Three-dimensional metal self-supporting catalytic bed for hydrogen production by methanol reforming and preparation method thereof
By coating Cu-Zn/Al2O3 catalyst and PTFE binder onto a foamed metal substrate, a porous composite catalytic buffer layer is formed, which solves the problem of easy damage to the catalyst under high temperature and high pressure moving conditions, improves the thermal conductivity and shock resistance of the catalyst, and realizes a long-life catalytic bed.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHINA HYDROGEN NEW ENERGY TECH CO
- Filing Date
- 2024-01-18
- Publication Date
- 2026-07-14
AI Technical Summary
Existing catalytic beds in methanol reforming for hydrogen production suffer from problems such as catalyst sintering and agglomeration, poor thermal conductivity, reduced tolerance and selectivity, and are prone to damage under high temperature and high pressure moving conditions, failing to meet the requirements for long-term operation.
A Cu-Zn/Al2O3 catalyst and a hydrophobic PTFE binder are coated onto a foam metal substrate. After drying, compaction and calcination, a multi-scale porous composite catalytic buffer layer is formed, which provides an effective mass transfer channel and a buffering and shock-resistant effect.
It achieves effective contact between the catalyst and the reactants, improves the thermal conductivity and shock resistance of the catalyst, extends the life of the catalyst bed, adapts to various working conditions, and meets the needs of industrial applications.
Smart Images
Figure CN117839774B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of methanol reforming for hydrogen production technology, and in particular to a three-dimensional metal self-supporting catalyst bed for methanol reforming for hydrogen production and its preparation method. Background Technology
[0002] Methanol steam reforming for hydrogen production boasts advantages such as high technological maturity, high hydrogen yield, suitable reaction temperature, and stable and mature material systems, making it the most widely used technology in methanol reforming for hydrogen production. One key aspect lies in the catalyst. Traditional CuZn / Al2O3 catalyst systems are relatively mature, but Cu, as the primary catalytic site, undergoes dynamic changes during the reaction process. Its poor thermal conductivity makes it prone to sintering and agglomeration under temperature shocks, leading to decreased tolerance and selectivity. Furthermore, insufficient catalyst strength results in the catalyst bed being subjected to the impact and vibration of acceleration during operation under high temperature, high pressure, and movement. Catalyst particles are damaged due to friction and collision, resulting in fly ash formation, which prevents contact between methanol and water molecules and the active sites of the catalyst, causing the catalyst's lifespan and stability to fail to meet the requirements for long-term operation.
[0003] Currently, there is a lack of a catalyst bed that meets the application requirements of methanol reforming for hydrogen production in terms of cost, lifespan, performance, and safety. Summary of the Invention
[0004] Based on the above analysis, the present invention aims to provide a three-dimensional metal self-supporting catalytic bed for methanol reforming to produce hydrogen and its preparation method, in order to solve the problems that the catalytic beds prepared by the prior art do not meet the requirements of cost, lifespan, performance and safety in methanol reforming to produce hydrogen.
[0005] On one hand, embodiments of the present invention provide a method for preparing a three-dimensional metal self-supporting catalyst bed for methanol reforming to produce hydrogen, comprising the following steps:
[0006] S1. Preparation of Cu-Zn / Al2O3 catalyst slurry, the components of which include isopropanol, Triton, Cu-Zn / Al2O3 catalyst and hydrophobic PTFE binder;
[0007] S2. The prepared slurry is uniformly coated on the upper surface of the foam metal substrate;
[0008] S3. Dry the foamed metal substrate after coating with the slurry and cool it to room temperature;
[0009] S4. Use a press to compact the foamed metal substrate after it has been cooled to room temperature and coated with slurry, so that the adhesion between the catalyst slurry and the foamed metal substrate reaches the set standard;
[0010] S5. After compaction and cooling to room temperature, the foamed metal coated with slurry is subjected to calcination heat treatment to form a shape, and then cooled to room temperature to obtain the final three-dimensional metal self-supporting catalytic bed.
