A methanol hydrogen production reaction device

Abstract

The application belongs to the technical field of hydrogen production, and specifically discloses a methanol hydrogen production reaction device, which comprises a raw material pretreatment unit, a integrated reaction heat exchanger, a gas-liquid separation unit and a PSA purification unit. The raw material pretreatment unit is used for mixing methanol and desalted water at a set ratio and preheating to a target temperature. The integrated reaction heat exchanger comprises three independent heat exchange sections. The pitch of the spiral baffle inside the integrated reaction heat exchanger gradually decreases along the liquid flow direction in the tube. The gas-liquid separation unit is used for cooling reaction gas and separating unreacted methanol-water mixture. The PSA purification unit is used for purifying hydrogen. According to the Nusselt criterion in heat transfer, the heat transfer coefficient in the turbulent state is much higher than that in the laminar flow, so as to improve the total heat transfer coefficient and reduce energy waste. In the actual implementation process, the gradual gradient of the pitch can be dynamically optimized according to the specific reaction scale and raw material processing capacity. By adjusting the pitch change rate, the heat exchange demand under different production capacities is adapted, and the balance between energy efficiency and processing capacity is realized.

Description

Technical Field

[0001] This application relates to the field of hydrogen production technology, and in particular to a methanol-to-hydrogen reactor. Background Technology

[0002] Currently, there are three main pathways for methanol-to-hydrogen production: methanol reforming, methanol cracking, and partial oxidation. Among these, partial oxidation produces hydrogen with a low hydrogen content, while methanol cracking generates CO, leading to severe poisoning of the platinum electrodes in fuel cells. Methanol reforming, as a highly feasible technology, offers advantages such as high energy density, easy storage, and wide availability, making it an excellent carrier for hydrogen energy. It is the most advantageous and technologically mature method among methanol-to-hydrogen technologies and is considered one of the most promising hydrogen production technologies for use in hydrogen fuel cells.

[0003] Patent document CN118026094A discloses a spiral tubular methanol reforming hydrogen production device and its operation method. It directly uses methanol solution and fuel cell anode tail gas as the combustion chamber supply source, utilizing the heat energy of the combustion chamber to exchange heat with the catalyst in the reforming chamber. Using the vaporized methanol-water solution as the reforming chamber supply source to complete hydrogen production has certain positive aspects, but also some drawbacks. For example, because heat exchange is required multiple times during hydrogen production (methanol cracking, CO conversion zone, and reactant gas cooling), multiple heat exchange devices are needed, resulting in a complex and cumbersome final hydrogen production equipment layout. Furthermore, the reactor and heat exchanger are separated, leading to high-temperature heat loss through pipelines during the reaction, low overall equipment integration, and high heat exchange temperature difference losses. Additionally, traditional spiral baffle heat exchangers use a constant pitch design, which cannot adapt to the different chemical conditions of raw material preheating (low pressure drop requirements) and reactant gas cooling (high heat transfer efficiency requirements), resulting in a low overall heat transfer coefficient and significant energy waste. Summary of the Invention

[0004] The purpose of this application is to provide a methanol-to-hydrogen reactor to solve the above-mentioned problems.

[0005] To achieve the above objectives, the technical solution of this application is as follows: A methanol-to-hydrogen reactor includes: The raw material pretreatment unit is used to mix methanol and demineralized water in a set ratio and preheat it to the target temperature; An integrated reaction heat exchanger includes three independent heat exchange sections; the pitch of the spiral baffles inside the integrated reaction heat exchanger gradually decreases along the direction of liquid flow in the tube side. A gas-liquid separation unit is used to cool the reaction gas and separate the unreacted methanol-water mixture; The PSA purification unit is used to purify hydrogen.

[0006] Furthermore, the independent heat exchange sections are a methanol cracking zone, a CO conversion zone, and a reaction gas cooling zone. The pitch of the spiral baffle corresponding to the methanol cracking zone is 100-120 mm, the pitch of the spiral baffle corresponding to the CO conversion zone is 70-90 mm, and the pitch of the spiral baffle corresponding to the reaction gas cooling zone is 40-60 mm.

