A vehicle-mounted mobile methanol autothermal reforming hydrogen production system and a hydrogen production method

Abstract

The application discloses a vehicle-mounted mobile methanol autothermal reforming hydrogen production system and a hydrogen production method. The system comprises a methanol storage tank and a desalted water storage tank, both of which are communicated with a mixed liquid tank, and the mixed liquid tank is sequentially communicated with a gasifier, a premixer, a hydrogen production reactor, a condensation heat exchange unit and a hydrogen purification unit. An air preheating unit is communicated with the premixer and delivers hot air to the premixer. Methanol and desalted water are mixed in the mixed liquid tank, methanol water solution is heated to form a methanol water vapor mixture in the gasifier, hot air is mixed with the methanol water vapor in the premixer, and a methanol autothermal reforming reaction occurs in the hydrogen production reactor. The reaction product is input into the condensation heat exchange unit and the hydrogen purification unit for treatment. The application has the advantages of compact structure, simple operation, good stability and the integration of hydrogen production, storage and utilization, and solves the problems of large hydrogen production system area, high hydrogen transportation safety risk and high hydrogen use cost in the prior art.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of hydrogen production process, and particularly relates to a vehicle-mounted mobile methanol autothermal reforming hydrogen production system and a hydrogen production method. BACKGROUND

[0002] At present, hydrogen production sites are mainly concentrated in chemical plants, and it is difficult to provide hydrogen for terminal users flexibly and in real time. The skid-mounted hydrogen production system has the advantages of overall installation and mobility, and can be moved to a hydrogen production site through hoisting equipment. However, for the hydrogen demand of mobile vehicles, the existing skid-mounted hydrogen production system has the problems of too large volume and too high weight, which is difficult to realize vehicle transportation, and still cannot flexibly and in real time provide hydrogen for mobile vehicles.

[0003] The raw material of the existing industrial hydrogen production is mainly natural gas, and the hydrogen production temperature of natural gas is generally 700-800 DEG C. For the skid-mounted system, the reaction temperature is too high, which is not suitable from the aspects of heat dissipation and safety, and in addition, natural gas is a gaseous raw material, which is not conducive to safe storage and transportation. Methanol, as a liquid hydrogen carrier, can be obtained by various ways such as coal chemical industry, biological synthesis gas and CO2 hydrogenation, has the advantages of high hydrogen storage capacity, convenient transportation, low price, low conversion temperature and good safety, and is suitable for being used as the raw material of the mobile vehicle-mounted hydrogen production system. The product hydrogen of methanol steam reforming has high concentration, low cost and mild reaction, and the presence of steam can promote the CO water gas shift reaction, inhibit the formation of CO and improve the CO2 selectivity, which is one of the most potential methanol conversion hydrogen production methods. However, the reaction is an endothermic reaction, and the energy consumption is large. SUMMARY

[0004] The technical problem to be solved by the present application is that the existing methanol reforming hydrogen production method has the problems of unsatisfactory hydrogen production effect and catalyst stability, and the present application provides a vehicle-mounted mobile methanol autothermal reforming hydrogen production system and a hydrogen production method, which have the advantages of compact structure, simple operation, good stability and can realize the integration of hydrogen production, storage and utilization.

[0005] To solve the above technical problems, the present application adopts the following technical solutions:

[0006] The application discloses a vehicle-mounted mobile methanol autothermal reforming hydrogen production system, which comprises a feed preheating unit, a hydrogen production unit and a product upgrading unit arranged in a container with high packaging property, the feed preheating unit comprises a methanol storage tank, a desalted water storage tank, a mixed liquid tank, a vaporizer, an air preheating unit and a premixer, the hydrogen production unit comprises a hydrogen production reactor, the methanol storage tank and the desalted water storage tank are communicated with the mixed liquid tank, the mixed liquid tank is communicated with the vaporizer, the premixer, the hydrogen production reactor and the product upgrading unit in sequence, the air preheating unit is communicated with the premixer so as to realize the input of hot air into the premixer, the mixed liquid tank is used for mixing methanol and desalted water and inputting into the vaporizer, the vaporizer is used for heating methanol water solution to form a methanol water vapor mixture and inputting into the premixer, the premixer is used for mixing hot air and the methanol water vapor and inputting into the hydrogen production reactor, the methanol autothermal reforming reaction occurs in the hydrogen production reactor, and the obtained reaction product is input into the product upgrading unit for treatment, so as to realize the collection of hydrogen and the external use of the hydrogen.

