A self-catalytic reformer based on 3D printing technology and a manufacturing method thereof

Abstract

The application provides a self-catalytic reformer based on a 3D printing technology and a manufacturing method thereof, and the method comprises the following steps: S1, respectively taking nickel-based alloy powder and / or iron-based alloy powder and nickel-aluminum alloy powder, mixing the powders uniformly in a mixing device to obtain printing powder; S2, using three-dimensional drawing software to obtain a shell structure with a reserved cavity; S3, using porous design software to obtain a porous structure, and the porous structure is matched with the reserved cavity of the shell structure; S4, 3D printing the self-catalytic reformer: taking the printing powder in step S1 and adding the powder into a powder supply bin of a 3D printer, then respectively taking the shell structure in step S2 and the porous structure in step S3 and introducing the structures into the 3D printer, and using 3D printing technology to print an integrally formed self-catalytic reformer. The self-catalytic reformer is obtained by the above method. The structure and function are integrated, no additional catalyst is needed, the catalytic efficiency is improved, and the production cost is reduced.

Description

Technical Field

[0001] This invention relates to the field of catalyst fabrication technology, specifically to an autocatalytic reformer based on 3D printing technology and its fabrication method. Background Technology

[0002] Hydrogen energy, as a highly efficient secondary energy source, is applied in the aerospace industry, including space shuttles and rockets, as well as in urban transportation. For example, it is used as a protective gas in the electronics industry; in the oil refining industry for the hydrorefining of naphtha, fuel oil, crude diesel, and heavy oil; in the metallurgical industry as a reducing agent for reducing metal oxides; in the food industry for the hydrorefining of vegetable oils to produce salad oil; and in the fine organic synthesis industry, hydrogen is also an important raw material. In recent years, hydrogen energy has also found new applications, namely as fuel for fuel cells. The role and value of hydrogen energy in the world's energy transition are increasingly recognized, and major developed countries around the world have been strongly supporting the development of the hydrogen energy industry in recent years.

[0003] Currently, the main global methods for hydrogen production include natural gas reforming, heavy oil reforming, and coal gasification. Compared to coal and oil, natural gas is the world's most abundant and highest-quality clean gas. Natural gas contains more hydrogen than raw coal and crude oil, making it a bridge to the world's entry into the clean energy era. The main component of natural gas is methane, which has extremely high chemical stability, making direct conversion methods difficult to industrialize. However, converting methane into hydrogen through catalytic reforming is the most economical and reasonable process for producing hydrogen from fossil fuels.

[0004] Steam reforming (SMR) of methane is extremely important for hydrogen production. It is currently a mature hydrogen production technology in industrial production and is also the most economical and simplest method. Under suitable catalytic conditions, methane and water vapor can be efficiently converted into hydrogen and carbon monoxide. The catalytic reformer plays a crucial role in improving the methane conversion rate. Existing catalytic reformers typically consist of a catalytic reactor and a catalyst packed within it. The catalyst mainly consists of three parts: the active catalyst component, the catalyst support, and the catalyst promoter. Currently, catalytic reactors are generally made of metal alloys to ensure the safe conduct of the reaction, while the catalyst ensures the methane conversion efficiency.

[0005] However, in actual operation, this type of catalytic reformer, which fills the catalytic reaction device with catalyst, faces challenges. The micropores within each catalyst particle create additional reaction surface area, and the particles themselves have pores through which liquids or gases can flow. Therefore, precise control of parameters such as porosity is difficult, and clogging is prone to occur, leading to reduced catalytic efficiency. Furthermore, the need to add additional catalyst results in high production costs. Summary of the Invention

[0006] The purpose of this invention is to provide an autocatalytic reformer and its fabrication method based on 3D printing technology, to solve the problems of existing catalytic reformers, such as difficulty in accurately controlling parameters like porosity, and the tendency to clog, leading to reduced catalytic efficiency. Furthermore, the need for additional catalysts results in high production costs.

[0007] To address the aforementioned technical problems, this invention provides a method for fabricating an autocatalytic reformer based on 3D printing technology, comprising the following steps:

[0008] S1. Printing powder preparation: Nickel-based alloy powder and / or iron-based alloy powder and nickel-aluminum alloy powder are added to a mixing device and mixed evenly to obtain printing powder;

[0009] S2. Shell structure design: Use 3D modeling software to obtain the shell structure with reserved cavities;

[0010] S3. Porous structure design: A porous structure is obtained using porous design software, and the porous structure is adapted to the reserved cavity of the shell structure.

[0011] S4. 3D Printing Autocatalytic Reformer: Take the printing powder from step S1 and add it to the powder supply chamber of the 3D printer. Then, take the shell structure from step S2 and the porous structure from step S3 and introduce them into the 3D printer. Use 3D printing technology to print an integrated autocatalytic reformer.

[0012] Furthermore, in step S1:

[0013] The nickel-aluminum alloy powder is an irregularly shaped, broken, ultrafine nickel-aluminum alloy powder; the nickel-based alloy powder is a spherical nickel-based alloy powder; and the iron-based alloy powder is a spherical iron-based alloy powder.

