Cross-scale structure catalytic reactor as well as preparation method and application thereof

Abstract

The invention provides a cross-scale structure catalytic reactor as well as a preparation method and application thereof. The preparation method comprises the following steps: S1, preparing an active component and an auxiliary agent into a catalyst solution for later use; s2, the catalytic reactor powder is subjected to continuous laser layer-by-layer forming to form a catalytic reactor with a porous structure, and a macro-microstructure catalytic reactor is obtained for standby application; s3, carrying out micromachining treatment on the surface of the macro-micro structure catalytic reactor obtained in the step S2 through ultrafast laser to form a micro-nano structure, meanwhile, spraying the catalyst solution obtained in the step S1 to the surface of the micro-nano structure through an aerosol spraying technology, and realizing atomic-scale in-situ loading through the ultrafast laser to obtain a micro-nano structure functional body; and S4, alternately carrying out S2 and S3 to obtain the cross-scale structure catalytic reactor. Integrated manufacturing of the cross-scale catalytic reactor is achieved through continuous laser-ultrafast laser assisted by the aerosol spraying technology, and the obtained cross-scale structure catalytic reactor is excellent in catalytic efficiency and performance and has wide application prospects.

Description

Technical Field

[0001] The present invention relates to the field of additive manufacturing technology, and in particular to a cross-scale structure catalytic reactor and a preparation method and application thereof. Background Art

[0002] The catalytic reactor is the core device of the methane reforming reaction. Current research mainly focuses on two directions: catalysts and reactors.

[0003] The catalyst is the "heart" of the catalytic reactor. Commercial catalysts are mostly solid catalysts in the form of particles such as spheres and cylinders. Solid catalysts with honeycomb and fiber structures are also common. Their preparation process is simple and they are easy to separate and recycle. However, the use of such solid catalysts is very limited. They have many disadvantages, such as uneven distribution of active components, large pressure drop, low heat and mass transfer efficiency, and easy pulverization, which limit the use of catalysts in catalytic reactors.

[0004] A reactor is a device used to carry out chemical processes, used to carry out single-phase liquid reactions and multiphase reactions such as liquid-liquid, gas-liquid, liquid-solid, and gas-liquid-solid reactions, providing a safe and reliable reaction space and environment for catalysts and reactants. Reactors primarily include tubular, kettle, fixed-bed, and fluidized-bed reactors. With the continuous advancement of micro-nanofabrication technology, research on microchannel reactors has also become increasingly popular. Microchannel reactors are new, miniaturized, continuous-flow tubular reactors that primarily achieve chemical synthesis through process intensification. They possess excellent heat and mass transfer performance, enable precise reaction control, and offer high safety. However, they face challenges such as complex microfabrication technology and insufficient machining accuracy.

[0005] Currently, catalysts and reactors are studied separately and in parallel, lacking systematic integration. This makes it difficult for hydrogen production efficiency and safety to meet the requirements for integrated, functional, and compact methane reforming catalytic reactors. Developing a multifunctional catalytic reactor with integrated material, structure, and function, along with efficient manufacturing technology, to achieve high activity, low pressure drop, efficient heat and mass transfer, and excellent mechanical properties, is a key breakthrough in promoting technological innovation in methane reforming.

[0006] Chinese patent CN116832735A, "A Mesoscale Flow Reactor and Its Construction Method," discloses a mesoscale flow reactor. This involves depositing an aqueous solution containing nanoparticles on the hydrophilic region of a hydrophobic, flexible substrate. After the uniformly distributed aqueous solution is treated at high temperature, the nanoparticles are deposited to efficiently load the catalyst. Finally, the substrate is rolled to form a mesoscale flow reactor. However, this method suffers from uneven distribution of the catalyst's active components, low catalytic activity, a simple reactor structure, and average mechanical properties. Its catalytic efficiency and performance still need to be improved.