[0007] As a further improvement of the application, the air preheating unit comprises an air compressor, an air purifier and an air preheater communicated in sequence, air is sucked into the system by the air compressor, filtered by the air purifier and preheated by the air preheater, and then enters the premixer.

[0008] As a further improvement of the application, a heat conducting oil tank is further included, and the heat required by the vaporizer and the air preheater and the heat required by the hydrogen production reactor in the starting stage are all provided by the heat conducting oil tank.

[0009] As a further improvement of the application, the product upgrading unit comprises a condensation heat exchange unit, the condensation heat exchange unit comprises a heat exchanger and a condenser communicated with each other, the outlet of the hydrogen production reactor is connected with the heat exchanger for waste heat utilization, the reaction product enters the condenser after passing through the heat exchanger, and the unreacted methanol water vapor is condensed and recovered.

[0010] As a further improvement of the application, the product upgrading unit comprises a hydrogen purification unit, the hydrogen purification unit comprises a pressure swing adsorption device, a buffer tank and a membrane separation device, the outlet of the condenser is connected with the pressure swing adsorption device, the reaction product enters the pressure swing adsorption device for H2 purification, and the purified H2 is input into the buffer tank for external use; CO2 and N2 in the reaction product enter the membrane separation device for separation and upgrading, the CO2 is captured and reused, and the N2 enters an instrument air system.

[0011] As a further improvement of the application, the pressure swing adsorption device comprises four adsorption towers, the execution time of the four adsorption towers is staggered and alternated in time sequence, so as to realize continuous production of hydrogen.

[0012] As a further improvement of the present application, the hydrogen production reactor adopts a shell-and-tube vertical reactor, the shell and the tube are separated, the catalyst is filled in the reactor tube, and the heat conducting oil is heated in the shell.

[0013] As a further improvement of the present application, the catalyst is Cu / ZnAlZrCeGaO x ; the Cu / ZnO / Al2O3 is pressed into a honeycomb structure, and then Zr, Ce and Ga are impregnated on the honeycomb structure by an impregnation method, and the sources of Zr, Ce and Ga are nitrate or chloride.

[0014] As a general technical concept, the present application also provides a hydrogen production method of the above-mentioned vehicle-mounted mobile methanol autothermal reforming hydrogen production system, which comprises the following steps:

[0015] Step S1, the methanol storage tank and the desalted water storage tank are connected with the first liquid pump, and the methanol and the desalted water are pumped into the mixed liquid tank by the first liquid pump;

[0016] Step S2, the mixed liquid tank is connected with the gasifier, and the methanol water mixed solution is heated into methanol water vapor in the gasifier under the flow of the protective gas N2;

[0017] Step S3, the gasifier is connected with the premixer, the air is treated by the air compressor, the air purifier and the air preheater and then enters the premixer, and the methanol water vapor is uniformly mixed with the hot air in the premixer;

[0018] Step S4, the premixer is connected with the hydrogen production reactor, the methanol water vapor occurs oxidation reforming reaction in the hydrogen production reactor, the methanol water vapor is converted into H2, CO2 and trace CO products in the hydrogen production reactor, the oxygen in the air participates in the reaction as an oxidizing agent, and the unreacted N2 and the products enter the heat exchanger;

[0019] Step S5, the outlet of the hydrogen production reactor is connected with the heat exchanger, and the reaction products exchange heat with the circulating cooling water in the heat exchanger to utilize the waste heat;

[0020] Step S6, the heat exchanger is connected with the condenser, the reaction products are cooled by the circulating cooling water in the condenser, and gas-liquid separation is performed, the unreacted methanol water vapor is condensed into methanol water solution and flows back to the mixed liquid tank;