[0014] The particle diameter of nickel-based alloy powder and iron-based alloy powder is 10μm-120μm; the particle diameter of nickel-aluminum alloy powder is 2μm-18μm.

[0015] Furthermore, in step S1:

[0016] When nickel-based alloy powder and nickel-aluminum alloy powder are mixed, the mass ratio between the nickel-based alloy powder and the nickel-aluminum alloy powder is any one of 9:1, 8:2, or 7:3.

[0017] When iron-based alloy powder and nickel-aluminum alloy powder are mixed, the mass ratio between the iron-based alloy powder and the nickel-aluminum alloy powder is any one of 9:1, 8:2, or 7:3.

[0018] The mass ratio of nickel to aluminum in the nickel-aluminum alloy powder is 1:1.

[0019] Furthermore, in step S2, the 3D drawing software is any one of Magics, Solidworks, UG, or VG.

[0020] In step S3, the porous design software can be any one of the following: 3-matic, 3DS-MAX, UG, solidworks, or ntopology.

[0021] Furthermore, in step S3, the porous structure can be any one of thin-walled porous structure, lattice porous structure, or microchannel porous structure.

[0022] Furthermore, the thin-walled porous structure can be any one of the following: minimal curved surface structure, torsion body structure, or wavy curved surface structure;

[0023] The lattice-type porous structure is either a space lattice structure or a cross structure with static mixing function; among them, the space lattice structure is any one of tetrahedron, octahedron, and dodecahedron;

[0024] Microchannel porous structures include multiple sets of microchannels with turbulence-inducing structures.

[0025] Furthermore, in step S4, the specific process for 3D printing the autocatalytic reformer is as follows:

[0026] The printing powder from step S1 is added to the powder supply chamber of the 3D printer. Then, the outer shell structure from step S2 is introduced into the 3D printer, and the 3D printing process parameters for the outer shell structure are set as follows: laser power of 180W to 320W, scanning speed of 700mm / s to 1400mm / s, and layer thickness of 35 to 50μm. The porous structure from step S3 is introduced into the 3D printer, and the 3D printing process parameters for the porous structure are set as follows: laser power of 90W to 180W, scanning speed of 300mm / s to 900mm / s, and layer thickness of 35 to 50μm. Then, the outer shell structure and the porous structure are printed using 3D printing technology to obtain an integrally formed autocatalytic reformer.

[0027] Furthermore, it also includes the following steps:

[0028] S5. Surface immersion: Take the autocatalytic reformer from step S4 and immerse it in an alkaline solution.

[0029] S6. High-temperature sintering: Take the autocatalytic reformer soaked in step S5 and put it into a sintering furnace. After sintering at 700℃~1100℃ for 1~3 hours, place the autocatalytic reformer at 500℃~900℃ for hydrogen reduction for 5~7 hours to obtain an autocatalytic reformer with good catalytic performance.

[0030] Furthermore, in step S5, the specific process of surface soaking is as follows:

[0031] Take the autocatalytic reformer from step S4 and place it into an ultrasonic cleaning device. After ultrasonically cleaning the autocatalytic reformer, immerse it in a pre-prepared alkaline solution for 2 to 10 hours. The alkaline solution is a dilute sodium hydroxide solution or a dilute potassium hydroxide solution.

[0032] Furthermore, the present invention also provides an autocatalytic reformer, which is obtained by the above-described method for preparing an autocatalytic reformer.

[0033] Compared with the prior art, the technical solution provided by this invention has the following advantages:

[0034] (1) The present invention provides a method for fabricating an autocatalytic reformer based on 3D printing technology. By using high-strength, high-temperature-resistant nickel-based alloy powder and / or iron-based alloy powder as raw materials, and mixing them with catalytically active ultrafine nickel-aluminum alloy powder to form the printing powder for preparing the reformer, a high-strength, high-temperature-resistant reformer can be fabricated, and the fabricated reformer also possesses reforming functionality. Therefore, no additional catalyst particles are required. Compared to the existing technology that uses catalyst particles for filling, this method not only allows for precise control of parameters such as porosity but also prevents clogging, significantly improving catalytic efficiency; simultaneously, it reduces production costs.

[0035] (2) This invention provides a method for fabricating an autocatalytic reformer based on 3D printing technology. By using 3D printing technology, uniformly mixed printing powder can be directly molded into an autocatalytic reformer in one piece. Therefore, it is possible to prepare a highly integrated reformer with a high-precision complex structure and miniaturize the reformer. It achieves the integration of structure and function, eliminates the need for assembly, and can be better applied to catalytic reforming reactions.

[0036] (3) The present invention provides a method for fabricating an autocatalytic reformer based on 3D printing technology. By using 3D drawing software and porous design software to design the shell structure model and porous structure model, the target autocatalytic reformer can be obtained relatively accurately. In addition, by designing a porous structure, the specific surface area of ​​the channels can be increased, thereby improving the catalytic performance of the autocatalytic reformer.

[0037] (4) The present invention provides a method for fabricating an autocatalytic reformer based on 3D printing technology. By setting different 3D printing process parameters for the shell structure and porous structure of the autocatalytic reformer, the prepared autocatalytic reformer has a shell structure with higher strength and mechanical properties, and the microscopic surface structure of the porous structure of the autocatalytic reformer is made more refined, and a larger specific surface area is obtained. Moreover, the autocatalytic reformer obtained by 3D printing technology has a dense external structure, which can ensure the sealing of internal gas or liquid. Its internal channels are filled with macro- and micro-porous structures, and the surface of the porous structure has catalytically active components.