[0007] Therefore, it is of great significance to provide a cross-scale structure catalytic reactor with high catalytic activity, efficient heat and mass transfer, excellent mechanical properties, excellent catalytic efficiency and performance, and a preparation method and application thereof. Summary of the Invention

[0008] In view of the problems that the existing catalytic reactors have low catalytic activity of catalysts, general reactor performance, and catalytic efficiency and performance still need to be further improved, the present invention provides a cross-scale structure catalytic reactor and its preparation method and application. Through continuous laser-ultrafast laser, supplemented by aerosol injection technology, the integrated manufacturing of the cross-scale catalytic reactor is realized. The obtained cross-scale structure catalytic reactor has multiple scales of macro, micro and nano, the active components of the catalyst are evenly distributed, the dispersion is high, and the catalyst utilization rate is high. The reactor has a dense shell and an internal millimeter-level porous structure. The surface has an undulating micro-nano structure with efficient heat and mass transfer and excellent mechanical properties, excellent catalytic efficiency and performance, and has broad application prospects.

[0009] To achieve the above object, the technical solution adopted by the present invention is:

[0010] A method for preparing a cross-scale structure catalytic reactor comprises the following steps:

[0011] S1. The active component and the additive are configured as a catalyst solution for use;

[0012] S2. The catalytic reactor powder is formed layer by layer by continuous laser additive manufacturing technology into a catalytic reactor having a 50-1000 μm-level porous structure to obtain a macro-microstructure catalytic reactor for use;

[0013] S3. The surface of the macro-microstructured catalytic reactor obtained in S2 is micro-processed by ultrafast laser to form a 10-1000 nm micro-nanostructure. Simultaneously, the catalyst solution obtained in S1 is sprayed onto the surface of the micro-nanostructure using aerosol jet technology. Ultrafast laser is used to achieve atomic-level in-situ loading, with atomic-level dispersed particle size ≤ 5 nm, to obtain a micro-nanostructure functional body.

[0014] S4. Alternately perform S2 and S3 to form a macro-microstructured catalytic reactor layer by layer and prepare a micro-nanostructured functional body on the surface to obtain the cross-scale structured catalytic reactor.

[0015] Furthermore, the active component described in S1 is one or more of an iron source, a cobalt source, a nickel source, a copper source, a platinum source, a palladium source, a rhodium source, and an iridium source.

[0016] Furthermore, the auxiliary agent in S1 is one or more of a magnesium source, a calcium source, a yttrium source, a lanthanum source, and a cerium source.

[0017] Furthermore, the mass ratio of the active component to the auxiliary agent in S1 is (5-20):1, and the concentration of the active component in the catalyst solution is 5-50wt.%.

[0018] Furthermore, the catalytic reactor powder in S2 is one or more of stainless steel powder, nickel-based alloy powder, and cobalt-based alloy powder.

[0019] Furthermore, the continuous laser additive manufacturing technology described in S2 has a laser power of 80-300W and a scanning speed of 200-1000mm / s.

[0020] Furthermore, the ultrafast laser power in S3 is 100-5000 mW, and the repetition rate is 200-1000 kHz.

[0021] Furthermore, the aerosol spray technology described in S3 has an atomization power of 100-1000W.

[0022] Another object of the present invention is to provide a cross-scale structure catalytic reactor.

[0023] A cross-scale structure catalytic reactor is prepared according to any of the above-mentioned methods for preparing a cross-scale structure catalytic reactor.

[0024] Another object of the present invention is to provide an application of a cross-scale structure catalytic reactor.

[0025] An application of the aforementioned cross-scale structure catalytic reactor in a methane reforming reaction.

