Natural gas and methanol coupling type integrated hydrogen production device

Abstract

The invention relates to the technical field of hydrogen production, and discloses a natural gas and methanol coupling type integrated hydrogen production device, which is used for producing high-purity hydrogen through synergistic reforming of natural gas and methanol, and comprises: a raw material input unit, which comprises a natural gas compressor, a methanol pump and a water treatment system, the compressed natural gas, the liquid methanol and the purified water are respectively provided; the pretreatment unit comprises a desulfurizer, a methanol vaporizer and a steam generator and is used for removing sulfides in the natural gas, converting methanol into gas and generating high-pressure steam; in the third reaction area, water gas shift and in-situ CO2 capture are carried out through a WGS catalyst and an adsorbent, the CO conversion rate is larger than or equal to 95%, the CO2 capture rate is larger than or equal to 90% and is increased by 10-20% compared with post-treatment capture, TSA regeneration is carried out, specifically, a thermal coupling heat exchanger provides heat for driving TSA regeneration, and the purity gt of released CO2 is achieved; 95% of the CO2 is conveyed to a CO2 collecting tank. An external heat source is not needed, and energy consumption is saved by 10-15%.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen production, and particularly to a natural gas and methanol coupled integrated hydrogen production device. Background Technique

[0002] As a clean and efficient energy carrier, hydrogen has broad application prospects in the fields of fuel cells, chemical synthesis, and energy storage. With the increasing global demand for low-carbon energy, efficient and environmentally friendly hydrogen production technologies have become a research hotspot. Natural gas steam reforming (SMR) and methanol steam reforming (MSR) are two mature hydrogen production technologies, which use natural gas (mainly composed of methane) and methanol as raw materials respectively, and generate syngas rich in hydrogen through catalytic reactions. However, the existing hydrogen production technologies have the following deficiencies: After water-gas shift (WGS) in traditional hydrogen production devices, CO2 is mixed with hydrogen and needs to be separated by pressure swing adsorption (PSA). The PSA load is high (the gas treatment volume increases by 30–40%), and efficient in-situ capture of CO2 is not achieved. Summary of the Invention

[0003] The present invention provides a natural gas and methanol coupled integrated hydrogen production device, which solves the problems raised in the above background technique.

[0004] The present invention provides the following technical solution: A natural gas and methanol coupled integrated hydrogen production device for producing high-purity hydrogen through the co-reforming of natural gas and methanol, the device includes: A raw material input unit, including a natural gas compressor, a methanol pump, and a water treatment system, which are respectively used to provide compressed natural gas, liquid methanol, and purified water; A pretreatment unit, including a desulfurizer, a methanol vaporizer, and a steam generator, which are used to remove sulfides in natural gas, convert methanol into gas, and generate high-pressure steam; A mixer, which is used to mix preheated natural gas, gaseous methanol, and steam to form a first feed stream and a second feed stream; A mixed reaction-adsorption module, which is of a cylindrical structure, and is internally divided into a first reaction area, a second reaction area, and a third reaction area with a concentric configuration by an outer thermal conduction wall and an inner thermal conduction wall. Moreover, both the outer thermal conduction wall and the inner thermal conduction wall are inlaid with microchannels; The first reaction area is connected to the first feed stream outlet of the mixer through a pipeline equipped with a regulating valve, and natural gas steam reforming is carried out at a temperature of 800–1000 °C using a Ni-based catalyst to generate a first syngas (CO + 3H2), which is transported to the WGS reaction inlet of the third reaction area through an internal pipeline; The second reaction zone is connected to the second feed stream outlet of the mixer through a pipeline equipped with a regulating valve. Methanol steam reforming is carried out at a temperature of 200–300 °C using a Cu-based catalyst to generate a second syngas (CO2 + 3H2), which is transported to the third reaction zone through an internal pipeline; The third reaction zone is connected to the syngas outlets of the first and second reaction zones through internal pipelines. The TSA regeneration outlet is connected to a CO2 collection tank through a pipeline equipped with a pneumatic valve. The gas outlet is connected to a cooler through a pipeline. The water-gas shift reaction is carried out at a temperature of 200–400 °C using a WGS catalyst, and CO2 is in-situ captured by an adsorbent to generate a hydrogen stream; The microchannel heat exchanger network includes: A preheated natural gas heat exchanger connected by a pipeline to the hot side exhaust outlet of the first reaction zone and the cold side outlet of natural gas of the desulfurizer, which is used to preheat natural gas; A vaporized methanol heat exchanger connected by a pipeline to the hot side exhaust outlet of the third reaction zone and the cold side inlet of methanol of the methanol vaporizer, which is used to vaporize methanol; A thermally coupled heat exchanger, which is of a plate-frame structure and can withstand high temperatures up to 1000 °C. The thermally coupled heat exchanger is used to distribute the heat of the first reaction zone to the methanol reforming in the second reaction zone and the TSA regeneration in the third reaction zone; A purification unit, including a cooler and a pressure swing adsorption device, which is used for the output gas of the third reaction zone and separates high-purity hydrogen; A cooler, which is connected to the gas outlet of the third reaction zone through a pipeline; A pressure swing adsorption device, which is connected to the outlet of the cooler through a pipeline and separates hydrogen with a purity of ≥99.99%; A CO2 collection tank, which is used to store the high-purity CO2 released by the TSA regeneration in the third reaction zone; A burner, which is used to burn the residual gas of the pressure swing adsorption device to provide auxiliary heat to the steam generator; A burner, which is connected to the residual gas outlet of the pressure swing adsorption device through a pipeline. After combustion, the auxiliary heat is transported to the steam generator through a pipeline; A PLC control system dynamically adjusts the feed ratio of natural gas to methanol, the reaction conditions, and the TSA cycle time by monitoring the temperature, pressure, gas composition, and adsorbent state; Among them, the hybrid reaction-adsorption module realizes the synergistic effects of thermal coupling and in-situ CO2 capture through the microchannel heat exchanger network.

