An integrated reforming reactor for solid oxide fuel cells

Abstract

The application provides an integrated reforming reaction device suitable for a solid oxide fuel cell, comprising: a reforming reaction tube, which is internally provided with a desulfurization cavity and a reforming catalyst cavity which are sequentially communicated, the desulfurization cavity is filled with a desulfurizer for making raw gas to carry out a desulfurization reaction, and the reforming catalyst cavity is filled with a reforming catalyst for making the raw gas after desulfurization to carry out a reforming reaction; the reforming reaction tube is provided with a feeding port and a discharging port, the feeding port is communicated with the desulfurization cavity, and the discharging port is communicated with the reforming catalyst cavity; a heater has a high-temperature flue gas inlet and a high-temperature flue gas outlet, the reforming reaction tube is located in the interior of the heater and can carry out heat exchange with the high-temperature flue gas, so as to provide heat for the desulfurization and the reforming reaction; the application greatly simplifies a hydrogen production process of the fuel cell, greatly improves heat exchange efficiency, reduces overall energy consumption of the system, and greatly compresses the overall volume of the equipment through integrated design of desulfurization, reforming and heat exchange functions.

Description

Technical Field

[0001] This invention relates to the field of energy and chemical equipment technology, and more specifically, to an integrated reforming reaction device suitable for solid oxide fuel cells. Background Technology

[0002] Currently, SOFC and PEM fuel cells, which utilize hydrogen energy for power generation, have achieved initial marketization, but a mature hydrogen supply network is not yet available internationally. For high-temperature solid oxide fuel cell systems, among various hydrogen production methods, natural gas and steam catalytic reforming technology is the simplest and most economical in-situ hydrogen production method. The natural gas used for reforming reactions has a complex composition, mainly alkanes, but also contains some sulfides. The presence of these sulfides can lead to a series of problems such as catalyst deactivation, increased side reactions, and reaction instability; in fuel cell systems, sulfur compounds severely affect the electrode activity of the fuel cell, significantly reducing its lifespan. Therefore, undesulfurized natural gas cannot be directly used for reforming reactions and fuel cell power generation.

[0003] The main forms of sulfides in natural gas are hydrogen sulfide, sulfur dioxide, carbon oxysulfide, mercaptans, and thiophene. Low-temperature adsorption desulfurizers show good selectivity for inorganic sulfur such as hydrogen sulfide and sulfur dioxide, but poor selectivity for organic sulfur such as thiophenes and mercaptans. When the organic sulfur content in natural gas is high, high-temperature desulfurization equipment is required to meet the sulfur content requirements of fuel cell systems. However, in existing technologies, desulfurization devices and reformers are mostly designed independently, resulting in complex hydrogen production processes for fuel cells, high system energy consumption, and large equipment size, which cannot adapt to the trend of miniaturization in fuel cell equipment.

[0004] Chinese invention patent application CN120402907A discloses an integrated catalytic combustion reformer and reforming method. This device integrates the burner and reformer into one unit. By coating the outer wall of a single-tube structure with a combustion catalyst and the inner wall with a reforming catalyst, it achieves integration of combustion heat exchange and reforming reaction, improving energy utilization, reducing material costs, and solving the problems of high heat transfer loss and large system volume in traditional steam reforming. However, this integrated catalytic combustion reformer only integrates combustion and reforming; it lacks a desulfurization module and cannot remove sulfides from natural gas. In practical applications, an additional high-temperature desulfurization device is still required, and the aforementioned technical problems are not overcome. Summary of the Invention

[0005] In view of this, the present invention aims to propose an integrated reforming reactor suitable for solid oxide fuel cells to solve the problems of complex hydrogen production processes, high system energy consumption, and large equipment size in the existing fuel cell technology, which cannot adapt to the trend of miniaturization of fuel cell equipment.

[0006] To achieve the above objectives, the technical solution of the present invention is implemented as follows:

[0007] An integrated reforming reactor suitable for solid oxide fuel cells includes:

[0008] The reforming reaction tube has a desulfurization chamber and a reforming catalytic chamber connected in sequence inside. The desulfurization chamber is filled with a desulfurizing agent to desulfurize the feed gas, and the reforming catalytic chamber is filled with a reforming catalyst to reform the desulfurized feed gas. The reforming reaction tube has an inlet and an outlet. The inlet is connected to the desulfurization chamber, and the outlet is connected to the reforming catalytic chamber.

[0009] The heater has a high-temperature flue gas inlet and a high-temperature flue gas outlet. The reforming reaction tube is located inside the heater and can exchange heat with the high-temperature flue gas to provide heat for desulfurization and reforming reactions.

[0010] In some embodiments, a raw material gas premixing chamber is provided at the feed inlet, the raw material gas premixing chamber is located upstream of the desulfurization chamber, and a flow guiding structure is provided inside the raw material gas premixing chamber to ensure uniform mixing of the raw material gas.

[0011] In some embodiments, a buffer chamber is provided at the discharge port, a partition plate is provided between the feed gas premixing chamber and the desulfurization chamber, and a partition plate is provided between the reforming catalytic chamber and the buffer chamber. The partition plate is provided with multiple through holes for the feed gas to pass through.

