Compact self-heating methanol reforming hydrogen production reaction device and system

Abstract

The embodiment of the invention provides a compact self-heating methanol reforming hydrogen production reaction device and system, and belongs to the technical field of hydrogen production. The reaction device comprises a plurality of groups of stacked methanol-to-hydrogen reactors, each group of methanol-to-hydrogen reactor comprises a combustion chamber plate, and a flow channel suitable for mixed combustion of air and methanol and generating and conveying high-temperature flue gas is formed in the combustion chamber plate; the reforming cavity plate is closely attached to the combustion cavity plate, a groove area is formed in the surface, facing the combustion cavity plate, of the reforming cavity plate, and the groove area and the combustion cavity plate cooperate to form a flowing channel for the methanol aqueous solution to flow from the first input end to the first output end; the plurality of catalyst bed layers are stacked and laid in the groove areas, so that a flowing methanol aqueous solution is subjected to a reforming reaction to obtain a mixed gas mainly containing hydrogen, and the mixed gas exchanges heat with high-temperature flue gas to achieve the purpose of preliminary preheating. And the temperature is gradually reduced in the direction perpendicular to the first input end to the first output end so as to adapt to the bed temperature after combustion and reforming heat exchange.

Description

Technical Field

[0001] This invention relates to the field of hydrogen production technology, and in particular to a compact, self-heating methanol reforming hydrogen production reactor and system. Background Technology

[0002] Faced with energy shortages and environmental pollution, there is a need to develop energy-saving, emission-reducing, clean, and renewable new energy sources. Compared to traditional energy sources, hydrogen is a green, carbon-free, renewable new energy source with advantages such as high energy density, high conversion efficiency, and high storage capacity.

[0003] In related technologies, methanol steam reforming is often used to produce hydrogen, but it has a large volume and poor equipment flexibility. Furthermore, methanol reforming for hydrogen production often uses heat transfer oil circulation for indirect heating, which requires corresponding heat transfer oil storage devices, increasing the complexity of the reaction equipment and resource consumption. When the heat released from catalytic combustion is transferred to the catalytic reforming bed, there is a large temperature gradient, which makes the reforming area near the catalytic combustion side prone to local overheating, resulting in low catalyst utilization efficiency and easy sintering and deactivation. Summary of the Invention

[0004] In view of this, embodiments of the present invention provide a compact self-heating methanol-to-hydrogen reactor, which includes multiple stacked methanol-to-hydrogen reactors. Each methanol-to-hydrogen reactor includes: a combustion chamber plate, in which a flow channel is formed suitable for the mixed combustion of air and methanol to generate and transport high-temperature flue gas; a reforming chamber plate, which is sealed and fitted to the combustion chamber plate, and a groove region is formed on the surface of the reforming chamber plate facing the combustion chamber plate. The groove region cooperates with the combustion chamber plate to form a flow channel for the methanol-water solution to flow from a first input end to a first output end; and multiple catalyst beds, each catalyst bed being stacked and laid in the groove region, so that the flowing methanol-water solution undergoes a reforming reaction to obtain a hydrogen-based mixture and exchanges heat with the methanol combustion reaction. The temperature of the multiple catalyst beds gradually decreases along the direction perpendicular to the first input end to the first output end.

[0005] Embodiments of the present invention also provide a methanol-to-hydrogen reaction system, comprising a plurality of the above-described compact self-heating methanol-to-hydrogen reaction devices; a first methanol container suitable for supplying methanol to a combustion chamber plate; an air pump suitable for supplying air to the combustion chamber plate; a second methanol container suitable for supplying heated methanol-water solution to a first input end; and a hydrogen separation device connected to a first output end, the hydrogen separation device being suitable for purifying a hydrogen-dominant mixture.

[0006] The compact self-heating methanol-to-hydrogen reactor and system based on the above embodiments of the present invention achieves efficient conversion of the heat released from methanol combustion and the waste heat from the high-temperature flue gas generated by methanol combustion into the chemical energy of methanol-to-hydrogen through a sealed and fitted combustion chamber plate and a reforming chamber plate. This improves energy utilization efficiency. Multiple catalyst beds are stacked within the grooved area of ​​the reforming chamber plate. The catalyst beds are partitioned along the stacking direction (i.e., perpendicular to the direction from the first input end to the first output end), causing the temperature of the catalyst beds to gradually decrease along the stacking direction to adapt to the bed temperature after heat exchange from methanol combustion and reforming. This avoids the catalyst sintering failure problem that may be caused by the heat released from methanol combustion and the waste heat from the high-temperature flue gas, enhances the heat and mass transfer performance of the catalyst, and protects the catalyst activity while ensuring reaction performance. Attached Figure Description

[0007] The above and other objects, features and advantages of the present invention will become more apparent from the following description of embodiments of the invention with reference to the accompanying drawings, in which:

[0008] Figure 1 The schematic diagram illustrates the structure of a combustion chamber plate according to an embodiment of the present invention;

[0009] Figure 2 This diagram schematically illustrates the gas flow direction of a combustion chamber plate according to an embodiment of the present invention.

[0010] Figure 3 This schematically illustrates a perspective view of a methanol-to-hydrogen reactor with a combustion chamber plate on top, according to an embodiment of the present invention.