[0005] As a preferred technical solution of the present invention: The first reaction zone is located in the outer layer and filled with Ni / Al₂O₃ catalyst. The catalyst is doped with CeO₂ to improve sulfur resistance. Ni accounts for 10–20 wt% of the total mass of the catalyst, CeO₂ accounts for 1–10 wt%, and Al₂O₃ accounts for 70–85 wt%. The operating pressure is 10–15 bar; The second reaction zone is located in the middle layer and filled with Cu / ZnO / Al₂O₃ catalyst to optimize hydrogen selectivity; The third reaction zone is filled with a combination of Fe-Cr and Cu-Zn catalysts, where the Fe-Cr catalyst accounts for 50–70 wt% and the Cu-Zn catalyst accounts for 30–50 wt%. Through layered or mixed filling, in cooperation with a CaO adsorbent or a modified hydrotalcite adsorbent, the adsorbent accounts for 20–40% of the reaction bed volume; The combined catalyst covers a temperature range of 200–400 °C, with a CO conversion rate ≥ 95% and an H₂ selectivity ≥ 98%.

[0006] As a preferred technical solution of the present invention: The adsorbent in the third reaction zone captures CO₂ at 200–400 °C to form CaCO₃ or adsorbed CO₂; In the regeneration stage, heat of 400–600 °C is provided by a heat-coupled heat exchanger, and CO₂ with a purity > 95% is released to a CO₂ collection tank; The TSA cycle time is 1–2 hours and is dynamically adjusted by a PLC control system according to the adsorbent saturation and hydrogen demand; The CO₂ capture rate ≥ 90%, reducing the purification load of the subsequent pressure swing adsorption device.

[0007] As a preferred technical solution of the present invention: The heat-coupled heat exchanger is connected to the exhaust outlet of the first reaction zone through a pipeline. The hot fluid in the heat-coupled heat exchanger circulates through the microchannels embedded in the outer heat conduction wall and the inner heat conduction wall of the hybrid reaction-adsorption module, transferring heat to the TSA regeneration reaction inlets of the second reaction zone and the third reaction zone, and the remaining heat returns to the steam generator through a pipeline.

[0008] As a preferred technical solution of the present invention: The PLC control system includes: Collecting temperature, pressure, and gas composition data of the first reaction zone, the second reaction zone, and the third reaction zone through sensors, as well as the hydrogen purity of the pressure swing adsorption device and the CO₂ concentration of the CO₂ collection tank; Dynamically adjusting the feed ratio of natural gas and methanol, the temperature of the first reaction zone, and the TSA cycle frequency according to the hydrogen demand and the principle of minimizing energy consumption.