[0012] In some embodiments, a partition plate is provided between the desulfurization chamber and the reforming catalyst chamber, the partition plate being used to isolate and fix the desulfurizing agent and the reforming catalyst.

[0013] In some embodiments, the reforming reaction tube is a U-shaped tube, which includes a first straight pipe section and a second straight pipe section arranged in parallel, and an arc-shaped connecting section connecting the first straight pipe section and the second straight pipe section; the feed inlet is located at the end of the first straight pipe section, and the discharge outlet is located at the end of the second straight pipe section; the feed gas premixing chamber and the desulfurization chamber are located in the first straight pipe section, the buffer chamber is located in the second straight pipe section, and the reforming catalytic chamber is located in the arc-shaped connecting section and the second straight pipe section.

[0014] In some embodiments, the heater includes a body, a left cover on the left side and a right cover on the right side; the interior of the body has a receiving cavity for accommodating the reforming reaction tube; the front end of the receiving cavity is connected to the high-temperature flue gas inlet and the rear end is connected to the high-temperature flue gas outlet.

[0015] In some embodiments, the upper part of the body is provided with an upper guide plate, the upper guide plate is provided with an upper cavity, the lower end of the upper guide plate is provided with a first guide port, the left end is provided with a second guide port, and the right end is provided with a third guide port.

[0016] The lower part of the main body is provided with a lower guide plate, the lower guide plate is provided with a lower cavity, the upper end of the lower guide plate is provided with a fourth guide port, the left end is provided with a fifth guide port, and the right end is provided with a sixth guide port.

[0017] The reforming reaction tube cooperates with the body to isolate the receiving cavity, forming a first receiving cavity and a second receiving cavity. The first receiving cavity is connected to the high-temperature flue gas inlet, and the second receiving cavity is connected to the high-temperature flue gas outlet.

[0018] The first and fourth flow guide ports are located within the first receiving cavity, while the second, third, fifth, and sixth flow guide ports are located within the second receiving cavity.

[0019] High-temperature flue gas enters the first receiving cavity through the high-temperature flue gas inlet. A portion of the high-temperature flue gas enters the upper cavity through the first guide port, and then flows through the second guide port and the left hood, the third guide port and the right hood respectively, before converging into the high-temperature flue gas outlet and being discharged. Another portion of the high-temperature flue gas enters the lower cavity through the fourth guide port, and then flows through the fifth guide port and the left hood, the sixth guide port and the right hood respectively, before converging into the high-temperature flue gas outlet and being discharged.

[0020] In some embodiments, the reforming reaction tube is composed of multiple U-shaped tubes stacked in series. The U-shaped tube where the feed inlet is located is upstream and has a feed gas premixing chamber, a desulfurization chamber, and a buffer chamber connected in sequence inside. The remaining U-shaped tubes are all located downstream and connected in series. They also have a feed gas premixing chamber, a reforming catalytic chamber, and a buffer chamber connected in sequence inside.

[0021] In some embodiments, adjacent reforming reaction tubes are connected together by welding.

[0022] In some embodiments, the feed inlet is provided with a first temperature detector for detecting the temperature of the feed inlet, and the discharge outlet is provided with a second temperature detector for detecting the temperature of the discharge outlet.

[0023] Compared with existing technologies, the integrated reforming reactor for solid oxide fuel cells described in this invention has the following advantages:

[0024] 1) The desulfurization chamber and the reforming catalyst chamber in the reforming reaction tube are sequentially connected. The feed gas can complete the continuous reaction of desulfurization and reforming in a single pipeline, eliminating the connection pipeline between the desulfurization and reforming units, greatly simplifying the process of hydrogen production from fuel cells, and reducing the loss of feed gas and heat in the pipeline.

[0025] 2) The reforming reaction tube is placed in the high-temperature flue gas circulation space of the heater. The high-temperature flue gas can directly exchange heat with the reforming reaction tube, providing heat for the desulfurization reaction and the strongly endothermic reforming reaction simultaneously. This replaces the traditional external heat exchanger heat exchange method, greatly improving heat exchange efficiency and reducing the overall energy consumption of the system.

[0026] 3) The integrated design of desulfurization, reforming and heat exchange functions has greatly reduced the overall size of the equipment, which is in line with the development trend of miniaturization of solid oxide fuel cell equipment. Attached Figure Description

[0027] Figure 1 This is a schematic diagram of the integrated reforming reactor described in an embodiment of the present invention;

[0028] Figure 2 for Figure 1 A schematic diagram of the structure after removing the right cover;

[0029] Figure 3 for Figure 2 A schematic diagram of the structure after removing the reforming reaction tube;

[0030] Figure 4 This is a schematic diagram of the reforming reaction tube described in Embodiment 1 of the present invention;

[0031] Figure 5 This is a schematic diagram of the reforming reaction tube described in Embodiment 2 of the present invention;

[0032] Figure 6 for Figure 5 A structural diagram from a second-person perspective.

