A product co-enhanced hydrogen production system for methanol autothermal reforming based on self-feedback control

Abstract

The present invention provides a product synergistic enhancement type methanol autothermal reforming hydrogen production system based on self-feedback control, which includes two groups of autothermal reforming reactors, a reaction material supply system, and a hydrogen fuel cell stack; the pure hydrogen outlet ends of the two groups of autothermal reforming reactors are respectively communicated with the inlet of the hydrogen fuel cell stack; one outlet of the hydrogen fuel cell stack is respectively communicated with the residual hydrogen inlet ends of the two groups of autothermal reforming reactors; the air supply device is respectively communicated with the air inlet ends of the two groups of autothermal reforming reactors; the regeneration purge gas outlet ends of the two groups of autothermal reforming reactors are respectively communicated with the methanol vaporizer; the reformed gas inlet ends of the two groups of autothermal reforming reactors are communicated with the mixed gas outlet of the methanol vaporizer; the hydrogen-oxygen combustion waste gas interface ends of the two groups of autothermal reforming reactors are communicated with each other. The system of the present invention has high methanol-water conversion rate and energy utilization efficiency.

Description

Technical Field

[0001] The present invention relates to the field of hydrogen production from methanol, and particularly to a product synergistic enhanced methanol autothermal reforming hydrogen production system based on self-feedback control. Background Art

[0002] To reduce global carbon emissions and achieve the goals of carbon peak and carbon neutrality, hydrogen fuel cell vehicles have been widely studied and applied. Since the construction costs of traditional hydrogen production, storage, transportation, and hydrogen refueling stations remain high, and the safety of high-pressure hydrogen cylinders is highly questioned, using on-site methanol reforming to produce hydrogen instead of high-pressure hydrogen cylinders as the source of hydrogen is a solution.

[0003] Generally, methanol steam reforming (MSR) for hydrogen production needs to be carried out at a relatively high temperature, generally 250 - 350 °C, which requires a large amount of energy for heating. While methanol autothermal reforming (ATR) for hydrogen production can proceed spontaneously at a relatively low initial temperature, generally 100 °C, and the energy consumption is greatly reduced by adjusting the ratio of CH3OH / H2O / O2. Methanol steam reforming (MSR) is shown in Equation 1 below, and methanol autothermal reforming (ATR) is shown in Equation 2 below.

[0004] Equation 1:

[0005] Equation 2:

[0006] It can be seen from Equation 2 that by adjusting the ratio of CH3OH / H2O / O2, the heat released by the reaction can be controlled. On the one hand, the initial temperature required for the reaction can be reduced as much as possible and the optimal hydrogen production temperature can be achieved. On the other hand, the CO concentration can be effectively reduced. However, there is no existing self-feedback control system that can adjust the ratio of CH3OH / H2O / O2 in the reaction materials in real time according to the temperature of the catalyst bed layer of the autothermal reforming reaction, resulting in too low or too high actual catalyst bed layer temperature, which is not conducive to the progress of the reforming reaction; at the same time, the conversion rate of the autothermal reforming reactants is relatively low, and there is a phenomenon of rapid heat release during the reaction, resulting in agglomeration and inactivation of the active sites, which need to be solved. Summary of the Invention

[0007] Aiming at the deficiencies in the prior art, the present invention provides a product synergistic enhanced methanol autothermal reforming hydrogen production system based on self-feedback control, which has high methanol-water conversion rate and energy utilization efficiency, and can proceed spontaneously and continuously at a low temperature (100 °C).

[0008] The present invention achieves the above technical objectives through the following technical means.

[0009] A product synergistic enhanced methanol autothermal reforming hydrogen production system based on self-feedback control includes two groups of autothermal reforming reactors, a reaction material supply system, and a hydrogen fuel cell stack;

[0010] The reaction material supply system includes a methanol-water supply device, a methanol-water vaporizer, and an air supply device; the methanol-water supply device is used to input a mixture of methanol and pure water into the methanol-water vaporizer;

[0011] Two groups of the autothermal reforming reactors work alternately; the autothermal reforming reactor includes a pure hydrogen outlet end A, a residual hydrogen inlet end B, an air inlet end C, a regeneration purge gas outlet end D, a reformed gas inlet end E, and a hydrogen-oxygen combustion exhaust gas interface end F; the pure hydrogen outlet ends A of the two groups of autothermal reforming reactors are respectively communicated with the inlet of the hydrogen fuel cell stack; one outlet of the hydrogen fuel cell stack is respectively communicated with the residual hydrogen inlet ends B of the two groups of autothermal reforming reactors; the air supply device is respectively communicated with the air inlet ends C of the two groups of autothermal reforming reactors; the regeneration purge gas outlet ends D of the two groups of autothermal reforming reactors are respectively communicated with the methanol-water vaporizer; the reformed gas inlet ends E of the two groups of autothermal reforming reactors are communicated with the mixed gas outlet of the methanol-water vaporizer; the hydrogen-oxygen combustion exhaust gas interface ends F of the two groups of autothermal reforming reactors are communicated with each other.

[0012] Furthermore, the autothermal reforming reactor includes a hydrogen flameless combustion chamber, an autothermal reforming reaction chamber, a supported Pd membrane alloy membrane module, and a hydrogen enrichment chamber; the supported Pd membrane alloy membrane module is separated from the hydrogen enrichment chamber by the supported Pd membrane alloy membrane module; a pure hydrogen outlet is provided on the hydrogen enrichment chamber; the hydrogen flameless combustion chamber and the autothermal reforming reaction chamber are separated by a second heat conducting plate; a CO2 adsorption-methanol autothermal reforming catalyst layer is provided in the autothermal reforming reaction chamber; a second heating device is provided in the CO2 adsorption-methanol autothermal reforming catalyst layer; a first interface, a second interface, a sixth interface, and a seventh interface are provided on the autothermal reforming reaction chamber;

[0013] A third interface, a fourth interface, and a fifth interface are respectively provided on the hydrogen flameless combustion chamber; a gas flow guide plate is provided in the hydrogen flameless combustion chamber near the third interface; a hydrogen-oxygen combustion catalyst is coated on the bottom of the hydrogen flameless combustion chamber; a third heating device is provided in the hydrogen flameless combustion chamber; the pure hydrogen outlet is the pure hydrogen outlet end A; the inlet of the third interface is the residual hydrogen inlet end B; the fifth interface and the second interface are connected by a three-way solenoid valve-flow controller, and the other inlet of the three-way solenoid valve-flow controller is the air inlet end C; the outlet of the sixth interface and the seventh interface after intersection is the regeneration purge gas outlet end D; the inlet of the first interface is the reformed gas inlet end E; the outlet of the fourth interface is the hydrogen-oxygen combustion exhaust gas interface end F.