[0009] As a preferred technical solution of the present invention: the adsorbent in the third reaction zone is CaO and modified hydrotalcite, where: The CaO adsorbent is doped with Al2O3 or ZrO2 to improve high-temperature stability; The modified hydrotalcite is doped with K2CO3 to enhance the CO2 adsorption capacity at 200–400 °C; The adsorbent is mixed and filled with the WGS catalyst to optimize the gas contact efficiency.

[0010] As a preferred technical solution of the present invention: the pressure swing adsorption device includes 4–6 adsorption beds, configured as: Activated carbon or molecular sieve is used as the adsorption material to separate hydrogen from residual gases (CO, CH4, CO2); The residual gases (CO, CH4, CO2) are transported through pipelines to the burner to provide auxiliary heat, or partially recycled to the mixer to improve the raw material utilization rate.

[0011] As a preferred technical solution of the present invention: the natural gas and methanol coupled integrated hydrogen production device adopts a modular design, where: The mixed reaction-adsorption module, the microchannel heat exchanger network and the purification unit are integrated into a single containerized structure; The modular configuration allows multiple R1 units to operate in parallel, and the hydrogen production capacity can be expanded to 100–5000 Nm 3 / h; Suitable for distributed applications, including hydrogen refueling stations for fuel cell vehicles or energy systems in remote areas.

[0012] The present invention has the following beneficial effects: 1. For the natural gas and methanol coupled integrated hydrogen production device, the preheated natural gas heat exchanger utilizes the exhaust heat of the first reaction zone to preheat natural gas through microchannels, and the heat recovery efficiency is ≥70%, which is 15–20% higher than that of traditional heat exchangers. The vaporized methanol heat exchanger utilizes the exhaust heat of the third reaction zone to vaporize methanol to 150–200 °C through microchannels, with a heat demand of 500–600 kJ / kgCH3OH, without external electric heating, saving about 5–10% of energy consumption; The heat-coupled heat exchanger distributes the heat of the first reaction zone to the second reaction zone, the TSA regeneration of the third reaction zone and the steam generator through the microchannels embedded in the outer heat conduction wall and the inner heat conduction wall of the mixed reaction-adsorption module. The heat transfer efficiency is ≥80%, which is 20–30% higher than that of traditional heat exchangers, and the heat loss is reduced to 5–10%. By setting the microchannel structure, the heat exchange area is increased by 2–3 times compared with traditional heat exchangers.

[0013] 2. The natural gas and methanol coupled integrated hydrogen production device uses Ni / Al2O3 catalyst to reform natural gas in the first reaction zone, with a methane conversion rate of ≥95% to generate the first synthesis gas (CO+3H2); The second reaction zone uses Cu / ZnO / Al2O3 catalyst for methanol reforming, with H2 selectivity ≥98% and CO content <1%, which is better than traditional MSR.

[0014] The third reaction zone uses WGS catalyst and adsorbent for water gas shift and in-situ CO2 capture, with a CO conversion rate ≥95% and a CO2 capture rate ≥90%, which is 10–20% higher than post-processing capture.

[0015] TSA regeneration: The thermally coupled heat exchanger provides heat to drive TSA regeneration, releasing CO2 with a purity of >95% and transporting it to the CO2 collection tank. No external heat source is required, saving 10–15% of energy consumption.

[0016] 3. The natural gas and methanol coupled integrated hydrogen production device embeds the heat-conducting wall of the mixed reaction-adsorption module unit through a thermal coupling heat exchanger, which reduces the length of the external pipeline and reduces the heat loss to 5-10%, making it more compact than traditional heat exchangers; The modular design supports multiple hybrid reaction-adsorption modules in parallel (M1 and PSA1 are connected by stainless steel pipes), and the output can be expanded to 100–5000Nm 3 / h, suitable for distributed applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a schematic diagram of the process of the natural gas and methanol coupling hydrogen production device; Figure 2 This is a schematic diagram of the structure of the hybrid reaction-adsorption module of the present invention; Figure 3 It is a schematic diagram of the connection between the third reaction zone and the thermal coupling heat exchanger of the present invention.