[0033] Explanation of reference numerals in the attached figures:

[0034] 1. Reforming reaction tube; 101. First straight pipe section; 102. Second straight pipe section; 103. Arc-shaped connecting section; 11. Desulfurization chamber; 12. Reforming catalytic chamber; 13. Feed gas premixing chamber; 14. Buffer chamber; 15. Separator plate; 161. First temperature detector; 162. Second temperature detector; 171. Feed pipe; 172. Discharge pipe; 2. Heater; 20. Body; 201. Receptacle chamber; 202. Left cover; 203. Right cover; 21. High-temperature flue gas inlet; 22. High-temperature flue gas outlet; 23. Upper guide plate; 231. Third guide port; 24. Lower guide plate; 241. Fourth guide port; 242. Sixth guide port. Detailed Implementation

[0035] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the described embodiments are only some, not all, of the embodiments of this invention. The specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. It should be noted that, unless otherwise specified, the embodiments and features described in these embodiments can be combined with each other.

[0036] Example 1

[0037] like Figure 1-4 As shown, this embodiment provides an integrated reforming reactor suitable for solid oxide fuel cells, comprising:

[0038] The reforming reaction tube 1 has a desulfurization chamber 11 and a reforming catalytic chamber 12 connected in sequence inside. The desulfurization chamber 11 is filled with a desulfurizing agent for desulfurizing the feed gas, and the reforming catalytic chamber 12 is filled with a reforming catalyst for reforming the desulfurized feed gas. The reforming reaction tube 1 has an inlet and an outlet. The inlet is connected to the desulfurization chamber 11, and the outlet is connected to the reforming catalytic chamber 12.

[0039] Heater 2 has a high-temperature flue gas inlet 21 and a high-temperature flue gas outlet 22. The reforming reaction tube 1 is located inside heater 2 and can exchange heat with the high-temperature flue gas to provide heat for desulfurization and reforming reactions.

[0040] Specifically, this application integrates a desulfurization chamber 11 and a reforming catalytic chamber 12 inside the reforming reaction tube 1, and embeds the reforming reaction tube 1 within the heater 2, achieving an integrated heat exchange design. Compared with existing technologies, this design has the following advantages: First, the desulfurization chamber 11 and the reforming catalytic chamber 12 within the reforming reaction tube 1 are sequentially connected, allowing the feed gas to complete continuous desulfurization and reforming reactions within a single pipeline. This eliminates the need for connecting pipelines between the desulfurization and reforming units, significantly simplifying the fuel cell hydrogen production process and reducing feed gas loss and heat dissipation in the pipeline. Second, the entire reforming reaction tube 1 is placed within the high-temperature flue gas circulation space of the heater 2, ensuring efficient heat exchange. The gas can directly exchange heat with the reforming reaction tube 1, simultaneously providing heat for the desulfurization reaction and the strongly endothermic reforming reaction, replacing the traditional external heat exchanger method. This significantly improves heat exchange efficiency and reduces the overall energy consumption of the system. Thirdly, the integrated design of desulfurization, reforming, and heat exchange functions greatly reduces the overall size of the equipment, aligning with the miniaturization trend of solid oxide fuel cell equipment. Fourthly, the feed gas undergoes deep desulfurization in the desulfurization chamber 11 before entering the reforming catalytic chamber 12, effectively avoiding the problem of sulfides causing catalyst deactivation and protecting the subsequent fuel cell stack electrodes from sulfur contamination, thus extending the service life of the catalyst and fuel cell. This design fundamentally solves the technical problems of complex process flow, high system energy consumption, large equipment size, and inability to adapt to fuel cell miniaturization caused by the independent design of the desulfurization unit and reformer in existing technologies.

[0041] In detail, the outer shell of heater 2 is made of high-heat-resistant stainless steel, such as 310S, Inconel 625, 06Cr25Ni20, 1Cr17, etc., or a design using heat-resistant stainless steel lined with corundum. The shape can be appropriately adjusted according to the design of the fuel cell system. After natural gas or other unreacted fuels are burned inside the burner, high-temperature exhaust gas is formed. This high-temperature exhaust gas enters the interior of heater 2 and provides heat to the reforming reaction tube 1 through heat exchange.

[0042] The core components of the desulfurizing agent are zinc oxide (ZnO) and aluminum oxide (Al2O3), with a content typically greater than or equal to 90%. It also includes small amounts of auxiliary components such as iron oxide (Fe2O3), manganese dioxide (MnO2), and calcium oxide (CaO) to enhance the mechanical strength and reactivity of the desulfurizing agent. This desulfurizing agent can adsorb and react directly with H2S, and can convert organic sulfur compounds, such as thiols and sulfides, into H2S before being absorbed by zinc oxide at high temperatures.

[0043] The reforming catalyst is made of alumina (Al2O3) and other forming aids (such as CaO, SiO2, etc.), with its surface coated with metal catalysts such as Ru, Rh, Pt, or Ni. These catalyst particles are generally spherical, but can also be prepared into honeycomb columnar shapes. This catalyst can catalyze the reforming of methane and water vapor to produce hydrogen at high temperatures, and also has some catalytic effect on ethane and propane. The main reaction formula is: .

[0044] Preferably, the inlet is provided with an inlet pipe 171 and the outlet is provided with an outlet pipe 172.