[0007] Furthermore, the shell corresponding to the methanol cracking zone is provided with a first inlet and a first outlet, the first outlet being connected to the feed preheater in the feed pretreatment unit; the shell corresponding to the CO conversion zone is provided with a second inlet and a second outlet, the second inlet being connected to the mixing tank jacket of the feed pretreatment unit; the shell corresponding to the reaction gas cooling zone is provided with a third inlet and a third outlet, the third outlet being connected to the regeneration gas preheater in the PSA purification unit.

[0008] Furthermore, the surface of the spiral baffle is coated with a polytetrafluoroethylene-ceramic composite coating, and the bonding strength between the coating and the baffle substrate is ≥5MPa.

[0009] Furthermore, the interior of the tube is provided with a first hollow mounting frame, a second hollow mounting frame, and a flow-dispersing frame corresponding to the methanol cracking zone, the CO conversion zone, and the reaction gas cooling zone, respectively; the first hollow mounting frame is provided with a copper-zinc-aluminum cracking catalyst bed, the second hollow mounting frame is provided with a copper-based conversion catalyst bed, and the flow-dispersing frame is used to mix the flow material inside the tube.

[0010] Furthermore, the outer wall of the first hollow mounting bracket is provided with a clearance groove, and the end face of the second hollow mounting bracket facing the first hollow mounting bracket is connected to a mounting rod, which is located outside the tube through the clearance groove.

[0011] Furthermore, each of the three independent heat exchange sections is provided with a baffle plate at both ends, and the tubes are all rotatably arranged through the baffle plate and the spiral baffle plate. The integrated reaction heat exchanger has a feed chamber and a discharge chamber at both ends; the two ends of the tube are located in the feed chamber and the discharge chamber respectively; the part of the tube located in the feed chamber has a spiral blade inside, and the spiral blade is configured to drive the tube to rotate relative to the baffle and the spiral baffle when the material flows through the tube.

[0012] Furthermore, the surface of the spiral baffle is provided with spiral guide grooves.

[0013] Furthermore, each of the three independent heat exchange sections is equipped with a temperature sensor, which is electrically connected to the PLC control system.

[0014] Furthermore, the outlet of the condenser separator of the gas-liquid separation unit is connected to the mixing tank of the raw material pretreatment unit via a reflux pump.

[0015] The methanol-to-hydrogen reactor disclosed in this application significantly reduces the equipment footprint and piping connections, lowering the risk of heat loss through pipelines. The gradually decreasing pitch design of the spiral baffle is optimized based on the operating conditions of different heat exchange stages: low pressure drop is required during the feed preheating stage to reduce fluid transport energy consumption, while high heat transfer efficiency is needed for rapid cooling of the reactant gas. The gradually decreasing pitch gradually enhances the fluid turbulence. According to the Nusselt criterion in heat transfer, the heat transfer coefficient in turbulent flow is much higher than that in laminar flow, thereby improving the overall heat transfer coefficient and reducing energy waste. In actual implementation, the gradual pitch gradient can be dynamically optimized according to the specific reaction scale and feed throughput. By adjusting the pitch change rate, it adapts to the heat exchange requirements under different production capacities, achieving a balance between energy efficiency and throughput. Attached Figure Description

[0016] Figure 1 This is a schematic diagram illustrating the principle of this application; Figure 2 This refers to the integrated reaction heat exchanger in this application; Figure 3 This is a schematic diagram of the internal structure of the integrated reaction heat exchanger in this application; Figure 4 This is a cross-sectional view of the integrated reaction heat exchanger in this application; Figure 5 This is another cross-sectional view of the integrated reaction heat exchanger in this application; Figure 6 This is a schematic diagram of the first hollow mounting frame structure in this application; Figure 7 This is a front view of the spiral baffle in this application; Figure 8 This is a perspective view of the spiral baffle in this application; Figure 9 This is a schematic diagram of the assembly state of the spiral baffle and the tube side in this application; Figure 10 This is a schematic diagram of the first and second hollow mounting frames in this application; Figure 11 for Figure 7 Enlarged view of a portion of point A in the middle; Figure 12 This is a schematic diagram of the spoiler structure in this application; Figure 13 This is a schematic diagram of the internal helical blade structure of the tube in this application.