[0011] The beneficial effects of the above technical solution are as follows: It provides a method for preparing a three-dimensional metal self-supporting catalytic bed for methanol reforming to hydrogen production, enabling the engineering development and application of a methanol steam reformer with superior performance, long lifespan, and strong adaptability to various operating conditions. Furthermore, because the catalytic reaction bed is subjected to the impact and vibration of acceleration during operation under high temperature, high pressure, and moving conditions, it solves the problem of catalyst particle damage and fly ash due to friction and collision. The multi-scale porous composite catalytic buffer layer (a multi-scale porous composite catalytic buffer layer is formed between the Cu-Zn / Al2O3 catalyst slurry and the foamed metal substrate) provides an effective mass transfer channel for the contact between the catalyst and reactants, playing a crucial role in mitigating performance degradation under special moving conditions. This three-dimensional metal self-supporting catalytic bed uses foamed metal as the three-dimensional self-supporting material substrate, and is formed by pressing metal catalyst powder and the substrate together. One side is a metal surface with excellent thermal conductivity, while the other side serves as a buffer bed for the attached catalyst, providing buffering and shock resistance for the internal packing. By filling the substrate surface and interior with catalyst, the composite effect between the catalyst and the substrate is enhanced, forming an integrated catalytic bed. The contact between the catalyst and the reactants provides an effective mass transfer channel. The preparation process is simple, with low equipment requirements, and can meet the requirements of industrial use, enabling the engineering development and application of methanol steam reformers with superior performance, long life, and strong adaptability to various operating environments.
[0012] Based on a further improvement to the above method, step S1 further includes:
[0013] S11. Mix isopropanol, Triton, deionized water, and Cu-Zn / Al2O3 catalyst in a certain proportion;
[0014] S12. Add hydrophobic PTFE binder to the mixed material and stir at high speed;
[0015] S13. During high-speed stirring, the ratio of Cu-Zn / Al2O3 catalyst and PTFE binder in the slurry is adjusted in real time to obtain a Cu-Zn / Al2O3 catalyst slurry with a set viscosity.
[0016] Furthermore, the materials of the foam metal include at least one of Al, Ni, and Cu.
[0017] Furthermore, step S2 further includes:
[0018] The above slurry is bonded to the foamed metal substrate by scraping, so that the slurry is evenly scraped on the upper surface of the foamed metal substrate, with no bare surfaces on the upper surface of the foamed metal substrate, and the thickness of the slurry is 200~400 micrometers.
[0019] Furthermore, step S5 further includes:
[0020] S51. After compaction and cooling to room temperature, the foamed metal coated with slurry is placed in a muffle furnace for calcination heat treatment to form a shape.
[0021] S52. Cool the molded coated metal foam to room temperature to obtain the final three-dimensional metal self-supporting catalytic bed.
[0022] Furthermore, step S11 further includes:
[0023] Isopropanol, Triton, deionized water, and Cu-Zn / Al2O3 catalyst were mixed in a certain proportion and then ultrasonically dispersed.
[0024] Furthermore, in step S11, the mixing ratio of isopropanol, Triton, and Cu-Zn / Al2O3 catalyst is 50ml:10ml:10g, and the ultrasonic dispersion time is 30~50min.
[0025] Furthermore, in step S13, the ratio of Cu-Zn / Al2O3 catalyst to PTFE binder in the slurry is 1:1 to 1:2.
[0026] Furthermore, in step S51, the calcination heat treatment temperature is 250~350℃ and the holding time is 30min~2h.
[0027] On the other hand, embodiments of the present invention provide a three-dimensional metal self-supporting catalytic bed for methanol reforming to produce hydrogen, which is prepared by the above-described method for preparing a three-dimensional metal self-supporting catalytic bed for methanol reforming to produce hydrogen.
[0028] The summary section is provided to present the chosen concepts in a simplified form, which will be further described in the detailed embodiments below. The summary section is not intended to identify essential or essential features of the invention, nor is it intended to limit the scope of the invention. Attached Figure Description
[0029] The above and other objects, features and advantages of the present invention will become more apparent from the more detailed description of exemplary embodiments of the invention in conjunction with the accompanying drawings, wherein the same reference numerals generally represent the same parts.
[0030] Figure 1 A schematic diagram of the method steps in Example 1 is shown;
[0031] Figure 2 A schematic diagram of the three-dimensional metal self-supporting catalytic bed structure of Example 3 is shown;
[0032] Figure 3 A macroscopic digital image of the three-dimensional metal self-supporting catalytic bed of Example 3 is shown;
[0033] Figure 4 The SEM image of the three-dimensional metal self-supporting catalytic bed in Example 3 is shown.