[0018] In the figure: 1. Natural gas compressor; 2. Desulfurizer; 3. Methanol pump; 4. Methanol vaporizer; 5. Water treatment system; 6. Steam generator; 7. Mixer; 8. First reaction area; 9. Second reaction area; 10. Third reaction area; 11. Preheating natural gas heat exchanger; 12. Vaporization methanol heat exchanger; 13. Thermal coupling heat exchanger; 14. Cooler; 15. Pressure swing adsorption device; 16. CO2 collection tank; 17. Burner; 18. PLC control system; 19. Mixed reaction-adsorption module. DETAILED DESCRIPTION

[0019] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0020] Please refer to Figures 1 - 3 , a natural gas and methanol coupled integrated hydrogen production device for producing high-purity hydrogen through the co-reforming of natural gas and methanol. The device includes: A raw material input unit, including a natural gas compressor 1, a methanol pump 3, and a water treatment system 5, which are respectively used to provide compressed natural gas, liquid methanol, and purified water; A pretreatment unit, including a desulfurizer 2, a methanol vaporizer 4, and a steam generator 6, which are used to remove sulfides in natural gas, convert methanol into a gas state, and generate high-pressure steam; A mixer 7, which is used to mix preheated natural gas, gaseous methanol, and steam to form a first feed stream and a second feed stream; A mixed reaction-adsorption module 19, which is of a cylindrical structure and is internally divided into a first reaction area 8, a second reaction area 9, and a third reaction area 10 arranged concentrically through an outer thermal conduction wall and an inner thermal conduction wall. Moreover, both the outer thermal conduction wall and the inner thermal conduction wall are inlaid with microchannels; The first reaction area 8 is connected to the first feed stream outlet of the mixer 7 through a pipeline equipped with a regulating valve, and natural gas steam reforming is carried out at a temperature of 800–1000 °C using a Ni-based catalyst to generate a first syngas CO + 3H2, which is transported to the WGS reaction inlet of the third reaction area 10 through an internal pipeline; TSA is an adsorption separation technology based on temperature change. It adsorbs the target gas at a lower temperature and desorbs and regenerates the adsorbent at a higher temperature to release high-purity target gas.

[0021] In the adsorption stage, the adsorbent selectively captures CO2 at a lower temperature, such as 200–400 °C; in the regeneration stage, by increasing the temperature, such as 400–600 °C, the adsorbent releases CO2 and restores its adsorption capacity.

[0022] The role in the hydrogen production device: TSA is mainly applied to the third reaction area 10 of the mixed reaction-adsorption module 19 to in-situ capture CO2 generated by the water gas shift reaction WGS, CO + H2O → CO2 + H2.

[0023] Through TSA, the third reaction area 10 realizes: CO2 Capture: At 200–400 °C, adsorbents such as CaO form CaCO3, or modified hydrotalcite adsorbs CO2 with a capture rate of ≥90%, reducing the amount of CO2 entering the subsequent pressure swing adsorption unit 15.

[0024] CO2 Release: At 400–600 °C, the adsorbent is regenerated, releasing high-purity CO2 >95%, which is transported through a pipeline to the CO2 collection tank 16.

[0025] Hydrogen Purification: In-situ CO2 capture improves the hydrogen selectivity to ≥98%, reducing the load on the pressure swing adsorption unit 15.