[0017] In the picture: 1. Raw material pretreatment unit; 2. Integrated reaction heat exchanger; 20. Methanol cracking zone; 201. First inlet; 202. First outlet; 21. CO conversion zone; 210. Second inlet; 211. Second outlet; 22. Reactant gas cooling zone; 23. Baffle; 220. Third inlet; 221. Third outlet; 3. Gas-liquid separation unit; 4. PSA purification unit; 5. Tube side; 50. Spiral blades; 6. Spiral baffle; 7. First hollow mounting bracket; 70. Clearance groove; 8. Second hollow mounting bracket; 80. Mounting rod; 9. Baffle. Detailed Implementation

[0018] The present application will now be described in further detail with reference to the accompanying drawings. The drawings are simplified schematic diagrams, illustrating only the basic structure of the present application, and therefore only show the components relevant to the present application.

[0019] like Figure 1-13 As shown, a methanol-to-hydrogen reactor includes: Raw material pretreatment unit 1 is used to mix methanol and demineralized water in a set ratio and preheat to the target temperature; The integrated reaction heat exchanger 2 includes three independent heat exchange sections; the pitch of the spiral baffle 6 inside the integrated reaction heat exchanger 2 gradually decreases along the direction of liquid flow in the tube side 5. Gas-liquid separation unit 3 is used to cool the reaction gas and separate the unreacted methanol-water mixture; PSA purification unit 4 is used to purify hydrogen.

[0020] The raw material pretreatment unit 1 provides the reaction with precisely proportioned and temperature-controlled feedstock, ensuring stable initial reaction conditions. The integrated reaction heat exchanger 2 integrates the three core heat exchange reaction processes, significantly reducing heat loss from pipeline connections and improving equipment integration. Its internal spiral baffle 6 adopts a gradually decreasing pitch design, with the pitch decreasing along the fluid flow direction to increase fluid turbulence intensity. It also adapts to the low pressure drop requirements of the raw material preheating stage and the high heat transfer requirements of the reaction gas cooling stage. That is, the inlet pressure is reduced to ensure normal fluid entry, and the downstream section requires rapid cooling. The heat exchange path of the fluid is increased by increasing the pitch, thereby improving the heat exchange intensity. The gas-liquid separation unit 3 and the PSA purification unit 4 respectively realize the recovery of unreacted raw materials and the purification of crude hydrogen, forming a complete hydrogen production process.

[0021] This hydrogen production unit significantly reduces the equipment footprint and piping connections, lowering the risk of heat loss through pipelines. The spiral baffle with a gradually decreasing pitch design is optimized based on the operating requirements of different heat exchange stages: low pressure drop is needed during the feedstock preheating stage to reduce fluid transport energy consumption, while high heat transfer efficiency is required for rapid cooling during the reactant gas cooling stage. The gradually decreasing pitch gradually increases the degree of fluid turbulence. According to the Nusselt criterion in heat transfer, the heat transfer coefficient in turbulent flow is much higher than in laminar flow, thereby improving the overall heat transfer coefficient and reducing energy waste. In actual implementation, the gradual pitch gradient can be dynamically optimized according to the specific reaction scale and feedstock throughput. By adjusting the pitch change rate, it adapts to the heat exchange requirements under different production capacities, achieving a balance between energy efficiency and throughput.

[0022] Furthermore, the independent heat exchange sections are methanol cracking zone 20, CO conversion zone 21 and reaction gas cooling zone 22. The pitch of the spiral baffle 6 corresponding to methanol cracking zone 20 is 100-120 mm, the pitch of the spiral baffle 6 corresponding to CO conversion zone 21 is 70-90 mm, and the pitch of the spiral baffle 6 corresponding to reaction gas cooling zone 22 is 40-60 mm.

[0023] In the independent heat exchange sections, the pitch ranges of the methanol cracking zone 20, CO conversion zone, and reactant gas cooling zone 22 are precisely matched based on the reaction characteristics and heat exchange requirements of each zone. The methanol cracking zone 20 needs to control the pressure drop while ensuring the reaction proceeds fully. A pitch of 100-120 mm provides sufficient fluid residence time for the cracking reaction while avoiding excessive energy consumption due to excessive pressure drop. The CO conversion zone 21 needs to balance reaction rate and heat transfer efficiency; a pitch of 70-90 mm is suitable for the heat release rate of the conversion reaction, achieving efficient heat removal. The reactant gas cooling zone 22 needs to rapidly reduce the reactant gas temperature to meet the subsequent PSA purification requirements; a small pitch of 40-60 mm maximizes fluid turbulence and improves the heat transfer coefficient.