[0034] Figure 5 A schematic diagram of weight loss under long-term vibration conditions in Example 3 is shown;
[0035] Figure 6 A schematic diagram of the thermal conductivity test results for Example 3 is shown;
[0036] Figure 7 A schematic diagram of the thermogravimetric analysis results for Example 3 is shown;
[0037] Figure 8 A schematic diagram of the porosity test results of the mercury porosimeter in Example 3 is shown;
[0038] Figure 9 A schematic diagram of the performance test results for Example 3 is shown. Detailed Implementation
[0039] Embodiments of the invention will now be described in more detail with reference to the accompanying drawings. While embodiments of the invention are shown in the drawings, it should be understood that the invention can be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that the invention will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
[0040] The term “comprising” and its variations as used herein signify open inclusion, i.e., “including but not limited to”. Unless otherwise stated, the term “or” means “and / or”. The term “based on” means “at least partially based on”. The terms “one example embodiment” and “one embodiment” mean “at least one example embodiment”. The term “another embodiment” means “at least one additional embodiment”. The terms “first,” “second,” etc., may refer to different or the same objects. Other explicit and implicit definitions may also be included below.
[0041] Example 1
[0042] One embodiment of the present invention discloses a method for preparing a three-dimensional metal self-supporting catalytic bed for methanol reforming to produce hydrogen, aiming to improve hydrogen production performance by optimizing the composition, ratio, and preparation method of the catalytic bed. Figure 1As shown, the preparation method of this three-dimensional metal self-supporting catalyst bed for methanol reforming to hydrogen production includes the following steps:
[0043] S1. Prepare Cu-Zn / Al2O3 catalyst slurry, the components of which include isopropanol, Triton, Cu-Zn / Al2O3 catalyst and hydrophobic PTFE binder; specifically, the slurry is made by mixing isopropanol, Triton, Cu-Zn / Al2O3 catalyst, hydrophobic PTFE binder and other components in a certain proportion;
[0044] S2. The prepared slurry is uniformly coated on the upper surface of the foam metal substrate;
[0045] S3. Dry the foamed metal substrate after coating with the slurry and cool it to room temperature;
[0046] S4. Use a press to compact the foamed metal substrate after it has been cooled to room temperature and coated with slurry, so that the adhesion between the catalyst slurry and the foamed metal substrate reaches the set standard;
[0047] S5. After compaction and cooling to room temperature, the foamed metal coated with slurry is subjected to calcination heat treatment to form a shape, and then cooled to room temperature to obtain the final three-dimensional metal self-supporting catalytic bed.
[0048] Compared with existing technologies, the method for preparing a three-dimensional metal self-supporting catalytic bed for methanol reforming to hydrogen proposed in this embodiment enables the engineering development and application of a methanol steam reformer with superior performance, long lifespan, and strong adaptability to various operating conditions. Furthermore, because the catalytic reaction bed is subjected to the impact and vibration of acceleration during operation under high temperature, high pressure, and movement, this method addresses the issues of catalyst particle damage and fly ash caused by friction and collision. The resulting multi-scale porous composite catalytic buffer layer (a multi-scale porous composite catalytic buffer layer is formed between the Cu-Zn / Al2O3 catalyst slurry and the foamed metal substrate) provides an effective mass transfer channel for the contact between the catalyst and reactants, playing a crucial role in mitigating performance degradation under special moving operating conditions. This three-dimensional metal self-supporting catalytic bed uses foamed metal as the three-dimensional self-supporting material substrate, and is formed by pressing metal catalyst powder and the substrate together. One side is a metal surface with excellent thermal conductivity, while the other side serves as a buffer bed for the attached catalyst, providing buffering and shock resistance to the internal packing material. By filling the substrate surface and interior with catalyst, the composite effect between the catalyst and the substrate is enhanced, forming an integrated catalytic bed. The contact between the catalyst and the reactants provides an effective mass transfer channel. The preparation process is simple, with low equipment requirements, and can meet the requirements of industrial use, enabling the engineering development and application of methanol steam reformers with superior performance, long life, and strong adaptability to various operating environments.
[0049] Example 2
[0050] Based on Example 1, the preparation process of the Cu-Zn / Al2O3 catalyst slurry in step S1 is further improved by including:
[0051] S11. Isopropanol, Triton, deionized water, and Cu-Zn / Al2O3 catalyst are mixed in a certain proportion and then ultrasonically dispersed; preferably, the mixing ratio of isopropanol, Triton, and Cu-Zn / Al2O3 catalyst is 50ml:10ml:10g, and the ultrasonic dispersion time is 30min.