[0021] Step S7, the condenser is connected with the pressure swing adsorption device, the protective gas N2, the N2 in the air and the gas products H2, CO2 and trace CO enter the pressure swing adsorption device, and 99.99% high-purity H2 is obtained after purification, and the obtained H2 is stored in the buffer tank for external use;

[0022] Step S8, the pressure swing adsorption device is connected with the membrane separation device, the tail gas CO2 and N2 of the pressure swing adsorption device are subjected to upgrading by membrane separation, the separated CO2 is captured, and the N2 is incorporated into the instrument air system.

[0023] As a further improvement of the present application, in the step S2, the temperature of the gasifier is controlled at 110-160 DEG C.

[0024] As a further improvement of the present application, in the step S4, the hydrogen production reactor is filled with the Cu / ZnAlZrCeGaO x catalyst in a honeycomb coal structure.

[0025] As a further improvement of the present application, in the step S6, the desalted water in the circulating cooling water system is used, the circulating cooling water is circulated between the heat exchangers requiring cooling water in the system by a circulating pump, and the circulating cooling water flows back to the desalted water tank after heat exchange.

[0026] Compared with the prior art, the present application has the following advantages:

[0027] 1. The vehicle-mounted mobile methanol autothermal reforming hydrogen production system and method of the present application have the characteristics of high packaging, smaller area and volume, and are packaged in a container, which is easy to install and transport. The hydrogen production system equipment is arranged in the container, the container can be equipped on a vehicle, and the in-situ hydrogen production, gas transportation and hydrogen supply are integrated, which is beneficial to popularization and application.

[0028] 2. The vehicle-mounted mobile methanol autothermal reforming hydrogen production system and method of the present application have more flexible energy supply mode and lower energy consumption compared with the traditional pry-mounted hydrogen production system. In the starting stage, the electric heating heat conducting oil is heated, in the hydrogen production stage, O2 is introduced to realize the methanol autothermal reforming, and the heat conducting oil does not need to be continuously heated. The heat exchanger in the system can recover the waste heat of the product, and the waste heat utilization is realized through the circulation of the heat conducting oil, which greatly reduces the energy consumption of hydrogen production.

[0029] 3. The vehicle-mounted mobile methanol autothermal reforming hydrogen production system and method of the present application use the Cu / ZnAlZrCeGaO x, by pressing Cu / ZnO / Al2O3 into a honeycomb coal structure, and then impregnating Zr, Ce and Ga elements. Compared with the traditional powder stack catalyst Cu / ZnO / Al2O3, the honeycomb coal structure can not only increase the contact area of the catalyst with methanol steam, but also help the flow of raw gas and the diffusion of product gas, effectively improving the methanol conversion rate and hydrogen yield. The added Zr can improve the sintering resistance and help improve the stability of the catalyst; the added Ce can provide more oxygen vacancies, which helps to increase the active sites; the added Ga can improve the element dispersion, which helps to highly disperse the active phase Cu and improve the hydrogen production performance. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 Figure 1 is a schematic diagram of the structure and principle of a vehicle-mounted mobile methanol autothermal reforming hydrogen production system according to an embodiment of the present application.

[0031] Figure 2 Figure 2 is a flowchart of a vehicle-mounted mobile methanol autothermal reforming hydrogen production method according to an embodiment of the present application.

[0032] Figure legend: 1, methanol storage tank; 2, desalted water storage tank; 3, first liquid pump; 4, mixed liquid tank; 5, second liquid pump; 6, gasifier; 7, heat conducting oil tank; 8, air compressor; 9, air purifier; 10, air preheater; 11, premixer; 12, hydrogen production reactor; 13, heat exchanger; 14, condenser; 15, pressure swing adsorption device; 16, buffer tank; 17, membrane separation device. DETAILED DESCRIPTION

[0033] The present application will be further described below in conjunction with the accompanying drawings and specific preferred embodiments, but the protection scope of the present application is not limited thereby.