[0024] By setting different screw pitches, the heat exchange efficiency of each region can reach the optimal state, avoiding the problem of "choosing one over another" in the traditional equal-pitch design, and ensuring the conversion rate of methanol cracking, the thoroughness of CO conversion and the cooling rate of the reaction gas.

[0025] In practice, the pitch range can be fine-tuned according to parameters such as catalyst activity and reaction temperature. For example, when the catalyst activity decreases, the pitch of the methanol cracking zone can be appropriately reduced by 20 to increase the contact frequency between the fluid and the catalyst and make up for the problem of insufficient catalyst activity.

[0026] Furthermore, the shell corresponding to the methanol cracking zone 20 is provided with a first inlet 201 and a first outlet 202, and the first outlet 202 is connected to the raw material preheater in the raw material pretreatment unit 1; the shell corresponding to the CO conversion zone 21 is provided with a second inlet 210 and a second outlet 211, and the second inlet 210 is connected to the mixing tank jacket of the raw material pretreatment unit 1; the shell corresponding to the reaction gas cooling zone 22 is provided with a third inlet 220 and a third outlet 221, and the third outlet 221 is connected to the regeneration gas preheater in the PSA purification unit 4.

[0027] The first outlet 202 of the methanol cracking zone 20 is connected to the feed preheater, which uses the waste heat generated by the cracking reaction to preheat the feed and reduce the external energy consumption required for feed preheating. The second inlet 210 of the CO conversion zone is connected to the mixing tank jacket, which uses the waste heat of the conversion reaction to maintain the temperature stability of the feed mixing process. The mixing tank jacket is used to first heat-preheat the mixed methanol, and then the mixed material is preheated again by the feed preheater.

[0028] The third outlet 221 of the reaction gas cooling zone 22 is connected to the PSA regeneration gas preheater, which uses the heat released during the reaction gas cooling process to preheat the PSA regeneration gas and improve the regeneration efficiency.

[0029] By recovering heat from different stages, the waste heat from the reaction is utilized in a cascade manner, minimizing heat loss inside the equipment and improving energy efficiency.

[0030] In addition, this waste heat recovery path can be optimized according to the energy consumption requirements of each unit. By adjusting the valve opening, the waste heat distribution ratio can be controlled to ensure that the waste heat recovery efficiency is precisely matched with the operating requirements of each unit.

[0031] Furthermore, the surface of the spiral baffle 6 is coated with a polytetrafluoroethylene-ceramic composite coating, and the bonding strength between the coating and the baffle substrate is ≥5MPa.

[0032] The polytetrafluoroethylene-ceramic composite coating on the surface of the spiral baffle 6 is designed to address the problems of corrosiveness of the reaction medium and fluid erosion wear in the methanol-to-hydrogen process.

[0033] Polytetrafluoroethylene (PTFE) has excellent corrosion resistance, which can resist the corrosion of the baffle plate by methanol, CO, and trace acidic substances. The ceramic component can improve the wear resistance of the coating and enhance the baffle plate's ability to resist fluid erosion.

[0034] The coating has a bonding strength of ≥5MPa with the substrate, ensuring that the coating will not peel off under long-term high temperature and turbulent conditions, thus guaranteeing its service life.

[0035] The coating design extends the service life of the spiral baffle 6, reduces equipment maintenance costs, and prevents coating peeling from contaminating the reaction medium and catalyst.

[0036] In practice, the composition ratio of the composite coating can be adjusted according to the corrosiveness of the reaction medium, fluid flow rate, and other working conditions. For example, under more corrosive conditions, the proportion of polytetrafluoroethylene can be increased, and under conditions with higher fluid flow rates, the proportion of ceramic components can be increased to achieve targeted protective effects.

[0037] Furthermore, the interior of tube 5 is provided with a first hollow mounting frame 7, a second hollow mounting frame 8, and a flow-dispersing frame 9, corresponding to the methanol cracking zone 20, the CO conversion zone 21, and the reaction gas cooling zone 22, respectively. The first hollow mounting frame 7 is provided with a copper-zinc-aluminum cracking catalyst bed, the second hollow mounting frame 8 is provided with a copper-based conversion catalyst bed, and the flow-dispersing frame 9 is used to mix the flow material inside tube 5.