[0026] The second reaction zone 9 is connected to the second feed stream outlet of the mixer 7 through a pipeline equipped with a regulating valve. Methanol steam reforming is carried out at a temperature of 200–300 °C using a Cu-based catalyst to generate a second syngas CO2 + 3H2, which is transported through an internal pipeline to the third reaction zone 10; The third reaction zone 10 is connected to the syngas outlets of the first reaction zone 8 and the second reaction zone 9 through internal pipelines. The TSA regeneration outlet is connected to the CO2 collection tank 16 through a pipeline equipped with a pneumatic valve, and the gas outlet is connected to the cooler 14 through a pipeline. The water gas shift reaction is carried out at a temperature of 200–400 °C using a WGS catalyst, and CO2 is in-situ captured by the adsorbent to generate a hydrogen stream; The microchannel heat exchanger network includes: The preheated natural gas heat exchanger 11, which is connected to the hot side exhaust outlet of the first reaction zone 8 and the cold side outlet of the natural gas of the desulfurizer 2 through a pipeline, is used to preheat natural gas; The vaporized methanol heat exchanger 12, which is connected to the hot side exhaust outlet of the third reaction zone 10 and the cold side inlet of the methanol of the methanol vaporizer 4 through a pipeline, is used to vaporize methanol; The thermally coupled heat exchanger 13, which is of a plate-frame structure and can withstand high temperatures up to 1000 °C, is used to distribute the heat of the first reaction zone 8 to the methanol reforming in the second reaction zone 9 and the TSA regeneration in the third reaction zone 10; The preheated natural gas heat exchanger 11 and the vaporized methanol heat exchanger 12 are independent external heat exchangers. The thermally coupled heat exchanger 13 is integrated with the hybrid reaction-adsorption module 19 through microchannels embedded in the outer thermal conduction wall and the inner thermal conduction wall of the hybrid reaction-adsorption module 19.

[0027] Both the outer thermal conduction wall and the inner thermal conduction wall are connected to the thermally coupled heat exchanger 13. The outer thermal conduction wall mainly transfers heat to the second reaction zone 9, and the inner thermal conduction wall transfers heat to the third reaction zone 10. The microchannel network of the thermally coupled heat exchanger 13 spans across the two thermal conduction walls.

[0028] Purification unit, including a cooler 14 and a pressure swing adsorption device 15, for the output gas of the third reaction zone 10 and separating high-purity hydrogen; Cooler 14, connected to the gas outlet of the third reaction zone 10 through a pipeline; Pressure swing adsorption device 15, connected to the outlet of the cooler 14 through a pipeline, separating hydrogen with a purity ≥ 99.99%; CO2 collection tank 16, for storing the high-purity CO2 released by the TSA regeneration of the third reaction zone 10; CO2 collection tank 16, connected to the TSA regeneration outlet of the third reaction zone 10 through a pipeline, storing CO2 with a purity > 95%; Burner 17, for burning the residual gas of the pressure swing adsorption device 15 to provide auxiliary heat to the steam generator 6; Burner 17, connected to the residual gas outlet of the pressure swing adsorption device 15 through a pipeline, and after burning, conveying the auxiliary heat to the steam generator 6 through a pipeline; PLC control system 18, dynamically adjusting the feed ratio of natural gas and methanol, reaction conditions and TSA cycle time by monitoring temperature, pressure, gas composition and adsorbent state; Among them, the hybrid reaction-adsorption module 19 realizes thermal coupling and in-situ CO2 capture synergy through a microchannel heat exchanger network.

[0029] Among them, the first reaction zone 8 is located in the outer layer, filled with Ni / Al2O3 catalyst, and the catalyst is doped with CeO2 to improve sulfur resistance. Ni accounts for 10–20 wt% of the total mass of the catalyst, CeO2 accounts for 1–10 wt%, and Al2O3 accounts for 70–85 wt%. The operating pressure is 10–15 bar; The second reaction zone 9 is located in the middle layer, filled with Cu / ZnO / Al2O3 catalyst to optimize hydrogen selectivity; The third reaction zone 10 is filled with a combination of Fe-Cr and Cu-Zn catalysts, where the Fe-Cr catalyst accounts for 50–70 wt% and the Cu-Zn catalyst accounts for 30–50 wt%. Through layered or mixed filling, in combination with CaO adsorbent or modified hydrotalcite adsorbent, the adsorbent accounts for 20–40% of the reaction bed volume; The combined catalyst covers a temperature range of 200–400 °C, with a CO conversion rate ≥ 95% and an H2 selectivity ≥ 98%.

[0030] Among them, the adsorbent in the third reaction zone 10 captures CO2 at 200–400 °C to form CaCO3 or adsorbed CO2; In the regeneration stage, heat of 400–600 °C is provided by the thermal coupling heat exchanger 13, and CO2 with a purity > 95% is released to the CO2 collection tank 16; The TSA cycle time is 1–2 hours and is dynamically adjusted by the PLC control system 18 according to the adsorbent saturation and hydrogen demand; The CO2 capture rate is ≥90%, reducing the purification load of the subsequent pressure swing adsorption device 15.