[0014] Furthermore, the methanol vaporizer includes a vaporization heat exchange chamber, a first heat conducting plate, and a methanol water vaporization chamber; the vaporization heat exchange chamber is separated from the methanol water vaporization chamber by the first heat conducting plate; the vaporization heat exchange chamber is communicated with the regeneration purge gas outlet end D; the methanol water vaporization chamber is provided with a methanol water inlet, a mixed gas outlet, and a carrier gas inlet; the methanol water inlet is communicated with a methanol water supply device; the mixed gas outlet is communicated with the reformed gas inlet end E; the carrier gas inlet is communicated with an air supply device; the methanol water vaporization chamber is provided with a first heating device.

[0015] Furthermore, a first temperature sensor is provided in the methanol water vaporization chamber for detecting the temperature of the methanol water vaporization chamber;

[0016] A second temperature sensor is provided in the autothermal reforming reaction chamber for detecting the temperature of the autothermal reforming reaction chamber; a CO2 concentration sensor is provided at the regeneration purge gas outlet end D for detecting the CO2 concentration at the regeneration purge gas outlet end D.

[0017] Furthermore, a control system is further included; the control system obtains the values detected by the first temperature sensor and the second temperature sensors of two groups of autothermal reforming reactors;

[0018] When the detected temperature of the first temperature sensor < 140 °C, if the detected temperature of the second temperature sensor of any group of autothermal reforming reactors ≥ 400 °C, then the control system connects the regeneration purge gas outlet end D of the autothermal reforming reactor to the vaporization heat exchange chamber for preheating the methanol water vaporization chamber; if the detected temperatures of the second temperature sensors of the two groups of autothermal reforming reactors < 400 °C, then the control system controls the first heating device to heat the methanol water vaporization chamber.

[0019] Furthermore, when the detected temperature of the second temperature sensor of a group of autothermal reforming reactors < 100 °C, if the detected temperature of the second temperature sensor of the other group of autothermal reforming reactors ≥ 400 °C, then the control system connects the hydrogen-oxygen combustion exhaust gas interface ends F of the two groups of autothermal reforming reactors to each other through controlling the sixth solenoid valve - flow controller for preheating the CO2 adsorption - methanol autothermal reforming catalyst layer; if the detected temperature of the second temperature sensor of the other group of autothermal reforming reactors < 400 °C, then the control system controls the second heating device to heat the CO2 adsorption - methanol autothermal reforming catalyst layer.

[0020] Further, when the detected value of the CO2 concentration sensor of a group of autothermal reforming reactors is greater than the threshold value, the control system controls another group of autothermal reforming reactors to operate; when the detected temperature of the second temperature sensor of another group of autothermal reforming reactors > 400 °C, the control system controls the residual hydrogen inlet end B of another group of autothermal reforming reactors to communicate with the third interface of a group of autothermal reforming reactors, and controls the air inlet end C of another group of autothermal reforming reactors to communicate with the fifth interface of a group of autothermal reforming reactors, controls the third heating device of a group of autothermal reforming reactors to heat the flameless hydrogen combustion chamber, and burns through the flameless hydrogen combustion chamber of a group of autothermal reforming reactors, so as to regenerate the hydrogen-oxygen combustion catalyst of a group of autothermal reforming reactors.

[0021] The beneficial effects of the present invention are as follows:

[0022] 1. For the product synergistic enhanced methanol autothermal reforming hydrogen production system based on self-feedback control described in the present invention, by setting a supported Pd membrane alloy membrane component on the autothermal reforming reactor, the separation and purification of hydrogen are realized in-situ during the autothermal reforming reaction, improving the energy utilization efficiency.

[0023] 2. For the product synergistic enhanced methanol autothermal reforming hydrogen production system based on self-feedback control described in the present invention, Cu-ZnO x / CeO 2-x is used as the methanol autothermal reforming catalyst, and K2CO3-modified [Mg6Al2(OH) 16 CO3]·4H2O hydrotalcite (K2CO3-MgAl-HTs) is used as the CO2 adsorbent. After ball milling and granulation of the two, a uniform bifunctional catalyst for CO2 adsorption - methanol autothermal reforming is formed, which can simultaneously realize the methanol autothermal reforming reaction and the adsorption of CO2.

[0024] 3. For the product synergistic enhanced methanol autothermal reforming hydrogen production system based on self-feedback control described in the present invention, according to the principle of chemical reaction equilibrium shift, the CO2 adsorption and in-situ hydrogen separation and purification are synergistic, that is, the two reaction products are synergistic, promoting the forward progress of the methanol autothermal reforming reaction and greatly improving the conversion rates of the reactants methanol and water.

[0025] 4. For the product synergistic enhanced methanol autothermal reforming hydrogen production system based on self-feedback control described in the present invention, by using the initial temperature self-feedback control subsystem for controlling the initial temperature of the catalyst bed layer in the autothermal reforming reactor, the ratio of the reactants CH3OH / H2O / O2 is regulated in real time, enabling the methanol autothermal reforming reaction to proceed autothermally at a lower temperature (100 °C), reducing the energy consumption required for the autothermal reforming reaction.

[0026] 5. The product co-enhanced methanol autothermal reforming hydrogen production system based on self-feedback control according to the present invention adopts two groups of methanol autothermal reforming reactors and corresponding CO2 concentration self-feedback control subsystems, enabling the methanol autothermal reforming reaction process and the catalyst purge and regeneration process to alternate, thereby achieving the purpose of continuous hydrogen production.

[0027] 6. The product co-enhanced methanol autothermal reforming hydrogen production system based on self-feedback control according to the present invention utilizes the unreacted residual hydrogen at the anode of the hydrogen fuel cell and the oxygen in the air for hydrogen-oxygen catalytic combustion (Pt-TiO2 is proposed to be used as the hydrogen-oxygen catalytic combustion catalyst) to provide heat for the catalyst purge and regeneration process; at the same time, the exhaust gas from the hydrogen-oxygen combustion is introduced into the flameless combustion chamber of hydrogen in another group of the autothermal reforming reactors for heat exchange to provide initial energy (100 °C) for the methanol autothermal reforming; the heated catalyst purge and regeneration gas is introduced into the vaporization heat exchange chamber of the methanol vaporizer for heat exchange to provide heat for the methanol vaporization. All the energy required by the system is provided by the hydrogen-oxygen combustion, greatly improving the energy utilization efficiency of the system. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. The drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, it is obvious that other drawings can also be obtained according to these drawings.

[0029] Figure 1 It is a schematic diagram of the product co-enhanced methanol autothermal reforming hydrogen production system based on self-feedback control according to the present invention.

[0030] Figure 2 It is a schematic diagram of the autothermal reforming reactor according to the present invention.

[0031] Figure 3 It is a simplified structural diagram of the methanol vaporizer according to the present invention.

[0032] Figure 4 It is an internal structure diagram of the autothermal reforming reactor according to the present invention.

[0033] Figure 5 It is a flow chart of the methanol vaporization self-feedback control subsystem according to the present invention.

[0034] Figure 6 It is a flow chart of the initial temperature self-feedback control subsystem according to the present invention.

[0035] Figure 7 It is a flow chart of the CO2 concentration self-feedback control subsystem according to the present invention.