[0038] The first hollow mounting bracket 7, the second hollow mounting bracket 8, and the turbulence-disrupting bracket 9 within the tube side 5 achieve the integration of the catalyst bed with the heat exchange tube side 5, as well as the uniform mixing of the fluid.

[0039] The copper-zinc-aluminum cracking catalyst bed in the first hollow mounting frame 7 provides a reaction site for the methanol cracking reaction. The hollow structure ensures heat transfer between the shell side and the tube side 5, so that the heat required for the reaction is supplied in a timely manner. The copper-based shift catalyst bed in the second hollow mounting frame 8 efficiently converts CO and avoids its poisoning effect on the subsequent fuel cell electrode. The same hollow design ensures the heat exchange requirements of the shift reaction. The turbulence frame 9 breaks the fluid boundary layer, so that the fluid in the tube side 5 is fully mixed, avoiding local overheating or incomplete reaction.

[0040] By further integrating the reaction and heat exchange functions, the compactness of the equipment is improved, while ensuring the uniformity and thoroughness of the reaction.

[0041] Specifically, the perforation rate of the first perforated mounting frame 7 and the second perforated mounting frame 8 can be optimized according to the heat transfer requirements and the amount of catalyst filling. If the perforation rate is too high, it will reduce the structural strength, and if it is too low, it will affect the heat transfer efficiency. By balancing the two, the best match between the reaction effect and the heat exchange efficiency can be achieved. The structural form of the flow-dispersing frame 9 can be adjusted according to the fluid flow rate. For example, different flow-dispersing structures such as spiral and grid types can be used to adapt to the mixing requirements under different working conditions.

[0042] Furthermore, the outer wall of the first hollow mounting bracket 7 is provided with a clearance groove 70, and the end face of the second hollow mounting bracket 8 facing the first hollow mounting bracket 7 is connected with a mounting rod 80, which is located outside the tube 5 through the clearance groove 70.

[0043] The clearance groove 70 of the first hollow mounting bracket 7 and the mounting rod 80 of the second mounting bracket are designed to facilitate the installation, disassembly and replacement of the catalyst bed.

[0044] The mounting rod 80 extends to the outside of the tube side 5 via the clearance groove 70, allowing the second mounting bracket to be precisely positioned relative to the first mounting bracket. Furthermore, when catalyst replacement is required, the second perforated mounting bracket 8 can be pulled out simply by removing the mounting rod 80 from the outside of the tube side 5, without disassembling the entire heat exchanger. This structure simplifies the catalyst bed maintenance process, reduces maintenance time and costs, and improves equipment maintainability.

[0045] Furthermore, each of the three independent heat exchange sections is equipped with a baffle plate 23 at both ends, and the tube side 5 passes through the baffle plate 23 and the spiral baffle plate 6 is rotatably arranged. The integrated reaction heat exchanger 2 has a feed chamber and a discharge chamber at both ends; the two ends of the tube side 5 are located in the feed chamber and the discharge chamber respectively; the part of the tube side 5 located in the feed chamber is provided with a spiral blade 50, which is configured to drive the tube side 5 to rotate relative to the partition plate 23 and the spiral baffle plate 6 when the material flows through the tube side 5.

[0046] The baffles 23 at both ends of the three independent heat exchange sections, the rotating arrangement of the tube side 5, and the spiral blades 50 in the feed chamber constitute a synergistic structure for dynamic heat exchange and reaction. The baffles 23 separate the heat exchange sections and ensure that the shell-side fluids do not cross-flow. The rotating arrangement of the tube side 5, passing through the baffles 23 and the spiral baffles 6, provides the structural basis for the dynamic operation of the tube side 5. During material flow, the spiral blades 50 in the feed chamber are driven by the fluid thrust to rotate the tube side 5 relative to the baffles 23 and the spiral baffles 6, causing relative motion between the catalyst bed and the reaction medium within the tube side 5. This enhances the contact frequency between the reactants and the catalyst, while preventing catalyst particle agglomeration and coking. The effect of this design is to improve the reaction conversion rate and catalyst lifespan, and to enhance heat exchange efficiency.

[0047] Moreover, the rotating tube side 5 can disrupt the stratification of the material inside the tube side 5, and the centrifugal force can also cause the material located in the center of the tube side 5 to flow towards the position closer to the inner wall of the tube side 5, thereby improving the heat exchange efficiency.