[0045] In some embodiments, a raw material gas premixing chamber 13 is provided at the feed inlet. The raw material gas premixing chamber 13 is located upstream of the desulfurization chamber 11. The raw material gas premixing chamber 13 is provided with a flow guiding structure, which is used to make the raw material gas mix evenly.

[0046] Specifically, the preheated natural gas and water vapor enter the feed gas premixing chamber 13 as feed gas. The flow guiding structure enables the natural gas and water vapor to be fully and evenly mixed in the feed gas premixing chamber 13, avoiding uneven local concentration of feed gas that leads to insufficient subsequent desulfurization reaction, as well as carbon buildup or low conversion rate in the reforming reaction, thereby improving the efficiency of desulfurization and reforming reactions.

[0047] The feed gas premixing chamber 13 serves as a transition chamber between the feed inlet and the desulfurization chamber 11. It also buffers the feed gas flow, preventing direct impact of the gas flow on the desulfurizing agent within the chamber 11. This prevents the desulfurizing agent from pulverizing or being lost due to the gas flow impact, thus extending its service life. The uniformly mixed feed gas can fully contact the desulfurizing agent within the chamber 11, improving the removal efficiency of sulfides and providing pure feed gas for subsequent reforming reactions, thereby enhancing the catalytic activity of the reforming catalyst.

[0048] After being uniformly mixed by the flow guiding structure, the raw gas enters the desulfurization chamber 11. Under high temperature conditions, the raw gas reacts or adsorbs with the desulfurizing agent, reducing the sulfur content of the raw gas to below 0.1 ppm. Simultaneously, due to direct heat exchange with the desulfurizing agent, the temperature of the raw gas rises above the reforming reaction temperature (600–700°C). After desulfurization, the raw gas continues to flow and reaches the reforming catalytic chamber 12, where it reacts under the action of the reforming catalyst to produce hydrogen, carbon monoxide, and carbon dioxide.

[0049] In some embodiments, a buffer chamber 14 is provided at the discharge port, and a partition plate 15 is provided between the raw material gas premixing chamber 13 and the desulfurization chamber 11, and between the reforming catalytic chamber 12 and the buffer chamber 14. The partition plate 15 is provided with a plurality of small holes for the raw material gas to pass through.

[0050] Specifically, the buffer chamber 14 can stabilize the flow of the hydrogen-rich mixed gas discharged from the reforming catalyst chamber 12, avoid pressure fluctuations in the discharge gas flow, ensure stable fuel gas flow and pressure entering the fuel cell stack, and improve the stability of fuel cell power generation.

[0051] The separator 15 physically separates the feed gas premixing chamber 13 from the desulfurization chamber 11, and the reforming catalytic chamber 12 from the buffer chamber 14, while the through holes ensure smooth flow of the feed gas. The through hole design of the separator 15 enables secondary uniform distribution of the airflow, ensuring that the feed gas maintains a uniform flow state when entering the desulfurization chamber 11 and exiting the reforming catalytic chamber 12, thereby improving the uniformity of the desulfurization and reforming reactions.

[0052] Understandably, the feed gas enters the reforming reaction tube 1 through the feed inlet, and then flows sequentially through the feed gas premixing chamber 13, the desulfurization chamber 11, the reforming catalytic chamber 12 and the buffer chamber 14, and finally exits through the discharge port to the anode side of the fuel cell stack for power generation.

[0053] In some embodiments, a partition plate 15 is provided between the desulfurization chamber 11 and the reforming catalyst chamber 12, and the partition plate 15 is used to isolate and fix the desulfurizing agent and the reforming catalyst.

[0054] Specifically, the partition plate 15 can limit and fix the desulfurizing agent in the desulfurization chamber 11 and the reforming catalyst in the reforming catalyst chamber 12, preventing the desulfurizing agent and reforming catalyst from moving between adjacent chambers under the action of airflow, and ensuring the functional independence of each chamber.

[0055] Preferably, the partition plate 15 is a metal mesh, which is connected to the pipe wall by welding.

[0056] In some embodiments, the feed inlet is provided with a first temperature detector 161 for detecting the temperature of the feed inlet, and the discharge outlet is provided with a second temperature detector 162 for detecting the temperature of the discharge outlet.

[0057] Specifically, the two temperature detectors can detect the temperature of the inlet and outlet in real time and accurately, enabling full monitoring of the reaction temperature. This ensures that the inlet temperature is stable at 100-200℃ and the outlet temperature is stable at 600-700℃, allowing the desulfurization and reforming reactions to proceed within the optimal temperature range, thereby improving desulfurization efficiency and reforming reaction conversion rate.

[0058] Based on the detection data of the temperature detector, the temperature of the reaction device can be controlled by adjusting the flue gas temperature of the burner. If the temperature does not reach the set value, the high temperature flue gas temperature is increased in time. If the temperature is too high, the flue gas temperature is appropriately reduced. This can prevent abnormal temperature from causing deactivation of the desulfurizer and reforming catalyst, and extend the service life of the catalyst and desulfurizer.