[0011] Figure 4 The schematic diagram illustrates the structure of a reforming cavity plate according to an embodiment of the present invention;

[0012] Figure 5 This schematic diagram illustrates the gas flow direction of a reforming chamber plate according to an embodiment of the present invention.

[0013] Figure 6 A perspective view of a methanol-to-hydrogen reactor with a reforming chamber plate on top, according to an embodiment of the present invention, is shown schematically.

[0014] Figure 7 A schematic diagram illustrating the catalyst filling of a catalyst bed according to an embodiment of the present invention is shown; and

[0015] Figure 8 The schematic diagram illustrates the structure of a combination of multiple methanol-to-hydrogen reactors according to an embodiment of the present invention.

[0016] [Explanation of Labels in the Attached Image]

[0017] 1-Combustion chamber plate;

[0018] 11-Shell;

[0019] 12-Guiding protrusion;

[0020] 13-Combustion chamber;

[0021] 14 - Second input terminal;

[0022] 15 - Second output terminal;

[0023] 16-Methanol-water solution flow holes;

[0024] 17- Reforming product flow holes;

[0025] 2-Sorting plate;

[0026] 21 - Groove area;

[0027] 22 - First input terminal;

[0028] 23 - First output terminal;

[0029] 24-Catalyst bed;

[0030] 241 - First catalyst bed;

[0031] 242 - Second catalyst bed;

[0032] 25-Methanol, air flow holes;

[0033] 26 - Flue gas flow holes;

[0034] A - First catalyst;

[0035] B - Second catalyst. Detailed Implementation

[0036] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to specific embodiments and accompanying drawings.

[0037] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. The terms “comprising,” “including,” etc., as used herein indicate the presence of the stated features, steps, operations, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, or components.

[0038] All terms used herein, including technical and scientific terms, have the meanings commonly understood by those skilled in the art, unless otherwise defined. It should be noted that the terms used herein are to be interpreted in a manner consistent with the context of this specification, and not in an idealized or overly rigid way.

[0039] When using expressions such as "at least one of A, B, and C," the meaning should generally be interpreted according to the understanding of someone skilled in the art. For example, "a system having at least one of A, B, and C" should include, but is not limited to, systems having A alone, having B alone, having C alone, having A and B, having A and C, having B and C, and / or having A, B, and C. Similarly, when using expressions such as "at least one of A, B, or C," the meaning should generally be interpreted according to the understanding of someone skilled in the art. For example, "a system having at least one of A, B, or C" should include, but is not limited to, systems having A alone, having B alone, having C alone, having A and B, having A and C, having B and C, and / or having A, B, and C.

[0040] It should also be noted that the directional terms mentioned in the embodiments, such as "up," "down," "front," "back," "left," and "right," are only for reference to the directions in the accompanying drawings and are not intended to limit the scope of protection of the present invention. Throughout the accompanying drawings, the same elements are represented by the same or similar reference numerals. Conventional structures or constructions will be omitted where they may cause confusion in understanding the present invention.

[0041] In related technologies, hydrogen production is mostly achieved through methanol steam reforming. The methanol steam reforming hydrogen production reactors used in this method are often located in fixed chemical plants, resulting in a non-compact scale and difficulty in relocation. They generally suffer from large size, poor plant flexibility, and a tendency for catalyst sintering. Furthermore, traditional hydrogen production methods utilize circulating heat transfer oil for indirect heating, leading to complex processes, significant heat losses, and high energy consumption for hydrogen production.

[0042] In realizing the concept of this invention, it was discovered that, in order to solve the above-mentioned problems, the combustion chamber plate and the reforming chamber plate are sealed and fitted together to form a methanol-to-hydrogen reactor. The heat released from methanol combustion and the resulting high-temperature flue gas is used for efficient heat exchange with the endothermic reaction of methanol reforming to produce hydrogen, simplifying the reactor structure and reducing heat and energy loss. This invention integrates the methanol-to-hydrogen reactor into a compact reactor, making the entire reactor smaller, lighter, and more mobile. However, during the heat exchange process, it was found that the catalyst bed has poor thermal conductivity, resulting in an unavoidable large temperature gradient between the combustion chamber plate and the reforming chamber plate. A large temperature difference exists in the catalyst bed along the stacking direction, making the side of the catalyst bed closest to the combustion chamber plate prone to local overheating. This easily leads to low catalyst utilization efficiency, easy sintering and loss of activity, thereby reducing the efficiency of methanol-to-hydrogen production and wasting catalyst.

[0043] Furthermore, in order to solve the above problems, a partitioned design is adopted in the stacking direction of the catalyst bed, so that the temperature of multiple catalyst beds gradually decreases along the direction perpendicular to the first input end to the first output end (i.e., the stacking direction), thereby reducing the problem of catalyst sintering failure.

[0044] Therefore, this invention forms a compact methanol-to-hydrogen reactor by sealing the combustion chamber plate and reforming chamber plate together, improving the heat exchange efficiency between methanol combustion and methanol reforming, saving the volume of the reaction unit, and offering high flexibility in layout and ease of relocation. By partitioning the catalyst bed in the stacking direction, the large temperature gradient between the combustion chamber plate and the reforming chamber plate is reduced, thus mitigating catalyst sintering failure under the influence of the exothermic effects of methanol combustion and the generated high-temperature flue gas. The device of this invention helps to better integrate the heat released by catalytic combustion with the heat absorbed by the reforming reaction, improving thermochemical reaction performance and thereby increasing the hydrogen yield and energy utilization efficiency of the entire reaction unit.