[0052] S12. Add 15 ml of hydrophobic PTFE binder to the mixed material and stir at high speed (exemplarily, 10000 rpm) for 20-40 minutes to make it evenly mixed;
[0053] S13. During high-speed stirring, the ratio of Cu-Zn / Al2O3 catalyst to PTFE binder in the slurry is adjusted in real time to obtain a Cu-Zn / Al2O3 catalyst slurry with a set viscosity; preferably, the ratio of Cu-Zn / Al2O3 catalyst to PTFE binder in the slurry is 1:1, 1:1.5, or 1:2. That is, adjusting the ratio of Cu-Zn catalyst to PTFE binder (1:1, 1:1.5, 1:2) achieves the control of slurry viscosity.
[0054] Preferably, the material of the foam metal includes at least one of Al, Ni, and Cu.
[0055] Preferably, step S2 further includes: bonding the slurry to the foamed metal substrate by a scraping method, so that the slurry is uniformly scraped onto the upper surface of the foamed metal substrate, with no exposed areas on the upper surface of the foamed metal substrate, and the scraping thickness of the slurry is 200-400 micrometers. The near-absence of exposed foamed nickel substrate indicates that the catalyst layer effectively covers the foamed metal substrate, achieving a good composite effect between the catalyst layer and the foamed metal substrate, thereby improving the mass transfer effect during the reaction and thus enhancing the catalytic effect of the methanol reforming reaction.
[0056] The aforementioned slurry and foam metal (Al, Ni, Cu) substrate are mounted and combined using a scraping method to form an integrated self-supporting catalytic bed initial structure that can be used for methanol reforming to produce hydrogen.
[0057] Preferably, step S3 further includes: placing the coated foam metal substrate in a 50°C oven for drying (complete drying) and cooling to room temperature.
[0058] Preferably, step S5 further includes:
[0059] S51. After compaction and cooling to room temperature, the foamed metal coated with slurry is placed in a muffle furnace for calcination heat treatment to form a shape; preferably, the calcination heat treatment temperature is 250~350℃, and the holding time is 30min, 1h or 2h.
[0060] S52. Cool the molded coated metal foam to room temperature to obtain the final three-dimensional metal self-supporting catalytic bed.
[0061] Preferably, the substrate is aluminum foam.
[0062] Preferably, the ultrasonic dispersion time is 30 min and the high-speed stirring time is 30 min.
[0063] Preferably, the ratio of Cu-Zn / Al2O3 catalyst to PTFE binder is 1:1.5.
[0064] Preferably, the thickness of the three-dimensional metal self-supporting catalytic bed coating is 200 micrometers.
[0065] Preferably, the calcination temperature in the muffle furnace is 300℃ and 350℃, and the holding time is 1 hour.
[0066] Compared with existing technologies, the three-dimensional metal self-supporting catalytic bed for methanol reforming to hydrogen production provided in this embodiment has the following beneficial effects:
[0067] 1. The prepared three-dimensional metal self-supporting catalytic bed has a strong bonding force between the catalyst layer and the substrate, which can solve the impact and vibration of the catalyst under high temperature, high pressure and moving conditions. It enhances the ability of the catalyst system to cope with long-term operation, temperature shock and mechanical shock. It can solve the related problems of Cu as the main catalytic site and its dynamic changes during the reaction stage. For example, its poor thermal conductivity makes it easy to sinter and agglomerate under temperature shock, resulting in a decrease in tolerance and selectivity.
[0068] 2. The design of a three-dimensional metal self-supporting catalytic bed can effectively solve the problems of insufficient catalyst loading, small contact area with reactants, and catalytic activity. It constructs a hierarchical pore structure to form an integrated "macro-micro-nano" catalyst bed, thereby effectively improving the overall performance of the catalytic bed.
[0069] Example 3
[0070] Another embodiment of the present invention discloses a three-dimensional metal self-supporting catalytic bed for methanol reforming to hydrogen production. This catalytic bed is prepared using the preparation method for a three-dimensional metal self-supporting catalytic bed for methanol reforming to hydrogen production described in Example 1 or Example 2, and its structure is as follows: Figures 2-4 As shown. Figure 3 (a) is a frontal image of a three-dimensional metal self-supporting catalytic bed. Figure 3 (b) is a back view of the three-dimensional metal self-supporting catalytic bed. Figure 4 (a) is a surface morphology image of a three-dimensional metal self-supporting catalytic bed. Figure 4 (b) is a cross-sectional image of a three-dimensional metal self-supporting catalytic bed.
[0071] Figure 5 The comparison of the weight loss of the three-dimensional metal self-supporting catalyst bed for methanol reforming to hydrogen production under long-term vibration conditions with the prior art shows that the weight loss of the improved catalyst bed described in the example is significantly reduced.