[0036] In the figure:

[0037] 1 - Methanol storage tank; 2 - Pure water storage tank; 3 - Dual-channel peristaltic pump; 4 - Air compressor; 5 - Methanol water vaporizer; 6 - First autothermal reforming reactor; 6’ - Second autothermal reforming reactor; 7 - Hydrogen fuel cell stack; 8 - First solenoid valve - flow controller; 9 - Second solenoid valve - flow controller; 10 - Third solenoid valve - flow controller; 11 - First solenoid valve.

[0038] 5 - 1 - Methanol water inlet; 5 - 2 - Mixed gas outlet; 5 - 3 - Regeneration purge waste gas inlet; 5 - 4 - Regeneration purge waste gas outlet; 5 - 5 - First heating rod; 5 - 6 - First heat conducting plate; 5 - 7 - Carrier gas inlet; 5 - 8 - Vaporization heat exchange cavity; 5 - 9 - Methanol water vaporization cavity; 5 - 10 - First temperature sensor.

[0039] 6 - 1 - First interface; 6 - 2 - Second interface; 6 - 3 - Third interface; 6 - 4 - Fourth interface; 6 - 5 - Pure hydrogen outlet; 6 - 6 - Fifth interface; 6 - 7 - Autothermal reforming reaction cavity; 6 - 8 - Supported Pd membrane alloy membrane module; 6 - 9 - Hydrogen flameless combustion cavity; 6 - 10 - Hydrogen enrichment cavity; 6 - 11 - Second heating rod; 6 - 12 - Sixth interface; 6 - 13 - Third heating rod; 6 - 14 - CO2 adsorption - methanol autothermal reforming catalyst layer; 6 - 15 - Second heat conducting plate; 6 - 16 - Gas deflector; 6 - 17 - Hydrogen - oxygen combustion catalyst; 6 - 18 - Second solenoid valve; 6 - 19 - Fourth solenoid valve - flow controller; 6 - 20 - Three - way solenoid valve - flow controller; 6 - 21 - Fifth solenoid valve - flow controller; 6 - 22 - Sixth solenoid valve - flow controller; 6 - 23 - Third solenoid valve; 6 - 24 - Seventh solenoid valve - flow controller; 6 - 25 - Second temperature sensor; 6 - 26 - Seventh interface; 6 - 27 - CO2 concentration sensor.

[0040] A - Pure hydrogen outlet end; B - Residual hydrogen inlet end; C - Air inlet end; D - Regeneration purge gas outlet end; E - Reformed gas inlet end; F - Hydrogen - oxygen combustion waste gas interface end. Detailed implementation manners

[0041] The embodiments of the present invention will be described in detail below. The examples of the embodiments are shown in the drawings, where the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the drawings are exemplary and are intended to explain the present invention, and should not be construed as a limitation to the present invention.

[0042] In the description of the present invention, it should be understood that the orientation or positional relationships indicated by the terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "axial", "radial", "vertical", "horizontal", "inner", "outer", etc. are based on the orientation or positional relationships shown in the drawings. These are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation. Therefore, it should not be construed as a limitation to the present invention. In addition, the terms "first" and "second" are only used for descriptive purposes and cannot be construed as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include one or more of such features. In the description of the present invention, "a plurality of" means two or more unless otherwise specifically defined.

[0043] In the present invention, unless otherwise clearly specified and limited, the terms "mounted", "connected", "connected to", "fixed", etc. should be understood in a broad sense. For example, it may be a fixed connection, a detachable connection, or an integral connection; it may be a mechanical connection or an electrical connection; it may be directly connected or indirectly connected through an intermediate medium, and it may be the communication inside two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0044] As Figure 1 shown, the product co-enhanced methanol autothermal reforming hydrogen production system based on self-feedback control described in the present invention includes two groups of autothermal reforming reactors, a reaction material supply system, and a hydrogen fuel cell stack 7;

[0045] The reaction material supply system includes a methanol-water supply device, a methanol water vaporizer 5, and an air supply device; the methanol-water supply device is used to input a mixture of methanol and pure water into the methanol water vaporizer 5; the methanol-water supply device includes a methanol storage tank 1, a pure water storage tank 2, and a dual-channel peristaltic pump 3; the methanol storage tank 1 and the pure water storage tank 2 are respectively connected to the inlet of the dual-channel peristaltic pump 3, and the outlet of the dual-channel peristaltic pump 3 enters the methanol-water inlet 5-1 of the methanol water vaporizer 5 through a first solenoid valve 11.

[0046] The two groups of autothermal reforming reactors are respectively a first autothermal reforming reactor 6 and a second autothermal reforming reactor 6'; the structures of the first autothermal reforming reactor 6 and the second autothermal reforming reactor 6' are the same. Hereinafter, taking the first autothermal reforming reactor 6 as an example, as Figure 2 and 4As shown, the first autothermal reforming reactor 6 includes a flameless hydrogen combustion chamber 6-9, an autothermal reforming reaction chamber 6-7, a supported Pd membrane alloy membrane module 6-8, and a hydrogen enrichment chamber 6-10; the supported Pd membrane alloy membrane module 6-8 separates the hydrogen enrichment chamber 6-10; a pure hydrogen outlet 6-5 is provided on the hydrogen enrichment chamber 6-10; the flameless hydrogen combustion chamber 6-9 and the autothermal reforming reaction chamber 6-7 are separated by a second heat conducting plate 6-15; a CO2 adsorption-methanol autothermal reforming catalyst layer 6-14 is provided in the autothermal reforming reaction chamber 6-7; the CO2 adsorption-methanol autothermal reforming catalyst layer 6-14 uses Cu-ZnO x / CeO 2-x as the methanol autothermal reforming catalyst, K2CO3 modified [Mg6Al2(OH) 16K2CO3·4H2O hydrotalcite (K2CO3-MgAl-HTs) is used as a CO2 adsorbent. After ball milling, grinding and granulation of the two, a uniform bifunctional catalyst for CO2 adsorption-methanol autothermal reforming is formed, which can simultaneously realize the methanol autothermal reforming reaction and the adsorption of CO2. A second heating rod 6-11 is provided in the CO2 adsorption-methanol autothermal reforming catalyst layer 6-14; a first interface 6-1, a second interface 6-2, a sixth interface 6-12 and a seventh interface 6-26 are provided on the autothermal reforming reaction chamber 6-7; a third interface 6-3, a fourth interface 6-4 and a fifth interface 6-6 are respectively provided on the hydrogen flameless combustion chamber 6-9; a gas guide plate 6-16 is provided in the hydrogen flameless combustion chamber 6-9 near the third interface 6-3; a hydrogen-oxygen combustion catalyst 6-17 is coated on the bottom of the hydrogen flameless combustion chamber 6-9; a third heating device is provided in the hydrogen flameless combustion chamber 6-9; the outlet of the pure hydrogen outlet 6-5 is the pure hydrogen outlet end A; a second solenoid valve 6-18 and a fourth solenoid valve-flow controller 6-19 are successively arranged between the pure hydrogen outlet 6-5 and the pure hydrogen outlet end A; the second solenoid valve 6-18 is used to recover the excess gas. The inlet of the third interface 6-3 is the residual hydrogen inlet end B; a fifth solenoid valve-flow controller 6-21 is arranged between the third interface 6-3 and the residual hydrogen inlet end B; the fifth interface 6-6 is connected to the second interface 6-2 through a three-way solenoid valve-flow controller 6-20, and the other inlet of the three-way solenoid valve-flow controller 6-20 is the air inlet end C; the outlet of the intersection of the sixth interface 6-12 and the seventh interface 6-26 is the regeneration purge gas outlet end D; a CO2 concentration sensor 6-27 is arranged at the intersection of the sixth interface 6-12 and the seventh interface 6-26, and a seventh solenoid valve-flow controller 6-24 is arranged between the seventh interface 6-26 and the CO2 concentration sensor 6-27; the inlet of the first interface 6-1 is the reformed gas inlet end E; a third solenoid valve 6-23 is arranged at the first interface 6-1; the outlet of the fourth interface 6-4 is the hydrogen-oxygen combustion exhaust gas interface end F, and a sixth solenoid valve-flow controller 6-22 is arranged at the fourth interface 6-4.