[0045] Figure 1 The schematic diagram illustrates the structure of a combustion chamber plate according to an embodiment of the present invention. Figure 2 The diagram illustrates the gas flow direction of a combustion chamber plate according to an embodiment of the present invention. Figure 3 The diagram schematically shows a perspective view of a methanol-to-hydrogen reactor with a combustion chamber plate on top, according to an embodiment of the present invention. Figure 4 The schematic diagram illustrates the structure of a reforming chamber plate according to an embodiment of the present invention. Figure 5 The diagram illustrates the gas flow direction of a reforming chamber plate according to an embodiment of the present invention. Figure 6 A perspective view of a methanol-to-hydrogen reactor with a reforming chamber plate on top, according to an embodiment of the present invention, is shown schematically.

[0046] The following combination Figures 1-6 A compact, self-heating methanol-to-hydrogen reactor according to an embodiment of the present invention will be described in detail.

[0047] like Figures 1-6 As shown, the compact self-heating methanol-to-hydrogen reactor provided in the embodiments of the present invention includes multiple stacked methanol-to-hydrogen reactors. Specifically, each methanol-to-hydrogen reactor includes a combustion chamber plate 1 and a reforming chamber plate 2.

[0048] The combustion chamber plate 1 is a closed structural unit made of high-temperature resistant material. This material is mild in nature, does not react with methanol, air, or high-temperature flue gas, and can withstand the thermal stress caused by temperatures above 500°C. Metal or quartz glass can be selected as needed, with 316H stainless steel being preferred. The combustion chamber plate 1 forms a flow channel suitable for the mixing and combustion of air and methanol, generating and transporting high-temperature flue gas.

[0049] The reforming plate 2 is a structural unit made of a high-temperature resistant material. This material is stable, does not react with the methanol-water solution, and can withstand thermal stress at temperatures above 500°C. For example, it can be made of metal or quartz glass, preferably 316H stainless steel. The material of the reforming plate 2 can be the same as or different from that of the combustion plate 1. A groove region 21 is formed on the surface of the reforming plate 2 opposite to the combustion plate 1. The reforming plate 2 and the combustion plate 1 are tightly fitted together, so that the groove region 21 partially forms a sealed space, cooperating with the combustion plate 1 to form a flow channel for the methanol-water solution to flow from the first input end 22 to the first output end 23.

[0050] Multiple catalyst beds 24 are stacked within the groove region 21, allowing the flowing methanol-water solution to undergo a reforming reaction, producing a hydrogen-dominated mixture, which also reacts with the methanol combustion and exchanges heat with the high-temperature flue gas. The temperature of the multiple catalyst beds 24 gradually decreases along a direction perpendicular to the first input end 22 to the first output end 23 (i.e., the stacking direction).

[0051] Specifically, preheated air and methanol are introduced into combustion chamber plate 1, which is filled with a catalyst, such as a nickel-based catalyst. Under the catalytic action of the nickel-based catalyst, methanol undergoes a flameless catalytic combustion reaction with oxygen in the air. The reaction process is as follows:

[0052] .

[0053] Before introducing the methanol-water solution into the reforming chamber 2, liquid methanol can be mixed with water as needed to obtain a mixed methanol-water solution. The methanol-water solution is then introduced into the reforming chamber 2 through the first input terminal 22. The heat provided by the methanol catalytic combustion reaction and the high-temperature flue gas drives the methanol-water solution to convert into a gaseous state. Under the catalytic action of the catalyst bed 24, a hydrogen production reaction takes place. The reaction process is as follows:

[0054] .

[0055] According to some embodiments of the present invention, by sealing and bonding the combustion chamber plate 1 and the reforming chamber plate 2 together, a compact, plate-type, self-heating methanol-to-hydrogen reactor is formed. From a structural design perspective, this reactor is highly compact, small in size, and offers high flexibility in layout, facilitating movement and use. The space occupied by the main body of the compact self-heating methanol-to-hydrogen reactor can be controlled to within 1m² as needed. 3The following invention is suitable for a wide range of applications, particularly distributed hydrogen production systems, and is beneficial for large-scale methanol reforming hydrogen production processes. The reaction device used in this invention has self-heating characteristics. By using a flameless methanol combustion reaction to replace high-temperature external heating, it avoids the disadvantages of external heating devices, such as numerous reactors and large equipment size, and improves reaction safety. Furthermore, the reaction device of this invention fully utilizes the heat generated by the methanol combustion reaction, making the heating more uniform. It eliminates the need for intermediate heat exchangers, reducing irreversible losses in the heat exchange process and achieving high energy utilization efficiency. It can achieve relatively rapid start-up at room temperature, solving the problem of slow start-up speed in conventional reactors. By stacking a catalyst bed 24 in the groove region 21 of the reforming chamber plate 2, and designing the catalyst bed 24 in a partitioned manner along the stacking direction (i.e., perpendicular to the direction from the first input end 22 to the first output end 23), the temperature of the catalyst bed 24 gradually decreases along the stacking direction. This avoids the problem of catalyst sintering failure caused by the heat released from methanol combustion and the residual heat of high-temperature flue gas, enhances the heat and mass transfer performance of the catalyst, and protects the catalyst activity while ensuring reaction performance. The methanol-to-hydrogen reactor used in this invention features easily disassembled plates, facilitating cleaning and maintenance, and promoting large-scale deployment. Furthermore, the reactor is environmentally friendly, as its exhaust gas does not contain NO. x and SO x .