[0031] Among them, the heat-integrated heat exchanger 13 is connected to the exhaust outlet of the first reaction zone 8 through a pipeline. The hot fluid in the heat-integrated heat exchanger 13 circulates through the microchannels embedded in the outer heat conduction wall and the inner heat conduction wall of the hybrid reaction-adsorption module 19, transferring heat to the TSA regeneration reaction inlets of the second reaction zone 9 and the third reaction zone 10, and the remaining heat returns to the steam generator 6 through a pipeline.

[0032] Among them, the PLC control system 18 includes: Collecting temperature, pressure, and gas composition data of the first reaction zone 8, the second reaction zone 9, and the third reaction zone 10 through sensors, as well as the hydrogen purity of the pressure swing adsorption device 15 and the CO2 concentration of the CO2 collection tank 16; Dynamically adjusting the feed ratio of natural gas to methanol, the temperature of the first reaction zone 8, and the TSA cycle frequency according to the hydrogen demand and the principle of minimizing energy consumption.

[0033] Among them, the adsorbent in the third reaction zone 10 is CaO and modified hydrotalcite, where: The CaO adsorbent is doped with Al2O3 or ZrO2 to improve the high-temperature stability; The modified hydrotalcite is doped with K2CO3 to enhance the CO2 adsorption capacity at 200–400°C; The adsorbent is mixed with the WGS catalyst for filling to optimize the gas contact efficiency.

[0034] CaO (calcium oxide): Captures CO2 at 200–400°C through the carbonation reaction (CaO + CO2 → CaCO3), and doping with Al2O3 or ZrO2 improves the high-temperature stability, with a cycle life of ≥1000 times.

[0035] Modified hydrotalcite: Enhances the CO2 adsorption capacity (≥0.5 mol / kg) at 200–400°C by doping with K2CO3 or Na2CO3, and is suitable for medium and low-temperature operations.

[0036] The adsorbent is mixed or layered with the WGS catalyst (Fe-Cr 50–70 wt%, Cu-Zn 30–50 wt%) for filling to optimize the gas contact efficiency.

[0037] Operating conditions: Adsorption stage: 200–400°C, pressure 1–5 bar, CO2 capture rate ≥90%.

[0038] Regeneration stage: 400–600 °C. Heat is provided by the thermally coupled heat exchanger 13 through the microchannels embedded in the inner thermal conduction wall to release CO2.

[0039] Among them, the pressure swing adsorption device 15 includes 4–6 adsorption beds, configured as: Using activated carbon or molecular sieve as the adsorption material to separate hydrogen from the residual gases CO, CH4, and CO2; The residual gases CO, CH4, and CO2 are transported through pipelines to the burner 17 to provide auxiliary heat, or partially recycled to the mixer 7 to improve the raw material utilization rate.

[0040] Among them, the natural gas and methanol coupled integrated hydrogen production device adopts a modular design, where: The hybrid reaction-adsorption module 19, the microchannel heat exchanger network, and the purification unit are integrated into a single containerized structure; The modular configuration allows multiple R1 units to operate in parallel, and the hydrogen production capacity can be expanded to 100–5000 Nm 3 / h; Suitable for distributed applications, including hydrogen refueling stations for fuel cell vehicles or energy systems in remote areas.

[0041] Working principle: Natural gas, methanol, and purified water are provided respectively by the natural gas compressor 1, the methanol pump 3, and the water treatment system 5; sulfides in the natural gas are removed in the desulfurizer 2, methanol is converted into gas state in the methanol vaporizer 4, and high-pressure steam is generated in the steam generator 6; preheated natural gas, gaseous methanol, and steam are mixed in the mixer 7 to form the first feed stream and the second feed stream; in the hybrid reaction-adsorption module 19: in the first reaction zone 8, natural gas steam reforming is carried out at 800–1000 °C with a Ni-based catalyst to generate the first syngas; in the second reaction zone 9, methanol steam reforming is carried out at 200–300 °C with a Cu-based catalyst to generate the second syngas; in the third reaction zone 10, the water-gas shift reaction is carried out at 200–400 °C with a WGS catalyst, and CO2 is in-situ captured by a CaO or modified hydrotalcite adsorbent; the heat in the first reaction zone 8 is transferred to the TSA regeneration of the second reaction zone 9 and the third reaction zone 10 through the thermally coupled heat exchanger 13, the TSA regeneration temperature is 400–600 °C, and high-purity CO2 is released to the CO2 collection tank 16; the output gas of the third reaction zone 10 is cooled by the cooler 14, and hydrogen with a purity ≥99.99% is separated by the pressure swing adsorption device 15; the reaction conditions are monitored by the PLC control system 18, and the feed ratio of natural gas to methanol, the reaction temperature, and the TSA cycle time are dynamically adjusted.