[0047] The pure hydrogen outlet ends A of the first autothermal reforming reactor 6 and the second autothermal reforming reactor 6' are respectively communicated with the inlet of the hydrogen fuel cell stack 7; one outlet of the hydrogen fuel cell stack 7 is respectively communicated with the residual hydrogen inlet ends B of the first autothermal reforming reactor 6 and the second autothermal reforming reactor 6'; the air supply device is respectively communicated with the air inlet ends C of the first autothermal reforming reactor 6 and the second autothermal reforming reactor 6'; the regeneration purge gas outlet ends D of the first autothermal reforming reactor 6 and the second autothermal reforming reactor 6' are respectively communicated with the methanol vaporizer 5; the reformed gas inlet ends E of the first autothermal reforming reactor 6 and the second autothermal reforming reactor 6' are communicated with the mixed gas outlet of the methanol vaporizer 5; the hydrogen-oxygen combustion waste gas interface ends F of the first autothermal reforming reactor 6 and the second autothermal reforming reactor 6' are communicated with each other.

[0048] As Figure 3 shown, the methanol vaporizer 5 includes a vaporization heat exchange chamber 5-8, a first heat conducting plate 5-6 and a methanol vaporization chamber 5-9; the vaporization heat exchange chamber 5-8 and the methanol vaporization chamber 5-9 are separated by the first heat conducting plate 5-6; the vaporization heat exchange chamber 5-8 is communicated with the regeneration purge gas outlet end D; the methanol vaporization chamber 5-9 is provided with a methanol-water inlet 5-1, a mixed gas outlet 5-2 and a carrier gas inlet 5-7; the methanol-water inlet 5-1 is communicated with the methanol-water supply device; the mixed gas outlet 5-2 is communicated with the reformed gas inlet end E; the carrier gas inlet 5-7 is communicated with the air supply device; the methanol vaporization chamber 5-9 is provided with a first heating rod 5-5.

[0049] A first temperature sensor 5-10 is arranged in the methanol vaporization chamber 5-9 for detecting the temperature of the methanol vaporization chamber 5-9; a second temperature sensor 6-25 is arranged in the autothermal reforming reaction chamber 6-7 for detecting the temperature of the autothermal reforming reaction chamber 6-7; a CO2 concentration sensor 6-27 is arranged at the regeneration purge gas outlet end D for detecting the CO2 concentration at the regeneration purge gas outlet end D.

[0050] It further includes a control system; the control system obtains the values detected by the first temperature sensor 5-10, the second temperature sensor 6-25 of the first autothermal reforming reactor 6 and the second temperature sensor 6-25 of the second autothermal reforming reactor 6'.

[0051] As Figure 5As shown, when the detected temperature of the first temperature sensor 5-10 < 140°C, if the detected temperature of the second temperature sensor 6-25 of the first autothermal reforming reactor 6 ≥ 400°C, the control system will connect the regeneration purge gas outlet end D of the first autothermal reforming reactor 6 to the vaporization heat exchange chamber 5-8 for preheating the methanol vaporization chamber 5-9; if the detected temperature of the second temperature sensor 6-25 of the second autothermal reforming reactor 6' ≥ 400°C, the control system will connect the regeneration purge gas outlet end D of the second autothermal reforming reactor 6' to the vaporization heat exchange chamber 5-8 for preheating the methanol vaporization chamber 5-9; if the detected temperatures of the second temperature sensor 6-25 of the first autothermal reforming reactor 6 and the second temperature sensor 6-25 of the second autothermal reforming reactor 6' < 400°C, the control system will control the first heating rod 5-5 to heat the methanol vaporization chamber 5-9.

[0052] As Figure 6 Shown, when the detected temperature of the second temperature sensor 6-25 of the first autothermal reforming reactor 6 < 100°C, if the detected temperature of the second temperature sensor 6-25 of the second autothermal reforming reactor 6' ≥ 400°C, the control system will connect the hydrogen-oxygen combustion exhaust gas interface ends F of the two groups of autothermal reforming reactors to each other through controlling the sixth solenoid valve - flow controller 6-22 for preheating the CO2 adsorption - methanol autothermal reforming catalyst 6-14; similarly, when the detected temperature of the second temperature sensor 6-25 of the second autothermal reforming reactor 6' < 100°C, if the detected temperature of the second temperature sensor 6-25 of the first autothermal reforming reactor 6 ≥ 400°C, the control system will connect the hydrogen-oxygen combustion exhaust gas interface ends F of the two groups of autothermal reforming reactors to each other through controlling the sixth solenoid valve - flow controller 6-22 for preheating the CO2 adsorption - methanol autothermal reforming catalyst 6-14; when the detected temperature of the second temperature sensor 6-25 of the first autothermal reforming reactor 6 < 100°C, if the detected temperature of the second temperature sensor 6-25 of the second autothermal reforming reactor 6' < 400°C, the control system will control the second heating rod 6-11 to heat the CO2 adsorption - methanol autothermal reforming catalyst 6-14; similarly, when the detected temperature of the second temperature sensor 6-25 of the second autothermal reforming reactor 6' < 100°C, if the detected temperature of the second temperature sensor 6-25 of the first autothermal reforming reactor 6 < 400°C, the control system will control the second heating rod 6-11 to heat the CO2 adsorption - methanol autothermal reforming catalyst 6-14.