[0059] Real-time temperature monitoring can promptly detect problems such as abnormal heat exchange and flue gas supply in the device, enabling early warning of device malfunctions and improving the reliability and safety of device operation.

[0060] Temperature detection at the discharge port can directly reflect the temperature state of the reforming reaction, ensuring that the reforming reaction is carried out in a high-temperature range of 600-700℃, meeting the heat requirements of the reforming reaction, and ensuring that the reforming rate reaches more than 90% above 600℃ and more than 98% above 750℃.

[0061] The feed inlet temperature detection ensures that the raw gas reaches a suitable preheating temperature before entering the desulfurization chamber 11, improves the conversion efficiency of the desulfurizing agent for organic sulfur, ensures the desulfurization effect, and makes the sulfur content of the raw gas stably drop to below 0.1ppm.

[0062] Preferably, the temperature detector is a thermocouple.

[0063] In some embodiments, the reforming reaction tube 1 is a U-shaped tube, comprising a first straight tube section 101 and a second straight tube section 102 arranged in parallel, and an arc-shaped connecting section 103 connecting the first straight tube section 101 and the second straight tube section 102; the feed inlet is located at the end of the first straight tube section 101, and the discharge outlet is located at the end of the second straight tube section 102; the feed gas premixing chamber 13 and the desulfurization chamber 11 are located in the first straight tube section 101, the buffer chamber 14 is located in the second straight tube section 102, and the reforming catalytic chamber 12 is located in the arc-shaped connecting section 103 and the second straight tube section 102.

[0064] Specifically, compared to the straight tube structure, the U-tube structure significantly increases the contact heat exchange area between the reforming reaction tube 1 and the high-temperature flue gas in the heater 2 within the same equipment space, improving heat exchange efficiency and providing sufficient heat for the reforming reaction to ensure its smooth progress. The compact structure of the U-tube can fully utilize the internal space of the heater 2 housing cavity 201, further reducing the overall volume of the device and meeting the design requirements for fuel cell miniaturization.

[0065] In some embodiments, the heater 2 includes a body 20, with a left cover 202 on the left side and a right cover 203 on the right side;

[0066] The body 20 has an internal cavity 201 for accommodating the reforming reaction tube 1;

[0067] The front end of the receiving cavity 201 is connected to the high-temperature flue gas inlet 21, and the rear end is connected to the high-temperature flue gas outlet 22.

[0068] Specifically, the enclosed structure of the main body 20, together with the left cover 202 and the right cover 203, can form a relatively sealed heat exchange space, reducing the heat loss of high-temperature flue gas to the outside, significantly improving energy utilization, and reducing the heat exchange energy consumption of the system. The high-temperature flue gas inlet 21 and the high-temperature flue gas outlet 22 are respectively connected to the front and rear ends of the receiving cavity 201, realizing the directional flow of high-temperature flue gas in the receiving cavity, avoiding local stagnation of flue gas, ensuring the heat exchange uniformity of each part of the reforming reaction tube 1, and preventing local overheating or insufficient heat exchange.

[0069] Preferably, the left cover 202 and the right cover 203 are detachable structures, which facilitates the disassembly, repair and replacement of the reforming reaction tube 1 inside the heater 2, and improves the maintenance convenience of the device.

[0070] In some embodiments, the upper part of the body 20 is provided with an upper guide plate 23, the upper guide plate 23 is provided with an upper cavity, the lower end of the upper guide plate 23 is provided with a first guide port, the left end is provided with a second guide port, and the right end is provided with a third guide port 231.

[0071] The lower part of the body 20 is provided with a lower guide plate 24, the lower guide plate 24 is provided with a lower cavity, the upper end of the lower guide plate 24 is provided with a fourth guide port 241, the left end is provided with a fifth guide port, and the right end is provided with a sixth guide port 242.

[0072] The reforming reaction tube 1 cooperates with the body 20 to isolate the receiving cavity 201, forming a first receiving cavity and a second receiving cavity. The first receiving cavity is connected to the high-temperature flue gas inlet 21, and the second receiving cavity is connected to the high-temperature flue gas outlet 22.

[0073] The first and fourth guide ports 241 are located in the first receiving cavity, and the second, third, fifth, and sixth guide ports 242 are located in the second receiving cavity.

[0074] High-temperature flue gas enters the first receiving cavity through the high-temperature flue gas inlet 21. A portion of the high-temperature flue gas enters the upper cavity through the first guide port, and then flows through the second guide port and the left cover 202, the third guide port 231 and the right cover 203 respectively, before converging into the high-temperature flue gas outlet 22 for discharge. Another portion of the high-temperature flue gas enters the lower cavity through the fourth guide port 241, and then flows through the fifth guide port and the left cover 202, the sixth guide port 242 and the right cover 203 respectively, before converging into the high-temperature flue gas outlet 22 for discharge.

[0075] Specifically, the flow guiding structure of the upper guide plate 23 and the lower guide plate 24 can guide the high-temperature flue gas to achieve multi-path flow, so that the high-temperature flue gas can fully contact the upper, lower, left and right parts of the reforming reaction tube 1, which completely solves the problem of insufficient contact between flue gas and reaction tube in traditional heat exchange methods, improves heat exchange efficiency, and ensures that the reforming reaction obtains sufficient heat.