[0026] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0027] The cross-scale structure catalytic reactor provided by the present invention realizes the integrated manufacturing of the cross-scale catalytic reactor through continuous laser-ultrafast laser, supplemented by aerosol jet technology. The resulting cross-scale structure catalytic reactor has multiple scales of macro, micro and nano, and the active components of the catalyst are evenly distributed, with high dispersion and high catalyst utilization. The reactor has a dense shell and an internal millimeter-level porous structure, which provides a mass transfer channel with a high specific surface area and excellent mechanical properties for the reactants; the surface has an undulating micro-nano structure, which provides sufficient load space for the loading of the catalytic active components and improves the dispersion and utilization of the active components; the atomic-level dispersed active components are evenly distributed, the catalytic activity is high, and it can provide efficient and stable catalytic efficiency for the reaction. In addition, the integrated cross-scale structure catalytic reactor has a continuous skeleton structure, which provides support for efficient heat transfer and stable mechanical properties, excellent catalytic efficiency and performance, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The invention is further described with reference to the accompanying drawings, but the embodiments in the accompanying drawings do not constitute any limitation to the invention. A person skilled in the art can obtain other drawings based on the following drawings without inventive effort.

[0029] Figure 1 It is a structural schematic diagram of the cross-scale structure catalytic reactor of this application.

[0030] Figure 2 This is a characterization test result diagram of the cross-scale structure catalytic reactor in Example 1 of the present application.

[0031] Figure 3 This is a characterization test result diagram of the cross-scale structure catalytic reactor in Example 3 of the present application. DETAILED DESCRIPTION

[0032] To better illustrate the objectives, technical solutions, and advantages of the present invention, the present invention is further described by the following examples. Obviously, the following examples are only a part of the embodiments of the present invention, rather than all the embodiments; it should be understood that the embodiments of the present invention are only used to illustrate the technical effects of the present invention, and are not used to limit the scope of protection of the present invention.

[0033] The raw materials in the examples can be obtained commercially; unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0034] Example 1

[0035] A method for preparing a cross-scale structure catalytic reactor comprises the following steps:

[0036] S1. Prepare a 20wt.% catalyst solution of nano-nickel oxide and cerium oxide in a ratio of 20:1 and set aside;

[0037] S2. Stainless steel powder is formed layer by layer by continuous laser additive manufacturing technology into a catalytic reactor with a porous structure of 50-1000 μm. The laser power is 170 W and the scanning speed is 600 mm / s to obtain a macro-microstructure catalytic reactor for use.

[0038] S3. The surface of the macro-microstructured catalytic reactor obtained in S2 was micro-machined using an ultrafast laser with a laser power of 200 mW and a repetition rate of 100 kHz to form a concave and convex micro-nanostructure with a diameter of 10-1000 nm. Simultaneously, the catalyst solution obtained in S1 was sprayed onto the surface of the micro-nanostructure using an aerosol jet technique with an atomization power of 150 W. Ultrafast laser was used to achieve atomic-level in-situ loading, with atomically dispersed nickel particles ≤ 5 nm in size, to obtain a micro-nanostructured functional body.

[0039] S4. Alternately perform S2 and S3 to form a macro-microstructured catalytic reactor layer by layer and prepare a micro-nanostructured functional body on the surface to obtain the cross-scale structured catalytic reactor.

[0040] Example 2

[0041] A method for preparing a cross-scale structure catalytic reactor comprises the following steps:

[0042] S1. Nickel nitrate and cerium nitrate are configured in a ratio of 15:1 to form a 20wt.% catalyst solution and set aside;

[0043] S2. Stainless steel powder is formed layer by layer by continuous laser additive manufacturing technology into a catalytic reactor with a porous structure of 50-1000 μm. The laser power is 200 W and the scanning speed is 700 mm / s to obtain a macro-microstructure catalytic reactor for use;

[0044] S3. The surface of the macro-microstructured catalytic reactor obtained in S2 was micro-machined using an ultrafast laser with a laser power of 200 mW and a repetition rate of 150 kHz to form a concave and convex micro-nanostructure with a diameter of 10-1000 nm. Simultaneously, the catalyst solution obtained in S1 was sprayed onto the surface of the micro-nanostructure using an aerosol jet technique with an atomization power of 200 W. Ultrafast laser was used to achieve atomic-level in-situ loading, with atomically dispersed nickel particles ≤ 3 nm in size, to obtain a micro-nanostructured functional body.

[0045] S4. Alternately perform S2 and S3 to form a macro-microstructured catalytic reactor layer by layer and prepare a micro-nanostructured functional body on the surface to obtain the cross-scale structured catalytic reactor.