[0038] (5) The present invention provides a method for fabricating an autocatalytic reformer based on 3D printing technology. By immersing the printed autocatalytic reformer in an alkaline solution, more aluminum in the nickel-aluminum alloy can be corroded away, thereby increasing the pores on the surface of the autocatalytic reformer and increasing the specific surface area. The increase in specific surface area helps to load more active component nickel onto the inner surface of the reformer, thereby improving the overall catalytic performance.

[0039] (6) The present invention provides a method for fabricating an autocatalytic reformer based on 3D printing technology. By sintering the soaked autocatalytic reformer at high temperature and reducing the autocatalytic reformer with hydrogen under high temperature conditions, the strength, toughness and catalytic performance of the autocatalytic reformer are greatly improved.

[0040] (7) The present invention provides a method for fabricating an autocatalytic reformer based on 3D printing technology, which plays an important role in the pretreatment and miniaturization of fuel in fuel cells in the field of energy utilization, and can reduce the volume of fuel cell components and expand their application areas. Attached Figure Description

[0041] To more clearly illustrate the technical solutions of the prior art and the embodiments of this application, the drawings used in the description of the prior art and the embodiments of this application will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0042] Figure 1 The present invention provides a flowchart of a method for fabricating an autocatalytic reformer based on 3D printing technology.

[0043] Figure 2 This is a schematic diagram of the overall structure of an autocatalytic reformer with a porous lattice structure.

[0044] Figure 3 for Figure 2 The right view.

[0045] Figure 4 for Figure 2 Cross-sectional view.

[0046] Figure 5 for Figure 2 A schematic diagram of a medium-sized lattice porous structure.

[0047] Figure 6 This is a schematic diagram of the overall structure of an autocatalytic reformer with a porous structure of another type of lattice porous structure.

[0048] Figure 7 for Figure 6 The right view.

[0049] Figure 8 for Figure 6 Cross-sectional view.

[0050] Figure 9 for Figure 6 A schematic diagram of a medium-sized lattice porous structure.

[0051] Figure 10 This is a schematic diagram of the overall structure of an autocatalytic reformer with a porous structure and a minimal curved surface.

[0052] Figure 11 for Figure 10 The right view.

[0053] Figure 12 for Figure 10 Cross-sectional view.

[0054] Figure 13 for Figure 10 A schematic diagram of the structure of the medium-small curved surface.

[0055] Figure 14 This is a schematic diagram of the structure of a regular tetrahedron, a regular octahedron, and a regular dodecahedron in a space lattice structure.

[0056] Figure labeling: 1. Autocatalytic reformer; 11. Shell structure; 12. Porous structure; a. Tetrahedron; b. Octahedron; c. Dodecahedron. Detailed Implementation

[0057] To better understand the purpose, structure, and function of this invention, the following detailed description, in conjunction with the accompanying drawings, provides an autocatalytic reformer based on 3D printing technology and its fabrication method.

[0058] Please see Figure 1 As shown, a method for fabricating an autocatalytic reformer based on 3D printing technology includes the following steps:

[0059] S1. Preparation of printing powder.

[0060] Nickel-based alloy powder and / or iron-based alloy powder and nickel-aluminum alloy powder are added to a mixing device and mixed evenly to obtain printing powder.

[0061] Specifically, the mass ratio of nickel to aluminum in the nickel-aluminum alloy powder is 1:1; when nickel-based alloy powder and nickel-aluminum alloy powder are mixed, the mass ratio between the nickel-based alloy powder and the nickel-aluminum alloy powder is any one of 9:1, 8:2, or 7:3; when iron-based alloy powder and nickel-aluminum alloy powder are mixed, the mass ratio between the iron-based alloy powder and the nickel-aluminum alloy powder is any one of 9:1, 8:2, or 7:3.

[0062] In this invention, spherical nickel-based alloy powder and / or iron-based alloy powder, as well as irregularly shaped crushed ultrafine nickel-aluminum alloy powder, are used as raw materials. The nickel-based alloy powder and / or iron-based alloy powder and nickel-aluminum alloy powder are mixed using a mixing device to obtain printing powder for preparing a reformer. The particle diameter of the nickel-based alloy powder and iron-based alloy powder is 10μm to 120μm, and the nickel-based alloy powder grades include, but are not limited to, GH3625, GH4169, GH3536, C276, and INCONEL738; the particle diameter of the nickel-aluminum alloy powder is 2μm to 18μm. This method not only improves the mixing effect but also helps reduce costs while ensuring suitability for laser 3D printing. Furthermore, the use of ultrafine nickel-aluminum alloy powder is more conducive to improving catalytic activity.

[0063] The particle diameter of the nickel-based alloy powder and the iron-based alloy powder can be at least one of 10 μm, 15 μm, 53 μm, 100 μm, and 120 μm, or any value between any two; the particle diameter of the nickel-aluminum alloy powder can be at least one of 2 μm, 5 μm, 6 μm, 10 μm, 15 μm, and 18 μm, or any value between any two. Preferably, the irregularly broken ultrafine nickel-aluminum alloy powder is Raney nickel.

