectional view of the structural unit of the 3D printed catalyst support model obtained in Example 1;

[0018] Figure 5 This is a physical image of the dynamically responsive 3D-printed catalyst support prepared in Example 1;

[0019] Figure 6 The graph shows the methanol conversion rate of the 3D-printed catalyst support prepared in Examples 1-2 and the catalyst prepared on the ordinary porous support in Comparative Example 1 at different gas hourly space velocities during the methanol steam reforming hydrogen production reaction.

[0020] Figure 7 The graph shows the methane yield data of the syngas methanation reaction of the 3D-printed catalyst support prepared in Examples 1-2 and the catalyst prepared in the ordinary porous support of Comparative Example 1 at different gas hourly space velocities. Detailed Implementation

[0021] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0022] In the description of this invention, it should be understood that the terms "longitudinal," "lateral," "upper," "lower," "vertical," "horizontal," "top," "bottom," "axial," and "radial," etc., indicating orientation or positional relationships, are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this invention. In addition, "inner" and "outer" refer to the inner and outer contours relative to the outline of each component itself.

[0023] The first aspect of the present invention provides a 3D printed catalyst support model, which is obtained by periodically arranging structural units in three-dimensional space; wherein, the structural unit comprises a porous matrix with a cavity structure and a sphere located inside the cavity structure, and the porous matrix has a structure in which the portion intersecting with the body-centered cubic structure is removed from the cube.

[0024] The 3D-printed catalyst carrier model described in this invention can be created using commonly used 3D modeling software in the field, such as 3D MAX, Solidworks, AutoCAD, UG, ProE / Creo, Inventor, etc. This invention uses Solidworks to create the 3D-printed catalyst carrier model.

[0025] According to the present invention, preferably, the porous matrix includes small holes and medium holes, and the small holes and medium holes are in communication with the cavity structure.

[0026] According to the present invention, preferably, the small hole is located at the upper end of the cavity structure, and the middle hole is located at the lower end of the cavity structure. In this preferred embodiment, during a chemical reaction, the air intake through the middle hole at the lower end of the cavity structure is greater than the air intake through the small hole at the upper end of the cavity structure, creating a certain pressure difference that helps to lift the small ball.

[0027] In this invention, "upper end of cavity structure" and "lower end of cavity structure" refer to the fact that, with the radial diameter of the cavity structure as the axis, the part at the lower end of the radial diameter is considered to be at the lower end of the cavity structure, and the part at the upper end of the radial diameter is considered to be at the upper end of the cavity structure.

[0028] The small hole described in this invention can be located at the upper end of the cavity structure, and its specific location is not particularly limited. The middle hole described in this invention can be located at the lower end of the cavity structure, and its specific location is not particularly limited.

[0029] The present invention allows for a wide range of choices regarding the number of small holes and medium holes. Preferably, the number of small holes and medium holes is 2-5 each, and more preferably 3-5.

[0030] According to the present invention, preferably, the holes are arranged symmetrically along the axial direction of the model.

[0031] According to the present invention, preferably, the central holes are arranged symmetrically along the axial direction of the model.

[0032] According to the present invention, preferably, the ratio of the diameter of the central hole to the diameter of the small hole is 3-7:2-4, more preferably 4-6:2-3. In this preferred embodiment, during a chemical reaction, the pressure difference between the air intake through the central hole at the lower end of the cavity structure and the air intake through the small hole at the upper end of the cavity structure can overcome the gravity of the sphere, which is more conducive to the disordered movement of the sphere inside the cavity structure to interfere with the airflow path. When the difference between the diameters of the central hole and the small hole is small, the pressure difference between their air intakes is insufficient to overcome the gravity of the sphere itself, requiring an increase in atmospheric space velocity, which may result in the reactants not having enough time to contact the catalyst, thus leading to a low reactant conversion rate. When the difference between the diameters of the central hole and the small hole is too large, the pressure difference between their air intakes is too large, directly blowing the sphere to the top of the cavity structure, rendering the sphere ineffective, similarly resulting in a low reactant conversion rate.

[0033] According to the present invention, preferably, the diameter of the central hole is 0.3-0.7 mm, more preferably 0.4-0.6 mm.