[0046] Example 3

[0047] A method for preparing a cross-scale structure catalytic reactor comprises the following steps:

[0048] S1. The chloroiridic acid and magnesium oxide were configured in a ratio of 12:1 to form a 25wt.% catalyst solution and set aside;

[0049] S2. Stainless steel powder is formed layer by layer by continuous laser additive manufacturing technology into a catalytic reactor with a porous structure of 50-1000 μm. The laser power is 150 W and the scanning speed is 800 mm / s to obtain a macro-microstructure catalytic reactor for standby use;

[0050] S3. The surface of the macro-microstructured catalytic reactor obtained in S2 was micro-machined using an ultrafast laser with a laser power of 300 mW and a repetition rate of 220 kHz to form a concave and convex micro-nanostructure with a diameter of 10-500 nm. Simultaneously, the catalyst solution obtained in S1 was sprayed onto the surface of the micro-nanostructure using an aerosol jet technique with an atomization power of 300 W. Ultrafast laser loading was achieved at the atomic level, with atomically dispersed iridium particles ≤ 3 nm in size, to obtain a micro-nanostructured functional body.

[0051] S4. Alternately perform S2 and S3 to form a macro-microstructured catalytic reactor layer by layer and prepare a micro-nanostructured functional body on the surface to obtain the cross-scale structured catalytic reactor.

[0052] Comparative Example 1

[0053] A method for preparing a catalytic reactor comprises the following steps:

[0054] S1. Prepare a 20wt.% catalyst solution of nano-nickel oxide and cerium oxide in a ratio of 20:1 and set aside;

[0055] S2. Stainless steel powder is formed layer by layer by continuous laser additive manufacturing technology into a catalytic reactor with a porous structure of 50-1000 μm. The laser power is 170 W and the scanning speed is 600 mm / s to obtain a macro-microstructure catalytic reactor for use.

[0056] S3. The catalyst solution obtained in S1 was sprayed onto the surface of the micro-nanostructure using an aerosol jet technique with an atomization power of 150 W. Atomic-level in-situ loading was achieved using an ultrafast laser with a laser power of 200 mW and a repetition rate of 100 kHz. Simultaneously, atomically dispersed nickel particles with a size of ≤5 nm were obtained to obtain a micro-nanostructure functional body.

[0057] S4. Alternately perform S2 and S3 to form a macro-microstructure catalytic reactor layer by layer and prepare a micro-nanostructure functional body on the surface to obtain the catalytic reactor.

[0058] Compared with Example 1, the main difference of this comparative example is that it does not have a micro-nano structure.

[0059] Comparative Example 2

[0060] A method for preparing a catalytic reactor comprises the following steps:

[0061] S1. Nickel nitrate and cerium nitrate are configured in a ratio of 15:1 to form a 20wt.% catalyst solution and set aside;

[0062] S2. Stainless steel powder is formed layer by layer by continuous laser additive manufacturing technology into a catalytic reactor with a porous structure of 50-1000 μm. The laser power is 200 W and the scanning speed is 700 mm / s to obtain a macro-microstructure catalytic reactor for use;

[0063] S3. The surface of the macro-microstructured catalytic reactor obtained in S2 was micro-machined by ultrafast laser at a laser power of 200 mW and a repetition rate of 150 kHz to form a 10-1000 nm uneven micro-nanostructure. The catalyst solution obtained in S1 was sprayed onto the surface of the micro-nanostructure using an aerosol jet technique with an atomization power of 200 W and a nickel particle size of 10-50 nm to obtain a micro-nanostructure functional body.

[0064] S4. Alternately perform S2 and S3 to form a macro-microstructure catalytic reactor layer by layer and prepare a micro-nanostructure functional body on the surface to obtain the catalytic reactor.

[0065] Compared with Example 2, the main difference of this comparative example is that the particle size of the catalytic active component is 10-50 nm.