[0042] It should be noted that in this text, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "comprising", "including" or any other variant thereof is intended to cover non-exclusive inclusion, such that a process, method, article or device comprising a series of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article or device.

[0043] Although the embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A hydrogen production device integrating natural gas and methanol coupling, characterized in that: Comprising: A hybrid reaction-adsorption module (19), the hybrid reaction-adsorption module (19) having a concentric region layout, comprising: A first reaction region (8) for carrying out natural gas steam reforming; A second reaction region (9) for carrying out methanol steam reforming; And a third reaction region (10) for carrying out water gas shift and in-situ carbon dioxide capture, the third reaction region (10) being in communication with the first reaction region (8) and the second reaction region (9) to receive their reaction products; And a microchannel heat exchanger network integrated inside the hybrid reaction-adsorption module (19) for selectively transferring the heat generated in the first reaction region (8) to the second reaction region (9) to drive the methanol reforming reaction and to the third reaction region (10) to achieve heating and regeneration of the adsorbent; A feedstock supply system connected to the hybrid reaction-adsorption module (19) for providing reaction materials; A purification unit connected to the third reaction region (10) for separating and purifying hydrogen from the reaction products.

2. The integrated hydrogen production device for coupling natural gas and methanol according to claim 1, wherein: The feedstock supply system includes: A feedstock input unit, including a natural gas compressor (1), a methanol pump (3) and a water treatment system (5), respectively for providing compressed natural gas, liquid methanol and purified water; A pretreatment unit, including a desulfurizer (2), a methanol vaporizer (4) and a steam generator (6), for removing sulfides from natural gas, converting methanol into a gas and generating high-pressure steam; A mixer (7) for mixing preheated natural gas, gaseous methanol and steam to form a first feed stream and a second feed stream, the first feed stream being supplied to the first reaction region (8) and the second feed stream being supplied to the second reaction region (9).

3. The integrated hydrogen production device coupling natural gas and methanol according to claim 2, characterized in that: The microchannel heat exchanger network includes: A preheated natural gas heat exchanger (11) connected by a pipeline to the hot-side exhaust outlet of the first reaction region (8) and the cold-side outlet of the natural gas of the desulfurizer (2), the preheated natural gas heat exchanger (11) being used for preheating natural gas; A vaporized methanol heat exchanger (12) connected by a pipeline to the exhaust hot-side outlet of the third reaction region (10) and the cold-side inlet of the methanol of the methanol vaporizer (4), the vaporized methanol heat exchanger (12) being used for vaporizing methanol; A heat-coupled heat exchanger (13), having a plate-frame structure and being heat-resistant up to 1000 °C, the heat-coupled heat exchanger (13) being used for distributing the heat of the first reaction region (8) to the methanol reforming in the second reaction region (9) and the TSA regeneration in the third reaction region (10).

4. A natural gas and methanol coupled integrated hydrogen production device according to claim 3, characterized in that: It also includes: A cooler (14) connected by a pipeline to the gas outlet of the third reaction region (10); A pressure swing adsorption device (15) connected by a pipeline to the outlet of the cooler (14) for separating hydrogen with a purity of ≥99.99%; A CO2 collection tank (16) for storing the high-purity CO2 released by the third reaction region (10) through TSA regeneration; A burner (17) for burning the residual gas of the pressure swing adsorption device (15) to provide auxiliary heat to the steam generator (6); The PLC control system (18) dynamically adjusts the feed ratio of natural gas to methanol, the reaction conditions, and the TSA cycle time by monitoring the temperature, pressure, gas composition, and the state of the adsorbent.