[0056] According to some embodiments of the present invention, the plurality of catalyst beds 24 include: a first catalyst bed 241 and a second catalyst bed 242. The first catalyst bed 241 is filled with a foam metal skeleton structure to accommodate the first catalyst A, enhance heat and mass transfer performance, support the first catalyst A and the first catalyst bed 241, and prevent the first catalyst bed 241 from collapsing. Specifically, the first catalyst bed 241 includes a foam metal skeleton, pores, and a metal mesh. The foam metal skeleton serves as a carrier, and has three-dimensional irregular pores, in which the first catalyst A particles are layered and filled in the three-dimensional irregular pores and channels. The geometry, pore size, and porosity of the foam metal skeleton can be designed according to the reaction type and the structural shape of the reaction device. Specifically, the geometry of the foam metal skeleton can be, for example, a cylinder, a disc, a cube, etc., preferably a cube as the foam metal skeleton of the present invention. The first catalyst A is accommodated in the pores, and a metal mesh is used as an outer protective layer to cover the outer wall of the foam metal skeleton to prevent the first catalyst A from falling off. The metal mesh can be, for example, a metal wire mesh or a sieve plate. The second catalyst bed 242 is filled with a foamed metal skeleton structure to house the second catalyst B, enhance heat and mass transfer performance, and support both the second catalyst B and the second catalyst bed 242, preventing the second catalyst bed 242 from collapsing. The structure of the second catalyst bed 242 is largely the same as that of the first catalyst bed 241, except that the second catalyst bed 242 is designed to house the second catalyst B, which will not be elaborated further here. Each catalyst bed 24 is constructed as a modular foamed metal skeleton structure, which offers structural stability, better mass and heat transfer performance, higher strength, and more uniform temperature distribution.

[0057] Specifically, the preparation process of the first catalyst bed 241 or the second catalyst bed 242 is as follows: For example, a cubic structure of foamed metal with a certain porosity and pore size can be used as the catalyst skeleton, which is then washed with water and dried. The first catalyst A and / or the second catalyst B are filled into the pores and channels of the foamed metal skeleton. A wire mesh or sieve plate is used as an outer protective layer to cover the outer wall of the foamed metal skeleton, and the encapsulated catalyst is calcined. After cooling, the catalyst bed 24 is formed.

[0058] More specifically, after the multiple catalyst beds 24 are prepared, they are arranged periodically in the stacking direction and respectively housed in the groove region 21 of the reforming chamber plate 2.

[0059] Figure 7 A schematic diagram illustrating the catalyst filling of a catalyst bed according to an embodiment of the present invention is shown. Figure 7As shown, the first catalyst bed 241 is positioned close to the combustion chamber plate 1 along the flow direction of the methanol-water solution perpendicular to the flow from the first input end 22 to the first output end 23. It exchanges heat with the methanol combustion reaction and the high-temperature flue gas generated in the combustion chamber plate 1, thus cooling the flue gas. Simultaneously, under the catalytic action of the first catalyst A, the methanol-water solution undergoes a reforming reaction. The second catalyst bed 242 is positioned away from the combustion chamber plate 1 along the flow direction of the methanol-water solution perpendicular to the flow from the first input end 22 to the first output end 23. The methanol-water solution exchanges heat with the methanol combustion reaction and the cooled high-temperature flue gas in the second catalyst bed 242. Under the catalytic action of the second catalyst B, the methanol-water solution undergoes a reforming reaction. The heat resistance temperature of the first catalyst A is higher than that of the second catalyst B. In the stacking direction of the catalyst bed 24, the catalyst bed 24 is divided into high-temperature side and medium-low temperature side zones for different temperature regions. The first catalyst bed 241 is arranged in the region where the heat exchange temperature between the high-temperature flue gas and the methanol working medium is relatively high. That is, the side closer to the combustion chamber plate 1 uses the first catalyst A, which has a relatively high temperature tolerance, and the corresponding foamed metal carrier. In the stacking direction of the first catalyst bed 242, the side away from the combustion chamber plate 1 is set with the second catalyst bed 242, which uses the second catalyst B, which has a relatively low temperature tolerance, and the corresponding foamed metal carrier. The catalyst bed 24 is set in a zoned manner along the stacking direction, which further avoids the catalyst sintering failure problem that may be caused by methanol combustion and high-temperature flue gas exothermic reaction. Compared with the case of flat filling and the use of a single type of catalyst, the present invention helps to improve the heat and mass transfer capacity of the catalyst bed 24, reduce the temperature distribution non-uniformity of the catalyst bed 24, solve the problem of easy coking of the catalyst, and more effectively improve the safety of the reactor operation and the thermochemical reaction performance.