[0048] A sealed bearing or a rotating hole can be installed on the partition plate 23 to allow the tube 5 to rotate.

[0049] Furthermore, the surface of the spiral baffle 6 is provided with spiral guide grooves.

[0050] The spiral guide grooves on the surface of the spiral baffle 6 are a further optimization of the gradually changing pitch design, used to guide the flow direction of the shell-side fluid. The guide grooves ensure orderly fluid flow along the spiral direction, avoiding eddies and dead zones within the shell side, while simultaneously increasing the contact frequency between the fluid and the tube-side wall 5, thus improving heat transfer efficiency. The effect of this design is to further optimize the flow field distribution in the shell side, reduce fluid resistance, and increase the overall heat transfer coefficient, working synergistically with the gradually changing pitch design.

[0051] In practice, the depth and width of the guide channel can be adjusted according to the flow velocity and viscosity of the shell-side fluid. For fluids with higher viscosity, the size of the guide channel can be increased to reduce flow resistance. For fluids with higher flow velocity, the size of the guide channel can be reduced to enhance the disturbance effect, so as to achieve the optimal flow and heat transfer state.

[0052] Furthermore, each of the three independent heat exchange sections is equipped with a temperature sensor, which is electrically connected to the PLC control system.

[0053] The electrical connection between the temperature sensors on the three independent heat exchange sections and the PLC control system constitutes an automated temperature control system for the equipment.

[0054] Temperature sensors monitor the reaction temperature of each heat exchange section in real time and transmit the temperature signals to the PLC control system. The PLC automatically adjusts operating parameters such as feed flow rate and heat exchange medium flow rate based on preset temperature parameters to ensure that the temperature at each reaction stage remains stable within the optimal range. This design avoids the lag and errors of manual adjustments, improves the accuracy of reaction temperature control, ensures reaction stability and product purity, and reduces the risk of catalyst deactivation and equipment damage caused by temperature fluctuations.

[0055] In other embodiments, the PLC control system can integrate more control logic, such as predicting the reaction state based on temperature change trends and adjusting operating parameters in advance to achieve predictive control; at the same time, it can be networked with the factory's central control system to achieve remote monitoring and centralized management, thereby improving the intelligence level of the equipment.

[0056] Furthermore, the outlet of the condenser separator of the gas-liquid separation unit 3 is connected to the mixing tank of the raw material pretreatment unit 1 via a reflux pump.

[0057] The outlet of the condenser separator of the gas-liquid separation unit 3 is connected to the reflux of the mixing tank of the raw material pretreatment unit 1, thus constructing a raw material recycling system.

[0058] After cooling the reaction gas, the gas-liquid separation unit 3 separates the unreacted methanol-water mixture, which is then sent back to the mixing tank by a reflux pump. After being mixed with new raw materials, it participates in the pretreatment and reaction process again.

[0059] The design improves the utilization rate of raw materials, reduces waste and pollutant emissions, lowers production costs, and avoids pollution caused by the direct discharge of unreacted raw materials.

[0060] Specifically, the flow rate of the reflux pump can be adjusted according to the separation efficiency and raw material conversion rate of the gas-liquid separation unit 3 to ensure a stable mixing ratio of unreacted raw materials and new raw materials, and to avoid affecting the reaction effect due to fluctuations in the reflux ratio. At the same time, a purity detection device can be installed on the reflux pipeline. When the impurity content in the unreacted raw materials exceeds the set value, the system will automatically switch to the discharge or treatment process to ensure the purity of the raw materials.

[0061] In actual implementation, the spiral baffle 6 can be formed in the following manner: First, based on the helical helix angle and lead required by the heat exchanger design, the complete helical surface is unfolded into several approximately elliptical plate units. The geometric dimensions, inner and outer arc lengths, and tilt angle parameters of each plate are accurately calculated using a pre-built mathematical model. Based on the obtained data, the metal plate is precisely blanked using laser cutting equipment to obtain blanks with flat edges and accurate dimensions.