[0076] The flue gas is diverted into the upper and lower cavities through the first and fourth guide ports 241, and then evenly distributed to the left and right sides of the reforming reaction tube 1 through the second, third, fifth, and sixth guide ports 231, 231, 242, and 242. This ensures a more uniform temperature distribution in the reforming reaction tube 1, preventing local overheating that could lead to catalyst sintering and deactivation, and also preventing insufficient local heat exchange that could reduce the reforming reaction conversion rate. The multi-path flow design of the flue gas increases the residence time of the flue gas in the heater 2, further improving heat exchange efficiency and reducing heat waste from the high-temperature flue gas.

[0077] Fuel consumption of a 1kW fuel cell system under rated operating conditions: hydrogen consumption is approximately 6-8 SLM (standard liters per minute). The integrated reforming reactor from Example 1 of this application is used as the fuel pretreatment unit, wherein the total length of the U-shaped tube in the integrated reforming reactor is 50cm, and the tube opening size is 3×1.5cm. The amount of desulfurizer filled is... The loading amount of the reforming catalyst is Using natural gas with a flow rate of 2 SLM and pure water at 4.5 g / min, the sulfur content in ordinary pipeline natural gas can be reduced to below 50 ppb. When the outlet temperature is adjusted to above 600℃, the reforming rate can reach over 90%, and when the temperature is adjusted to above 750℃, the reforming rate can reach over 98%.

[0078] Example 2

[0079] like Figure 5-6 As shown, the difference between this embodiment and Embodiment 1 is that the reforming reaction tube 1 in this embodiment is composed of multiple U-shaped tubes stacked and connected in series. The structure of a single U-shaped tube is also different from that in Embodiment 1. The U-shaped tube where the feed inlet is located is filled with desulfurizing agent, and the other U-shaped tubes are filled with reforming catalyst. The U-shaped tube where the feed inlet is located is upstream, and its interior is provided with a feed gas premixing chamber 13, a desulfurization chamber 11, and a buffer chamber 14 connected in sequence. The other U-shaped tubes are all located downstream and connected in series, and their interiors are provided with a feed gas premixing chamber 13, a reforming catalyst chamber 12, and a buffer chamber 14 connected in sequence.

[0080] Specifically, a modular design employing multiple U-shaped tubes stacked in series allows for flexible adjustment of the number of U-shaped tubes according to the power requirements of the fuel cell system, adapting to different feed gas flow rates and significantly improving the adaptability and versatility of the device. A desulfurization chamber 11 is only located in the upstream U-shaped tube where the feed inlet is located. After a deep desulfurization process, the feed gas enters the downstream multiple U-shaped tubes for reforming. This setup ensures both effective desulfurization and increased feed gas reforming capacity, meeting the hydrogen production needs of high-power fuel cell systems.

[0081] The multiple U-shaped tubes are arranged in a stacked series configuration, making full use of the vertical space of heater 2 without increasing its horizontal footprint, thus further reducing the overall size of the device and conforming to the trend of miniaturization in fuel cell equipment. After upstream single-tube desulfurization, the feed gas undergoes reforming reaction sequentially in downstream multi-tube configuration, extending the contact time between the feed gas and the reforming catalyst, improving the conversion rate of the reforming reaction, and ensuring that the methane conversion rate is consistently greater than 98%.

[0082] Preferably, the reforming reaction tube is composed of a first reforming reaction tube, a second reforming reaction tube, a third reforming reaction tube and a fourth reforming reaction tube stacked and connected in series from bottom to top. The first reforming reaction tube is provided with a feed inlet, and the uppermost fourth reforming reaction tube is provided with a discharge outlet.

[0083] The first reforming reaction tube is provided with a feed gas premixing chamber 13, a desulfurization chamber 11 and a buffer chamber 14 in sequence along the gas flow direction; the second reforming reaction tube is provided with a feed gas premixing chamber 13, a reforming catalyst chamber 12 and a buffer chamber 14 in sequence along the gas flow direction; the second, third and fourth reforming reaction tubes have the same structure.

[0084] The raw gas enters the first reforming reaction tube through the feed inlet for desulfurization. The desulfurized raw gas then enters the second, third, and fourth reforming reaction tubes in sequence for reforming. Finally, it is discharged from the outlet on the fourth reforming reaction tube.

[0085] Connection holes are provided between the buffer chamber 14 of the first reforming reaction tube and the feed gas premixing chamber 13 of the second reforming reaction tube, between the buffer chamber 14 of the second reforming reaction tube and the feed gas premixing chamber 13 of the third reforming reaction tube, and between the buffer chamber 14 of the third reforming reaction tube and the feed gas premixing chamber 13 of the fourth reforming reaction tube. This arrangement facilitates the flow of feed gas between the various reforming reaction tubes and simplifies the structure of the device.