[0064] This invention utilizes high-strength, high-temperature-resistant nickel-based alloy powder and / or iron-based alloy powder as raw materials, which are then mixed with catalytically active ultrafine nickel-aluminum alloy powder to form the printing powder for preparing reformers. This allows for the fabrication of reformers that possess both high strength and high-temperature resistance, as well as reforming functionality. Therefore, no additional catalyst particles are required. Compared to existing technologies that rely on filling catalyst particles, this approach allows for precise control of parameters such as porosity, prevents clogging, significantly improves catalytic efficiency, and reduces production costs.

[0065] S2. Shell structure design.

[0066] Design a shell structure with a reserved cavity using any of the following 3D drawing software: Magics, Solidworks, UG, or VG, and export it in STL format for later use.

[0067] S3, porous structure design.

[0068] Import the shell structure from step S2 into the porous design software. Use the porous design software to fill the reserved cavities of the shell structure, thereby constructing a porous structure that matches the reserved cavities of the shell structure. Export the structure in STL format for later use. The porous design software can be any one of 3-matic, 3DS-MAX, UG, SolidWorks, or ntopology.

[0069] Furthermore, porous structures include, but are not limited to, thin-walled porous structures, lattice-type porous structures, and microchannel-type porous structures. Further, thin-walled porous structures include, but are not limited to, minimal curved surface structures, torsion structures, and wavy curved surface structures. Preferably, the thin-walled porous structure is a torsion structure, which not only increases the specific surface area of ​​the channel but also changes the gas flow direction to a flow-around mode, increasing the flow length and the probability of gas collision with the surface. Lattice-type porous structures include, but are not limited to, spatial lattice structures and cross structures with static mixing functions. Further, spatial lattice structures include, but are not limited to, a regular tetrahedron (a), a regular octahedron (b), and a regular dodecahedron (c). Please refer to [link to relevant documentation]. Figure 14 As shown. The microchannel porous structure includes multiple sets of microchannels with turbulence-inducing structures.

[0070] This invention utilizes 3D modeling software and porous design software to design the shell structure model and porous structure model, enabling a relatively accurate acquisition of the target autocatalytic reformer. Furthermore, designing a porous structure can increase the specific surface area of ​​the channels, thereby improving the catalytic performance of the autocatalytic reformer.

[0071] S4, 3D printed autocatalytic reformer.

[0072] The printing powder from step S1 is added to the powder supply chamber of the 3D printer. Then, the outer shell structure from step S2 is introduced into the 3D printer, and the 3D printing process parameters for the outer shell structure are set as follows: laser power of 180W to 320W, scanning speed of 700mm / s to 1400mm / s, and layer thickness of 35 to 50μm. The porous structure from step S3 is introduced into the 3D printer, and the 3D printing process parameters for the porous structure are set as follows: laser power of 90W to 180W, scanning speed of 300mm / s to 900mm / s, and layer thickness of 35 to 50μm. Then, the outer shell structure and the porous structure are printed simultaneously using 3D printing technology to obtain an integrally formed autocatalytic reformer.

[0073] The 3D printing process parameters for the outer shell structure can also be: the laser power for printing is at least one or any two of 180W, 200W, 220W, 280W and 320W; the scanning speed is at least one or any two of 700mm / s, 1400mm / s, 900mm / s, 1000mm / s, 1200mm / s and 1400mm / s; and the layer thickness is at least one or any two of 35μm, 40μm and 50μm. The 3D printing process parameters for porous structures can also be: the printing laser power is at least one of 90W, 100W, 150W and 180W or any two of them; the scanning speed is at least one of 300mm / s, 500mm / s, 700mm / s and 900mm / s or any two of them; and the layer thickness is at least one of 35μm, 40μm and 50μm or any two of them.

[0074] This invention utilizes 3D printing technology to directly and integrally mold uniformly mixed printing powder into an autocatalytic reformer, enabling the fabrication of highly integrated reformers with complex structures and miniaturization. Furthermore, by setting different 3D printing process parameters for the outer shell and porous structure of the autocatalytic reformer, the fabricated reformer possesses an outer shell structure with higher strength and mechanical properties, and a finer microscopic surface structure with a larger specific surface area. Moreover, the external structure of the 3D-printed autocatalytic reformer is dense, ensuring the sealing of internal gases or liquids. Its internal channels are filled with macro- and micro-porous structures, and the surface of these porous structures contains catalytically active components. Since the autocatalytic reformer itself possesses catalytic properties, there is no need to add additional catalyst particles, achieving structural and functional integration without assembly, allowing for better application in catalytic reforming reactions.

[0075] S5. Surface soaking.

[0076] Take the autocatalytic reformer from step S4 and place it into an ultrasonic cleaning device. After ultrasonically cleaning the autocatalytic reformer, immerse it in a pre-prepared alkaline solution for 2-10 hours. The alkaline solution is a dilute sodium hydroxide solution or a dilute potassium hydroxide solution with a concentration range of 3-8 mol / L, preferably with a concentration of 5 mol / L.