[0062] Secondly, the oblique hole machining is performed. Since the spiral baffle 6 is tilted after assembly, the hundreds of holes on the plate need to form a predetermined angle with the plate surface. To achieve efficient batch drilling of these oblique holes, multiple fan-shaped blanks of the same specification are aligned, stacked, and spot-welded into a pile. This pile is then fixed to the tilting table of a CNC machine tool. By rotating the table, the tool axis forms the aforementioned predetermined angle with the plate surface. Then, all the plates are drilled through at once according to the hole layout program, ensuring the consistency of the angle and position of the oblique holes in each layer. As an alternative, for situations where multi-axis linkage equipment is unavailable, a special drilling mold with an inclined guide sleeve can be made. Each fan-shaped plate is positioned within the mold, and the oblique holes are machined one by one using a conventional drilling machine. Subsequently, the spiral surface is assembled and formed. The fan-shaped plates with the oblique holes already machined are placed one by one along the tube bundle axis in the design order. Adjacent plates are arranged in a continuous or staggered overlapping manner and sealed and welded at the same time. They are then connected in series and positioned by passing through the oblique holes with spacer tubes (or tapered spacer tubes). After ensuring the continuity of the helical surface curvature, the plates are spot welded to the spacer tubes to form a baffle assembly with an approximately continuous helical surface.

[0063] The partition plate 23 can be divided so that it can be directly welded to the spiral baffle plate 6.

[0064] The spiral blades 50 in the tube 5 can be connected by welding, and then the tube is passed through the inclined holes on the spiral baffle 6.

[0065] Rotation of tube 5 can be achieved by a sealed bearing, which can be installed in a hole in the partition plate.

[0066] The first hollow mounting bracket 7, the second hollow mounting bracket 8, and the spoiler 9 can be directly nested inside the tube 5. The spiral blade 50 at the inlet end of the tube 5 is used to block one end, and the other end can be blocked by spot welding a protrusion inside the tube 5 to prevent the first hollow mounting bracket 7, the second hollow mounting bracket 8, and the spoiler 9 from shaking or sliding.

[0067] Working principle The raw material pretreatment unit 1 first mixes methanol and demineralized water in a mixing tank according to a set ratio. During the mixing process, the waste heat from the shell side of the CO conversion zone is used to heat the mixing tank jacket, maintaining a stable temperature of the mixed system. The mixed raw material enters the raw material preheater, where it is preheated by the waste heat from the shell side of the methanol cracking zone 20. After reaching the target temperature, it is sent to the feed chamber of the integrated reaction heat exchanger 2. After entering the feed chamber, the raw material flows through the spiral blades 50 in the tube side 5. Under the action of fluid thrust, the tube side 5 is driven to rotate relative to the baffle 23 and the spiral baffle 6. During the rotation of the tube side 5, the raw material first enters the tube side 5 of the methanol cracking zone 20 and comes into full contact with the copper-zinc-aluminum cracking catalyst bed in the first hollow mounting frame 7. Under the heat provided by the waste heat from the shell side and the action of the catalyst, a methanol reforming cracking reaction occurs, generating a hydrogen-containing mixed gas. The hydrogen-containing mixed gas then enters the tube side 5 of the CO conversion zone and comes into contact with the copper-based conversion catalyst bed in the second hollow mounting frame 8, converting the CO in the mixed gas into CO2. The heat generated by the conversion reaction is discharged through the shell side to heat the mixing tank jacket. The CO-converted gas mixture enters the tube side 5 of the reaction gas cooling zone 22, where it is thoroughly mixed under the action of the baffle 9. The cooling medium in the shell side cools the mixture to a suitable temperature. The residual heat released during the cooling process is transported through the third outlet 221 to the regeneration gas preheater of the PSA purification unit 4, providing energy for the preheating of the regeneration gas. The cooled gas mixture enters the gas-liquid separation unit 3, where unreacted methanol-water mixture is separated. This mixture is returned to the mixing tank of the raw material pretreatment unit 1 via a reflux pump to participate in the mixing reaction again. The separated gas enters the PSA purification unit 4, where it is purified to obtain high-purity hydrogen. The gas required for the PSA regeneration process is preheated by the residual heat of the reaction gas cooling zone 22, improving the regeneration efficiency. Throughout the process, temperature sensors in each independent heat exchange section monitor the temperature in real time. The PLC control system automatically adjusts the operating parameters based on the monitoring data. The design of the spiral baffle 6, including its gradually changing pitch, composite coating, and spiral guide grooves, optimizes the flow field and heat transfer efficiency. The rotation of the tube 5 enhances the contact between the reaction medium and the catalyst. The waste heat recovery and raw material circulation systems of each unit improve energy efficiency and raw material utilization, ultimately achieving a highly efficient, stable, and energy-saving methanol-to-hydrogen process.