5. The integrated hydrogen production device by coupling natural gas and methanol according to claim 4, wherein: The first reaction zone (8) is located in the outer layer and filled with Ni / Al2O3 catalyst. The catalyst is doped with CeO2 to improve sulfur resistance. Ni accounts for 10–20 wt% of the total mass of the catalyst, CeO2 accounts for 1–10 wt%, and Al2O3 accounts for 70–85 wt%. The operating pressure is 10–15 bar; The second reaction zone (9) is located in the middle layer and filled with Cu / ZnO / Al2O3 catalyst to optimize hydrogen selectivity; The third reaction zone (10) is filled with a combination of Fe-Cr and Cu-Zn catalysts, where the Fe-Cr catalyst accounts for 50–70 wt% and the Cu-Zn catalyst accounts for 30–50 wt%. By layered or mixed filling, it is combined with CaO adsorbent or modified hydrotalcite adsorbent, and the adsorbent accounts for 20–40% of the reaction bed volume; The catalyst filled in the third reaction zone (10) covers a temperature range of 200–400 °C, with a CO conversion rate ≥ 95% and an H2 selectivity ≥ 98%.

6. The integrated hydrogen production device by coupling natural gas and methanol according to claim 5, wherein: The adsorbent in the third reaction zone (10) captures CO2 at 200–400 °C to form CaCO3 or adsorbed CO2; In the regeneration stage, heat of 400–600 °C is provided by the thermally coupled heat exchanger (13), and CO2 with a purity > 95% is released to the CO2 collection tank (16); The TSA cycle time is 1–2 hours, which is dynamically adjusted by the PLC control system (18) according to the adsorbent saturation and hydrogen demand; The CO2 capture rate ≥ 90%, reducing the purification load of the subsequent pressure swing adsorption device (15).

7. The integrated hydrogen production device coupling natural gas and methanol according to claim 6, characterized in that: The thermally coupled heat exchanger (13) is connected to the exhaust outlet of the first reaction zone (8) through a pipeline. The hot fluid in the thermally coupled heat exchanger (13) circulates through the microchannels embedded in the outer thermal conduction wall and the inner thermal conduction wall of the hybrid reaction-adsorption module (19), transferring heat to the TSA regeneration reaction inlets of the second reaction zone (9) and the third reaction zone (10), and the remaining heat returns to the steam generator (6) through a pipeline.

8. A natural gas and methanol coupled integrated hydrogen production device according to claim 7, characterized in that: The PLC control system (18) includes: Collecting temperature, pressure, and gas composition data of the first reaction zone (8), the second reaction zone (9), and the third reaction zone (10) through sensors, as well as the hydrogen purity of the pressure swing adsorption device (15) and the CO2 concentration of the CO2 collection tank (16); Dynamically adjusting the feed ratio of natural gas to methanol, the temperature of the first reaction zone (8), and the TSA cycle frequency according to the hydrogen demand and the principle of minimizing energy consumption.

9. The integrated hydrogen production device coupling natural gas and methanol according to claim 6, wherein: The adsorbent in the third reaction zone (10) is CaO and modified hydrotalcite, where: The CaO adsorbent is doped with Al2O3 or ZrO2 to improve high-temperature stability; Modified hydrotalcite doped with K2CO3 enhances the CO2 adsorption capacity at 200–400 °C; The adsorbent is mixed and filled with the WGS catalyst to optimize the gas contact efficiency.

10. A natural gas and methanol coupled integrated hydrogen production device according to claim 4, wherein: The natural gas and methanol coupled integrated hydrogen production device adopts a modular design, wherein: The hybrid reaction-adsorption module (19), the microchannel heat exchanger network and the purification unit are integrated into a single containerized structure; The pressure swing adsorption device (15) includes 4–6 adsorption beds configured as: Activated carbon or molecular sieve is used as the adsorption material to separate hydrogen from the residual gases (CO, CH4, CO2); The residual gases (CO, CH4, CO2) are transported through a pipeline to the burner (17) to provide auxiliary heat, or partially recycled to the mixer (7) to improve the raw material utilization rate.

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