[0034] Example 1

[0035] As Figure 1As shown, the vehicle-mounted mobile methanol autothermal reforming hydrogen production system of the present application comprises a feed preheating unit, a reforming hydrogen production unit, a product upgrading unit and a distribution box arranged in a container with high packaging, the feed preheating unit comprises a methanol storage tank 1, a desalted water storage tank 2, a mixed liquid tank 4, a gasifier 6, an air preheating unit and a premixer 11, and the reforming hydrogen production unit comprises a hydrogen production reactor 12. The methanol storage tank 1 and the desalted water storage tank 2 are both communicated with the mixed liquid tank 4, and the methanol and the desalted water are respectively extracted from the methanol storage tank 1 and the desalted water storage tank 2 by a first liquid pump 3 and mixed uniformly in the mixed liquid tank 4. The mixed liquid tank 4 is sequentially communicated with the gasifier 6, the premixer 11, the hydrogen production reactor 12 and the product upgrading unit. The air preheating unit is communicated with the premixer 11 to realize the input of hot air into the premixer 11, and the partial oxidation of methanol is realized by introducing air, so that a large amount of energy consumption is saved for the methanol autothermal reforming. The mixed liquid tank 4 is used to realize the mixing of methanol and desalted water, the methanol water mixed solution is input into the gasifier 6 by a second liquid pump 5, the gasifier 6 is used to realize the heating of the methanol water solution to form a methanol water vapor mixture and input into the premixer 11, the premixer 11 is used to realize the mixing of hot air and methanol water vapor and input into the hydrogen production reactor 12, the methanol autothermal reforming reaction occurs in the hydrogen production reactor 12, the H2, CO2 and trace CO products are produced in the reactor, and the obtained reaction products are input into the product upgrading unit for treatment to realize the collection of hydrogen and supply to the outside for use.

[0036] All the equipment and facilities of the present embodiment are highly concentrated and packaged in the container, the length of the container is controlled to be 11-15 m, the width is controlled to be 2.5-3.5 m, the height is controlled to be 3-4 m, and the volume is controlled to be 100-150 m 3 .

[0037] As shown in Figure 1 , in the present embodiment, the air preheating unit comprises an air compressor 8, an air purifier 9 and an air preheater 10 communicated sequentially, air is extracted into the system by the air compressor 8, filtered and preheated by the air purifier 9 and the air preheater 10, and then enters the premixer 11.

[0038] As shown in Figure 1 , in the present embodiment, a heat conducting oil tank 7 is further included, and the heat required by the gasifier 6 and the air preheater 10 and the heat required by the hydrogen production reactor 12 in the starting stage are all provided by the heat conducting oil tank 7.

[0039] As shown in Figure 1 , in the present embodiment, the product upgrading unit comprises a condensation heat exchange unit, the condensation heat exchange unit comprises a heat exchanger 13 and a condenser 14 communicated with each other, the outlet of the hydrogen production reactor 12 is connected to the heat exchanger 13 for waste heat utilization, and the reaction products enter the condenser 14 after passing through the heat exchanger 13 to condense and recover the unreacted methanol water vapor.

[0040] As shown in Figure 1 , in this embodiment, the product upgrading unit includes a hydrogen purification unit, which includes a pressure swing adsorption device 15, a buffer tank 16 and a membrane separation device 17. The outlet of the condenser 14 is connected to the pressure swing adsorption device 15. The reaction product enters the pressure swing adsorption device 15 for H2 purification, and the purified H2 is input into the buffer tank 16 for external use. The CO2 and N2 in the reaction product enter the membrane separation device 17 for separation and upgrading. The CO2 is captured for reuse, and the N2 enters the instrument air system. The hydrogen production capacity of the system after purification is 200-280 Nm 3 .

[0041] In this embodiment, the pressure swing adsorption device 15 includes four adsorption towers, and adopts a process of 4 adsorption towers, 1 adsorption, 2 equalization and flushing desorption. The execution times of the four adsorption towers are staggered and alternated to achieve continuous production of hydrogen.