[0068] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this application.

Claims

1. A methanol-to-hydrogen reactor, characterized in that, include: The raw material pretreatment unit (1) is used to mix methanol and demineralized water in a set ratio and preheat it to the target temperature; The integrated reaction heat exchanger (2) includes three independent heat exchange sections; the pitch of the spiral baffle (6) inside the integrated reaction heat exchanger (2) gradually decreases along the liquid flow direction in the tube side (5); A gas-liquid separation unit (3) is used to cool the reaction gas and separate the unreacted methanol-water mixture; The PSA purification unit (4) is used to purify hydrogen.

2. The methanol-to-hydrogen reactor according to claim 1, characterized in that, The independent heat exchange sections are a methanol cracking zone (20), a CO conversion zone (21), and a reaction gas cooling zone (22). The pitch of the spiral baffle (6) corresponding to the methanol cracking zone (20) is 100-120 mm, the pitch of the spiral baffle (6) corresponding to the CO conversion zone (21) is 70-90 mm, and the pitch of the spiral baffle (6) corresponding to the reaction gas cooling zone (22) is 40-60 mm.

3. The methanol-to-hydrogen reactor according to claim 2, characterized in that, The methanol cracking zone (20) is provided with a first inlet (201) and a first outlet (202) on its shell. The first outlet (202) is connected to the raw material preheater in the raw material pretreatment unit (1). The CO conversion zone (21) is provided with a second inlet (210) and a second outlet (211) on its shell. The second inlet (210) is connected to the mixing tank jacket of the raw material pretreatment unit (1). The reaction gas cooling zone (22) is provided with a third inlet (220) and a third outlet (221) on its shell. The third outlet (221) is connected to the regeneration gas preheater in the PSA purification unit (4).

4. The methanol-to-hydrogen reactor according to claim 1, characterized in that, The surface of the spiral baffle (6) is coated with a polytetrafluoroethylene-ceramic composite coating, and the bonding strength between the coating and the baffle substrate is ≥5MPa.

5. The methanol-to-hydrogen reactor according to claim 2, characterized in that, The interior of the tube (5) is provided with a first hollow mounting frame (7), a second hollow mounting frame (8), and a flow turbulence frame (9) corresponding to the methanol cracking zone (20), CO conversion zone (21), and reaction gas cooling zone (22), respectively. The first hollow mounting frame (7) is provided with a copper-zinc-aluminum cracking catalyst bed, the second hollow mounting frame (8) is provided with a copper-based conversion catalyst bed, and the flow turbulence frame (9) is used to mix the flow material inside the tube (5).

6. The methanol-to-hydrogen reactor according to claim 5, characterized in that, The first hollow mounting bracket (7) has a relief groove (70) on its outer wall. The second hollow mounting bracket (8) has a mounting rod (80) connected to its end face facing the first hollow mounting bracket (7). The mounting rod (80) is located outside the tube (5) through the relief groove (70).

7. The methanol-to-hydrogen reactor according to claim 1, characterized in that, Each of the three independent heat exchange sections is provided with a baffle (23) at both ends, and the tube (5) is rotatably arranged through the baffle (23) and the spiral baffle (6); The integrated reaction heat exchanger (2) has a feed chamber and a discharge chamber at both ends; the two ends of the tube (5) are located in the feed chamber and the discharge chamber respectively; the part of the tube (5) located in the feed chamber is provided with a spiral blade (50), and the spiral blade (50) is configured to drive the tube (5) to rotate relative to the partition plate (23) and the spiral baffle plate (6) when the material flows through the tube (5).

8. The methanol-to-hydrogen reactor according to claim 1, characterized in that, The surface of the spiral baffle (6) is provided with spiral guide grooves.

9. The methanol-to-hydrogen reactor according to claim 1, characterized in that, Each of the three independent heat exchange sections is equipped with a temperature sensor, which is electrically connected to the PLC control system.

10. The methanol-to-hydrogen reactor according to claim 1, characterized in that, The outlet of the condenser separator of the gas-liquid separation unit (3) is connected to the mixing tank of the raw material pretreatment unit (1) via a reflux pump.

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