[0034] According to the present invention, preferably, the body-centered cubic structure is composed of spheres with their centers distributed at the eight vertices and the center of the cube, which, together with the cube, form a cavity structure.

[0035] According to the present invention, preferably, the ratio of cube side length: vertex sphere diameter: center sphere diameter = 2: 1.5-1.53: 1.9-1.98.

[0036] According to the present invention, preferably, the side length of the cube is 0.8-3 mm, more preferably 1-2.5 mm. This preferred embodiment helps to increase the specific surface area.

[0037] According to the present invention, preferably, the ratio of cube side length to cavity structure diameter is 2:1.9-1.98.

[0038] The microspheres described in this invention can act as a catalyst and also as a valve to open or close the gas flow. By changing the flow direction of the gas flow in the porous matrix, the residence time of the gas flow is increased to improve the conversion rate of reactants and the yield of products.

[0039] According to the present invention, preferably, the volume of the sphere is no more than 50% of the volume of the cavity structure, more preferably 5-43% of the volume of the cavity structure.

[0040] According to the present invention, preferably, the diameter of the sphere is larger than the diameter of the central hole.

[0041] According to the present invention, more preferably, the diameter of the sphere is 1.1-3 times the diameter of the central hole.

[0042] According to the present invention, preferably, the diameter of the sphere is 0.6-1.3 mm, more preferably 0.7-1.2 mm.

[0043] According to the present invention, preferably, the structural unit further includes a support structure disposed in the cavity structure for fixing the ball.

[0044] The present invention does not impose any particular limitations on the shape and size of the support structure, as long as it can serve to fix the small ball. Preferably, the support structure is a hollow cylindrical structure to facilitate subsequent removal of the support structure.

[0045] According to the present invention, preferably, the support structure is in contact with the ball, and more preferably, the part connected to the ball is serrated.

[0046] Figure 1 This is a schematic diagram of the structure of the 3D printed catalyst support model prepared in Example 1 of the present invention, with dimensions of 70×40×2mm.

[0047] Figure 2 for Figure 1 The side view shows that during the catalytic reaction, the reactant gas flow enters from any one side and exits from the other side. The inlet and outlet of the chemical reaction in this invention are not uniquely fixed. The inlet and outlet of this invention are defined as follows: the side from which the gas flows in is the inlet, and the side from which the gas flows out is the outlet.

[0048] A second aspect of the present invention provides a 3D-printed catalyst support that can dynamically respond to the above-mentioned model.

[0049] According to the present invention, preferably, the dynamically responsive 3D printed catalyst carrier has a size of (35-140)×(20-80)×(1-80)mm, and more preferably (50-80)×(30-50)×(1-20)mm.

[0050] A third aspect of this invention provides a method for preparing a dynamically responsive 3D-printed catalyst support, comprising the following steps:

[0051] (1) The 3D printed catalyst support model described in the first aspect is 3D printed to obtain a 3D printed catalyst support blank.

[0052] (2) Anneal the 3D printed catalyst support blank and wire cut it to obtain the 3D printed catalyst support;

[0053] (3) Remove the support structure in the 3D printed catalyst support obtained in step (2) to obtain a dynamically responsive 3D printed catalyst support.

[0054] The present invention allows for a wide range of choices for the 3D printing materials, including commonly used metal materials in the field. Preferably, the 3D printing material in step (1) is selected from at least one of stainless steel powder, copper powder, and nickel powder.

[0055] According to the present invention, preferably, the 3D printing material has a particle size of 5-10 micrometers. This preferred embodiment facilitates catalyst adhesion.

[0056] The specific parameter settings for 3D printing in this invention can be selected with reference to conventional methods in the field. For example, but not limited to: powder thickness of 20μm, laser power of 150W, exposure time of 60μs, scanning speed of 1000mm / s, line spacing of 80μm, and layer height of 30μm.

[0057] According to the present invention, preferably, the annealing conditions in step (2) include: a temperature of 400-800℃, preferably 500-550℃; and a time of 3-8 hours, preferably 3-5 hours.