[0042] According to the device scale and in combination with the reduction of energy consumption, reduction of device land occupation and device stability, the pressure swing adsorption device 15 is provided with four adsorption towers, and adopts a process of 4 adsorption towers, 1 adsorption, 2 equalization and flushing desorption. Each adsorption tower needs to go through 9 steps of adsorption, first equalization and pressure reduction, forward release, second equalization and pressure reduction, reverse release, flushing, second equalization and pressure increase, first equalization and pressure increase, and final pressure increase. The four adsorption towers are staggered and alternated in executing the above steps to achieve the purpose of continuous production of hydrogen. In the adsorption-desorption process, the adsorbent is effectively regenerated through the process of 2 equalization and flushing.

[0043] In this embodiment, the hydrogen production reactor 12 adopts a hexagonal arrangement of tubular shell vertical reactors. The reactor material is plastic Al2O3, aluminum alloy and stainless steel. The reactor column is filled with catalyst, and the methanol water vapor is reformed to produce hydrogen in the column. The heat conducting oil provides heat for the column in the starting stage.

[0044] The methanol autothermal reforming reaction is composed of methanol water vapor reforming and methanol partial oxidation. The methanol water vapor reforming is an endothermic reaction, and the methanol partial oxidation is an exothermic reaction, so that the autothermal operation can be realized. The heat required in the starting stage and the heat required for preheating of raw materials is provided by the heat conducting oil. The heat conducting oil tank is heated by an electric heating method. The heat conducting oil provides heat for the gasifier and the air preheater. The heat conducting oil recovers the waste heat of the mixture outlet of the hydrogen production reactor in the heat exchanger.

[0045] Further, the catalyst filled in the reactor column is Cu / ZnAlZrCeGaO xThe Cu / ZnO / Al2O3 is pressed into a honeycomb structure, and then Zr, Ce, and Ga are impregnated onto the honeycomb structure using an impregnation method. The Zr, Ce, and Ga sources are all nitrates or chlorides. Preferably, nitrates are used as the Zr, Ce, and Ga sources.

[0046] In this embodiment, a honeycomb coal-structured catalyst Cu / ZnAlZrCeGaO is used in the hydrogen production reactor 12. x This catalyst, Cu / ZnO / Al2O3, is pressurized into a honeycomb structure and then impregnated with Zr, Ce, and Ga. Compared to traditional powder-stapled Cu / ZnO / Al2O3 catalysts, the honeycomb structure not only increases the contact area between the catalyst and methanol vapor but also facilitates the flow of feed gas and the diffusion of product gas, effectively improving methanol conversion and hydrogen yield. The added Zr improves anti-sintering properties, contributing to catalyst stability; the added Ce provides more oxygen vacancies, increasing catalytic active sites; and the added Ga improves elemental dispersion, contributing to the high dispersion of the active phase Cu and enhancing hydrogen production performance.

[0047] Example 2

[0048] like Figure 2 As shown, the vehicle-mounted mobile methanol autothermal reforming hydrogen production method of the present invention is implemented based on the hydrogen production system in Example 1, and includes the following steps:

[0049] Step S1: Connect both methanol storage tank 1 and demineralized water storage tank 2 to the first liquid pump 3, and pump methanol and demineralized water into the mixing tank 4 by the first liquid pump 3.

[0050] Step S2: The mixing tank 4 is connected to the vaporizer 6, and the methanol-water mixture is heated into methanol-water vapor in the vaporizer 6.

[0051] In step S3, the vaporizer 6 is connected to the premixer 11. Air is processed by the air compressor 8, air purifier 9, and air preheater 10 before entering the premixer 11. Methanol water vapor and hot air are uniformly mixed in the premixer 11.

[0052] In step S4, the premixer 11 is connected to the hydrogen production reactor 12. Methanol water vapor undergoes an oxidative reforming reaction in the hydrogen production reactor 12, and the methanol water vapor is converted into H2, CO2 and trace CO products in the hydrogen production reactor 12. Oxygen in the air participates in the reaction as an oxidant, and the unreacted N2 and products enter the heat exchanger 13.