[0066] Comparative Example 3

[0067] A method for preparing a catalytic reactor comprises the following steps:

[0068] S1. The chloroiridic acid and magnesium oxide were configured in a ratio of 12:1 to form a 25wt.% catalyst solution and set aside;

[0069] S2. Stainless steel powder was formed layer by layer into a catalytic reactor with a porous structure >1000 μm using continuous laser additive manufacturing technology. The laser power was 150 W and the scanning speed was 800 mm / s to obtain a macro-microstructured catalytic reactor for standby use.

[0070] S3. The surface of the macro-microstructured catalytic reactor obtained in S2 was micro-machined using an ultrafast laser with a laser power of 300 mW and a repetition rate of 220 kHz to form a concave and convex micro-nanostructure with a diameter of 10-500 nm. Simultaneously, the catalyst solution obtained in S1 was sprayed onto the surface of the micro-nanostructure using an aerosol jet technique with an atomization power of 300 W. Ultrafast laser loading was achieved at the atomic level, with atomically dispersed iridium particles ≤ 3 nm in size, to obtain a micro-nanostructured functional body.

[0071] S4. Alternately perform S2 and S3 to form a macro-microstructure catalytic reactor layer by layer and prepare a micro-nanostructure functional body on the surface to obtain the cross-scale structure catalytic reactor

[0072] Compared with Example 3, the main difference of this comparative example is that the porous structure of the reactor is above 1000 μm.

[0073] Example 1 and Example 3 were characterized and tested, and the results were as follows Figure 2 、 Figure 3 shown.

[0074] Figure 2 This is a characterization test result diagram of the cross-scale structure catalytic reactor of Example 1 of this application. Figure 2 It can be seen that the atomic-level dispersed catalyst sample on the cross-scale structure catalytic reactor of the present application presents a flower-like morphology, the metal particles are highly dispersed and evenly distributed, and the active component loading is high, indicating that the catalyst composition of the cross-scale structure catalytic reactor obtained in the present application is uniform, highly dispersed, and has a high loading capacity, and has excellent catalytic efficiency and performance.

[0075] Figure 3 This is a characterization test result diagram of the cross-scale structure catalytic reactor of Example 3 of this application. Figure 3 It can be seen that the atomic-level dispersed catalyst sample particles on the cross-scale structure catalytic reactor of the present application are small in size, evenly dispersed, and have no agglomeration phenomenon, indicating that the active center size of the catalyst in the cross-scale structure catalytic reactor obtained in the present application is small and evenly dispersed, which can provide a larger specific surface area and more active sites, and has excellent catalytic efficiency and performance.

[0076] The test results of the other embodiments are basically consistent with it.

[0077] The performance test of the above samples is carried out, and the experimental test method is as follows:

[0078] The methane carbon dioxide reforming reaction performance test was carried out by Examples 1-3 and Comparative Examples 1-3. The raw gas (N2 / CH4 / H2O=10 / 50 / 100) was passed under normal pressure at a flow rate of 160 mL / min and a space velocity GHSV of 24000 mL·g -1 ·h -1 The reaction was carried out at 800° C. The reaction products were analyzed online by gas chromatography GC (SP-2100A)-thermal conductivity detector TCD.

[0079] The test results are shown in the following table:

[0080] Table 1 Test results of Examples 1-3 and Comparative Examples 1-3

[0081] Initial conversion rate / % Reaction time / h Conversion rate after reaction / % Example 1 98 100 92 Example 2 98 100 96 Example 3 98 100 94 Comparative Example 1 87 100 68 Comparative Example 2 87 100 60 Comparative Example 3 85 100 70