[0060] Preferably, there are two catalyst beds: a first catalyst bed 241 is laid near the combustion chamber plate 1, which may be a sintering-resistant bed; and a second catalyst bed 242 is laid away from the combustion chamber plate 1, which may be an active catalyst layer.

[0061] More preferably, the first catalyst A comprises a nickel-based catalyst; and the second catalyst B comprises a copper-based catalyst. The exothermic combustion of methanol allows the temperature of the high-temperature flue gas to reach 400-500°C or higher, while the optimal reaction temperature for methanol reforming to produce hydrogen is around 200-300°C. During the experiments related to this invention, it was found that nickel-based catalysts (mainly composed of NiO, etc.) exhibit poor catalytic activity at 200-300°C, but they possess good anti-sintering properties and can maintain a certain level of catalytic activity at temperatures of 400-500°C or even higher. Copper-based catalysts (CuO / ZnO / Al2O3) show good activity at 200-300°C, but their heat resistance is poor; if the temperature exceeds 200-300°C, copper-based catalysts are more prone to sintering, resulting in a faster decline in their catalytic lifetime. Therefore, this invention arranges the first catalyst A and the second catalyst B in a partitioned manner in the stacking direction. Specifically, the first catalyst bed 241 contains a nickel-based catalyst, and the second catalyst bed 242 contains a copper-based catalyst, forming catalyst beds 24 with different foam metal frameworks. This reduces the possibility of catalyst sintering failure while maintaining the high catalytic efficiency of the second catalyst B, and balances efficient heat exchange in methanol combustion, temperature of the catalyst bed 24, and uniformity of reaction distribution, thereby improving the yield and conversion rate of hydrogen production from methanol reforming.

[0062] For example, the first catalyst bed 241 may be based on a nickel foam framework, with alumina or cerium oxide supported on it; the specific type of supported metal can be selected according to actual needs. The second catalyst bed 242 may be based on a copper foam framework, with CuO / ZnO / Al2O3 catalyst supported on it. When the catalysts used in the first catalyst bed 241 and the second catalyst bed 242 are the above-mentioned catalysts, their catalytic activity for the methanol reforming reaction is relatively higher, the catalytic effect is better, the hydrogen production and conversion rate are higher, and they have better heat and mass transfer capabilities. Furthermore, by using foam metal to fix the first catalyst A and the second catalyst B respectively, the unit volume processing capacity of the first catalyst bed 241 and / or the second catalyst bed 242 is improved.

[0063] According to some embodiments of the present invention, the thickness of the first catalyst bed 241 along the stacking direction is 0.5~1.5cm, for example, it can be 0.5cm, 1cm or 1.5cm. The length of the first catalyst bed 241 along the direction from the first input end 22 to the first output end 23 is 40~50cm, for example, it can be 40cm, 45cm or 50cm. The width is 15~25cm, for example, it can be 15cm, 20cm or 25cm. The thickness of the second catalyst bed 242 along the stacking direction is 0.5~1.5cm, for example, it can be 0.5cm, 1cm or 1.5cm. The length of the second catalyst bed 242 along the direction from the first input end 22 to the first output end 23 is 40~50cm, for example, it can be 40cm, 45cm or 50cm. The width is 15~25cm, for example, it can be 15cm, 20cm or 25cm. By setting the first catalyst bed 241 and the second catalyst bed 242 within the aforementioned size range, efficient heat exchange between methanol combustion and high-temperature flue gas waste heat and the methanol-to-hydrogen reaction can be ensured. Simultaneously, the temperature decreases after sufficient heat exchange between methanol combustion and high-temperature flue gas waste heat and the first catalyst bed 241, ensuring that the temperature of the high-temperature flue gas remains below 300°C when it continues to exchange heat with the methanol-water solution in the second catalyst bed. This prevents sintering failure of the second catalyst B, ensuring catalyst utilization efficiency and lifespan, increasing hydrogen production yield and conversion rate, and enhancing thermochemical reaction performance.

[0064] According to some embodiments of the present invention, the combustion chamber plate 1 includes: a closed shell 11, a plurality of guide protrusions 12, and a combustion chamber 13. Each guide protrusion 12 extends parallel and interlaced from the shell 11 into the combustion chamber 13 to form a baffle space for the mixing of air and methanol to undergo combustion and for the flow of high-temperature flue gas. By designing the baffle space, the heat exchange efficiency between the combustion chamber plate 1 and the reforming chamber plate 2 is effectively improved, as well as the utilization rate of the methanol combustion heat release and high-temperature flue gas waste heat of the combustion chamber plate 1. This can significantly reduce the temperature of the discharged flue gas, which helps to achieve the efficient conversion of waste heat into hydrogen fuel chemical energy and improve energy utilization efficiency.

[0065] According to some embodiments of the present invention, the combustion chamber plate 1 further includes a second input terminal 14 and a second output terminal 15 located on the same side as the first input terminal 22 and the first output terminal 23, respectively; the combustion chamber 13 is adapted to allow the high-temperature flue gas generated by the combustion reaction of air and methanol to exchange heat with the methanol aqueous solution of the reforming chamber plate 2, and the high-temperature flue gas cooled after heat exchange is output from the second output terminal 15.