[0077] This invention involves immersing the printed autocatalytic reformer in an alkaline solution, which corrodes more aluminum from the nickel-aluminum alloy, increasing the pores on the surface of the autocatalytic reformer and thus improving the specific surface area. The increased specific surface area helps to load more active nickel onto the inner surface of the reformer, thereby improving the overall catalytic performance.

[0078] S6. Take the autocatalytic reformer soaked in step S5 and put it into a sintering furnace. After sintering at 700℃~1100℃ for 1~3 hours, place the autocatalytic reformer at 500℃~900℃ for hydrogen reduction for 5~7 hours to obtain an autocatalytic reformer with good catalytic performance.

[0079] This invention significantly improves the strength, toughness, and catalytic performance of the autocatalytic reformer by subjecting the soaked autocatalytic reformer to high-temperature sintering and hydrogen reduction under high-temperature conditions.

[0080] The above steps enable the fabrication of highly integrated, complex reformers with high precision. The resulting autocatalytic reformer has a dense external structure, ensuring the airtightness of the internal gas or liquid components. Its internal channels are filled with macro- and micro-porous structures. The surfaces of these porous structures are treated with processes such as immersion corrosion, sintering, and hydrogen reduction to generate catalytically active components, thus completing the autocatalytic transformation. This achieves structural and functional integration, allowing for better application in catalytic reforming reactions. Simultaneously, in the field of energy utilization, it plays a crucial role in the pretreatment and miniaturization of fuel cells, reducing the size of fuel cell components and expanding their application areas.

[0081] Please see Figures 2 to 13 As shown, the present invention also provides an autocatalytic reformer 1, which is obtained by the above-described method for preparing an autocatalytic reformer. The autocatalytic reformer 1 includes a shell structure 11 and a porous structure 12, with the porous structure 12 disposed within the shell structure 11 and integrally formed with it. Since the autocatalytic reformer 1 is prepared by the above-described method, it inherently possesses catalytic performance, thus eliminating the need for additional catalyst particles, preventing channel blockage, and exhibiting good strength and toughness, as well as high catalytic efficiency.

[0082] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0083] Example 1

[0084] Step 1: Select GH3625 alloy powder with a particle diameter of 53μm and Raney nickel with a particle diameter of 6μm as raw materials, and mix GH3625 alloy powder and Raney nickel powder at a mass ratio of 9:1 to obtain a total mass of 10kg of printing powder. Mix the powder in a roller mixer for 5 hours and set aside.

[0085] Step 2: Design the shell structure using 3D modeling software. In this embodiment, the reformer is designed with a length of 100mm, an outer diameter of 10mm, and an inner diameter of 9mm for the reserved cavity. After the design is completed, export the shell structure as an STL file for later use.

[0086] Step 3: Import the shell structure model prepared in Step 2 into the porous design software. Use the porous design software to fill the reserved cavity of the shell structure to construct a porous structure that matches the reserved cavity of the shell structure. The diameter of the porous structure is 9 mm, the porous structure is a lattice type porous structure, the branch diameter is 0.5 mm, the porosity is 50%, and the pore size is 400 μm. After the design is completed, export the porous structure as an STL format for later use.

[0087] Step 4: Add the mixed printing powder from Step 1 to the powder supply chamber of the EOS M290 laser 3D printer. Import the shell structure model and porous structure model designed in Steps 2 and 3 into the software provided with the 3D printer. Set the 3D printing process parameters for the shell structure as follows: laser power 220W, scanning speed 1000mm / s, layer thickness 40μm. Set the 3D printing process parameters for the porous structure as follows: laser power 120W, scanning speed 600mm / s, layer thickness 40μm. After setting the 3D printing process parameters, use the EOS M290 laser 3D printer to print both the shell structure and the porous structure simultaneously.

[0088] Step 5: After cutting the self-catalytic reformer printed in Step 4 with a wire cutting machine, place it in an ultrasonic cleaning device. After ultrasonic cleaning the self-catalytic reformer, immerse it in a pre-prepared sodium hydroxide solution for 4 hours until no more bubbles are generated.

[0089] Step 6: Take out the autocatalytic reformer after soaking in Step 5, clean it with water and dry it, then put it into a tube furnace for sintering. The temperature of the tube furnace is set to 800℃. After calcination for 2 hours, the temperature of the tube furnace is set to 600℃, and hydrogen is introduced into the tube furnace to reduce the autocatalytic reformer for 6 hours.

[0090] Example 2

[0091] Step 1: Select GH3625 alloy powder with a particle diameter of 53μm and Raney nickel with a particle diameter of 6μm as raw materials, and mix GH3625 alloy powder and Raney nickel powder at a mass ratio of 8:2 to obtain a total mass of 10kg of printing powder. Mix the powder in a roller mixer for 5 hours and set aside.

[0092] Step 2: Design the shell structure using 3D modeling software. In this embodiment, the reformer is designed with a length of 100mm, an outer diameter of 10mm, and an inner diameter of 9mm for the reserved cavity. After the design is completed, export the shell structure as an STL file for later use.