[0058] According to the present invention, preferably, during the annealing process in step (2), the 3D printed catalyst support blank is heated to the annealing temperature at a heating rate of 5-10 / min.

[0059] According to the present invention, preferably, step (2) further includes cooling the billet obtained by annealing to 160-240°C at a cooling rate of 10-20°C / min, and then air cooling it after it is removed from the furnace.

[0060] The wire cutting method described in this invention can be used for precision machining of a carrier. This invention does not have any particular limitations on the wire cutting method, and it can be performed by referring to conventional methods in the field.

[0061] This invention removes the support structure, allowing the small balls to move freely. This invention does not specifically limit the method for removing the support structure; any method commonly used in the art can be used, as long as the purpose of removing the support structure is achieved. This invention uses a strong acid immersion method for removal. Preferably, the method for removing the support structure in step (3) includes: immersing the 3D-printed catalyst carrier obtained in step (2) in a strong acid solution, removing it, and repeating the immersion until all the small balls can move.

[0062] According to the present invention, preferably, the conditions for each impregnation include: a temperature of 15-35°C, preferably 15-30°C; and a time of 1-3 minutes, preferably 1-2 minutes. This preferred embodiment can accelerate the removal of the support.

[0063] According to the present invention, preferably, the concentration of the strong acid solution is 36-38 wt%. The present invention does not impose a particular limitation on the amount of the strong acid solution used, and it can be appropriately selected according to specific circumstances.

[0064] According to the present invention, preferably, the strong acid is selected from at least one of hydrochloric acid, sulfuric acid and aqua regia.

[0065] According to one specific embodiment of the present invention, the 3D-printed catalyst support is subjected to ultrasonication and drying after each impregnation. The impregnation, ultrasonication, and drying operations are repeated until all the microspheres are movable.

[0066] The present invention does not impose any particular limitations on the conditions of the ultrasound, which can be appropriately selected according to the specific circumstances, as long as the purpose of cleaning the residual support material can be achieved.

[0067] The present invention does not particularly limit the drying conditions, which can be appropriately selected according to specific circumstances. Preferably, the drying conditions include a temperature of 50-100°C.

[0068] The fourth aspect of the present invention provides the application of the dynamically responsive 3D-printed catalyst support described in the second aspect or the dynamically responsive 3D-printed catalyst support prepared by the preparation method described in the third aspect in gas-phase catalytic reactions, preferably in methanol reforming to produce hydrogen or syngas methanation reactions.

[0069] This invention places the catalyst support in a reactor with the central pore at the bottom and the small pores at the top. Initially, the small spheres are at the bottom of the cavity structure under gravity, partially obscuring the central pores. When reactants are introduced into the reactor for catalytic reaction, the pressure drop of the porous structure creates a uniform vector field across the entire fluid domain. Therefore, the actual airflow within all pores exhibits sinusoidal fluctuations. Furthermore, because the airflow through the central pore at the lower end of the cavity structure is greater than that through the small pores at the upper end, a pressure difference is generated when the airflow enters the upper and lower pores. This difference overcomes the gravity of the small spheres, causing them to move within the larger pores and block or interfere with the airflow path in different ways. This increases the residence time of the airflow within the reaction support, improving overall reaction efficiency and thus increasing the conversion rate of reactants and the yield of products. When the flow rate is low, the generated force is insufficient to overcome the gravity of the small spheres, and the spheres do not cause disturbance. As the flow rate increases, some spheres begin to move slightly, and with further increases in flow rate, more spheres are moved, thus achieving a dynamic response.

[0070] The carrier described in this invention can respond to different feed flow rates, improve reaction efficiency at higher gas hourly space velocities, thereby increasing the conversion rate of reactants and the yield of products.

[0071] According to the present invention, preferably, the conditions for the gas-phase catalytic reaction include: a gas hourly space velocity of 1000-50000 mL / (g·h), more preferably 1000-35000 mL / (g·h); a temperature of 240-400℃, more preferably 260-360℃; and a pressure of 0.1-0.2 MPa, more preferably 0.1-0.15 MPa.

[0072] The dynamically responsive 3D-printed catalyst support of this invention is used to obtain a catalyst by coating an active component. The active component described in this invention can be a conventional active component in the art.