[0066] Figure 8 The diagram illustrates the structure of a combination of multiple methanol-to-hydrogen reactors according to an embodiment of the present invention. Figure 8As shown, the combustion chamber plate 1 also includes methanol-water solution flow holes 16 and reforming product flow holes 17. The reforming chamber plate 2 also includes methanol and air flow holes 25 and flue gas flow holes 26. When multiple methanol-to-hydrogen reactors are stacked, refer to... Figures 2-3 , Figures 5-6 and Figure 8 As shown, the volumetric flow rates of the methanol solution and air are adjusted using an air pump. After preheating the methanol solution, the methanol is mixed with air in vapor form and introduced into the second input terminal 14. A small portion of the methanol-air mixture flows into the combustion chamber 13. Figure 2 As shown by the solid arrow, under the influence of the guide protrusion 12, the gas flows along the baffle space to the second output end 15. Methanol and air undergo a flameless combustion reaction under the catalytic action of the filled nickel-based catalyst, transferring the released heat to the stacked reforming chamber plates 2 on both sides. This lowers the temperature of the released high-temperature flue gas, which then flows out through the flue gas flow holes 26 of the reforming chamber plate 2. Most of the methanol and air mixture continues to flow into the next set of methanol-to-hydrogen reactors through the methanol and air flow holes 25 of the reforming chamber plate 2. The methanol-water solution flows through the methanol-water solution flow hole 16 through the first combustion chamber plate 1. Most of the methanol-water solution flows to the next group of methanol-to-hydrogen reactors, while a small portion flows into the catalyst bed 24 from the first input end 22. After receiving heat from the combustion of methanol, the methanol-water solution is converted into a gaseous state and undergoes methanol reforming to produce hydrogen under the action of a catalyst with foam metal as the supporting framework. After the reaction, the chamber temperature decreases, and a mixed gas containing hydrogen, carbon dioxide, carbon monoxide, and unreacted methanol working fluid is obtained. This mixed gas flows out of the reforming chamber plate 2 from the first output end 23 and flows into the next group of methanol-to-hydrogen reactors through the reaction product flow hole 17.

[0067] Preferably, the first input end 22 and the first output end 23 of the multiple methanol-to-hydrogen reactors are aligned and connected with the methanol-water solution flow hole 16 and the reforming product flow hole 17, respectively, in the stacking direction. The second input end 14 and the second output end 15 are aligned and connected with the methanol, air flow hole 25, and flue gas flow hole 26, respectively, in the stacking direction, so as to ensure sufficient heat exchange between methanol combustion and methanol reforming for hydrogen production. By modularizing and expanding the combustion chamber plate 1 and the reforming chamber plate 2 of the methanol-to-hydrogen reactor, it is possible to expand or reconfigure according to the waste heat recovery requirements. By stacking and integrating multiple methanol-to-hydrogen reactors, the reaction scale can be increased, making it suitable for different operating conditions. Furthermore, the plate-type design facilitates installation, disassembly, and maintenance.

[0068] According to some embodiments of the present invention, the heat resistance temperature of the first catalyst A is below 500°C, for example, it can be 400°C, 450°C, or 500°C; the heat resistance temperature of the second catalyst B is below 300°C, for example, it can be 200°C, 250°C, or 300°C. By separately setting the first catalyst A and the second catalyst B, the high-temperature resistance and anti-sintering ability of the first catalyst A are fully utilized, and the better reactivity and selectivity of the second catalyst B at low temperatures are also utilized.

[0069] In some specific embodiments, the volumetric flow rate of liquid methanol introduced into the combustion chamber plate 1 is 0.05~0.1 L / min, for example, 0.05 L / min, 0.08 L / min, or 0.1 L / min, preferably 0.06 L / min. The volumetric flow rate of air introduced into the combustion chamber plate 1 is 5~20 L / min, for example, 5 L / min, 10 L / min, 15 L / min, or 20 L / min, preferably 10 L / min. In the methanol-water solution, the molar ratio of water to methanol is 1:1.1~1:1.5, for example, 1:1.1, 1:1.2, 1:1.3, 1:1.4, or 1:1.5, preferably 1:1.3. The flow rate of the methanol-water solution into the reforming chamber plate 2 is 0.3~1L / min, for example, 0.3L / min, 0.5L / min, 0.8L / min, or 1L / min, preferably 0.5L / min. After preheating, the temperature of the methanol-water solution entering the reforming chamber plate 2 is 200~220℃, for example, 200℃, 210℃, or 220℃. By setting the flow rates of methanol and air, the mixing ratio of methanol and water, the flow rate of the methanol-water solution, and the preheating temperature of the methanol-water solution within the above ranges, it helps to maintain the temperature of the second catalyst bed below 300℃ when the heat released from methanol combustion is transferred to the second catalyst bed. This helps to prevent the sintering failure of the second catalyst B and maintain the high catalytic activity of the second catalyst B.

[0070] According to some embodiments of the present invention, the thickness ratio of the first catalyst bed 241 and the second catalyst bed 242 along the stacking direction is 1:4 to 1:1, for example, it can be 1:4, 1:3, 1:2 or 1:1, etc. By designing the thickness of the first catalyst bed 241 and the second catalyst bed 242 in a partitioned modular manner, it is helpful to improve the safety and thermochemical reaction performance of the device.