[0053] As Figure 7As shown, when the detected value of the CO2 concentration sensor 6-27 of the first autothermal reforming reactor 6 is greater than the threshold value, the control system controls the second autothermal reforming reactor 6' to participate in the operation; when the detected temperature of the second temperature sensor 6-25 of the second autothermal reforming reactor 6' ≥ 400 °C, the control system controls the residual hydrogen inlet end B of the second autothermal reforming reactor 6' to communicate with the third interface 6-3 of the first autothermal reforming reactor 6, and controls the air inlet end C of the second autothermal reforming reactor 6' to communicate with the second interface 6-2 and the fifth interface 6-6 of the first autothermal reforming reactor 6, and controls the third heating rod 6-13 of the first autothermal reforming reactor 6 to heat the flameless hydrogen combustion chamber 6-9, and the catalytic combustion heat release of the hydrogen-oxygen combustion catalyst 6-17 in the flameless hydrogen combustion chamber 6-9 of the first autothermal reforming reactor 6 is used to regenerate the CO2 adsorption-methanol autothermal reforming catalyst 6-14 of the first autothermal reforming reactor 6; if the detected temperature of the second temperature sensor 6-25 of the second autothermal reforming reactor 6' < 400 °C, the control system controls the second solenoid valve-flow controller 9 to make the air inlet end C communicate with the corresponding second interface 6-2 and the fifth interface 6-6 of the first autothermal reforming reactor 6, and controls the residual hydrogen inlet end B to communicate with the third interface 6-3 of the first autothermal reforming reactor 6, and controls the third heating rod 6-13 of the first autothermal reforming reactor 6 to heat the flameless hydrogen combustion chamber 6-9, and the catalytic combustion heat release of the hydrogen-oxygen combustion catalyst 6-17 in the flameless hydrogen combustion chamber 6-9 of the first autothermal reforming reactor 6 is used to regenerate the CO2 adsorption-methanol autothermal reforming catalyst 6-14 of the first autothermal reforming reactor 6.Conversely, when the detected value of the CO2 concentration sensor 6-27 of the second autothermal reforming reactor 6' is greater than the threshold, the control system controls the first autothermal reforming reactor 6 to participate in the operation; when the detected temperature of the second temperature sensor 6-25 of the first autothermal reforming reactor 6 ≥ 400 °C, the control system controls the residual hydrogen inlet end B of the first autothermal reforming reactor 6 to communicate with the third interface 6-3 of the second autothermal reforming reactor 6', and controls the air inlet end C of the first autothermal reforming reactor 6 to communicate with the second interface 6-2 and the fifth interface 6-6 of the second autothermal reforming reactor 6'. The control system controls the third heating rod 6-13 of the second autothermal reforming reactor 6' to heat the flameless hydrogen combustion chamber 6-9. Through the catalytic combustion heat release of the hydrogen-oxygen combustion catalyst 6-17 in the flameless hydrogen combustion chamber 6-9 of the second autothermal reforming reactor 6', it is used to regenerate the CO2 adsorption-methanol autothermal reforming catalyst 6-14 of the second autothermal reforming reactor 6'; if the detected temperature of the second temperature sensor 6-25 of the first autothermal reforming reactor 6 < 400 °C, the control system controls the second solenoid valve-flow controller 9 to make the air inlet end C communicate with the second interface 6-2 and the fifth interface 6-6 of the corresponding second autothermal reforming reactor 6', and controls the residual hydrogen inlet end B to communicate with the third interface 6-3 of the second autothermal reforming reactor 6'. The control system controls the third heating rod 6-13 of the second autothermal reforming reactor 6' to heat the flameless hydrogen combustion chamber 6-9. Through the catalytic combustion heat release of the hydrogen-oxygen combustion catalyst 6-17 in the flameless hydrogen combustion chamber 6-9 of the second autothermal reforming reactor 6', it is used to regenerate the CO2 adsorption-methanol autothermal reforming catalyst 6-14 of the second autothermal reforming reactor 6'. When the detected values of the CO2 concentration sensors 6-27 of the first autothermal reforming reactor 6 and the second autothermal reforming reactor 6' are both less than or equal to the threshold, the process ends.

[0054] During the implementation process, if the detected values of the second temperature sensors 6-25 of the first autothermal reforming reactor 6 and the second autothermal reforming reactor 6' are both less than 400 °C, the system enters the non-steady cold start stage; when the second temperature sensor 6-25 of the first autothermal reforming reactor 6 or the second temperature sensor 6-25 of the second autothermal reforming reactor 6' is greater than or equal to 400 °C, the system enters the steady continuous operation stage.

[0055] Working mode:

[0056] Air is compressed by the air compressor 4 and then divided into 2 streams after passing through the first solenoid valve-flow controller 8, which are the main reaction stream of methanol autothermal reforming and the catalyst purge and regeneration stream respectively.

[0057] In the main reaction stream of methanol autothermal reforming, after passing through the third solenoid valve - flow controller 10, it enters the methanol vaporization chamber 5-9 in the methanol water vaporizer 5 through the carrier gas inlet 5-7 as the carrier gas of methanol vapor; at the same time, methanol and water flow out from the methanol storage tank 1 and the pure water storage tank 2 respectively, are connected to the double-channel peristaltic pump 3 and the first solenoid valve 11 in sequence, and then enter the methanol water vaporization chamber 5-9 from the methanol water inlet 5-1 in the methanol water vaporizer 5 for vaporization to form methanol water vapor. The carrier gas and methanol water vapor are mixed in the methanol vaporization chamber 5-9 and flow out from the mixed gas outlet 5-2. The mixed gas outlet 5-2 of the methanol water vaporizer 5 is respectively connected to the reformed gas inlet end E of the first autothermal reforming reactor 6 and the reformed gas inlet end E of the second autothermal reforming reactor 6'. The carrier gas and methanol water vapor enter the autothermal reforming reaction chamber 6-10 through the third solenoid valve 6-23 and the raw material gas inlet 6-1, and an autothermal reforming reaction takes place at the bed of the CO2 adsorption - methanol autothermal reforming catalyst 6-14; during the reaction, the product gas separates and purifies hydrogen through the supported Pd membrane alloy membrane module 6-8, and the purified high-purity hydrogen flows out through the high-purity hydrogen outlet 6-5 and enters the anode of the hydrogen fuel cell stack 7 through the fourth solenoid valve - flow controller 6-19; at the same time, the unseparated and purified product waste gas flows out through the sixth interface 6-12 and is connected to the CO2 concentration sensor 6-27.

[0058] In the catalyst purge and regeneration stream, it is connected to the air interface C of the first autothermal reforming reactor 6 and the air interface C of the second autothermal reforming reactor 6' respectively through the second solenoid valve - flow controller 9. The catalyst purge and regeneration gas is divided into two paths by the three-way solenoid valve - flow controller 6-20. One path enters the autothermal reforming reaction chamber 6-7 through the second interface 6-2 for purge and regeneration. In the catalyst purge and regeneration gas, there is a small amount of purge and regeneration waste gas that passes through the supported Pd membrane alloy membrane module 6-8, the high-purity hydrogen outlet 6-5, and flows out through the second solenoid valve 6-18; in addition, most of the purge and regeneration waste gas flows out through the seventh interface 6-26. The seventh interface 6-26 is connected to the seventh solenoid valve - flow controller 6-24 and the CO2 concentration sensor 6-27 in sequence, and is connected to the purge and regeneration waste gas inlet 5-3 in the methanol water vaporizer 5 through the purge and regeneration gas interface D and enters the vaporization and heat exchange chamber 5-8, and flows out from the purge and regeneration waste gas outlet 5-4 after heat exchange through the first heat conducting plate 5-6; the other path enters the hydrogen flameless combustion chamber 6-9 through the air inlet 6-6.