[0072] Figure 6 The thermal conductivity test results of the three-dimensional metal self-supporting catalytic bed for methanol reforming to produce hydrogen show that, within the set temperature range, the thermal conductivity of the three-dimensional metal self-supporting catalytic bed for methanol reforming to produce hydrogen is good.
[0073] Figure 7 Thermogravimetric analysis curves of the three-dimensional metal self-supporting catalyst bed used for methanol reforming to produce hydrogen. Figure 8 This is a schematic diagram of the porosity test results using a mercury porosimeter. Figure 8 (a) is the curve of cumulative pore volume as a function of pore diameter. Figure 8 (b) shows the curves of change with pore size. It can be seen that the three-dimensional metal self-supporting catalytic bed has a rich pore structure, which is conducive to gas diffusion and improves mass transfer performance.
[0074] Figure 9 Performance test curves of the three-dimensional metal self-supporting catalytic bed for methanol reforming to produce hydrogen are shown. It can be seen that with long-term operation and temperature control at 230~260℃, the hydrogen production rate remained consistently at 110 m³ / s under good thermal conductivity. 3 / h, relatively stable.
[0075] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical applications, or improvements to the prior art of the embodiments, or to enable others skilled in the art to understand the embodiments disclosed herein.
Claims
1. A method for preparing a three-dimensional metal self-supporting catalytic bed for methanol reforming to produce hydrogen, characterized in that, Includes the following steps: S1. Preparation of Cu-Zn / Al2O3 catalyst slurry, the components of which include isopropanol, Triton, Cu-Zn / Al2O3 catalyst and hydrophobic PTFE binder; S2. The prepared slurry is uniformly coated on the upper surface of the foam metal substrate; S3. Dry the foamed metal substrate after coating with the slurry and cool it to room temperature; S4. Use a press to compact the foamed metal substrate after it has been cooled to room temperature and coated with slurry, so that the adhesion between the catalyst slurry and the foamed metal substrate reaches the set standard; S5. The foamed metal, after being compacted and cooled to room temperature and coated with slurry, is subjected to calcination heat treatment to form a shape, and then cooled to room temperature to obtain the final three-dimensional metal self-supporting catalytic bed. Step S1 further includes: S11. Mix isopropanol, Triton, deionized water, and Cu-Zn / Al2O3 catalyst in a certain proportion; S12. Add hydrophobic PTFE binder to the mixed material and stir at high speed; S13. During high-speed stirring, the ratio of Cu-Zn / Al2O3 catalyst and PTFE binder in the slurry is adjusted in real time to obtain a Cu-Zn / Al2O3 catalyst slurry with a set viscosity; Step S2 further includes: The above slurry is bonded to the foamed metal substrate by scraping, so that the slurry is evenly scraped on the upper surface of the foamed metal substrate, with no bare surfaces on the upper surface of the foamed metal substrate, and the thickness of the slurry is 200~400 micrometers. Step S11 further includes: Isopropanol, Triton, deionized water, and Cu-Zn / Al2O3 catalyst were mixed in a certain proportion and then ultrasonically dispersed. In step S11, the mixing ratio of isopropanol, Triton, and Cu-Zn / Al2O3 catalyst is 50ml:10ml:10g, and the ultrasonic dispersion time is 30~50min; In step S13, the ratio of Cu-Zn / Al2O3 catalyst to PTFE binder in the slurry is 1:1 to 1:
2.
2. The method for preparing a three-dimensional metal self-supporting catalytic bed for methanol reforming to hydrogen production according to claim 1, characterized in that, The materials for foamed metals include at least one of Al, Ni, and Cu.
3. The method for preparing a three-dimensional metal self-supporting catalytic bed for methanol reforming to hydrogen production according to claim 1, characterized in that, Step S5 further includes: S51. After compaction and cooling to room temperature, the foamed metal coated with slurry is placed in a muffle furnace for calcination heat treatment to form a shape. S52. Cool the molded coated metal foam to room temperature to obtain the final three-dimensional metal self-supporting catalytic bed.
4. The method for preparing a three-dimensional metal self-supporting catalytic bed for methanol reforming to hydrogen production according to claim 3, characterized in that, In step S51, the calcination heat treatment temperature is 250~350℃ and the holding time is 30min~2h.
5. A three-dimensional metal self-supporting catalytic bed for methanol reforming to produce hydrogen, characterized in that, The catalyst bed is prepared by the method for preparing a three-dimensional metal self-supporting catalyst bed for methanol reforming to produce hydrogen as described in any one of claims 1 to 4.