[0073] According to a specific embodiment of the present invention, a catalyst is obtained by coating the CuO / ZnO / Al2O3 active component onto a dynamically responsive 3D-printed catalyst support for use.

[0074] The method for coating the active component described in this invention can be prepared using conventional techniques in the art, such as a double-sided impregnation method. Specifically, the carrier can be impregnated with a solution containing a metal salt, followed by drying and calcination. The drying and calcination conditions can be performed under conventional conditions, which will not be elaborated upon here.

[0075] The drying and calcination conditions can be carried out under conventional conditions, and will not be described in detail here.

[0076] Preferably, based on the total weight of the catalyst, the content of the active component is 30-40% by weight, and the content of the support is 60-70% by weight.

[0077] This invention does not impose any particular requirements on the specific content of CuO, ZnO, and Al2O3 in the active components; these can be conventional choices in the field. The embodiments of this invention use an active component with a CuO:ZnO:Al2O3 weight ratio of 1:1:1 as an example.

[0078] In a preferred embodiment, the catalyst of the present invention is reduced before use.

[0079] The present invention does not impose any particular limitations on the specific conditions for the reduction, and can refer to the methods commonly used in the art.

[0080] Preferably, the reduction is carried out in a hydrogen-containing gas atmosphere.

[0081] Preferably, the hydrogen-containing gas is hydrogen and optionally a protective gas.

[0082] Preferably, the protective gas is at least one of nitrogen, helium, and argon.

[0083] Preferably, the hydrogen-containing gas is hydrogen and nitrogen.

[0084] Preferably, the volume ratio of hydrogen to nitrogen is 1:1.3-1.5.

[0085] According to a preferred embodiment of the present invention, before reduction, the catalyst is first purged with nitrogen gas at a rate of 200 mL / min and kept at a constant temperature of 380°C for 2 hours to remove air.

[0086] The present invention will be described in detail below through embodiments.

[0087] In the following embodiments, the 3D catalyst support blank of the present invention is obtained by printing with a Big Fish 3D printer.

[0088] Example 1

[0089] (1) Establishment of a 3D catalyst support model: The 3D printed catalyst support model is obtained by periodically arranging structural units in three-dimensional space; wherein, the structural unit includes a porous matrix with a cavity structure and small spheres located inside the cavity structure, and the porous matrix has a structure in which the part intersecting with the body-centered cubic structure is removed from the cube. The cube is set to 2×2×2mm, and the body-centered cubic structure is composed of spheres with their centers distributed at the eight vertices and the center of the cube, which are combined with the cube to form a cavity structure. The ratio of cube side length: vertex sphere diameter: center sphere diameter = 2:1.5:1.9.

[0090] The porous substrate includes small holes and medium holes, which communicate with the cavity structure. The cavity structure has four small holes at its upper end and four medium holes at its lower end, with both small and medium holes symmetrically arranged along the model's axial direction. The cavity structure has a diameter of 1.9 mm, the small holes have a diameter of 0.2 mm, the medium holes have a diameter of 0.4 mm, and the sphere has a diameter of 0.8 mm. The structural unit also includes a hollow cylindrical support structure disposed within the cavity structure to fix the sphere. The support structure is a hollow cylinder, and the portion connecting the support structure to the sphere is serrated. The structure of the structural unit is as follows: Figure 3 and Figure 4 As shown.

[0091] (2) 3D printing to obtain a dynamically responsive 3D catalyst support: 316L stainless steel powder with a particle size of 8 micrometers was selected as the 3D printing material. The 3D printing parameters were set as follows (specifically: powder thickness 20μm, laser power 150W, exposure time 60μs, scanning speed 1000mm / s, line spacing 80μm, layer height 30μm), and a 3D printed catalyst support blank was obtained. The obtained 3D printed catalyst support blank was annealed by heating to 500℃ at a heating rate of 5℃ / min, holding at that temperature for 3 hours, and then cooling to about 200℃ at a cooling rate of 15℃ / min. After that, it was removed from the furnace and air-cooled. Then, wire cutting was performed to obtain the 3D printed catalyst support. The 3D-printed catalyst support was immersed in a 38wt% aqua regia solution for 1 minute, then removed, ultrasonicated, and dried at 90°C. This process of immersion, ultrasonication, and drying was repeated until all the microspheres could move, resulting in a dynamically responsive 3D-printed catalyst support with dimensions of 70×40×2mm. (The physical sample is shown in the image.) Figure 5 As shown.