[0082] As can be seen from Table 1, the cross-scale structure catalytic reactors obtained by the present invention all have excellent performance. The initial conversion rates of Examples 1-3 are all higher than 95%. After 100 hours of reaction, they still have a methane conversion rate of not less than 90%, showing high and stable catalytic efficiency. However, Comparative Example 1 does not have a micro-nano structure, the surface-loaded catalyst active components are small, the dispersion is low, the catalyst utilization rate is not high, the initial conversion rate is 87%, and after 100 hours of reaction, the methane conversion rate drops to 68%, showing poor catalytic activity and stability; Comparative Example 2 has a catalytic active component particle size of 10-50 nm, a large active center size, and a catalytic activity lower than that of the examples. The initial conversion rate is 87%, and after 100 hours of reaction, the methane conversion rate drops to 60%, with general stability, low cycle performance, and poor catalytic performance; Comparative Example 3 has a porous structure of more than 1000 μm, and the mass transfer channel specific surface area is smaller than that of the examples. The initial conversion rate is only 85%, and after 100 hours of reaction, the methane conversion rate drops to 70%, showing low catalytic efficiency.

[0083] In summary, the present invention realizes the integrated manufacturing of cross-scale catalytic reactors through continuous laser-ultrafast laser, supplemented by aerosol jet technology. The resulting cross-scale structure catalytic reactor has multiple scales of macro, micro and nano, the active components of the catalyst are evenly distributed, the dispersion is high, and the catalyst utilization rate is high. The reactor has a dense shell and an internal millimeter-level porous structure. The surface has an undulating micro-nano structure with efficient heat and mass transfer and excellent mechanical properties, excellent catalytic efficiency and performance, and has broad application prospects.

[0084] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a cross-scale structure catalytic reactor, characterized in that: The following steps are involved: S1. The active component and the additive are configured as a catalyst solution for use; S2. The catalytic reactor powder is formed layer by layer by continuous laser additive manufacturing technology into a catalytic reactor having a 50-1000 μm-level porous structure to obtain a macro-microstructure catalytic reactor for use; S3. The surface of the macro-microstructured catalytic reactor obtained in S2 is micro-processed by ultrafast laser to form a 10-1000 nm micro-nanostructure. Simultaneously, the catalyst solution obtained in S1 is sprayed onto the surface of the micro-nanostructure using aerosol jet technology. Ultrafast laser is used to achieve atomic-level in-situ loading, with atomic-level dispersed particle size ≤ 5 nm, to obtain a micro-nanostructure functional body. S4. Alternately perform S2 and S3 to form a macro-microstructured catalytic reactor layer by layer and prepare a micro-nanostructured functional body on the surface to obtain the cross-scale structured catalytic reactor.

2. A method for preparing a cross-scale structure catalytic reactor according to claim 1, characterized in that: The active component in S1 is one or more of an iron source, a cobalt source, a nickel source, a copper source, a platinum source, a palladium source, a rhodium source, and an iridium source.

3. A method for preparing a cross-scale structure catalytic reactor according to claim 1, characterized in that: The auxiliary agent in S1 is one or more of a magnesium source, a calcium source, a yttrium source, a lanthanum source, and a cerium source.

4. A method for preparing a cross-scale structure catalytic reactor according to claim 1, characterized in that: The mass ratio of the active component to the auxiliary agent in S1 is (5-20):1, and the concentration of the active component in the catalyst solution is 5-50wt.%.

5. A method for preparing a cross-scale structure catalytic reactor according to claim 1, characterized in that: S2 The catalytic reactor powder is one or more of stainless steel powder, nickel-based alloy powder, and cobalt-based alloy powder.

6. A method for preparing a cross-scale structure catalytic reactor according to claim 1, characterized in that: The continuous laser additive manufacturing technology described in S2 has a laser power of 80-300W and a scanning speed of 200-1000mm / s.

7. A method for preparing a cross-scale structure catalytic reactor according to claim 1, characterized in that: The ultrafast laser power of S3 is 100-5000 mW, and the repetition rate is 200-1000 kHz.

8. A method for preparing a cross-scale structure catalytic reactor according to claim 1, characterized in that: The aerosol spray technology described in S3 has an atomization power of 100-1000W.

9. A cross-scale structure catalytic reactor, characterized in that: It is prepared according to the method for preparing a cross-scale structure catalytic reactor according to any one of claims 1-8.

10. Use of the cross-scale structure catalytic reactor according to claim 9 in a methane reforming reaction.

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