[0053] Step S5: The outlet of the hydrogen production reactor 12 is connected to a heat exchanger 13. The reaction products exchange heat with the circulating cooling water in the heat exchanger 13 to utilize the waste heat.

[0054] Step S6, the heat exchanger 13 is connected with the condenser 14, the reaction product is cooled by circulating cooling water in the condenser 14, gas-liquid separation is carried out, the unreacted methanol water vapor is condensed into methanol aqueous solution, and flows back to the mixed liquid tank 4.

[0055] Step S7, the condenser 14 is connected with the pressure swing adsorption device 15, the protective gas N2, N2 in the air and the gas product H2, CO2 and trace CO enter the pressure swing adsorption device, 99.99% high-purity H2 is obtained after purification, and the obtained H2 is stored in the buffer tank 16 for external use.

[0056] Step S8, the pressure swing adsorption device 15 is connected with the membrane separation device 17, the tail gas CO2 and N2 of the pressure swing adsorption device 15 are upgraded by membrane separation, the separated CO2 is captured, and the N2 is incorporated into the instrument air system.

[0057] In step S1 of the embodiment, the molar ratio of the desalted water to the methanol in the mixed liquid tank 4 is 1.0-1.8. The appropriate excess of the desalted water can promote the water gas shift reaction, which is beneficial to reduce the CO byproduct concentration in the hydrogen production stage; but the too high ratio of the desalted water will increase the energy consumption. Further, the molar ratio of the desalted water to the methanol in the mixed liquid tank is 1.0-1.5.

[0058] In step S2 of the embodiment, the temperature of the gasifier 6 is controlled at 110-160℃. Too low temperature will cause incomplete gasification of part of the methanol aqueous solution, and too high temperature will increase the energy consumption. Further, the temperature of the gasifier 6 is controlled at 120-140℃.

[0059] In step S4 of the embodiment, the hydrogen production reactor 12 is filled with the Cu / ZnAlZrCeGaO x catalyst with a honeycomb coal structure. The honeycomb coal structure is beneficial to improve the gas flowability, and at the same time improve the contact area of the methanol water vapor and the catalyst, which is beneficial to improve the methanol conversion rate. The doping of Zr is beneficial to improve the sintering resistance of the catalyst, the doping of Ce is helpful for the catalyst to produce more oxygen vacancies, which provides more active sites for the reaction, and the doping of Ga is helpful to improve the dispersion degree of the active phase.

[0060] In step S6 of the embodiment, the circulating cooling water uses the desalted water in the system, and the circulating pump is used to make the circulating cooling water flow between the heat exchangers in the system which need cooling water, and the circulating cooling water flows back to the desalted water tank after heat exchange.

[0061] Embodiment 3

[0062] In order to realize the hydrogen production demand of 240 Nm 3 / h, the total volume of the vehicle-mounted mobile methanol autothermal reforming hydrogen production system after packaging is 121.5m 3The energy supply mode adopts electric heating and heat conduction assisted autothermal reforming, the raw material liquid is gasified by heat exchange of heat conduction oil, and energy is supplied for the start-up stage of the hydrogen production reaction, and the hydrogen production stage is realized by the exothermic autothermal reforming of methanol partial oxidation. The hydrogen production reactor 12 is filled with honeycomb coal structure Cu / ZnAlZrCeGaO x The mass of the catalyst is 750 kg.

[0063] Example 4

[0064] To realize the hydrogen production of 200 Nm 3 / h demand, the total volume of the packaged vehicle-mounted mobile methanol autothermal reforming hydrogen production system is 101.3 m 3 The energy supply mode adopts electric heating and heat conduction assisted autothermal reforming, the raw material liquid is gasified by heat exchange of heat conduction oil, and energy is supplied for the start-up stage of the hydrogen production reaction, and the hydrogen production stage is realized by the exothermic autothermal reforming of methanol partial oxidation. The hydrogen production reactor 12 is filled with honeycomb coal structure Cu / ZnAlZrCeGaO x The mass of the catalyst is 625 kg.