[0092] Example 2

[0093] (1) Establishment of a 3D catalyst support model: The 3D printed catalyst support model is obtained by periodically arranging structural units in three-dimensional space; wherein, the structural unit includes a porous matrix with a cavity structure and small spheres located inside the cavity structure, and the porous matrix has a structure in which the part intersecting with the body-centered cubic structure is removed from the cube. The cube is set to 2×2×2mm, and the body-centered cubic structure is composed of spheres with their centers distributed at the eight vertices and the center of the cube, which are combined with the cube to form a cavity. The ratio of cube side length: vertex sphere diameter: center sphere diameter = 2:1.5:1.9.

[0094] The porous substrate includes small holes and medium holes, which communicate with the cavity structure. The cavity structure has four small holes at its upper end and four medium holes at its lower end, and both the small and medium holes are symmetrically arranged along the axial direction of the model. The cavity structure has a diameter of 1.9 mm, the small holes have a diameter of 0.3 mm, the medium holes have a diameter of 0.5 mm, and the sphere has a diameter of 1 mm. The structural unit also includes a hollow cylindrical support structure disposed in the cavity structure for fixing the sphere. The support structure is a hollow cylindrical structure, and the part of the support structure connected to the sphere is serrated.

[0095] (2) 3D printing to obtain a dynamically responsive 3D catalyst carrier: Stainless steel powder with a particle size of 8 micrometers was selected as the printing material. 3D printing parameters were set (specifically: powder thickness 20 μm, laser power 150 W, exposure time 60 μs, scanning speed 1000 mm / s, line spacing 80 μm, layer height 30 μm) to obtain a 3D printed catalyst carrier blank. The obtained 3D printed catalyst carrier blank was annealed, heated to 550℃ at a heating rate of 10℃ / min, held at that temperature for 5 hours, and then cooled to approximately 200℃ in the furnace at a cooling rate of 15℃ / min. It was then removed from the furnace and air-cooled. Wire cutting was then performed to obtain the 3D printed catalyst carrier. The 3D printed catalyst carrier was immersed in a 38wt% aqua regia solution for 1 min, then removed, ultrasonicated, and dried at 90℃. The immersion, ultrasonication, and drying processes were repeated until all the small balls could move, resulting in a dynamically responsive 3D printed catalyst carrier with dimensions of 70×40×2 mm.

[0096] Comparative Example 1

[0097] Common porous carriers in existing technologies

[0098] The foam iron for scientific research, measuring 70×40×2mm, was purchased from Suzhou Jieshide. Its porosity is 95PPI.

[0099] Test Example 1

[0100] This test example illustrates the use of the dynamically responsive 3D catalyst support of the present invention in methanol reforming for hydrogen production.

[0101] The CuO / ZnO / Al2O3 active components were coated onto the dynamically responsive 3D-printed catalyst supports of Examples 1-2 and the ordinary porous support of Comparative Example 1, respectively, to obtain catalyst AC. The active component content in the catalyst was 30 wt%, the support content was 70 wt%, and the weight ratio of CuO, ZnO, and Al2O3 was 1:1:1.

[0102] Catalyst AC was placed in a stacked microreactor with a chamber plate. Nitrogen gas was first introduced at a flow rate of 200 mL / min, and the reactor was kept at 380 °C for 2 hours. Then, reduction was carried out at 350 °C for 1 hour in a mixture of hydrogen and nitrogen gas at a flow rate of 100 mL / min. The reaction temperature was set at 340 °C, the reaction pressure at 0.1 MPa, and the molar ratio of methanol vapor to water vapor at the inlet was 1:1.3. Methanol reforming to hydrogen production was carried out sequentially under reaction conditions of GHSV = 9000, 13000, 16000, 19000, and 22000 mL / (g·h). Real-time reaction performance results are as follows: Figure 6 As shown.