[0071] According to some embodiments of the present invention, the mass flow ratio of methanol to methanol-water solution is 1:10 to 1:5, for example, it can be 1:9, 1:8, 1:7, 1:6, or 1:5. By setting the mass flow ratio of the two into the above range, it is possible to fully utilize the high-temperature flue gas while helping to maintain the methanol conversion rate at a high level.

[0072] Embodiments of the present invention also provide a methanol-to-hydrogen reaction system, comprising multiple compact self-heating methanol-to-hydrogen reaction devices as described above, a first methanol container, an air pump, a second methanol container, and a hydrogen separation device. The first methanol container is suitable for supplying methanol to the combustion chamber plate 1; the air pump is suitable for supplying air to the combustion chamber plate 1; the second methanol container is suitable for supplying heated methanol-water solution to the first input terminal 22; the hydrogen separation device is connected to the first output terminal 23 and is suitable for purifying the hydrogen-dominant mixture.

[0073] According to some embodiments of the present invention, a first methanol container delivers methanol solution to the second input end 14 of the combustion chamber plate 1 via a methanol feed pump, and an air pump delivers air to the second input end 14. After preheating, methanol enters the combustion chamber 1 in vapor form along with air for baffled transport, and undergoes a flameless methanol catalytic combustion reaction under the action of a nickel-based catalyst to generate high-temperature flue gas that provides heat. The methanol-water solution in the second methanol container is introduced into the reforming chamber plate 2 via the first input end 22. The high-temperature flue gas exchanges heat with the methanol-water solution, causing the methanol-water solution to undergo a reforming reaction to produce hydrogen, resulting in a hydrogen-dominated mixture. The mixture flows through the first output end 23 of each reforming chamber plate 2, through the reforming product flow holes 17 of the combustion chamber plate 1, and into the next group of methanol-to-hydrogen reactors. All the mixtures obtained from the reforming chamber plates 2 are collected at the first output end 23 of the lowest methanol-to-hydrogen reactor and introduced into a hydrogen separation device to purify the hydrogen. Multiple methanol-to-hydrogen reactors can be expanded or reconfigured according to actual application needs and waste heat recovery requirements. Using the methanol-to-hydrogen reaction system of this invention helps improve the heat exchange efficiency and unit volume processing capacity of the reactor, and by matching a suitable catalyst, it leverages the advantages of a compact reactor. Through partitioned catalyst arrangement in the stacking direction, the catalytic activity for methanol-to-hydrogen production is ensured while avoiding catalyst sintering failure. The reaction system of this invention effectively reduces the temperature of high-temperature flue gas while achieving compact hydrogen production.

[0074] According to some embodiments of the present invention, the compact self-heating methanol reforming hydrogen production reactor and system of the present invention are compact in size, highly flexible, and easy to move and use; the reactor of the present invention has low complexity, and the catalyst bed has strong anti-sintering ability, which helps to ensure the utilization efficiency of the catalyst while extending its service life.

[0075] In one specific embodiment, a single-unit methanol-to-hydrogen reactor is used. Both the combustion chamber plate 1 and the reforming chamber plate 2 are made of 316H stainless steel. 10g of nickel-based catalyst is placed in the combustion chamber 13, with a length of 60cm, a width of 20cm, and a thickness of 1cm. In the recessed area 21 of the reforming chamber plate 2, a foamed metal skeleton serves as the supporting structure, dividing the reactor into upper and lower layers, uniformly arranging a double-layer catalyst. The upper layer contains 5g of nickel-based catalyst, and the lower layer contains 5g of CuO / ZnO / Al2O3 catalyst. The thickness of the double-layer catalyst is set to 1cm, with the upper nickel-based catalyst layer being 0.5cm thick and the lower copper-based catalyst layer being 0.5cm thick. The length of the double-layer catalyst is 45cm and the width is 20cm.

[0076] By adjusting the methanol feed pump, the volumetric flow rate of the methanol solution entering combustion chamber 1 is controlled at 0.06 L / min, and the air volumetric flow rate is 10 L / min. After preheating to between 200 and 220°C, the methanol, in vapor form, enters combustion chamber 1 along with the air for baffled transport. Under the action of a nickel-based catalyst, a flameless methanol catalytic combustion reaction occurs, generating high-temperature flue gas that provides heat. A methanol-water solution is prepared by mixing methanol solution and deionized water at a molar ratio of 1:1.3, with a volumetric flow rate of 0.5 L / min. After receiving heat from the methanol catalytic combustion flue gas, the methanol-water solution converts into a gaseous state and enters reforming chamber 2. Under the action of a double-layer catalyst (nickel-based catalyst and copper-zinc-aluminum catalyst) with a foamed metal framework support structure, a methanol catalytic reforming reaction to produce hydrogen occurs.

[0077] Calculations show that the collected mixed gas, after purification, yields 3.03 kg / h of hydrogen. Based on the ratio of hydrogen yield per unit time to methanol feed rate, the methanol conversion rate is approximately 88.11%.