[0065] Example 5

[0066] To realize the hydrogen production of 220 Nm 3 / h demand, the total volume of the packaged vehicle-mounted mobile methanol autothermal reforming hydrogen production system is 111.4 m 3 The energy supply mode adopts electric heating and heat conduction assisted autothermal reforming, the raw material liquid is gasified by heat exchange of heat conduction oil, and energy is supplied for the start-up stage of the hydrogen production reaction, and the hydrogen production stage is realized by the exothermic autothermal reforming of methanol partial oxidation. The hydrogen production reactor 12 is filled with honeycomb coal structure Cu / ZnAlZrCeGaO x The mass of the catalyst is 687.5 kg.

[0067] Example 6

[0068] To realize the hydrogen production of 260 Nm 3 / h demand, the total volume of the packaged vehicle-mounted mobile methanol autothermal reforming hydrogen production system is 131.7 m 3 The energy supply mode adopts electric heating and heat conduction assisted autothermal reforming, the raw material liquid is gasified by heat exchange of heat conduction oil, and energy is supplied for the start-up stage of the hydrogen production reaction, and the hydrogen production stage is realized by the exothermic autothermal reforming of methanol partial oxidation. The hydrogen production reactor 12 is filled with honeycomb coal structure Cu / ZnAlZrCeGaO x The mass of the catalyst is 812.5 kg.

[0069] Although the present application is disclosed with reference to the preferred embodiments above, it is not intended to limit the present application. Any skilled person in the art, without departing from the spirit and technical solutions of the present application, can make many possible changes and modifications to the technical solutions of the present application disclosed above, or modify equivalent embodiments with equivalent changes. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present application, without departing from the content of the technical solutions of the present application, still belongs to the protection scope of the technical solutions of the present application.

Claims

1. A vehicle-mounted mobile methanol auto-thermal reforming hydrogen production system, characterized in that, The application relates to a high-packaging arrangement of a feed preheating unit, a hydrogen production unit and a product upgrading unit in a container, wherein the feed preheating unit comprises a methanol storage tank (1), a desalted water storage tank (2), a mixed liquid tank (4), a gasifier (6), an air preheating unit and a premixer (11), the hydrogen production unit comprises a hydrogen production reactor (12), the methanol storage tank (1) and the desalted water storage tank (2) are communicated with the mixed liquid tank (4), the mixed liquid tank (4) is communicated with the gasifier (6), the premixer (11), the hydrogen production reactor (12) and the product upgrading unit in sequence, the air preheating unit is communicated with the premixer (11) to realize the input of hot air into the premixer (11), the mixed liquid tank (4) is used for mixing methanol and desalted water and inputting the mixture into the gasifier (6), the gasifier (6) is used for heating methanol water solution to form a methanol water vapor mixture and inputting the mixture into the premixer (11), the premixer (11) is used for mixing hot air and the methanol water vapor and inputting the mixture into the hydrogen production reactor (12), a methanol autothermal reforming reaction occurs in the hydrogen production reactor (12), and the obtained reaction product is input into the product upgrading unit to realize hydrogen collection and external use. The air preheating unit comprises an air compressor (8), an air purifier (9) and an air preheater (10) communicated in sequence, air is sucked into the system by the air compressor (8), filtered by the air purifier (9) and preheated by the air preheater (10) and then enters the premixer (11). The application further comprises a heat conducting oil tank (7), and the required heat of the gasifier (6), the air preheater (10) and the required heat in the starting stage of the hydrogen production reactor (12) are all provided by the heat conducting oil tank (7). The product upgrading unit comprises a condensation heat exchange unit, the condensation heat exchange unit comprises a heat exchanger (13) and a condenser (14) communicated with each other, the outlet of the hydrogen production reactor (12) is connected with the heat exchanger (13) to utilize waste heat, and the reaction product enters the condenser (14) after passing through the heat exchanger (13) to condense and recover the unreacted methanol water vapor. The product upgrading unit further comprises a hydrogen purification unit, the hydrogen purification unit comprises a pressure swing adsorption device (15), a buffer tank (16) and a membrane separation device (17), the outlet of the condenser (14) is connected with the pressure swing adsorption device (15), the reaction product enters the pressure swing adsorption device (15) to purify H2, and the purified H2 is input into the buffer tank (16) for external use; CO2 and N2 in the reaction product enter the membrane separation device (17) to be separated and upgraded, CO2 is captured and reused, and N2 enters an instrument air system.