[0103] pass Figure 6 As can be seen, compared with ordinary porous supports, the catalyst prepared using the dynamically responsive 3D-printed catalyst support of this invention exhibits a higher methanol conversion rate under different gas hourly space velocities. With increasing gas hourly space velocity, the methanol conversion rate of all catalysts decreased, but the catalyst prepared using the dynamically responsive 3D-printed catalyst support of this invention showed a smaller rate of decrease compared to ordinary porous supports. This indicates that the small spheres inside the dynamically responsive 3D-printed catalyst support of this invention exhibit a better turbulence effect when the reaction gas flow increases, increasing the residence time of the reactant gas flow within the support and improving the contact frequency between the reactants and the catalyst, thereby increasing the conversion rate of the reactants and the yield of the products. However, this turbulence effect is also limited; as the gas hourly space velocity continues to increase, the turbulence effect weakens. Overall, the dynamically responsive 3D-printed catalyst support of this invention exhibits better methanol reforming performance. Due to its small sphere size, it is easier to agitate and reduces the likelihood of clogging during catalyst coating, making it a relatively good type of catalyst support currently available.

[0104] Test Example 2

[0105] This test case illustrates the application of the dynamically responsive 3D catalyst support of the present invention in the syngas methanation reaction.

[0106] The catalyst AC from Test Example 1 was placed in a stacked microreactor with a chamber plate. The reaction pressure was set to 0.1 MPa and the reaction temperature to 375 °C. Syngas methanation was carried out sequentially at gas hourly space velocities (GHSV) of 2000, 4000, 8000, 16000, and 24000 mL / (g·h). The real-time reaction performance results are as follows: Figure 7 As shown.

[0107] pass Figure 7The results show that the dynamically responsive catalyst support exhibits better methane yield at higher flow rates. Furthermore, compared to conventional porous supports, the catalyst prepared using the dynamically responsive 3D catalyst support of this invention demonstrates a better methane yield, which is of great significance for improving the methanation reaction of syngas.

[0108] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A 3D-printed catalyst support model, characterized in that, The 3D printed catalyst carrier model is obtained by periodically arranging structural units in three-dimensional space; wherein, the structural unit includes a porous matrix with a cavity structure and small spheres located inside the cavity structure, the porous matrix having a structure that removes the part intersecting with the body-centered cubic structure from the cube; the body-centered cubic structure is composed of spheres with their centers distributed at the eight vertices and the center of the cube, which combine with the cube to form a cavity structure; Wherein, the ratio of cube side length : vertex sphere diameter : center sphere diameter = 2 : 1.5-1.53 ​​: 1.9-1.98; The porous matrix comprises small pores and medium pores, and the small pores and medium pores are in communication with the cavity structure; Wherein, the small hole is located at the upper end of the cavity structure, and the middle hole is located at the lower end of the cavity structure; wherein, "upper end of cavity structure" and "lower end of cavity structure" mean that, with the radial diameter of the cavity structure as the axis, the part at the lower end of the radial diameter is considered to be at the lower end of the cavity structure, and the part at the upper end of the radial diameter is considered to be at the upper end of the cavity structure. The ratio of the diameter of the intermediate hole to the diameter of the small hole is 3-7:2-4; The volume of the sphere is no more than 50% of the volume of the cavity structure. The diameter of the small ball is larger than the diameter of the central hole.

2. The model according to claim 1, wherein, The number of small holes and medium holes is 2-5 each.

3. The model according to claim 2, wherein, The number of small holes and medium holes is 3-5 each.

4. The model according to claim 1, wherein, The small holes are arranged symmetrically along the axial direction of the model; The central holes are arranged symmetrically along the axial direction of the model.

5. The model according to claim 1, wherein, The ratio of the diameter of the intermediate hole to the diameter of the small hole is 4-6:2-3.

6. The model according to claim 1, wherein, The diameter of the central hole is 0.3-0.7 mm.

7. The model according to claim 6, wherein, The diameter of the central hole is 0.4-0.6 mm.

8. The model according to claim 1, wherein, The side length of the cube is 0.8-3mm.

9. The model according to claim 8, wherein, The side length of the cube is 1-2.5 mm.

10. The model according to any one of claims 1-9, wherein, The volume of the sphere is 5-43% of the volume of the cavity structure.