[0086] The volumes of the desulfurizing agent and reforming catalyst are calculated based on the space velocity ratio and the flow rate of the feed gas. The gas velocity should be maintained between 2 and 4 m / s. The dimensions of the integrated reforming reactor can be calculated based on these velocity and volume parameters. If the calculated total length of the reforming reactor tube 1 exceeds 50 cm, multiple reactor tubes should be considered. The total volume of the heater 2 should be designed based on the actual dimensions of the integrated reforming reactor. The design should consider parameters such as the design temperature requirements of the fuel cell system, the volume of the flue gas, and the flow rate to ensure sufficient heat exchange between the flue gas and the integrated reforming reactor.

[0087] In some embodiments, adjacent reforming reaction tubes 1 are connected together by welding.

[0088] Specifically, welded connections offer superior sealing, effectively preventing leakage of raw material gas at the connection points of reforming reaction tube 1, ensuring the airtightness of the reactor, and avoiding safety hazards caused by raw material gas loss and leakage of flammable and explosive hydrogen-rich gas mixtures. The welded connections also boast high structural strength, adapting to the high-temperature operating environment of the unit (600–800℃), preventing loosening under high-temperature thermal expansion and contraction and equipment vibration, thus ensuring the long-term structural stability of the unit. Furthermore, welded connections eliminate the need for additional connecting components such as flanges and joints, simplifying the connection structure between multiple reforming reaction tubes 1, further reducing the unit's size, and simultaneously lowering component costs and assembly complexity.

[0089] The fuel consumption of a 5kW fuel cell system under rated operating conditions is approximately 40-60 SLM (standard liters per minute) of hydrogen. The integrated reforming reactor from Example 2 of this application is used as the fuel pretreatment unit. This integrated reforming reactor employs five sets of U-tubes, each with a total length of 50cm and an opening size of 3×1.5cm. The amount of desulfurizing agent added is... The loading amount of the reforming catalyst is The first U-shaped pipe at the feed inlet is filled with desulfurizing agent, while the remaining U-shaped pipes are filled with reforming catalyst. Using natural gas with a flow rate of 12 SLM and pure water at 27 g / min, the sulfur content in ordinary pipeline natural gas can be reduced to below 50 ppb. When the outlet temperature is adjusted to above 600℃, the reforming rate can reach over 90%, and when the temperature is adjusted to above 750℃, the reforming rate can reach over 98%.

[0090] Fuel consumption under rated operating conditions for a 100kW fuel cell system: approximately 600-800 SLM (standard liters per minute) of hydrogen. The integrated reforming reactor described in Example 2 of this application is used as the fuel pretreatment unit. This integrated reforming reactor employs five sets of U-tubes, each with a total length of 100cm and an opening size of 5×2cm. The feed gas consists of 200 SLM of natural gas and 450g / min of pure water. The first U-tube at the inlet is filled with a desulfurizing agent, approximately 0.8L in volume, while the remaining U-tubes are filled with a reforming catalyst, approximately 4L in volume. This can reduce the sulfur content in conventional pipeline natural gas to below 50ppb. When the outlet temperature is adjusted to above 600℃, the reforming rate can reach over 90%, and when the temperature is adjusted to above 750℃, the reforming rate can reach over 98%.

[0091] This application can be used for the pretreatment of fuel gas in solid oxide fuel cells, converting natural gas into hydrogen, carbon monoxide, and carbon dioxide, and removing sulfides. The feed gas can be preheated to 600–700°C, resulting in a sulfur content below 0.1 ppm after desulfurization and a methane conversion rate >98%.

[0092] The operating temperature of the desulfurizing agent in the integrated reforming reactor is 0–500℃, and the sulfur space velocity ratio is [missing information]. The sulfur capacity is 18%. The desulfurizer is a composite material made of various metal oxides. The aluminum oxide in the material is mainly used to improve the material's temperature resistance. Zinc oxide is the main absorbent, and auxiliary materials such as iron oxide and manganese dioxide are mainly used to convert organic sulfur in the raw gas and enhance the activity of the catalyst.

[0093] The reforming catalyst in the integrated reforming reactor operates at a temperature of 500–800°C, with a carbon space velocity ratio of [missing value]. This catalyst employs a metal-coated substrate, with alumina as the base material and doped with materials such as CaO and SiO2 as forming aids to primarily improve high-temperature resistance and mechanical strength. A metal salt such as Ru, Rh, or Ni is coated onto the substrate using an impregnation process, followed by sintering to form a metal oxide capping layer. After reduction, the resulting material is shaped into the catalyst. This catalyst can catalyze the steam-to-hydrogen process of alkanes in natural gas, such as methane and ethane.

[0094] While the present invention has been disclosed above, it is not limited thereto. Any person skilled in the art can make various modifications and alterations without departing from the spirit and scope of the invention; therefore, the scope of protection of the present invention should be determined by the scope defined in the claims.

Claims

1. An integrated reforming reactor suitable for solid oxide fuel cells, characterized in that, include: The reforming reaction tube (1) has a desulfurization chamber (11) and a reforming catalytic chamber (12) connected in sequence inside. The desulfurization chamber (11) is filled with a desulfurizing agent for desulfurizing the raw gas. The reforming catalytic chamber (12) is filled with a reforming catalyst for reforming the desulfurized raw gas. The reforming reaction tube (1) has an inlet and an outlet. The inlet is connected to the desulfurization chamber (11), and the outlet is connected to the reforming catalytic chamber (12). The heater (2) has a high-temperature flue gas inlet (21) and a high-temperature flue gas outlet (22). The reforming reaction tube (1) is located inside the heater (2) and can exchange heat with the high-temperature flue gas to provide heat for desulfurization and reforming reaction.