[0093] Step 3: Import the shell structure model prepared in Step 2 into the porous design software. Use the porous design software to fill the reserved cavity of the shell structure to construct a porous structure that matches the reserved cavity of the shell structure. The diameter of the porous structure is 9 mm, the porous structure is a lattice type porous structure, the branch diameter is 0.5 mm, the porosity is 50%, and the pore size is 400 μm. After the design is completed, export the porous structure as an STL format for later use.

[0094] Step 4: Add the mixed printing powder from Step 1 to the powder supply chamber of the EOS M290 laser 3D printer. Import the shell structure model and porous structure model designed in Steps 2 and 3 into the software provided with the 3D printer. Set the 3D printing process parameters for the shell structure as follows: laser power 220W, scanning speed 1000mm / s, layer thickness 40μm. Set the 3D printing process parameters for the porous structure as follows: laser power 120W, scanning speed 600mm / s, layer thickness 40μm. After setting the 3D printing process parameters, use the EOS M290 laser 3D printer to print both the shell structure and the porous structure simultaneously.

[0095] Step 5: After cutting the self-catalytic reformer printed in Step 4 with a wire cutting machine, place it in an ultrasonic cleaning device. After ultrasonic cleaning the self-catalytic reformer, immerse it in a pre-prepared sodium hydroxide solution for 4 hours until no more bubbles are generated.

[0096] Step 6: Take out the autocatalytic reformer after soaking in Step 5, clean it with water and dry it, then put it into a tube furnace for sintering. The temperature of the tube furnace is set to 800℃. After calcination for 2 hours, the temperature of the tube furnace is set to 600℃, and hydrogen is introduced into the tube furnace to reduce the autocatalytic reformer for 6 hours.

[0097] Example 3

[0098] Step 1: Select GH3625 alloy powder with a particle diameter of 53μm and Raney nickel with a particle diameter of 6μm as raw materials, and mix GH3625 alloy powder and Raney nickel powder at a mass ratio of 7:3 to obtain a total mass of 10kg of printing powder. Mix the powder in a roller mixer for 5 hours and set aside for later use.

[0099] Step 2: Design the shell structure using 3D modeling software. In this embodiment, the reformer is designed with a length of 100mm, an outer diameter of 10mm, and an inner diameter of 9mm for the reserved cavity. After the design is completed, export the shell structure as an STL file for later use.

[0100] Step 3: Import the shell structure model prepared in Step 2 into the porous design software. Use the porous design software to fill the reserved cavity of the shell structure to construct a porous structure that matches the reserved cavity of the shell structure. The diameter of the porous structure is 9 mm, the porous structure is a lattice type porous structure, the branch diameter is 0.5 mm, the porosity is 50%, and the pore size is 400 μm. After the design is completed, export the porous structure as an STL format for later use.

[0101] Step 4: Add the mixed printing powder from Step 1 to the powder supply chamber of the EOS M290 laser 3D printer. Import the shell structure model and porous structure model designed in Steps 2 and 3 into the software provided with the 3D printer. Set the 3D printing process parameters for the shell structure as follows: laser power 220W, scanning speed 1000mm / s, layer thickness 40μm. Set the 3D printing process parameters for the porous structure as follows: laser power 120W, scanning speed 600mm / s, layer thickness 40μm. After setting the 3D printing process parameters, use the EOS M290 laser 3D printer to print both the shell structure and the porous structure simultaneously.

[0102] Step 5: After cutting the self-catalytic reformer printed in Step 4 with a wire cutting machine, place it in an ultrasonic cleaning device. After ultrasonic cleaning the self-catalytic reformer, immerse it in a pre-prepared sodium hydroxide solution for 4 hours until no more bubbles are generated.

[0103] Step 6: Take out the autocatalytic reformer after soaking in Step 5, clean it with water and dry it, then put it into a tube furnace for sintering. The temperature of the tube furnace is set to 800℃. After calcination for 2 hours, the temperature of the tube furnace is set to 600℃, and hydrogen is introduced into the tube furnace to reduce the autocatalytic reformer for 6 hours.

[0104] Example 4

[0105] Step 1: Select GH3625 alloy powder with a particle diameter of 53μm and Raney nickel with a particle diameter of 6μm as raw materials, and mix GH3625 alloy powder and Raney nickel powder at a mass ratio of 8:2 to obtain a total mass of 10kg of printing powder. Mix the powder in a roller mixer for 5 hours and set aside.

[0106] Step 2: Design the shell structure using 3D modeling software. In this embodiment, the reformer is designed with a length of 100mm, an outer diameter of 10mm, and an inner diameter of 9mm for the reserved cavity. After the design is completed, export the shell structure as an STL file for later use.

[0107] Step 3: Import the shell structure model prepared in Step 2 into the porous design software, and use the porous design software to fill the reserved cavity of the shell structure to construct a porous structure that matches the reserved cavity of the shell structure. The diameter of the porous structure is 9mm, and the porous structure is a minimal curved surface structure.