11. The model according to any one of claims 1-9, wherein, The diameter of the small ball is 1.1-3 times the diameter of the central hole.

12. The model according to any one of claims 1-9, wherein, The diameter of the sphere is 0.6-1.3 mm.

13. The model according to claim 12, wherein, The diameter of the sphere is 0.7-1.2 mm.

14. The model according to any one of claims 1-9, wherein, The structural unit also includes a support structure disposed in the cavity structure for fixing the ball.

15. The model according to claim 14, wherein, The supporting structure is a hollow cylindrical structure.

16. The model according to claim 14, wherein, The supporting structure is in contact with the small ball.

17. The model according to claim 16, wherein, The part of the support structure that connects to the ball is serrated.

18. A dynamically responsive 3D-printed catalyst support obtained by 3D printing the model described in any one of claims 1-17.

19. The 3D-printed catalyst support according to claim 18, wherein, The dynamically responsive 3D-printed catalyst support has a size of (35-140)×(20-80)×(1-80) mm.

20. The 3D-printed catalyst support according to claim 19, wherein, The dynamically responsive 3D-printed catalyst support has a size of (50-80) × (30-50) × (1-20) mm.

21. A method for preparing a dynamically responsive 3D-printed catalyst support, comprising the following steps: (1) The 3D printed catalyst support model according to any one of claims 1-17 is 3D printed to obtain a 3D printed catalyst support blank; (2) The 3D printed catalyst support blank is annealed and wire-cut to obtain the 3D printed catalyst support; (3) Remove the support structure in the 3D printed catalyst support obtained in step (2) to obtain a dynamically responsive 3D printed catalyst support.

22. The preparation method according to claim 21, wherein, In step (1), the 3D printing material is selected from at least one of stainless steel powder, copper powder and nickel powder.

23. The preparation method according to claim 21, wherein, The particle size of the 3D printing material is 5-10 micrometers.

24. The preparation method according to claim 21, wherein, The annealing conditions in step (2) include: a temperature of 400-800℃ and a time of 3-8 hours.

25. The preparation method according to claim 24, wherein, The annealing conditions in step (2) include: a temperature of 500-550℃ and a time of 3-5 hours.

26. The preparation method according to claim 21, wherein, During the annealing process described in step (2), the 3D printed catalyst support blank is heated to the annealing temperature at a heating rate of 5-10 / min.

27. The preparation method according to claim 21, wherein, Step (2) also includes cooling the billet obtained by annealing to 160-240°C at a cooling rate of 10-20°C / min, and then air cooling it after it is taken out of the furnace.

28. The preparation method according to claim 21, wherein, The method for removing the support structure in step (3) includes: immersing the 3D printed catalyst carrier obtained in step (2) in a strong acid solution, taking it out, and repeating the immersion until all the small balls can move; The conditions for each immersion are: temperature 15-35℃; time 1-3 minutes.

29. The preparation method according to claim 28, wherein, The conditions for each immersion are: temperature 15-30℃; time 1-2 minutes.

30. The preparation method according to claim 28, wherein, The concentration of the strong acid solution is 36-38 wt%. The strong acid is selected from at least one of hydrochloric acid, sulfuric acid, and aqua regia.

31. The application of the dynamically responsive 3D-printed catalyst support according to any one of claims 18-20 or the dynamically responsive 3D-printed catalyst support prepared by the preparation method according to any one of claims 21-30 in gas-phase catalytic reactions.

32. The application according to claim 31, wherein, Application of the 3D-printed catalyst support in methanol reforming for hydrogen production or syngas methanation.

33. The application according to claim 31, wherein, The conditions for the gas-phase catalytic reaction include: a space velocity of 1000-50000 mL / (g) h); temperature 240-400℃; pressure 0.1-0.2MPa.

34. The application according to claim 33, wherein, The conditions for the gas-phase catalytic reaction include: a space velocity of 1000-35000 mL / (g) h); temperature 260-360℃; pressure 0.1-0.15MPa.

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