[0078] The embodiments of the present invention have been described above. However, these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Although various embodiments have been described above, this does not mean that the measures in the various embodiments cannot be used advantageously in combination. The scope of the invention is defined by the appended claims and their equivalents. Various substitutions and modifications can be made by those skilled in the art without departing from the scope of the invention, and all such substitutions and modifications should fall within the scope of the invention.

Claims

1. A compact, self-heating methanol reforming hydrogen production reactor, comprising multiple stacked methanol-to-hydrogen reactors, each set of the methanol-to-hydrogen reactors comprising: Combustion chamber plate (1), wherein a flow channel is formed inside the combustion chamber plate (1) suitable for mixing and burning air and methanol to generate and transport high-temperature flue gas; as well as The reforming chamber plate (2) is sealed and fitted to the combustion chamber plate (1). A groove region (21) is formed on the surface of the reforming chamber plate (2) facing the combustion chamber plate (1). The groove region (21) and the combustion chamber plate (1) cooperate to form a flow channel for the methanol-water solution to flow from the first input end (22) to the first output end (23). Multiple catalyst beds (24) are stacked within the groove region (21), allowing the flowing methanol-water solution to undergo a reforming reaction to produce a hydrogen-based mixture, which then exchanges heat with the methanol combustion reaction and the high-temperature flue gas. In this process, along the direction perpendicular to the first input end (22) to the first output end (23), the temperature of the plurality of catalyst beds (24) gradually decreases.

2. The compact self-heating methanol-to-hydrogen reactor according to claim 1, wherein, The plurality of catalyst beds (24) include: The first catalyst bed (241) is filled with a foam metal skeleton structure to accommodate the first catalyst (A), enhance the heat and mass transfer performance and support the first catalyst (A) and the first catalyst bed (241), and prevent the first catalyst bed (241) from collapsing. The second catalyst bed (242) is filled with a foam metal skeleton structure to accommodate the second catalyst (B), enhance the heat and mass transfer performance and support the second catalyst (B) and the second catalyst bed (242), and prevent the second catalyst bed (242) from collapsing.

3. The compact self-heating methanol-to-hydrogen reactor according to claim 2, wherein, The first catalyst bed (241) is located on the side close to the combustion chamber plate (1) along the flow direction of the methanol aqueous solution perpendicular to the first input end (22) to the first output end (23). It reacts with the methanol combustion reaction of the combustion chamber plate (1) and exchanges heat with the high-temperature flue gas to cool down the high-temperature flue gas. Under the catalytic action of the first catalyst (A), the methanol aqueous solution undergoes a reforming reaction. The second catalyst bed (242) is located away from the combustion chamber plate (1) along the flow direction of the methanol aqueous solution perpendicular to the first input end (22) to the first output end (23). The methanol aqueous solution exchanges heat with the methanol combustion reaction and the high-temperature flue gas after cooling in the second catalyst bed (242). Under the catalytic action of the second catalyst (B), the methanol aqueous solution undergoes a reforming reaction.

4. The compact self-heating methanol-to-hydrogen reactor according to claim 2, wherein, The heat resistance temperature of the first catalyst (A) is higher than that of the second catalyst (B); Preferably, the first catalyst (A) comprises a nickel-based catalyst; the second catalyst (B) comprises a copper-based catalyst.

5. The compact self-heating methanol-to-hydrogen reactor according to claim 1, wherein, The combustion chamber plate (1) includes: Enclosed shell (11); Multiple guide protrusions (12), each of which extends parallel and interlaced from the housing (11) into the combustion chamber (13), to form a deflection space for the mixing of air and methanol to produce a combustion reaction and for the flow of the high-temperature flue gas.

6. The compact self-heating methanol-to-hydrogen reactor according to claim 5, wherein, The combustion chamber plate (1) also includes a second input terminal (14) and a second output terminal (15) located on the same side as the first input terminal (22) and the first output terminal (23), respectively, not perpendicular and intersecting. The combustion chamber (13) is adapted to allow the high-temperature flue gas generated by the combustion reaction of air and methanol to exchange heat with the methanol aqueous solution of the reforming chamber plate (2), so that the high-temperature flue gas cooled after heat exchange is output from the second output end (15).

7. The compact self-heating methanol-to-hydrogen reactor according to claim 2, wherein, The heat resistance temperature of the first catalyst (A) is below 500°C; The heat resistance temperature of the second catalyst (B) is below 300°C.

8. The compact self-heating methanol-to-hydrogen reactor according to claim 2, wherein, The thickness ratio of the first catalyst bed (241) and the second catalyst bed (242) along the stacking direction is 1:4 to 1:

1.

9. The compact self-heating methanol-to-hydrogen reactor according to claim 1, wherein, The mass flow ratio of methanol to the methanol-water solution is 1:10 to 1:

5.

10. A methanol-to-hydrogen reaction system, comprising a plurality of compact, self-heating methanol-to-hydrogen reaction devices as described in any one of claims 1 to 9; A first methanol container is adapted to supply methanol to the combustion chamber plate (1); An air pump is provided for supplying air to the combustion chamber plate (1); A second methanol container is adapted to supply a heated methanol-water solution to the first input terminal; as well as A hydrogen separation device is connected to a first output terminal, and the hydrogen separation device is suitable for purifying the hydrogen-based mixture.

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