[0108] Step 4: Add the mixed printing powder from Step 1 to the powder supply chamber of the EOS M290 laser 3D printer. Import the shell structure model and porous structure model designed in Steps 2 and 3 into the software provided with the 3D printer. Set the 3D printing process parameters for the shell structure as follows: laser power 220W, scanning speed 1000mm / s, layer thickness 40μm. Set the 3D printing process parameters for the porous structure as follows: laser power 120W, scanning speed 600mm / s, layer thickness 40μm. After setting the 3D printing process parameters, use the EOS M290 laser 3D printer to print both the shell structure and the porous structure simultaneously.

[0109] Step 5: After cutting the self-catalytic reformer printed in Step 4 with a wire cutting machine, place it in an ultrasonic cleaning device. After ultrasonic cleaning the self-catalytic reformer, immerse it in a pre-prepared sodium hydroxide solution for 4 hours until no more bubbles are generated.

[0110] Step 6: Take out the autocatalytic reformer after soaking in Step 5, clean it with water and dry it, then put it into a tube furnace for sintering. The temperature of the tube furnace is set to 800℃. After calcination for 2 hours, the temperature of the tube furnace is set to 600℃, and hydrogen is introduced into the tube furnace to reduce the autocatalytic reformer for 6 hours.

[0111] Step 6: Take out the autocatalytic reformer after soaking in Step 5, clean it with water and dry it, then put it into a tube furnace for sintering. The temperature of the tube furnace is set to 700℃. After calcination for 1 hour, the temperature of the tube furnace is set to 600℃, and hydrogen is introduced into the tube furnace to reduce the autocatalytic reformer for 5 hours.

[0112] Example 5

[0113] Step 1: Select GH3625 alloy powder with a particle diameter of 53μm and Raney nickel with a particle diameter of 6μm as raw materials, and mix GH3625 alloy powder and Raney nickel powder at a mass ratio of 8:2 to obtain a total mass of 10kg of printing powder. Mix the powder in a roller mixer for 5 hours and set aside.

[0114] Step 2: Design the shell structure using 3D modeling software. In this embodiment, the reformer is designed with a length of 100mm, an outer diameter of 10mm, and an inner diameter of 9mm for the reserved cavity. After the design is completed, export the shell structure as an STL file for later use.

[0115] Step 3: Import the shell structure model prepared in Step 2 into the porous design software. Use the porous design software to fill the reserved cavity of the shell structure to construct a porous structure that matches the reserved cavity of the shell structure. The diameter of the porous structure is 9mm. The porous structure is a cross structure with static mixing function, the branch diameter is 0.5mm, the porosity is 50%, and the pore size is 400μm. After the design is completed, export the porous structure as an STL format for later use.

[0116] Step 4: Add the mixed printing powder from Step 1 to the powder supply chamber of the EOS M290 laser 3D printer. Import the shell structure model and porous structure model designed in Steps 2 and 3 into the software provided with the 3D printer. Set the 3D printing process parameters for the shell structure as follows: laser power 220W, scanning speed 1000mm / s, layer thickness 40μm. Set the 3D printing process parameters for the porous structure as follows: laser power 120W, scanning speed 600mm / s, layer thickness 40μm. After setting the 3D printing process parameters, use the EOS M290 laser 3D printer to print both the shell structure and the porous structure simultaneously.

[0117] Step 5: After cutting the self-catalytic reformer printed in Step 4 with a wire cutting machine, place it in an ultrasonic cleaning device. After ultrasonic cleaning the self-catalytic reformer, immerse it in a pre-prepared sodium hydroxide solution for 4 hours until no more bubbles are generated.

[0118] Step 6: Take out the autocatalytic reformer after soaking in Step 5, clean it with water and dry it, then put it into a tube furnace for sintering. The temperature of the tube furnace is set to 800℃. After calcination for 2 hours, the temperature of the tube furnace is set to 600℃, and hydrogen is introduced into the tube furnace to reduce the autocatalytic reformer for 6 hours.

[0119] Comparative Example 1

[0120] The process of this comparative example is the same as that of Example 2, except that GH3625 alloy powder with a particle diameter of 53 μm and nickel alloy powder with a particle diameter of 6 μm are selected as printing powder raw materials to prepare the autocatalytic reformer.

[0121] Comparative Example 2

[0122] The process of this comparative example is the same as that of Example 2, except that GH3625 alloy powder with a particle diameter of 53 μm and aluminum alloy powder with a particle diameter of 6 μm are selected as printing powder raw materials to prepare an autocatalytic reformer.

[0123] Comparative Example 3

[0124] The process of this comparative example is the same as that of Example 2, except that GH3625 alloy powder with a particle diameter of 53 μm and Raney nickel powder with a particle diameter of 18 μm are selected as printing powder raw materials to prepare an autocatalytic reformer.

[0125] Experimental example:

[0126] Test subjects: Autocatalytic reformers prepared in Examples 1 to 5, Comparative Examples 1 and 2, and existing catalytic reformers requiring the addition of catalysts were used.

[0127] Test method: Catalytic tests were conducted on the inlet and outlet of the above-mentioned autocatalytic reformer. The fuel inlet was supplied with a mixture of methane, water vapor and nitrogen. The methane flow rate was 50 ml / min, the water vapor flow rate was 0.081 ml / min, and the nitrogen flow rate was 10 ml / min.