[0059] To improve the energy utilization efficiency of the overall reaction system, it is necessary to utilize the residual hydrogen in the hydrogen fuel cell stack 7, forming a residual hydrogen reflux utilization stream. That is, the residual hydrogen in the hydrogen fuel cell stack 7 is divided into two paths and introduced into the flameless hydrogen combustion chamber 6-9 of the first autothermal reforming reactor 6 and the flameless hydrogen combustion chamber 6-9 of the second autothermal reforming reactor 6'. Taking the first autothermal reforming reactor 6 as an example, the residual hydrogen in the hydrogen fuel cell stack 7 sequentially passes through the fifth solenoid valve - flow controller 6-21 and the fuel cell anode residual hydrogen inlet 6-3 and enters the flameless hydrogen combustion chamber 6-9. The residual hydrogen is fully mixed with air and catalytically combusts at the bed layer of the hydrogen-oxygen combustion catalyst 6-17 to generate heat, and the second heat conducting plate 6-15 is used to heat the catalyst purge regeneration gas. Then, the hydrogen-oxygen combustion exhaust gas is connected to the hydrogen-oxygen combustion exhaust gas interface end F of the second autothermal reforming reactor 6' through the fourth interface 6-4 and the sixth solenoid valve - flow controller 6-22, exchanges heat through the second heat conducting plate 6-15 in the second autothermal reforming reactor 6', provides initial energy for the methanol autothermal reforming, and then flows out through the third interface 6-3 and the fifth interface 6-6.

[0060] A first heating rod 5-5 is arranged in the methanol vaporization chamber 5-9 of the methanol vaporizer 5, and its function is to provide heat for methanol vaporization; a third heating rod 6-13 is arranged in the flameless hydrogen combustion chamber 6-9 of the autothermal reforming reactor 6, and its function is to provide initial heat for hydrogen-oxygen combustion; a second heating rod 6-11 is arranged in the autothermal reforming reaction chamber 6-7, and its function is to provide initial heat for the autothermal reforming reaction. The utilization of the residual hydrogen combustion heat and the setting of the heating rods above constitute the heat supply and waste heat utilization system.

[0061] The operation of the system can be divided into the methanol-water vaporization process, the methanol autothermal reforming process, and the purge regeneration process. The specific operation methods are as follows:

[0062] 1. Methanol vaporization process:

[0063] Methanol 1 and water 2 sequentially pass through an adjustable dual-channel peristaltic pump 3, a first solenoid valve 11, and enter the methanol-water vaporization chamber 5-9 of a methanol-water vaporizer 5 through a methanol-water inlet 5-1. In the methanol-water vaporizer 5, the temperature of a first temperature sensor 5-10 is first judged. If the temperature value of the first temperature sensor 5-10 < 140 °C, there are two heating and vaporization methods. When the detected temperatures of a second temperature sensor 6-25 of a first autothermal reforming reactor 6 and a second temperature sensor 6-25 of a second autothermal reforming reactor 6' are both less than 400 °C, the system is in an unsteady cold start stage. At this time, a first heating rod 5-5 is used to heat the methanol aqueous solution to 140 °C to form methanol water vapor. When the detected temperature of the second temperature sensor 6-25 of the first autothermal reforming reactor 6 or the detected temperature of the second temperature sensor 6-25 of the second autothermal reforming reactor 6' in the system ≥ 400 °C, the system is in a steady continuous operation stage. At this time, the purge and regeneration gas of the first autothermal reforming reactor 6 or the second autothermal reforming reactor 6' in the purge and regeneration process is connected to the methanol-water vaporizer 5. The specific connection method is as follows: If the detected temperature of the second temperature sensor 6-25 of the first autothermal reforming reactor 6 ≥ 400 °C, the control system will connect the regeneration purge gas outlet end D of the first autothermal reforming reactor 6 to the vaporization heat exchange chamber 5-8, and use a first heat conducting plate 5-6 for heat exchange to preheat the methanol-water vaporization chamber 5-9 to heat the methanol aqueous solution to 140 °C to form methanol water vapor, and the exhausted gas after heat exchange flows out from a purge and regeneration exhaust gas outlet 5-4. If the first temperature sensor 5-10 ≥ 140 °C, heating is not required.

[0064] Meanwhile, air passes through an air compressor 4, an adjustable first solenoid valve-flow controller 8, and a third solenoid valve-flow controller 10 and enters the methanol-water vaporization chamber 5-9 from a carrier gas inlet 5-7. At this time, the methanol water vapor carries the carrier gas and exits from a methanol water vapor outlet 5-2, passes through a reformed gas interface E, and enters a self-thermal reforming reaction chamber 6-7 of the first autothermal reforming reactor 6 from a first interface 6-1 of the first autothermal reforming reactor 6.

[0065] 2. Methanol autothermal reforming process

[0066] In the self-thermal reforming reaction chamber, to enable the reaction to proceed spontaneously at a relatively low initial temperature (100 °C), it is necessary to adjust the ratio of CH3OH / H2O / O2, that is, control the dual-channel peristaltic pump 3, the first solenoid valve-flow controller 8, and the second solenoid valve-flow controller 9 to adjust the CH3OH / H2O / O2 flow output in real time.

[0067] Meanwhile, heat the bed layer of the CO₂ adsorption - methanol autothermal reforming catalyst 6 - 14 in the autothermal reforming reaction chamber. There are two heating methods. First, when the detected temperature of the second temperature sensor 6 - 25 of the first autothermal reforming reactor 6 < 100 °C and the detected temperature of the second temperature sensor 6 - 25 of the second autothermal reforming reactor 6' < 400 °C, the system is in the non - steady - state cold - start stage, and the initial temperature of the reaction is provided by the heating of the second heating rod 6 - 11 of the first autothermal reforming reactor 6; when the detected temperature of the second temperature sensor 6 - 25 of the second autothermal reforming reactor 6' < 100 °C and the detected temperature of the second temperature sensor 6 - 25 of the first autothermal reforming reactor 6 < 400 °C, the system is in the non - steady - state cold - start stage, and the initial temperature of the reaction is provided by the heating of the second heating rod 6 - 11 of the second autothermal reforming reactor 6'. Second, when the detected temperature of the second temperature sensor 6 - 25 of the first autothermal reforming reactor 6 < 100 °C and the detected temperature of the second temperature sensor 6 - 25 of the second autothermal reforming reactor 6' ≥ 400 °C, the system is in the steady - state continuous - operation stage. At the same time, it can be known that the corresponding second autothermal reforming reactor 6' is in the purging and regeneration process. The fourth interface 6 - 4 of the second autothermal reforming reactor 6' is connected to the fourth interface 6 - 4 in the first autothermal reforming reactor 6, and heat exchange is carried out through the first heat - conducting plate 6 - 16 in the flameless hydrogen combustion chamber 6 - 9 of the first autothermal reforming reactor 6 to provide the initial energy (100 °C) for the methanol autothermal reforming of the first autothermal reforming reactor 6; when the detected temperature of the second temperature sensor 6 - 25 of the second autothermal reforming reactor 6' < 100 °C and the detected temperature of the second temperature sensor 6 - 25 of the first autothermal reforming reactor 6 ≥ 400 °C, the treatment method is similar to the above and will not be described again. If the detected temperature of the second temperature sensor 6 - 25 of the first autothermal reforming reactor 6 and the detected temperature of the second temperature sensor 6 - 25 of the second autothermal reforming reactor 6' ≥ 100 °C, then no heating is required.