2. The integrated reforming reactor for solid oxide fuel cells according to claim 1, characterized in that, A raw material gas premixing chamber (13) is provided at the feed inlet. The raw material gas premixing chamber (13) is located upstream of the desulfurization chamber (11). A flow guiding structure is provided inside the raw material gas premixing chamber (13) to make the raw material gas mix evenly.

3. The integrated reforming reactor for solid oxide fuel cells according to claim 2, characterized in that, A buffer chamber (14) is provided at the outlet. A partition plate (15) is provided between the raw material gas premixing chamber (13) and the desulfurization chamber (11), and a partition plate (15) is provided between the reforming catalytic chamber (12) and the buffer chamber (14). The partition plate (15) has multiple through holes for the raw material gas to pass through.

4. The integrated reforming reactor for solid oxide fuel cells according to claim 3, characterized in that, A partition plate (15) is provided between the desulfurization chamber (11) and the reforming catalyst chamber (12), and the partition plate (15) is used to isolate and fix the desulfurizing agent and the reforming catalyst.

5. The integrated reforming reactor for solid oxide fuel cells according to claim 3, characterized in that, The reforming reaction tube (1) is a U-shaped tube, which includes a first straight tube section (101) and a second straight tube section (102) arranged in parallel, and an arc-shaped connecting section (103) connecting the first straight tube section (101) and the second straight tube section (102); the feed inlet is located at the end of the first straight tube section (101), and the discharge outlet is located at the end of the second straight tube section (102); the raw material gas premixing chamber (13) and the desulfurization chamber (11) are located in the first straight tube section (101), the buffer chamber (14) is located in the second straight tube section (102), and the reforming catalyst chamber (12) is located in the arc-shaped connecting section (103) and the second straight tube section (102).

6. The integrated reforming reactor for solid oxide fuel cells according to claim 1, characterized in that, The heater (2) includes a body (20), with a left cover (202) on the left side and a right cover (203) on the right side; the body (20) has a receiving cavity (201) inside for receiving the reforming reaction tube (1); the front end of the receiving cavity (201) is connected to the high temperature flue gas inlet (21), and the rear end is connected to the high temperature flue gas outlet (22).

7. The integrated reforming reactor for solid oxide fuel cells according to claim 6, characterized in that, The upper part of the body (20) is provided with an upper guide plate (23), the upper guide plate (23) is provided with an upper cavity, the lower end of the upper guide plate (23) is provided with a first guide port, the left end is provided with a second guide port, and the right end is provided with a third guide port (231). The lower part of the body (20) is provided with a lower guide plate (24), the lower guide plate (24) is provided with a lower cavity, the upper end of the lower guide plate (24) is provided with a fourth guide port (241), the left end is provided with a fifth guide port, and the right end is provided with a sixth guide port (242). The reforming reaction tube (1) cooperates with the body (20) to isolate the accommodating cavity (201) to form a first accommodating cavity and a second accommodating cavity. The first accommodating cavity is connected to the high-temperature flue gas inlet (21), and the second accommodating cavity is connected to the high-temperature flue gas outlet (22). The first and fourth flow ports (241) are located in the first receiving cavity, and the second, third, fifth and sixth flow ports (242) are located in the second receiving cavity; High-temperature flue gas enters the first receiving cavity through the high-temperature flue gas inlet (21). A portion of the high-temperature flue gas enters the upper cavity through the first guide port, and then flows through the second guide port and the left cover (202), the third guide port (231) and the right cover (203) respectively, before being discharged through the high-temperature flue gas outlet (22). Another portion of the high-temperature flue gas enters the lower cavity through the fourth guide port (241), and then flows through the fifth guide port and the left cover (202), the sixth guide port (242) and the right cover (203) respectively, before being discharged through the high-temperature flue gas outlet (22).

8. The integrated reforming reactor for solid oxide fuel cells according to claim 3, characterized in that, The reforming reaction tube (1) is composed of multiple U-shaped tubes stacked in series. The U-shaped tube where the feed inlet is located is upstream, and its interior is provided with a feed gas premixing chamber (13), a desulfurization chamber (11), and a buffer chamber (14) connected in sequence. The remaining U-shaped tubes are all located downstream and connected in series. Their interiors are provided with a feed gas premixing chamber (13), a reforming catalytic chamber (12), and a buffer chamber (14) connected in sequence.

9. The integrated reforming reactor for solid oxide fuel cells according to claim 8, characterized in that, The adjacent reforming reaction tubes (1) are connected together by welding.

10. The integrated reforming reactor for solid oxide fuel cells according to claim 1, characterized in that, The feed inlet is equipped with a first temperature detector (161) for detecting the temperature of the feed inlet, and the discharge outlet is equipped with a second temperature detector (162) for detecting the temperature of the discharge outlet.

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