[0128] The final results of the methane steam reforming are as follows:

[0129]

[0130] Table 1

[0131] As shown in Table 1, the catalytic efficiency of the catalyst is improved to a certain extent as the proportion of nickel-aluminum alloy gradually increases. When the mass ratio of GH3625 alloy powder to Raney nickel powder changes from 9:1 to 8:2, the methane conversion rate at 800℃ increases from 72.75% to 80.71%. This is because with more nickel-aluminum alloy doping, more aluminum in the catalyst is corroded away by immersion in sodium hydroxide solution, increasing the porosity of the structural surface and thus increasing the specific surface area. The increased specific surface area helps to load more active nickel component onto the inner surface of the reformer, thereby improving the overall reforming performance. However, when the mass ratio of GH3625 alloy powder to Raney nickel powder is 7:3, the density and mechanical properties of the reformer shell structure prepared by laser 3D printing are found to decrease significantly. Therefore, the optimal mass mixing ratio of GH3625 alloy powder to Raney nickel powder is 8:2.

[0132]

[0133] Table 2

[0134] As can be seen from Table 2, by setting different types of porous structures for the autocatalytic reformer, the methane conversion rate tends to be consistent. That is, regardless of the type of porous structure used, the autocatalytic reformer with the best reforming effect is obtained when the mass mixing ratio of GH3625 alloy powder and Raney nickel powder is 8:2.

[0135]

[0136] Table 3

[0137] As can be seen from Table 3, when the mass ratio is 8:2, the autocatalytic reformer prepared by mixing Raney nickel powder and GH3625 alloy powder has the best reforming effect compared with mixing nickel alloy powder and GH3625 alloy powder or aluminum alloy powder and GH3625 alloy powder.

[0138]

[0139] Table 4

[0140] As shown in Table 4, the autocatalytic reformer prepared using Raney nickel with a particle diameter of 6 μm exhibits better reforming performance compared to that prepared using Raney nickel with a particle diameter of 18 μm. This is because the Raney nickel powder with a particle diameter of 6 μm mixes better, while the larger Raney nickel powder with a particle diameter of 18 μm is less prone to agglomeration, resulting in a less refined surface of the prepared autocatalytic reformer. Therefore, the autocatalytic reformer prepared by mixing Raney nickel powder with a smaller particle diameter with GH3625 alloy powder yields the best reforming performance.

[0141] It is understood that the present invention has been described through some embodiments, and those skilled in the art will recognize that various changes or equivalent substitutions can be made to these features and embodiments without departing from the spirit and scope of the invention. Furthermore, under the teachings of the present invention, these features and embodiments can be modified to adapt to specific situations and materials without departing from the spirit and scope of the invention. Therefore, the present invention is not limited to the specific embodiments disclosed herein, and all embodiments falling within the scope of the claims of this application are within the protection scope of the present invention.

Claims

1. A method for fabricating an autocatalytic reformer based on 3D printing technology, characterized in that, Includes the following steps: Step 1: Select GH3625 alloy powder with a particle diameter of 53μm and Raney nickel with a particle diameter of 6μm as raw materials, and mix GH3625 alloy powder and Raney nickel powder at a mass ratio of 8:2 to obtain a total mass of 10kg of printing powder. Mix the powder in a roller mixer for 5 hours and set aside. Step 2: Use 3D modeling software to design the shell structure. The designed reformer is 100mm long, 10mm in outer diameter, and has an inner diameter of 9mm for the reserved cavity. After the design is completed, export the shell structure as an STL file for later use. Step 3: Import the shell structure model prepared in Step 2 into the porous design software, and use the porous design software to fill the reserved cavity of the shell structure to construct a porous structure that matches the reserved cavity of the shell structure. The porous structure has a diameter of 9 mm, is a lattice type porous structure, has a branch diameter of 0.5 mm, a porosity of 50%, and a pore size of 400 μm. After the design is completed, export the porous structure as an STL format for later use. Step 4: Add the mixed printing powder from Step 1 to the powder supply chamber of the EOSM290 laser 3D printer. Import the shell structure model and porous structure model designed in Steps 2 and 3 into the software provided with the 3D printer. Set the 3D printing process parameters for the shell structure as follows: laser power 220W, scanning speed 1000mm / s, layer thickness 40 μm; set the 3D printing process parameters for the porous structure as follows: laser power 120W, scanning speed 600mm / s, layer thickness 40 μm. After setting the 3D printing process parameters, use the EOSM290 laser 3D printer to print both the shell structure and the porous structure simultaneously. Step 5: After cutting the self-catalytic reformer printed in Step 4 with a wire cutting machine, put it into an ultrasonic cleaning device. After ultrasonic cleaning the self-catalytic reformer, immerse it in a pre-prepared sodium hydroxide solution for 4 hours until no more bubbles are generated. Step 6: Take out the autocatalytic reformer after soaking in Step 5, clean it with water and dry it, then put it into a tube furnace for sintering. The temperature of the tube furnace is set to 800℃. After calcination for 2 hours, the temperature of the tube furnace is set to 600℃, and hydrogen is introduced into the tube furnace to reduce the autocatalytic reformer for 6 hours.

2. An autocatalytic reformer, characterized in that, The autocatalytic reformer is obtained by the method for manufacturing an autocatalytic reformer as described in claim 1.

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