[0068] The hydrogen generated by the first autothermal reforming reactor 6 is in - situ separated and purified through the supported Pd - membrane alloy membrane module 6 - 8 in the autothermal reforming reaction chamber 6 - 7. The purified high - purity hydrogen is introduced into the anode of the hydrogen fuel cell stack 7 through the high - purity hydrogen outlet 6 - 5. At this time, the fourth solenoid valve - flow controller 6 - 19 is opened, and at the same time, the second solenoid valve 6 - 18. During the autothermal reforming reaction process as described above, CO₂ is in - situ captured by the used CO₂ adsorption - methanol autothermal reforming catalyst 6 - 14. According to the principle of chemical reaction equilibrium shift, the in - situ separation and purification of hydrogen and the in - situ adsorption of CO₂ promote the forward progress of the autothermal reforming reaction and improve the conversion rate of methanol and water.

[0069] Meanwhile, the product waste gas not separated by the supported Pd membrane alloy membrane module 6-8 enters the CO2 concentration sensor 6-27 through the second interface 6-2. When the concentration of CO2 does not increase to the switching threshold, that is, the CO2 adsorption-methanol autothermal reforming catalyst 6-14 is not saturated in adsorption, the product waste gas flows out directly; when the concentration of CO2 reaches the switching threshold, that is, the CO2 in the CO2 adsorption-methanol autothermal reforming catalyst 6-14 is saturated in adsorption, the operation of the system is divided into two cases. If the detected temperature of the second temperature sensor 6-25 of the corresponding second autothermal reforming reactor 6' < 400 °C, the system is in the non-steady cold start stage. At this time, the second solenoid valve-flow controller 9 is opened, and the third solenoid valve-flow controller 10 is kept open. The third solenoid valve 6-23 of the first autothermal reforming reactor 6 is switched to the third solenoid valve 6-23 of the second autothermal reforming reactor 6'; the three-way solenoid valve-flow controller 6-20, the fifth solenoid valve-flow controller 6-21, and the sixth solenoid valve-flow controller 6-22 of the first autothermal reforming reactor 6 are opened. The first autothermal reforming reactor 6 transitions to the purge regeneration process and enters the steady-state continuous operation stage; when the detected temperature of the second temperature sensor 6-25 of the second autothermal reforming reactor 6' ≥ 400 °C, the system is in the steady-state continuous operation stage. At this time, the second solenoid valve-flow controller 8 and the third solenoid valve-flow controller 10 are kept open. At the same time, the third solenoid valve 6-23 of the first autothermal reforming reactor 6 is switched to the third solenoid valve 6-23 of the second autothermal reforming reactor 6'. The three-way solenoid valve-flow controller 6-20 of the second autothermal reforming reactor 6' is switched to the three-way solenoid valve-flow controller 6-20 of the first autothermal reforming reactor 6, the fifth solenoid valve-flow controller 6-21 of the second autothermal reforming reactor 6' is switched to the fifth solenoid valve-flow controller 6-21 of the first autothermal reforming reactor 6, and at the same time, the direction of the sixth solenoid valve-flow controller 6-22 is switched, that is, the 6-4 of the second autothermal reforming reactor 6' as the outlet of the hydrogen-oxygen combustion waste gas is switched to the 6-4 of the first autothermal reforming reactor 6 as the outlet of the hydrogen-oxygen combustion waste gas, and the 6-4 of the first autothermal reforming reactor 6 as the inlet of the hydrogen-oxygen combustion waste gas is switched to the 6-4 of the second autothermal reforming reactor 6' as the inlet of the hydrogen-oxygen combustion waste gas (changing the connection direction of the hydrogen-oxygen combustion waste gas interface F). Further, the fourth solenoid valve-flow controller 6-19 of the first autothermal reforming reactor 6 is closed, and the corresponding second solenoid valve 6-18 is opened; correspondingly, the fourth solenoid valve-flow controller 6-19 of the second autothermal reforming reactor 6' is opened, and the corresponding second solenoid valve 6-18 is closed. At this time, the first autothermal reforming reactor 6 transitions to the purge regeneration process, and at the same time, the corresponding second autothermal reforming reactor 6' transitions to the methanol autothermal reforming process.

[0070] The purging and regeneration process occurs during the steady-state continuous operation phase. Taking the entry of the first autothermal reforming reactor 6 into the purging and regeneration process as an example, the purging and regeneration gas passes through the opened second solenoid valve - flow controller 9 and the three-way solenoid valve - flow controller 6-20 of the first autothermal reforming reactor 6 and is introduced into the autothermal reforming reaction chamber 6-7 in the first autothermal reforming reactor 6 from the second interface 6-2. The flow rate introduced into the autothermal reforming reaction chamber 6-7 in the first autothermal reforming reactor 6 is regulated by the three-way solenoid valve - flow controller 6-20; the residual hydrogen flow rate of the hydrogen fuel cell stack 7 is regulated by the fifth solenoid valve - flow controller 6-21 of the first autothermal reforming reactor 6 and is introduced into the flameless hydrogen combustion chamber 6-9 from the third interface 6-3 of the first autothermal reforming reactor 6; at the same time, a part of the purging and regeneration gas enters the flameless hydrogen combustion chamber 6-9 through the fifth interface 6-6 of the first autothermal reforming reactor 6, and H2 and O2 are fully mixed; the flameless hydrogen combustion chamber 6-9 is heated by the third heating rod 6-13, and the heated hydrogen-oxygen mixture burns and releases heat on the hydrogen-oxygen combustion catalyst 6-17. The released heat heats the purging and regeneration gas through the second heat conducting plate 6-15 and makes the temperature of the CO2 adsorption - methanol autothermal reforming catalyst 6-14 bed reach 400°C.