2. The on-board mobile methanol auto-thermal reforming hydrogen generation system according to claim 1, characterized in that, The pressure swing adsorption device (15) comprises four adsorption towers, the execution time of the four adsorption towers is staggered and alternated in time sequence to realize continuous production of hydrogen.

3. The on-board mobile methanol auto-thermal reforming hydrogen generation system according to any one of claims 1 to 2, characterized in that, The hydrogen production reactor (12) adopts a tubular shell vertical reactor, the shell and the column are separated, catalysts are filled in the column, and heat conducting oil is used for heating in the shell.

4. The on-board mobile methanol auto-thermal reforming hydrogen generation system according to claim 3, characterized in that, The catalyst is Cu / ZnAlZrCeGaO x Cu / ZnO / Al2O3 is pressed into a honeycomb structure, and Zr, Ce, Ga are impregnated onto the honeycomb by impregnation method, and the sources of Zr, Ce, Ga are all nitrate or chloride.

5. A hydrogen production method based on the on-board mobile methanol autothermal reforming hydrogen production system according to any one of claims 1 to 4, characterized in that, The application further comprises the following steps: Step S1, methanol tank (1) and desalted water tank (2) are connected with the first liquid pump (3), methanol and desalted water are pumped into the mixed liquid tank (4) by the first liquid pump (3); Step S2, the mixed liquid tank (4) is connected with the gasifier (6), under the flow of protective gas N2, the methanol water mixed solution is heated into methanol water vapor in the gasifier (6); Step S3, the gasifier (6) is connected with the premixer (11), air is treated by the air compressor (8), air purifier (9) and air preheater (10) and then enters the premixer (11), methanol water vapor is uniformly mixed with hot air in the premixer (11); Step S4, the premixer (11) is connected with the hydrogen production reactor (12), methanol water vapor occurs oxidation reforming reaction in the hydrogen production reactor (12), and is converted into H2, CO2 and trace CO products in the hydrogen production reactor (12); Oxygen in the air participates in the reaction as an oxidizing agent, and unreacted N2 and the products enter the heat exchanger (13); Step S5, the outlet of the hydrogen production reactor (12) is connected with the heat exchanger (13), and the reaction products exchange heat with circulating cooling water in the heat exchanger (13) to utilize the waste heat; Step S6, the heat exchanger (13) is connected with the condenser (14), the reaction products are cooled by circulating cooling water in the condenser (14), and gas-liquid separation is carried out, unreacted methanol water vapor is condensed into methanol water solution and flows back to the mixed liquid tank (4); Step S7, the condenser (14) is connected with the pressure swing adsorption device (15), protective gas N2, N2 in the air and gas products H2, CO2 and trace CO enter the pressure swing adsorption device, and 99.99% high-purity H2 is obtained after purification, and the obtained H2 is stored in the buffer tank (16) for external use; Step S8, the pressure swing adsorption device (15) is connected with the membrane separation device (17), tail gas CO2 and N2 of the pressure swing adsorption device (15) are upgraded by membrane separation, separated CO2 is captured, and N2 is incorporated into the instrument air system.

6. The method of claim 5, wherein, In step S2, the temperature of the gasifier (6) is controlled at 110-160℃.

7. The method of claim 5, wherein, In the step S4, the hydrogen production reactor (12) is filled with the honeycomb coal structure of Cu / ZnAlZrCeGaO x catalyst.

8. The method of claim 5, wherein, In step S6, the circulating cooling water uses desalted water in the system, and the circulating cooling water flows between each heat exchanger in the system which needs cooling water by the circulating pump, and the circulating cooling water flows back to the desalted water tank after heat exchange.

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