[0071] It should be understood that although this specification is described according to each embodiment, not every embodiment only contains an independent technical solution. This narrative way of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

[0072] The series of detailed descriptions listed above are only specific descriptions of the feasible embodiments of the present invention, and they are not used to limit the protection scope of the present invention. Any equivalent embodiments or changes made without departing from the technical spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A product co-enhanced methanol autothermal reforming hydrogen production system based on self-feedback control, characterized in that, It includes two sets of autothermal reforming reactors, a reaction material supply system, and a hydrogen fuel cell stack (7); The reaction material supply system includes a methanol-water supply device, a methanol vaporizer (5), and an air supply device; the methanol-water supply device is used to input a mixture of methanol and pure water into the methanol vaporizer (5); Each autothermal reforming reactor includes a pure hydrogen outlet end A, a surplus hydrogen inlet end B, an air inlet end C, a regeneration purge gas outlet end D, a reformed gas inlet end E, and a hydrogen-oxygen combustion exhaust gas interface end F; the pure hydrogen outlet ends A of the two sets of autothermal reforming reactors are respectively communicated with the inlet of the hydrogen fuel cell stack (7); one outlet of the hydrogen fuel cell stack (7) is respectively communicated with the surplus hydrogen inlet ends B of the two sets of autothermal reforming reactors; the air supply device is respectively communicated with the air inlet ends C of the two sets of autothermal reforming reactors; the regeneration purge gas outlet ends D of the two sets of autothermal reforming reactors are respectively communicated with the methanol vaporizer (5); the reformed gas inlet ends E of the two sets of autothermal reforming reactors are communicated with the mixed gas outlet of the methanol vaporizer (5); the hydrogen-oxygen combustion exhaust gas interface ends F of the two sets of autothermal reforming reactors are communicated with each other; Each autothermal reforming reactor includes a flameless hydrogen combustion chamber (6-9), an autothermal reforming reaction chamber (6-7), a supported Pd membrane alloy membrane module (6-8), and a hydrogen enrichment chamber (6-10); the autothermal reforming reaction chamber (6-7) and the hydrogen enrichment chamber (6-10) are separated by the supported Pd membrane alloy membrane module (6-8); the hydrogen enrichment chamber (6-10) is provided with a pure hydrogen outlet (6-5); the flameless hydrogen combustion chamber (6-9) and the autothermal reforming reaction chamber (6-7) are separated by a second heat conducting plate (6-15); the autothermal reforming reaction chamber (6-7) is provided with a CO2 adsorption-methanol autothermal reforming catalyst layer (6-14) inside; a second heating device is arranged inside the CO2 adsorption-methanol autothermal reforming catalyst layer (6-14); the autothermal reforming reaction chamber (6-7) is provided with a first interface (6-1), a second interface (6-2), a sixth interface (6-12), and a seventh interface (6-26); The hydrogen flameless combustion chamber (6-9) is respectively provided with a third interface (6-3), a fourth interface (6-4) and a fifth interface (6-6); a gas guide plate (6-16) is arranged in the hydrogen flameless combustion chamber (6-9) near the third interface (6-3); a hydrogen-oxygen combustion catalyst (6-17) is coated on the bottom of the hydrogen flameless combustion chamber (6-9); a third heating device is arranged in the hydrogen flameless combustion chamber (6-9); the outlet of the pure hydrogen outlet (6-5) is the pure hydrogen outlet end A; the inlet of the third interface (6-3) is the surplus hydrogen inlet end B; the fifth interface (6-6) is connected with the second interface (6-2) through a three-way solenoid valve-flow controller (6-20), and the other inlet of the three-way solenoid valve-flow controller (6-20) is the air inlet end C; the outlet of the intersection of the sixth interface (6-12) and the seventh interface (6-26) is the regeneration purge gas outlet end D; the inlet of the first interface (6-1) is the reformed gas inlet end E; the outlet of the fourth interface (6-4) is the hydrogen-oxygen combustion exhaust gas interface end F; The methanol vaporizer (5) includes a vaporization heat exchange chamber (5-8), a first heat conducting plate (5-6) and a methanol water vaporization chamber (5-9); the vaporization heat exchange chamber (5-8) is separated from the methanol water vaporization chamber (5-9) by the first heat conducting plate (5-6); the vaporization heat exchange chamber (5-8) is communicated with the regeneration purge gas outlet end D; the methanol water vaporization chamber (5-9) is provided with a methanol water inlet (5-1), a mixed gas outlet (5-2) and a carrier gas inlet (5-7); the methanol water inlet (5-1) is communicated with a methanol water supply device; the mixed gas outlet (5-2) is communicated with the reformed gas inlet end E; the carrier gas inlet (5-7) is communicated with an air supply device; the methanol water vaporization chamber (5-9) is provided with a first heating device; A first temperature sensor (5-10) is arranged in the methanol water vaporization chamber (5-9) for detecting the temperature of the methanol water vaporization chamber (5-9); A second temperature sensor (6-25) is arranged in the autothermal reforming reaction chamber (6-7) for detecting the temperature of the autothermal reforming reaction chamber (6-7); a CO2 concentration sensor (6-27) is arranged at the regeneration purge gas outlet end D for detecting the CO2 concentration at the regeneration purge gas outlet end D; It further includes a control system; the control system obtains the values detected by the first temperature sensor (5-10) and the second temperature sensors (6-25) of 2 groups of autothermal reforming reactors; When the detected temperature of the first temperature sensor (5-10) < 140 °C, if the detected temperature of the second temperature sensor (6-25) of any group of autothermal reforming reactors ≥ 400 °C, the control system will connect the regeneration purge gas outlet end D of the autothermal reforming reactor with the vaporization heat exchange chamber (5-8) for preheating the methanol water vaporization chamber (5-9); if the detected temperatures of the second temperature sensors (6-25) of 2 groups of autothermal reforming reactors < 400 °C, the control system controls the first heating device to heat the methanol water vaporization chamber (5-9).

2. The product synergistic enhanced methanol autothermal reforming hydrogen production system based on self-feedback control according to claim 1, characterized in that When the detected temperature of the second temperature sensor (6-25) of a group of autothermal reforming reactors < 100°C, if the detected temperature of the second temperature sensor (6-25) of another group of autothermal reforming reactors ≥ 400°C, the control system will connect the hydrogen-oxygen combustion exhaust gas interface ends F of the two groups of autothermal reforming reactors through the control of the sixth solenoid valve-flow controller (6-22) for preheating the CO2 adsorption-methanol autothermal reforming catalyst layer (6-14); if the detected temperature of the second temperature sensor (6-25) of another group of autothermal reforming reactors < 400°C, the control system controls the second heating device to heat the CO2 adsorption-methanol autothermal reforming catalyst layer (6-14).

3. The product synergistic enhanced methanol autothermal reforming hydrogen production system based on self-feedback control according to claim 1, characterized in that When the detected value of the CO2 concentration sensor (6-27) of a group of autothermal reforming reactors is greater than the threshold, the control system controls another group of autothermal reforming reactors to operate; when the detected temperature of the second temperature sensor (6-25) of another group of autothermal reforming reactors > 400°C, the control system controls the residual hydrogen inlet end B of another group of autothermal reforming reactors to communicate with the third interface of a group of autothermal reforming reactors, and controls the air inlet end C of another group of autothermal reforming reactors to communicate with the fifth interface of a group of autothermal reforming reactors, and controls the third heating device of a group of autothermal reforming reactors to heat the flameless hydrogen combustion chamber (6-9), and burns through the flameless hydrogen combustion chamber (6-9) of a group of autothermal reforming reactors for regenerating the hydrogen-oxygen combustion catalyst (6-17) of a group of autothermal reforming reactors.

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